Journal of Molecular Structure 1148 (2017) 435e458

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Journal of Molecular Structure

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Review

Metal complexes of hydroxynaphthoquinones: Lawsone, bis-lawsone,

lapachol, plumbagin and juglone
Sunita Salunke-Gawali a, b, *, Eula

lia Pereira b, Umar Ali Dar a, Sujit Bhand a
a
Department of Chemistry, Savitribai Phule Pune University, Pune, 411007, India
b
REQUIMTE-LAQV, Departamento de Química e Bioquímica, Faculdade de Ci^ encias da Universidade Do Porto, 4069-007 Porto, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Coordination chemistry of hydroxynaphthoquinones viz. lawsone (2-hydroxy-1,4-napthoquinone; Lw)

Received 24 May 2017 derivatives, bis-lawsone (2,2
-bi(3-hydroxy-1,4-naphthoquinone; H2bhnq), lapachol (2-hydroxy-3-(3-
Accepted 28 June 2017 methylbut-2-enyl)naphthalene-1,4-dione; Lap), plumbagin (5-hydroxy-2-methyl-naphthlene-1,4-
Available online 30 June 2017
dione; PLN) and juglone (5-hydroxy-1,4-naphthalenedione) have been reviewed in brief with respect
to structural and spectroscopic properties. We aimed to gather most of the potential information of the
Keywords:
known metal complexes of hydroxynapthoquinone derivatives obtained by various chemical and
Hydroxynaphthoquinone
physical methods which are reported till date. A brief description of the synthetic and structural studies
Naphthoquinone
Lawsone
of hydroxynaphthoquinone ligands and their metal complexes are presented. The majority of the
Plumbagin complexes are mononuclear with distorted octahedral geometry, however dimers, trimers, tetramers and
Lapachol polymers also have been reported. In most of the cases various ancillary ligands are present due to
Bis-lawsone solvent or counterion binding, depending on the synthetic procedures. Several “cis, cis” and “trans, trans”
isomeric structures were also reported. The review is a complete information guide for hydrox-
ynapthoquinone and its derivative metal complexes.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction [4], antiviral [5] and antimalarial [6] etc are well known. The
electron accepting ability of naphthoquinone can be modified by
Quinone and their metal complexes have raised a considerable adding different substituents. One way to induce such modification
interest for many years due to their rich redox behavior [1,2]. It is is by the presence of essential metal ions, and different types of
known that the coordination of the hydroxynaphthoquinone to radical from of ligands for example 2,2'-bipyridine [7], pteridine [8],
metal ions varies the redox potential and stability of the semi- ortho, para semiquinone [9], flavin and petrin analogs [10], pyrazine
quinone form. Quinones can bind to metal ions in three different derivative [11], and lumazine derivatives [12]. Naphthoquinones
oxidation states, viz. (i) quinone (oxidized form), (ii) semiquinone are redox active ligands, as compared to other non-innocent li-
(one electron reduced form) and (iii) catechol (two electron gands, the coordination chemistry and catalytic application of these
reduced form), as shown in Fig. 1, for 2-oxido-1,4-naphthoquinone. ligands are least explored. This review highlights the versatility of
Hydroxynaphthoquinone ligands possess variety of structural hydroxynaphthoquinone ligands their metal complexes, biological
peculiarities forming mononuclear, di and polynuclear metal activities, structural and magnetic aspects. The figures of the metal
complexes with transition metal ions and lanthanides. Coordina- complexes presented in this review are generated from the cif files
tion complexes of quinones with different oxidation states reflect obtained from CCDC with the help of Mercury software. The
differences in their structure, magnetic and electrochemical prop- carbonyl bond distances were portrayed on the figures.
erties [2]. Binding ability of quinones in different oxidation states
allows them to play an important role in biological systems. Their
biological applications for example antiproliferative [3], antifungal 2. Overview of hydroxynaphthoquinones

Metal complexes of lawsone derivatives, bis-lawsone, lapachol,

* Corresponding author. Department of Chemistry, Savitribai Phule Pune Uni-
plumbagin and juglone are reviewed with respect to synthesis,
versity, Pune, 411007, India. characterization and molecular structures.
E-mail address: sunitas@chem.unipune.ac.in (S. Salunke-Gawali). Lawsone (2-hydroxy-1,4-naphthoquinone, Fig. 2, abbreviated as

http://dx.doi.org/10.1016/j.molstruc.2017.06.130
0022-2860/© 2017 Elsevier B.V. All rights reserved.
436 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

Bis-lawsone (Fig. 2) is a synthetic derivative of lawsone with po-

tential applications as an antileishmanial agent [24]. Lapachol (2-
hydroxy-3-(2-methyl-1-propenyl)-1,4-naphthoquinone) is a natu-
ral derivative of lawsone extractable from the lapacho tree, that
shows cytotoxic activity against several human cancers, among
other biological properties [25]. Plumbagin (5-hydroxy-2-methyl-
1,4-naphthoquinone) is also a natural dye, it is isolated from plants
of the plumbago family, that shows a wide range of pharmacolog-
ical activities, including anticancer, antimicrobial, etc [26]. Juglone
Fig. 1. Various redox forms of 2-oxido-1,4-naphthoquinone. (5-hydroxy-1,4-naphthoquinone) is a dye commonly used in food
and cosmetic industry, with herbicide properties [27,28]. Sawhney
et al. [29] reported the metal affinities of some hydroxynaph-
thoquinones, the indicator properties of lawsone, lapachol, juglone
and plumbagin.

3. 2-hydroxy-1,4-naphthoquinone (Lw) derivatives as ligands

2-hydroxy-1,4-naphthoquinone and its substituted derivatives

have been widely used as bi- or polydentate ligands for metal
complexation. The ligands generally coordinate as a bidentate
chelating donor system [30], through the 1-oxo group and the
oxygen of the deprotonated 2-hydroxy group. Several derivatives
(Fig. 2) have been studied in order to examine the effect of the
substituents and chelate ring size on coordination [31e33].

4. IR frequencies of lawsone derivatives

IR spectra of lawsone (2-hydroxy-1,4-naphthoquinone),

phthiocol (2-hydroxy-3-methyl-1,4-naphthoquinone) and chlor-
olawsone (2-chloro-3-hydroxy-1,4-naphthoquinone) has been
Fig. 2. Molecular structure of hydroxynaphthoquinones.
studied in CCl4 solvent [35] and the experimental values of nOH and
nC¼O vibrations are compared by DFT studies. Intramolecular
Lw), is a natural dye extractable from henna plant (Lawsonia iner- hydrogen bonding of the C-3 halogen (Cl, Br, I) derivatives were
mis) has been used for more than 5000 years as a skin and hair dye, discussed. FT-IR spectrum of lawsone at low temperature in ‘Ar’ and
currently several other applications in biochemistry and analytical ‘N2’ matrix was reported by Nowak et al. and the vibrational fre-
chemistry are well documented [13e21]. Hydroxynaph- quencies are compared well with those of calculated by Hartree-
thoquinones are also used as an electron transfer mediator in Fock and post Hartree-Fock methods [36]. The most important
biochemical fuel cells [22] and as a novel probe for the assessment
quences of hydroxynaphthoquinones are i) nOH,
vibrational fre
of hydrogen bond donor ability in pure and mixed solvents [23]. symmetric and asymmetric vibrations ~3400 cm1; ii) nC¼O, sym-
metric and asymmetric vibrations ~1650 cm1; iii) nC¼C,
~1585 cm1; iv) p-NQ (paranaphthoquinone) ~1280 cm1; v) nC-O,
~1220 cm1 [10].
O O
FT-IR region between 1600 and 1700 cm1 of naphthoquinones
OH OH is assigned to asymmetric and symmetric nC¼O vibrations. Two
bands are observed for lawsone centered at 1672 cm1 and
CH3 Cl 1661 cm1 in CCl4 and these have been assigned to two possible
O O forms resulting from intramolecular hydrogen bonding i) C(2) hy-
2-hydroxy-3-methyl-1,4-naphthoquinone 2-chloro-3-hydroxy-1,4-naphthoquinone
droxy group with C(1)O(1); Type I and ii) C(2) hydroxy group with
(Phthiocol; Phth) (Chlorolawsone; ClLw) C(3)-halogen as Type II (Scheme 1). The band centered at
O O ~1641 cm1 is completely lost upon complexation, in accordance
OH OH with the assignment of this band to intramolecular hydrogen
bonding with hydrogen of 2-hydroxy group.
Br I
O O

O H O O
2-bromo-3-hydroxy-1,4-naphthoquinone 2-hydroxy-3-iodo-1,4-naphthoquinone
(Bromolawsone; BrLw) (Iodolawsone; ILw) 7
8 1
O O O
H
O O 2

OH OH 6 X
4
3 X X
5
O O O
NO2 NH2
O O
Type I Type II
2-hydroxy-3-nitro-1,4-naphthoquinone 2-amino-3-hydroxy-1,4-naphthoquinone
(Nitrolawsone; NO2Lw) (Aminolawsone; NH2Lw) Scheme 1. Molecular structure of lawsone derivatives, where two types of intra-
molecular hydrogen bonding and delocalization of charge in quinonoid ring (extreme
Fig. 3. C (2)/C (3)derivatives of lawsone. right) is presented.
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 437

Selected FT-IR frequencies of halogen derivatives of lawsone are triethylamine is used, whereas trans, trans coordination is obtained
presented in Table 1 [35]. Minor variation in vibrational frequencies with 2 mmol of triethylamine [51] used in synthesis. In addition,
are due to the polymeric nature of these ligands and intra and inter coordination of hydroxynaphthoquinone with metal ions is always
molecular hydrogen bonding interactions with neighboring mole- anti, anti, when acetate ions are used in reaction mixture [42,56].
cules, resulting from the differences in electronegativity and atomic Most of the synthesis procedures are very similar with minor
size of the halogen group attached to C(2)/(3) position. modifications in the addition sequence of ligand to metal salt so-
lution. A limited number of methods use a mild base or high
5. X-ray crystal structures of lawsone derivatives temperatures for the synthesis. Salunke-Gawali et al. reported the
synthesis of the Cu(II) complex of lawsone [56] and extended their
X-ray crystal structures of lawsone derivatives known till date study to Zn(II) complexes of phthiocol [32], lawsone and chlor-
showed polymeric structures via intermolecular hydrogen bonding olawsone [33], in which Zn(CH3COO)2 was used for complexation.
[31,37e42]. Selected bond distances of the quinonoid ring of Briefly, the metal salt solution was prepared in anhydrous methanol
halogen derivatives of lawsone and their polymorphs are presented followed by drop wise addition to the ligand solution previously
in Table 2 [31,37e42]. Commonly observed molecular interactions prepared in anhydrous methanol. After constant magnetic stirring
are CeH/O, OeH/O and p-p stacking interaction of quinonoid for ~ 1 h, precipitation of the desired Cu(II) complex was observed,
and the benzenoid rings (Figs. 4e7). Polymorphs are differed form whereas for the Zn(II) complexes of lawsone and chlorolawsone the
each other with respect to their molecular association with nearby product precipitated only after addition of a saturated solution of
molecules. All derivatives of lawsone showed OeH/O intra- sodium acetate. Molina et al. [57] reported metal complexes of
molecular hydrogen bonding however, the D-H∙∙∙A angles of Co(II), Ni(II), Cu(II) where hot solution of Co(CH3COO)2$4H2O was
polymorphs are varied. Polymorphs of halogen derivatives of law- added to lapachol and the same procedure was followed for the
sone differed in torsion angles with respect to the plane of quino- copper complex with use of pyridine as base. Bustamante et al. [58],
noid ring and hydroxy group (Table 3). reported the synthesis of a Co(III) complex with lawsone, using
The CeC and CeO bond distances of quinones are sensitive to ratios of Co(CH3COO)2$4H2O, lawsone and triethylamine is 1:2:2 in
their oxidation states [1,2,43e50] and this can be used to adjudge methanol. Red crystalline precipitate of trans-[Co(II)(lawsona-
their oxidation state in metal complexes. The CeO bond distance in to)2(H2O)2]; which was then dissolved in hot methanol and heated
catechol complexes varies in range of 1.32e1.39 Å, while the CeC to reflux for 2 h in presence of N,N0 -bis(pyridin-2-ylmethyl)ethyl-
bond distance is close to aromatic CeC bond distances with an enediamine; (py2en) and NaBF4 to produce the mononuclear bis-
average value of 1.39e1.41 Å, for semiquinone complexes these lawsone complex [Co(III)(bhnq)(py2en)]BF4$H2O.
values are CeO; 1.28e1.31 Å, CeC; 1.42e1.45 Å, for complexes with Metal complexes of lawsone were also synthesized electro-
neutral quinones [43e50] the CeO bond length is ~1.23 Å, and CeC chemically [59e61]. Frontana et al. evaluated the electrochemical
is ~1.53 Å. However, a direct assignment of the oxidation state of reactivity for lawsone anions with Co(II), Ni(II) and Zn(II) ions in
quinones in metal complexes solely based in crystallographic evi- dimethylsulfoxide solution, in situ EPR measurements for the Zn(II)
dence may be misleading if there is presence of metal-semiquinone complex was performed [59]. Heteroleptic complexes of lawsone
antiferromagnetic interaction. and 2,2’-bipyridine (bpy), 1,10-phenanthroline (phen) and 1-
methylimidzole (N-MeIm) were synthesized with Co(II), Ni(II),
6. Metal complexes of lawsone derivatives Cu(II), Zn(II) and Cd(II) [60] electrochemically.
Lanthanide complexes of hydroxynaphthoquinones are syn-
Table 4 represents the metal complexes of hydroxynaph- thesized under nitrogen atmosphere by Chikate et al. [61].
thoquinones reported till date, in various oxidation states. Mostly
transition metal complexes have been synthesized, only a few re- 6.2. Group I metal complexes of lawsone derivatives
ports are known for s- and f-block metals.
There is only single report on K(I) complex of methyl derivative
6.1. Synthetic methods used for metal complexes of lawsone of lawsone commonly known as phthiocol [62], which is charac-
derivatives terized by single crystal X-ray diffraction studies. X-ray crystal
structure reveals that the phthiocol ligand binds to two K(I) ions in
Coordination of hydroxynaphthoquinone ligands to metal ions one electron reduced form (Fig. 8) viz. naphthosemiquinone form
requires deprotonation of the hydroxy group and so it is necessary (Fig. 1). The oxidation state of the ligand has been corroborated by
to perform the synthesis in the presence of a base. Several base X-band EPR studies. Polycrystalline X-band EPR spectra at 133 K
have been used, including pyridine [51], sodium acetate [52], further indicate magnetic coupling between neighboring phthiocol
ammonia [53], 4,4’-bipyridine [54], triethylamine [55], etc. anions, giving rise to a triplet state and half field signal appeared at
Depending on the type of base and its relative amount, the coor- g ¼ 4.1. Potassium ion shows a distorted octahedral geometry and
dination of hydroxynaphthoquinone ligands to metal ions may be coordinates to four phthiocol ligands and a water molecule. The
either cis, cis or trans, trans can be achieved. For example, the co- carbonyl and CeC bond distances in semiquinone complexes were
ordination of lawsone to Zn(II) is ‘cis, cis’ when 1 mmol of found to be 1.28e1.31 Å and 1.42e1.45 Å. 13C NMR spectra shows

Table 1
FT-IR bands of C(3)/C(2) derivatives of lawsone (Refer Fig. 3 for molecular structures) [34].

Assignment Lawsone (Lw) (cm1) Chlorolawsone (ClLw) (cm1) Bromolawsone (BrLw) (cm1) Iodolawsone (ILw) (cm1) Phthiocol (Phth) (cm1)

OH 3183 3274 3206 3154 3373

C¼O 1678 1678,1660,1639 1671,1633,1585 1671,1646,1619 1658
C¼C 1585 1587 1579 1578 1590
(p-NQ) 1284 1273 1265 1255 1276
CeO 1222 1220 1213 1211 1209
C-X (halogen) e 721 723 716 e
438 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

Table 2
Bond distances of quinonoid ring of lawsone derivatives [34] (for (vi) bond distances of three asymmetric molecules).

Lw(i) Pna21 (ii)P21/c (iii) P-1 ClLw (iv) Pc, (v)Pn BrLw (vi) Cc ILw (vii) P212121(viii) Cc (ix) Cc

C(4)-O(4) (i)1.212 (6) (iv)1.264, (vi)1.220 (4), (vii)1.216 (4),

(ii)1.224(4),1.215(3),1.219(3) (v)1.218 (3) (vi)1.211 (4), (viii)1.197(7),1.216(5),1.209(5)
(iii)1.207(2),1.209(3), (vi)1.212 (4), (ix)1.238(8),1.223(9),1.217(9)
C(3)-O(3) (i)1.334 (7) (iv)1.307, (vi)1.333 (4), (vii)1.332 (5)
(ii)1.331(4),1.339(3),1.343(3) (v)1.334 (3) (vi)1.341 (4), (viii)1.331(7), 1.345(7),1.330(7)
(iii)1.333(2),1.331(2) (vi)1.327 (4) (ix)1.31(1), 1.33(1), 1.35(1)
C(1)-O(1) (i)1.231 (6) (iv)1.276, (vi)1.209 (3), (vii)1.220 (5)
(ii)1.226(3),1.232(3),1.234(3) (v)1.220 (3) (vi)1.232 (4), (viii)1.222(5),1.215(5),1.226(5)
(iii)1.228(2),1.229(2) (vi)1.211 (4) (ix)1.221(8),1.221(9),1.208(9)
C(4)-C(3) (i)1.505 (7) (iv)1.477, (vi)1.489 (5), (vii)1.494 (5)
(ii)1.497(4),1.486(4),1.492(4) (v)1.490 (4) (vi)1.497 (5), (viii)1.514(6),1.495(6),1.510(6)
(iii)1.495(2),1.496(2) (vi)1.497 (5) (ix)1.49(1),1.51(1),1.48(1)
C(3)-C(2) (i)1.322 (7) (iv)1.339, (vi)1.333 (4), (vii)1.342 (5)
(ii)1.325(5),1.326(4),1.320(4) (v)1.342 (3) (vi)1.345 (4), (viii)1.345(6),1.333(6),1.339(6)
(iii)1.338(2),1.340(2) (vi)1.347 (4) (ix)1.351(9),1.35(1),1.36(1)
C(2)-C(1) (i)1.411 (7) (iv)1.405, (vi)1.474 (4), (vii)1.467 (6)
(ii)1.440(4),1.450(4),1.455(4) (v)1.467 (4) (vi)1.477 (5), (viii)1.457(7),1.485(7),1.455(7)
(iii)1.450(3),1.451(3) (vi)1.459 (5) (ix)1.46(1),1.48(1),1.45(1)
C(4)-C(10) (i)1.502 (7) (iv)1.427, (vi)1.483 (5), (vii)1.473 (5)
(ii)1.472(4),1.477(4),1.464(4) (v)1.473 (4) (vi)1.467 (5) (viii)1.484(8),1.482(7)1.474 (7)
(iii)1.474(3),1.474(2) (vi)1.486 (5) (ix)1.45(1),1.47(1),1.46(1)
C(1)-C(9) (i)1.502 (7) (iv)1.439, (vi)1.493 (5), (vii)1.502 (6)
(ii)1.500(4),1.492(4),1.484(4) (v)1.484 (4) (vi)1.481 (5) (viii)1.501(6),1.493(6),1.499(6)
(iii)1.474(3),1.486(2) (vi)1.489 (5) (ix)1.49(1),1.48(1),1.52(1)
C(2)-X e (iv)1.723, (vi)1.874 (3) (vii)2.077 (3)
(v)1.719 (3) (vi)1.870 (3) (viii)2.083(4),2.076(4),2.080(4)
(vi)1.885 (3) (ix)2.073(8),2.066(8),2.079(8)

O of all compounds reveals the naphthosemiquinone form of the li-

Quinonoid ring
OH gands. Yadav et al. reported [67] mixed ligand alkali metal com-
plexes of phthiocol with ligands including acetylacetone, benzoyl
R acetone, salicylaldehyde, o-hydroxynaphthaldehyde and ethyl-
O acetoacetate. IR spectra indicate hydrogen bonding in the
Benzenoid ring complexes.

Fig. 4. Representation of benzenoid and quinonoid rings.

6.3. Group III to XII (transition metal complexes) of lawsone
derivatives

deshielding of C(2) with d ¼ ~14.6 ppm and C(3) showed an up field Salunke-Gawali et al. [32,32,33], reported several Zn(II) com-
signal at d ¼ ~6.9 ppm due to complexation of phthiocol ligand with plexes of lawsone and its C(2)/C(3) derivatives, viz. [Zn(Lw)2(H2-
K(I). The experimental results and interpretation were supported O)2].3H2O; (1), [Zn(ClLw)2(H2O)2]$H2O; 2, [Zn(BrLw)2(H2O)2]; 3 [Zn
by DFT studies. (phthiocol)2(H2O)2]; 4. These complexes are useful as host for
Na(I) and K(I) complexes of lawsone [63,64], chlorolawsone adsorbed water molecules, as assessed by thermogravimetric (TG)
[60e65] and phthiocol [66] were synthesized by reaction of the studies, that showed loss of the three adsorbed water molecules in
ligand with NaOH, KOH, Na2CO3, K2CO3 and CH3COONa. EPR spectra complex 1, and one adsorbed water molecule in complex 2 ~100  C.

Fig. 5. Packing of molecules in lawsone (P21/c) (down b-axis) and lawsone (Pna21) (down c-axis).
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 439

Fig. 6. a) p-p stacking of symmetry equivalence polymorph of chlorolawsone (C2/c) chains down a-axis, b) Polymer chain formed by OeH/O and CeH/O of ‘chlorolawsone (C2/c)’
polymorph also showed inter chain CeH/Cl interaction down b-axis [39,40].

Fig. 7. Molecular packing of BrLw molecules down a-axis (left) and polymeric chains of BrLw molecules [31].

Table 3
Intramolecular hydrogen bonding and torsion angles of lawsone derivatives.

R Space group Molecules in asymmetric unit :a-b-c D…A :a-b-c-d :e-b-c-d

H P-1 2 115 (1) 2.672 (2) 0.3 (9) 179.9 (9)

115 (1) 2.67892) 4.9 (9) 176.3 (9)
P21/c 3 115.2 (2) 2.676 (3) 1.5 (4) 178.1 (3)
115.8 (2) 2.675 (3) 2.2 (4) 178.8 (3
115.4 (2) 2.673 (3) 4.4 (4) 176.1 (3)
Cl Pna21 1 115.9 (3) 2.676 (6) 7.4 (6) 172.7 (5)
Pc 1 e 2.643 e e
Pn 1 114.6 2.661 (3) 6.8 175.0
Br Cc 3 111.2 (2) 2.685 (4) 23.1 (4) 158.1 (3)
109.2 (2) 2.674 (4) 6.8 (4) 174.3 (8)
114.2 (2) 2.677 (4) 19.1 (4) 179.7 (8)
I P212121 1 112 (3) 2.653 (4) 8 (3) 162.0 (3)
Cc 3 116.7 (5) 2.61 (1) 1 (1) 179.9 (8)
115.4 (5) 2.68 (1) 1 (1) 179.9 (7)
114.5 (5) 2.66 (1) 0 (1) 179.7 (8)
Cc 3 109 (4) 2.691 (6) 3 (4) 179 (4)
119 (3) 2.668 (6) 10 (3) 171 (3)
115.4 (3) 2.6676) 2.4 (6) 179.8 (5)
eCH3 P21 1 114.2 2.655 (2) 5 (2) 177.7 (1)
440 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

Table 4
Metals in group forming complexes with hydroxynaphthoquinone.

s block d block p block f block

Groups

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

K, Na Be Y Zr Cr Mn Fe Co Ni Cu Zn Al Sn La, Ce,
Sb Pr, Nd, Pm, Sm, Gd, Dy
Ru Pd Au Cd Pb
Os Ir Pt Hg Bi

Fig. 8. a) Molecular structure of complex K(I) complex of phthiocol and b) Packing viewed down c-axis. Molecular packing showed channels with water molecules hydrogen bonded
to the phthiocol ligand.

Fig. 9. OeH/O hydrogen bonding network of 2 and polymeric chain formed by quinonoid oxygen O(2) (left) and coordinated H2O molecules in 4 (right).
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 441

Single crystal X-ray diffraction studies of 2, 3 and 4 showed dis-

torted octahedral geometry around Zn(II) [32], with trans, trans
coordination of ligands and a polymeric chain formed through
OeH/O and CeH/O hydrogen bonding interaction (Fig. 9). The
two chelating ligands are in plane with the Zn(II), while the two
water molecules are bound at the axial positions. Upon complex-
ation with the metal, the carbonyl stretching frequency shifts to
lower wavenumbers in all Zn(II) complexes. 1HNMR spectra
showed an up field shift to the benzenoid ring protons [32].

.
Bustamante et al. [55], reported Zn(II) complexes of bis-lawsone,
providing a new insight into isomerism and nuclearity control in
the (Lw) complexation reaction. Three new bis(lawsonato)zinc(II)
complexes were reported, namely cis, cis, cis-[Zn
(Lw)2(H2O)2]$ 2H2O; 5a, trans, trans, trans [Zn (Lw)2(H2O)2]; 6 and
[Zn2Lw4 (py)2]. 2H2O; 7. The coordination geometry and nuclearity
of the product was controlled through modification of the addition
sequence of reactants and through the type of the base (pyridine v/s
triethylamine) used in synthesis. Complex 5a has Zn(II) ion coor-
dinated to two lawsonate anions and two water molecules in a cis
configuration with distorted octahedral geometry. Complex 6 is the
trans isomer relative to complex 5a. Complex 7 is a dimer, where
each Zn(II) ion is coordinated to two lawsone anions in a cis
configuration and to one pyridine molecule. Authors further
showed that when these complexes are dissolved in DMSO, they
convert to monomeric species; [Zn (Lw)2 (DMSO)2], as supported
by 1H NMR and UVevisible spectra. Sandra et al. [68] synthesized
complex 5b using from Zn(CH3COO)2 as metal precursor. The bond .
distances of carbonyl in complex 5b are longer as compared to 5a, The lawsone ligand in complexes 5a and 6 coordinates to Zn(II)
thus the lawsone ligands are coordinated in naphthosemiquinone in the oxidized form, as assessed by the carbonyl bond distances.
form. The dimer Zn(II) complex 7 shows two types of coordination of the
442 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

113
Cd NMR spectrum of the complex shows one sharp peak close to
standard, suggesting it is a six coordinated species in DMSO solu-
tion. The percent mass loss in TG studies of adsorbed water mole-
cule and a coordinated water molecule are in accordance with the
number of water molecules observed in the X-ray structure.

Fig. 10. p-p stacking interaction between quinonoid and pyridine rings of 7.

lawsone ligands viz terminal and bridged. It is interesting to note

that the carbonyl bond distances of the bridged lawsone ligands of
7 were closer to the bond distances of the one electron reduced
form, i.e. the naphthosemiquinone form (Fig. 1). In addition, the
bridged lawsone ligands are not involved in p-p stacking interac-
tion, whereas the terminal lawsone ligands showed p-p stacking
interaction with the pyridine ligands (Fig. 10).
FTIR bands of the ‘cis’ isomer are broader than those of the ‘trans’ Swahney et al. reported binding constants of Hg(II) with law-
isomer suggesting a strong influence of intermolecular hydrogen sone for the 1:2 complex [76]. The potentiometric and IR data
bonding [69e71]. These results are also in good agreement with the support the deprotonation of the phenolic group and formation of a
work reported by Garge et al. [69], for the Fe(II) complex [Fe(L- chelate by coordination of the enolic anion and the adjoining keto
w)2(H2O)2]; (8). oxygen, forming a five-member ring. IR studies, supporting the
above conclusions and showed peaks at 3125 cm1 and 1650 cm1
attributable to OeH stretching vibration manifesting the strong
hydrogen bonding in lawsone and carbonyl stretching vibration,
respectively. The former band disappears whereas the latter is
shifted to 1577 cm1indicating the presence of a C]O∙ ∙∙∙Hg co-
ordinate bond, on chelation.
A supra molecular copper complex [Cu(Lw)2(H2O)2]n; 10, has
been reported by Salunke-Gawali et al. [56] X-ray studies showed
that the monomeric units of complex 10 are linked by three
different types of intermolecular hydrogen bonding (OeH∙∙∙O and
CeH∙∙∙O) through coordinated lawsone ligands and water mole-
High spin Fe(II) complexes of C(3) substituted eCH3, eCl, eBr, eI
cules, resulting in a supramolecular three dimensional hydrogen
and eNO2, eNH2 lawsone (Fig. 2) are characterized by 57Fe Moss-
bonding network (Fig. 11). As this copper complex is polymeric, its
bauer spectroscopy and by variable temperature magnetic sus-
magnetic susceptibility data was best fitted to the Bonner Fischer
ceptibility measurements [72]. Typically, 57Fe isomer shift
equation with the coupling parameter J ¼ 3.2 cm1, indicating a
d ¼ ~1.2 mm/s and quadrupole splitting of DEQ ¼ ~2.4 mm/s was weak antiferromagnetic interaction of Cu(II) ions in the polymeric
observed for these complexes. Padhye et al. also reported the X-ray
chain. The Cu(II) ion is hexacoordinated with two bidentate law-
crystal structure of the Mn(II) complex of the vitamin K3 analog,
sone ligands and two water molecules. The Cu(II) complex of law-
phthiocol [73], where the phthiocol and the pyridine ligands have a
sone with a pyridine adduct is also known [77].
trans, trans conformation.
Fe(II) complex of lawsone was synthesized electrochemically
[74]. The reduced naphthosemiquinone form of ligand forms a
stable complex with Fe(II). Magnetic susceptibility measurements
of the Fe(II) naphthosemiquinone complex indicate the existence of
an intramolecular charge transfer between the metal ion and one of
the naphthosemiquinone ligand, so that the metal center is best
described as Fe(III).
Cd(II) complex of lawsone, [Cd(Lw)4(H2O)4]$3H2O; (9) [75], was
found to be in isolated dimeric unit. The geometry of this complex
is pentagonal-bipyramidal and there are two independent depro-
tonated lawsone ligands per Cd(II) ions, one forming a chelate and
another forming a chelate and a bridge to another Cd(II) ion. The

Fig. 11. ORTEP view of molecular packing of [Cu(Lw)2(H2O)2]; 10 showing the possible
intermolecular hydrogen bonding networks (showing 30% probability thermal
ellipsoids).
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 443

ions Ni(II), Co(II), Zn(II) of empirical formula [M(II)(Lw)2(Py)2], in

DMSO. Spectroscopic and magnetic data (effective magnetic
moment for the Co(II) complex is 4.60 B.M. and for the Ni(II)
complex is 3.1 B.M.) are in good agreement with an octahedral
coordination around the metal ions.

zquez et al. [60] reported new homoleptic and heteroleptic
Va
compounds of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) with lawsone
with empirical formula [Co(Lw)2(H2O)2]$MeOH; 11, [Co(Lw)2(H2O)
(MeOH)]; 12, [Cu(Lw)2(N-MeIm)2]; 13 [Co(Lw)2(bipy)]; 14,
[Zn(Lw)2(bipy)]; 15 and [Cd(Lw)2 (bipy)]; 16. These complexes were
synthesized electrochemically, using the respective metal as the
anode in an acetonitrile solution containing the ligand [80e85].
X-ray crystal structure of hydroxynaphthoquinone complexes Except for the copper complex, the quinone binds as monoanionic
reveals that the water as well as other solvent molecules are either bidentate ligand. Elemental analysis data showed that the metal to
coordinated or present as solvates in the crystal lattice. Thermog- ligand molar ratio is 1:2 and this ratio is also corroborated by the
ravimetric tools play an important role in deciding the composition electrochemical efficiency; Ef, defined as the amount of metal dis-
of hydroxynaphthoquinones complexes [78,79]. Thermogravimetry solved per Faraday of charge, is in all cases close to 0.5 mol F1. This
(TG) can also provide the information on oxidation states of the behavior has been observed previously in the electrochemical
hydroxynaphthoquinone ligands, based on their decomposition synthesis of Cu(II) complexes [86e88]. X-ray studies showed that
[52,53,62]. the metal ions of complex 11 and 12 are in a distorted octahedral
Sandra et al. synthesized Zn(II), Cu(II), Ni(II), Co(II) and Mn(II) geometry, with a cis, cis coordination in 11 and trans, trans in 12
complexes of lawsone and studied their cytotoxic activity against a with a varying molecular packing, as shown in Fig. 12, dominated
mouse leukemic macrophagic RAW 264.7 cell line [68]. Authors by OeH/O intermolecular interactions. Carbonyl bond distances of
further reported that the significant growth inhibition was compounds 11 and 12 suggest the lawsone ligand coordinates in
observed to copper complex with IC50 value of 2.5 mM. The cyto- the naphthosemiquinone form. Moreover the two coordinated
toxic activity of Cu(II) complex was further evaluated on human lawsone ligands have different p-p stacking interactions in com-
cancer cell lines, including HT-29 (human colorectal adenocarci- plex 11 and 12. In complex 13, the Cu(II) ion has a regular square
noma), HePG2 (human hepatocytecarcinoma) and HeLa, (human planar environment with the lawsone ligand in a trans, trans co-
cervical adenocarcinoma). X-ray crystal structures of the Zn(II) and ordination, whereas in 14, 15 the complexes are six coordinated
Co(II) complexes were also reported. with distorted octahedral geometry while complex 16 has a
Frontana et al. [59] reported the changes in the reactivity of a trigonal prismatic geometry.
series of lawsone anion and pyridine (Py) complexes with metal

Fig. 12. Molecular packing of 11 (left) and 12 (right) down b-axis.

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446 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

Co(II) complexes of lawsone with empirical formula [Co(L- showed that the cis, cis isomer is more stable than the trans, trans
w)2(im)2].C6H5CH3;17, [Co(Lw)2(py)2].CH3OH;18, [Co(Lw)2(phen)] isomer. Furthermore, electrochemical studies demonstrate that the
(C4H8O)2;19, [Co(Lw)2(2,2
-bpy)2].C6H5CH3;20 and [Co(Lw)2(2,2
- redox properties of the lawsone ligand can be significantly tuned by
bpy)2]; 21, possess a cis, cis coordination of lawsone ligands [89]. X- the substituent's in the ancillary pyridine ligands. Carbonyl bond
ray crystal structure showed similar coordination around the Co(II) distances in lawsone in the complex are typical of the naph-
ion i.e. four oxygen atoms from two lawsone ligands and two ni- thosemiquinone form.
trogen atom from the ancillary ligands in a distorted octahedral The ‘trans, trans’ conformer was found to be 8 kJ mol-1 lower in
geometry. Authors suggested that complex 21 is a valence energy than the ‘cis’ conformer of Zn(II) complex of lawsone
tautomer; (VT) and the results are compared with the valence (Fig. 13) [31].
tautomer complex [Co(3,5-DTSQ)(3,5-DTCat)bpy]. However, EPR
spectra of all complexes showed no evidence of radical coordina-
tion or high spin Co(III) species.

Panja et al. [90] reported the synthesis of two cis, cis, Co(II)
complexes 22, 23 with lawsone containing two ancillary pyridine
ligands with electron donating and electron withdrawing func-
tional groups. Mild basic condition were used in the synthesis using
Co(NO3)2 2.5H2O as the metal precursor. However when Co(CH3-
COO)2 $4H2O was used as the metal precursor the complex formed
is the trans, trans isomer of [Co(Lw)2(H2O)2]; 24 [68]. DFT studies
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 447

Fig. 13. Optimized structure calculated by DFT (wB97x) for ‘cis, cis’ and ‘trans, trans’ [Zn (Lw)2(H2O)2].

[Cu(L)(H2O)(m-Cl)Cu(L)Cl]; 26, [CuCl(L)(m-Cl)Cu(amp)Cl]; 27, and a

Ir(II) complexes are known as potential anticancer agents polymeric compound, [Cu(L)Cl)]n.
with coordinated ligands having general formula [IrCp*(Lw)Cl];

25, in this complex lawsone ligand is bidentate and binds to the 6.4. Inner transition metal complexes of lawsone derivatives
metal upon deprotonation [91].
El-Hendawy reported complexes of lawsone with uranium, The inner transition metals of lawsone were rarely studied.
molybdenum, ruthenium and osmium and their use as organic Lanthanide complexes La(III), Ce(III), Pr(III), Nd(III), Sm(III), Gd(III)
oxidants [92]. The ruthenium complex [RuCl2(AsPPh3)2(Lw)] was and Dy(III) of the type ML3.nH2O (where M stands for trivalent rare
found to be a more efficient catalyst than the osmium complex for earth metal ion, L for lawsone and n ¼ 0 or 1) are known [94]. The
the oxidation of primary alcohols to aldehydes and secondary al- chelates of Pr(III), Sm(III) and Dy(III) show slightly higher values of
cohols to ketones in the presence of methyl morpholine-N-oxide as the magnetic moments which might partly be due to the low lying
the co-oxidant. excited states which are appreciably populated at room tempera-
A novel versatile tridentate 3-(aminomethyl)-1,4- ture [95]. The data are consistent with octahedral geometry for
naphthoquinone proligand, 3-[N-(2-pyridylmethyl) amino most of the complexes, except for those of Ce(III), Gd(III) and Dy(III)
benzyl]-2-hydroxy-1,4-naphthoquinone; (L) (Fig. 14) [93] has been which show a slight deviation from such symmetry.
obtained via Mannich reaction of lawsone with 2- Chikate et al. [61] reported octa-coordinated La(III), Ce(III),
aminomethylpyridine (amp) and benzaldehyde. The reactions of Nd(III), Sm(III), Gd(III), and Dy(III) of aminolawsone (Fig. 1) having
(L) with CuCl2 $2H2O yielded two novel dinuclear Cu(II) complexes, the empirical formula [M(NH2Lw)3(H2O)2]. Spectral data indicates

Fig. 14. Molecular structure of L and its metal complexes (L, 26 and 27).
448 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

that the C(2) hydroxy and C(3) amino groups are the binding sites ligand interactions such as p-p stacking and hydrogen bonding
for amino-lawsone, while the uncoordinated quinone carbonyls are interaction, which could maintain the high stability of solid state
involved in intermolecular hydrogen bonding with coordinated structures. Complexes synthesized with this hinge like ligand
water molecules. Thermogravimetric studies showed that thermal provides cavities between adjacent molecules which could be uti-
decomposition occurs in two steps: a first step with loss of one lized to host for small guest molecules in the crystal. After
coordinated water molecule and one ligand molecule; and a second complexation this ligand could also act as a chiral ligand, through
step with loss of one coordinated water molecule and two ligand restricted rotation along the CeC single bond.
molecules. The higher activation energy of the first step in com-

parison to the second step was related to the extended intra- The deprotonated form of bislawsone ligand; bhnq crystallizes
molecular hydrogen bonding, which was also corroborated by the in P-1 space group [97]. The carbonyl bond distances of both the
low magnetic moments of these complexes. naphthoquinone moieties to that of the oxidized form of the ligand
Binuclear octa-coordinated lanthanide (III) complexes of 2,3- is hydrogen bonded to pyridinium cation. There is p-p stacking for
dihydroxy-1,4-naphthoquinone (isnphth) with empirical formula bhnq neighboring molecules through benzenoid and quinonoid
[M2L3(H2O)4] (M ¼ lanthanide) L¼ (C30H20O16) has been reported rings and also through the pyridinium cation (Fig. 15).
[96]. The thermal decomposition revealed two stage patterns; stage Several complexes of first row transition metal ions are known
I corresponding to loss of four coordinated water molecules and in [98] viz., {[Cu(bhnq)(H2O)2](H2O) (EtOH)3}n;29,
stage II the structure of these complexes is reorganized forming {[Cu(bhnq)(THF)2](THF)}n;30, {[Cu(bhnq)(H2O)2](diox-
two distinct monomeric species, implying that the ligand bridges as ane)(H2O)4}n;31, {[Co(bhnq) (H2O)(EtOH)](H2O)2(EtOH)}n;32,
well as the intermolecular associations are essential for thermal {[Zn(bhnq)(H2O)(thf)](H2O)(THF)}n;33, [Ni4(bhnq)4(H2O)8](-
stability. Energy of activation (Ea) for stage II exhibits linear in- H2O)10(EtOH)6;34, [Ni4(bhnq)4(H2O)8](H2O)16(THF)4;35,
crease with decrease in the size of lanthanide ion. 1H and 13C NMR [Zn2(bhnq)2(MeOH)4](MeOH)2;36, {[Zn (bhnq)(H2O)2](H2O)2}n;37,
spectrum of (isnphth) and its lanthanide chelate also evidenced {[Zn(bhnq)(H2O)(EtOH)](H2O)(EtOH)2}n;38. The bis-lawsone
strong intermolecular hydrogen-binding between hydroxy oxygen ligand bridged between the Cu(II) centers of complexes 29e31
and quinone carbonyl. IR data indicate bonding via hydroxy oxygen that leads to one-dimensional ‘zig zag’ chain structure. Due to
with quinone carbonyls acting as bridged between lanthanide ions presence of hydrogen bonding interactions and stacking
and forming an extended network of intermolecular hydrogen
bonding involving coordinated water and quinone carbonyls.

7. Metal complexes of 2,2
-bi(3-hydroxy-1,4-naphthoquinone)

(H2bhnq; bis lawsone)

2,2’-bi(3-hydroxy-1,4-naphthoquinone) (Fig. 2) is a hinge like

ligand which can be derived from lawsone. There are two naph-
thoquinone moieties in this ligand joined by CeC single bond. This
allows the rotation along CeC single bond, providing conforma-
tional flexibility to this ligand. The p conjugation in this ligand is
influenced by the dihedral angle between the two naphthoquinone
rings. The degree of conjugation can be changed in metal com-
plexes with this hinge like ligand, which could offer structural
advantages for solid state materials. There are four different type of
architectures of assemblies that might exist with this hinge ligand,
viz. zig-zag, helix, square and dimer. The one dimensional chain
with this hinge ligand is so flexible that the chain can easily expand
and contract with the change of dihedral angles between naph- Fig. 15. Molecular packing of 28 down a axis p-p stacking is visible benzenoid and the
thoquinone groups. Hinge like ligands may enhance the inter- pyridinium ring.
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 449

interactions, the resulting solid structure is highly porous. Co(II); 32 and it is obtained by reaction of Zn(II) and bhnq2 in methanol. The
and Zn(II); 33 complexes form one dimensional helix chain with authors further suggested that the vapochromic behavior is based
chiral cavities formed perpendicular to the helices. Ni(II) complexes in the hinge like flexibility of the bhnq2 ions.
34 and 35 form cyclic tetramers, whereas complex 36 forms a dimer
450 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

8. Metal complexes of juglone and plumbagin

Juglone and plumbagin are isomers of lawsone. Juglone is pre-

sent in Juglandaceae family of plants (Black walnut, Butternut, Eu-
ropean walnut) [99] and plumbagin is present in Plumbaginaceae
(Plumbago), Droseraceae (Drosera) and Ebenaceae (Diospyros)
family [27,100]. Both juglone and plumbagin have two important
components such as 1,4-naphthoquinone moiety and an aryl ring
with a phenolic hydroxyl group at C(5) position (Fig. 1). The
quinone moiety and the phenolic functionality are amenable for a
wide range of chemical transformations to synthesize diverse new
chemical entities to identify potent lead molecules. Plumbagin (H-
PLN) is a potent toxic natural product extracted from Plumbago
zeylanica L. (Plumbaginaceae), which has been used in China and
other Asian countries for the treatment of rheumatoid arthritis,
dysmenorrhea, injury and cancer.
Cu(II), Zn(II), Co(II), Ni(II) and Pb(II) complexes of juglone [18]
with general formula MRn.xH2O and (x ¼ 0, 1, 2, 3) are studied
for their spectral and thermal properties [101]. The dissociation
constants of Ni(II) and Zn(II) juglonates have been reported by
Koptenko et al. [102]. IR and EPR studies on Ni(II) juglone salts have
been studied by Aizenber et al. [103]. Pawar et al. synthesized metal
chelates of type M [L]2 (Juglone; L) where M ¼ Zn(II), Cd(II), Hg(II),
Sn(II) and Pb(II) [104]. FT-IR spectra showed absorption at
3073 cm1 indicating of CeH stretching in all complexes except
Cd(II) complex. The free carbonyl and hydrogen bonded carbonyl
are assigned to 1665 and 1643 cm1, respectively in IR spectra. Kido
et al. [105] assigned these absorptions at 1670, 1647 cm1, respec-
tively. UVevisible bands were assigned to benzenoid, quinonoid
and n-p* transition.
Fielder et al. [106], reported two mononuclear Fe(II) p-semi-
quinonate (p-SQ) complexes 37, 38. The two Fe(II) complexes
contain the juglone derivative ligand and the ligand hydrotris (3,5- with Cu(II) salt yielded [Cu(PLN)2]$2H2O; 39. With 2,2'-bipyridine
diphenylpyrazol-1-yl)borate bound to the Fe(II) central ion. Spec- as a co-ligand, PLN reacts with Cu(II) to give [Cu(PLN)(bipy)(-
troscopy, computational and EPR results supports that the (p-SQ) H2O)]2(NO3)2$4H2O; 40. Single crystal X-ray diffraction studies re-
ligand is ferromagnetically coupled to the high-spin Fe(II) center. veals that complex 39, is square planar monomeric and the PLN
Chen et al. [107] reported Cu(II) complex of plumbagin, as well ligands coordinated in ‘trans’ form. The bite angle of O(1)-Cu(1)-
as its 2,2'-bipyridine (bipy) adduct. Reaction of plumbagin (PLN) O(2) is 93.21 (14) , indicating a slightly distorted square plane
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 451

around Cu(II). X-ray crystal structure of complex 40 consists of isolated from natural sources, like lapacho trees (Tabebuia ipe).
dicationic [Cu(PLN)(bipy)(H2O)]2þ 2 , two uncoordinated nitrate an- Batista et al. [ 25] reported Ru(II)/(III) complexes containing lapa-
ions and four water solvent molecules. The complex crystallizes as a chol as bidentate ligand with empirical formula [Ru(Lap)(PPh3)2
dimer with the Cu(II) center in a distorted octahedral N2O4 coor- (bipy)]PF6;41, [Ru(Lap)(PPh3)2(Me-bipy)]PF6;42, [Ru(Lap)(PPh3)2(-
dination sphere, in which the equatorial plane is formed by two MeO-bipy)]PF6;43, [Ru(Lap) (PPh3)2(phen)]PF6;44, [RuCl2(-
nitrogen atoms from bipyridine and two oxygen atoms from PLN Lap)(dppb)]; 45 with diimine, 2,2'-bipyridine (bipy), 1,10-
ligand, and the two apical sites are occupied by one water molecule phenanthroline (phen), 4,4'-methylbipyridine (Me-bipy), 4,4'-
oxygen with Cu(1)-O(4) of 2.357 (5) Å and one carbonyl oxygen methoxybipyridine (MeO-bipy), [1,4-bis(diphenylphosphine)
O(3A) of PLN ligand with Cu(1)-O(3A) of 2.7539 (2) Å. The dihedral butane]; (dppb)as ancillary ligands. cis-[RuCl2(PPh3)2(X-bipy)] or
angle between the plane defined by Cu(1), O(1) and O(2) and to cis-[RuCl2(PPh3)2 (phen)] used as starting material in there syn-
Cu(1), N(1) and O(2) is 7.989 (24) , which indicates a distortion of thesis. The crystal structure of the complexes 41 and 45 shows that
the N2O2 equatorial plane. the ruthenium binds through oxygens O(1) and O(2) of lapachol
ligand.

Black coloured complexes of [Fe(Lap)2] and [Fe(Lap)3] have been

synthesized and characterized [108]. The complexes of Co(II), Zn(II),
Cd(II) and Cu(II) with lapachcol are known [109e112]. Complexes of
lapachol with Co(II), Ni(II) and Cu(II) with empirical formula
[Co(Lap)2(EtOH)2]; 46, [Ni(Lap)2 (EtOH)2]; 47, [Cu(Lap)2py2]; 48,
have been reported by Molina et al. [57]. The Co(II), Cu(II) and Ni(II)
complexes form octahedral trans adducts with two bidentate
lapachol ligands and two ethanol molecules in the axial position.

9. Lapachol complexes

Lapachol; (2-hydroxy-3-(3’-methyl-2’-buthenyl)-1,4-
naphthoquinone) can be obtained synthetically or it can be
452 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

isomorphous and polymeric complexes showed a supramolecular

arrangement to their lattice (Fig. 16, Fig. 17).

A new series of lapachol complexes with Zn(II); 49, Mn(II);50,

Cd(II);51 are reported by Farfa
n et al. [113]. In complex 49,
[Zn(Lap)2(DMF)(H2O)] the Zn(II) ion is in a distorted octahedral
environment coordinated to two different and nearly perpendic-
ular laphacol ligands. The remaining two cis coordination sites are
occupied by water and DMF molecules. Complex 50 and 51 are

Fig. 17. Molecular packing of [Cd(Lap)2]n;51 down b-axis.

Fig. 16. Polymeric network of [Mn(Lap)2]n; 50 down b-axis.

 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 453

Mn(II) complex 50, undergoes temperature-reversible metal to Molecular structures with coordinated DMF are known for
ligand electron transfer [114]. Two ligands binds to metal through complexes of Co(II); 52 [115] Ni(II).; 53 [116] and Zn(II); 49 [113]. A
their ortho oxygen (O(1), O(2)) moiety while two para oxygens, drastic difference in molecular packing was observed in these
from other lapachol ligands, in the octahedral coordination sphere. structures (Fig. 18)..
Thus far, all reported lapachol metal complexes are mononuclear, Complex 46 is a two dimensional polymer formed via inter-
lack the metal-trans-quinonic (para) oxygen binding and have molecular CeH/O and p∙∙∙p stacking interactions, while complex
lapachol as a bidentate ligand. The bond distances for the complex 52 [115] is a dimer through interaction of coordinated water and
suggests the coordination of naphthosemiquinone form. DMF as solvent molecules through OeH/O, CeH/O and CeH∙∙∙p
interactions and a Co/Co distance of 4.95 Å.

Fig. 18. a) Molecular packing of [Co(Lap)2 (EtOH)2]; 46 down c-axis b) molecular packing down b axis and c) dimeric unit of [Co(Lap)2(H2O)DMF]; 52.
454 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

Farfa
n et al. studied a Ni(II) compound [Ni(Lap)2DMF(H2O)]; 53,

where the orientation of the two lapachol ligands is cis [111] and
the coordinated DMF is involved in CeH/O interaction and the
water molecules take part in CeH/O as well as OeH/O hydrogen
bonding (Fig. 19a). When compared to ethanol coordinated struc-
ture of [Ni(II)(Lap)2(EtOH)2]; 47 complex studied by Molina et al.
[57], the protons of butenyl group take part in CeH/O hydrogen
bonding forming a two dimensional polymer (Fig. 19b).

Martinez et al. reported ethanol coordinated complex of lapa-

chol [Zn(II)(Lap)2(EtOH)2]; 54 [116]. The complex was synthesized
in absolute ethanol using Zn(CH3COO)2 as a precursor for metal.
Fig. 19. a) Molecular packing of [Ni(Lap)2DMF(H2O)]; 53 down c axis and b) Molecular Unlike the Co(II); 46 and Ni(II); 47 complexes, this complex showed
packing of [Ni(Lap)2(EtOH)2]; 47.
two dimensional polymeric network via intermolecular hydrogen
bonding as shown in Fig. 20a. The DMF and water coordinated
complex, [Zn(II)(Lap)2(DMF)(H2O)]; 49 forms three dimensional
polymeric network Fig. 20b.

Fig. 20. a) Molecular packing of [Zn(II) (Lap)2(EtOH)2]; 54 down c axis b) Molecular packing of [Zn(II) (Lap)2(DMF)(H2O)]; 49 down b-axis.
 Fig. 21. Molecular packing of a) [Cu(Lap)2(DMF)2]; 55 down a axis b) [Co(Lap)2(DMF)2]; 56.

both the complexes in 103 M solutions in dimethylsulphoxide

(DMSO) were 5.68 and 7.05 mS/cm, indicating the absence of ionic
species in solution. A shift of ~98 cm1 and ~110 cm1 in the
carbonyl stretching frequency is observed in comparison to the
parent lapachol ligand (1660 cm1).

57

Farfa
n et al. also reported [117] trans, trans bound DMF coordi-
nated complexes of Cu(II), [Cu(Lap)2(DMF)2]; 55 and Co(II) complex
[Co(Lap)2(DMF)2]; 56. Both complexes were two dimensional p-p
stacked polymers (Fig. 21).
Bhatia et al. [118] reported determination of stability constant
and thermodynamic function [119] of Y(III), Rh(III), In(III), Sm(III),
Gd(III) and Dy(III) complexes of lapachol.
The complexes of Sb(V) and Bi(V) with lapachol are known
[120]. The Sb(V) complex a monomeric derivative, (Lap) (Ph3Sb)OH;
58 and the Bi(V) complex is a dinuclear compound bridged by an
oxygen atom, (Lap)2(Ph3Bi)2O; 59. Conductivity measurements of
456 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458

with lawsone, lapachol, juglone and plumbagin and their thermo-

Longer carbonyl distances >1.35 Å was observed in these com- dynamic stability.
plexes. Demicheli et al. [121] also synthesized 58 and 59, which Chen et al. studied lanthanide (III) complexes of Y, La, Gd, Dy, Sm
inhibited the growth of a chronic myelogenous leukemia cell line with molecular formula [M(PLN)3(H2O)2]; 60 [125]. Cytotoxic ac-
and the complex of Bi(V) was about five times more active than free tivity of these complexes have been studied against BEL7404 (liver
lapachol ligand. This work provides a rare example of an organo- cancer) cell lines. The cytotoxic activity was significantly enhanced
Bi(V) complex showing significant cytotoxic activity. compared to plumbagin suggesting a synergetic effect upon
Parrilha et al. studied Bi(III) compound viz [Bi(Lap)2]Cl that plumbagin coordination to the lanthanide (III)..
exhibit antiangiogenic and antiinflammatory activities, which have
been attributed to the presence of the lapachol ligand [122].

10. Inner transition metal complexes of juglone, plumbagin

and lapachol

Bhatia et al. [123,124] reported complexes of juglone with

UO2(II), Y(III), Rh(III), Sm(III), Gd(III) and Dy(III) and studied the
thermodynamic stability of these complexes. In addition, the au-
thors extended the study to Cd(II), Pr(III) and Nd(III) complexes.
Kinetic parameters for the decomposition of anhydrous Cd(II), Y(III)
and Sm(III) juglone complexes were determined. Hydrated com-
plexes lose water at 50e125  C and air oxidation occurs at 60
50e900  C for anhydrous complexes. Stability constants and ther-
modynamic parameters were reported for Cd(II) juglone salt at 20
and 40  C.
Due to its C(5) hydroxyl group, plumbagin is capable of forming Synthesis, characterization and antibacterial activity, thermal
very stable chelates with several trace metals of biological rele- properties of lanthanide complexes of plumbagin are reported
vance, and such interactions have been thought to be one of the [126e129].
possible mechanisms of its biological activities [107]. Sawhney et al.
[13], reported the solution investigation of interaction of Eu(III)

Fig. 22. Molecular packing down b-axis a) Ruthenium complex 61 and b) Osmium complex 62.
 S. Salunke-Gawali et al. / Journal of Molecular Structure 1148 (2017) 435e458 457

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