research communications ISSN 2056-9890 Bis[N-2-hydroxyethyl,N-methyldithiocarbamatoj2S,S)’-4-{[(pyridin-4-ylmethylidene)hydrazinylidene}methyl]pyridine-jN1)zinc(II): crystal structure and Hirshfeld surface analysis Grant A. Broker,a Mukesh M. Jotanib‡ and Edward R. T. Tiekinkc* Received 31 August 2017 Accepted 5 September 2017 Edited by W. T. A. Harrison, University of Aberdeen, Scotland ‡ Additional correspondence author, e-mail: mmjotani@rediffmail.com. Keywords: crystal structure; zinc; dithiocarbamate; 4-pyridinealdazine; hydrogen bonding. CCDC reference: 1572824 Supporting information: this article has supporting information at journals.iucr.org/e a 2020 Eldridge Parkway, Apt 1802, Houston, Texas 77077, USA, bDepartment of Physics, Bhavan’s Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and cResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia. *Correspondence e-mail: edwardt@sunway.edu.my In the title compound, [Zn(C4H8NOS2)2(C12H10N4)], the ZnII atom exists within a NS4 donor set defined by two chelating dithiocarbamate ligands and a pyridylN atom derived from a terminally bound 4-pyridinealdazine ligand. The distorted coordination geometry tends towards square-pyramidal with the pyridyl-N atom occupying the apical position. In the crystal, hydroxyl-O— H  O(hydroxyl) and hydroxyl-O—H  N(pyridyl) hydrogen-bonding give rise to a supramolecular double-chain along [110]; methyl-C—H  (chelate ring) interactions help to consolidate the chain. The chains are connected into a threedimensional architecture via pyridyl-C—H  O(hydroxyl) interactions. In addition to the contacts mentioned above, the Hirshfeld surface analysis points to the significance of relatively weak – interactions between pyridyl rings [inter-centroid distance = 3.901 (3) Å]. 1. Chemical context In the realm of coordination polymers/metal–organic framework structures, bridging bipyridyl ligands have proven most effective in connecting metal centres. This is equally true in the construction of coordination polymers of cadmium(II) dithiocarbamates, Cd(S2CNR2)2, R = alkyl. Thus, one-dimensional polymers have been found in the crystals of [Cd(S2CNR2)2(NN)]n in cases where R = Et and NN = 1,2bis(4-pyridyl)ethylene (Chai et al., 2003), R = Et and NN = 1,2bis(4-pyridyl)ethane (Avila et al., 2006) and R = Benz, NN = 4,40 -bipyridyl (Fan et al., 2007). In an extension of these studies, hydrogen-bonding functionality, in the form of hydroxyethyl groups was included in at least one of the R groups of Cd(S2CNR2)2. It was of some surprise that coordination polymers based on Cd N dative bonds were not formed as the putative bridging NN ligand was terminally bound. The first example of this phenomenon was noted in a compound closely related to the title compound, i.e. Cd[S2CN(n-Pr)CH2CH2OH)]2(4-pyridinealdazine)2 (Broker & Tiekink, 2011), for which both potentially bidentate ligands are monodentate. The non-coordinating pyridyl-N atoms participate in hydroxyl-O—H  N(pyridyl) hydrogen-bonds. In another interesting example, regardless of the stoichiometry of the reaction between Cd[S2CN(i-Pr)CH2CH2OH]2 and 1,2-bis(4-pyridyl)ethylene, i.e. 1:2, 1:1 and 2:1, only the binuclear compound {Cd[S2CN(i-Pr)CH2CH2OH)]2}2[1,2bis(4-pyridyl)ethylene]3, featuring one bridging and two 1458 https://doi.org/10.1107/S2056989017012725 Acta Cryst. (2017). E73, 1458–1464 research communications terminally bound 1,2-bis(4-pyridyl)ethylene ligands, could be isolated (Jotani et al., 2016). Finally, in an unprecedented result, the original binuclear {Cd[S2CN(i-Pr)CH2CH2OH]2}2 aggregate was retained in the structure of [{Cd[S2CN(iPr)CH2CH2OH]2}2(3-pyridinealdazine)]2 with two terminally bound 3-pyridinealdazine ligands (Arman et al., 2016). This is unusual as there are no precedents of adduct formation by the zinc-triad dithiocarbamates that resulted in the retention of the original binuclear core (Tiekink, 2003). Table 1 Selected geometric parameters (Å,  ). Zn—S1 Zn—S2 Zn—S3 S1—Zn—S3 2.4152 (12) 2.5152 (11) 2.3890 (12) Zn—S4 Zn—N3 136.48 (4) S2—Zn—S4 2.5162 (11) 2.068 (3) 155.56 (4) (Lai & Tiekink, 2003). This difference in behaviour, i.e. polymer formation for cadmium but not for zinc dithiocarbamates, is explained in terms of the larger size of cadmium versus zinc, which enables cadmium to increase its coordination number. In continuation of our studies in this area, the title compound, Zn[S2CN(Me)CH2CH2OH)]2(4-pyridinealdazine), (I), was isolated and shown to feature a terminally bound 4-pyridinealdazine ligand. Herein, its crystal and molecular structures are described as is an analysis of the calculated Hirshfeld surface. 2. Structural commentary The molecular structure of (I) is shown in Fig. 1 and selected geometric parameters are given in Table 1. The zinc(II) atom is coordinated by two chelating dithiocarbamate ligands and a nitrogen atom derived from a monodentate 4-pyridinealdazine ligand. There are relatively small differences in the By contrast to the chemistry described above for cadmium dithiocarbamates, no polymeric structures have been observed for zinc analogues with potentially bridging bipyridyl molecules. Instead, only binuclear compounds of the general formula [Zn(S2CNRR0 )2]2(NN), i.e. R = CH2CH2OH and R0 = Me, Et or CH2CH2OH for NN = 4,40 -bipyridyl (Benson et al., 2007), R = R0 = CH2CH2OH and NN = pyrazine (Jotani et al., 2017), and R = CH2CH2OH and R0 = Me for NN = (3-pyridyl)CH2N(H)C( Y)C( Y)N(H)CH2(3-pyridyl) where Y = O (Poplaukhin & Tiekink, 2010) and Y = S (Poplaukhin et al., 2012). There are also several all-alkyl species adopting the binuclear motif with a notable example being the product of the reaction of [Zn(S2CNR2)2]2 with an excess of 1,2-bis(4pyridyl)ethylene in which the binuclear species co-crystallized with an uncoordinated molecule of 1,2-bis(4-pyridyl)ethylene Acta Cryst. (2017). E73, 1458–1464 Figure 1 The molecular structure of (I), showing the atom-labelling scheme and displacement ellipsoids at the 50% probability level. Broker et al.  [Zn(C4H8NOS2)2C12H10N4)] 1459 research communications Table 2 Hydrogen-bond geometry (Å,  ). Cg1 is the centroid of the Zn/S1/S2/C1 ring. D—H  A i O1—H1O  O2 O2—H2O  N6ii C20—H20  O1iii C6—H6B  Cg1i Symmetry codes: x; y  32; z þ 12. (i) D—H H  A D  A D—H  A 0.85 (5) 0.84 (4) 0.95 0.99 1.92 (5) 1.95 (4) 2.32 2.59 2.721 (5) 2.769 (5) 3.233 (6) 3.540 (4) 158 (5) 163 (5) 162 162 x; y þ 1; z þ 1; (ii) x þ 1; y  1; z þ 1; four sulfur atoms [r.m.s. deviation = 0.1790 Å] in the direction of the pyridyl-N atom. The dihedral angle between the best plane through the four sulfur atoms and the coordinating pyridyl residue is 84.82 (9) , consistent with a nearly symmetric perpendicular relationship. The 4-pyridinealdazine molecule has an all-trans conformation and is essentially planar as seen in the dihedral angle of 2.7 (3) formed between the rings. (iii) 3. Supramolecular features Zn—S bond lengths formed by each dithiocarbamate ligand, i.e.
Zn—S = (Zn—Slong  Zn—Sshort) = 0.10 Å for the S1dithiocarbamate ligand which increases to ca 0.12 Å for the second ligand. This symmetric mode of coordination is reflected in the equivalence of the associated C—S bond lengths. The resulting NS4 donor set is highly distorted as shown by the value of  of 0.32 which is intermediate between ideal square-pyramidal ( = 0.0) and trigonal-bipyramidal ( = 1.0) geometries (Addison et al., 1984) but, with a tendency towards the former. In the square-pyramidal description, the zinc(II) centre lies 0.7107 (7) Å out of the plane defined by the Both conventional and non-conventional hydrogen-bonding interactions feature in the crystal of (I), Table 2. HydroxylO—H  O(hydroxyl) hydrogen-bonds between centrosymmetrically related molecules lead to 28-membered {  HOC2NCSZnSCNC2O}2 synthons. On either side of this aggregate are hydroxyl-O—H  N(pyridyl) hydrogen bonds leading to centrosymmetric 40-membered {  HOC2NCSZnNC4N2C4N}2 synthons. The result is a supramolecular double-chain with the appearance of a ladder that extends along [110], Fig. 2a. Within the chains there are notable methylene-C—H  (chelate ring) interactions, Figure 2 Molecular packing for (I): (a) the supramolecular double chain sustained by O—H  O and O—H  N hydrogen-bonding, shown as orange and blue, dashed lines, respectively, (b) a view of the immediate environment of one chain down the direction of propagation highlighting the role of C—H  O interactions (purple dashed lines) in sustaining the three-dimensional architecture and (c) a view of the unit-cell contents in projection down the b axis. 1460 Broker et al.  [Zn(C4H8NOS2)2C12H10N4)] Acta Cryst. (2017). E73, 1458–1464 research communications Table 3 Table 4 Summary of short inter-atomic contacts (Å) in (I). Percentage contributions of inter-atomic contacts to the Hirshfeld surfaces for (I). Contact Distance Symmetry operation H1O  H2O H4B  H13 Zn  C6 Zn  H6B C1  H6B S1  H6B S1  H15 S2  H7B S4  C14 C2  H4A C5  H18 C18  H2O C19  H2O N5  H8A 2.21 (7) 2.30 3.835 (4) 3.00 2.88 2.92 2.98 2.89 3.217 (4) 2.88 2.77 2.89 (5) 2.85 (4) 2.73 x, 1  y, 1  z x, 12 + y, 12  z x, 1  y, 1  z x, 1  y, 1  z x, 1  y, 1  z x, 1  y, 1  z x, 1 + y, z x, y, 1  z x, 1 + y, z x,  12 + y, 12  z 1  x, 1  y, 1  z 1  x, 1  y, 1  z 1  x, 1  y, 1  z 1  x, y, 1  z Table 2, which are garnering greater attention in the chemical crystallographic community (Tiekink, 2017). While the hydroxyl-O2 atom participates in acceptor O—H  O and donor O—H  N hydrogen-bonds, the O1 atom only forms a O—H  O hydrogen-bond. This being stated, this atom accepts a close pyridyl-C—H interaction so that each chain is associated with four other chains. As seen from Fig. 2b, the surrounding chains are inclined by approximately 90 and have orientations orthogonal to the reference chain. In this manner, a three-dimensional architecture is constructed as illustrated in Fig. 2c. 4. Hirshfeld surface analysis Additional insight into the intermolecular interactions influential in the crystal of (I) was obtained from an analysis of the Hirshfeld surfaces which were calculated in accord with a recent publication on related zinc dithiocarbamate compounds (Jotani et al., 2017). On the Hirshfeld surface mapped over dnorm, Fig. 3, the donors and acceptors of the O— H  O and O—H  N hydrogen-bonds are viewed as brightred spots near hydroxyl-H1O, H2O, hydroxyl-O2 and pyridylN6 atoms, located largely at the extremes of the molecule. The Contact Percentage contribution H  H S  H/H  S C  H/H  C N  H/H  N O  H/H  O C  C S  N/N  S S  S C  S/S  C C  N/N  C Zn  H/H  Zn Zn  S/S  Zn 44.6 15.4 13.1 10.2 6.7 2.8 2.8 1.5 1.2 1.0 0.6 0.1 presence of bright-red spots near the H1O and H2O atoms in Fig. 3 are also indicative of short inter-atomic H  H and C  H/H  C contacts, see Table 3. The diminutive-red spots near the methyl-C14, sulfur-S4, pyridyl-H20 and hydroxyl-O1 atoms characterize the influence of short inter-atomic C  S/ S  C contacts, Table 3, and intermolecular pyridine-C20— H20  O1 interactions. The donors and acceptors of the above intermolecular interactions are also represented with blue and red regions on the Hirshfeld surface mapped over electrostatic potential shown in Fig. 4. The immediate environments about a reference molecule within dnorm-mapped Hirshfeld surface highlighting intermolecular O—H  O, O—H  N and C— H  O, short inter-atomic C  S/S  C contacts, — stacking interactions and C—H  (chelate) interactions are illustrated in Fig. 5a–c, respectively. The overall two dimensional fingerprint plot, Fig. 6a, and those delineated into H  H, C  H/H  C, N  H/H  N, S  H/H  S, O  H/H  O, C  C, C  S/S  C and Zn  H/ H  Zn contacts (McKinnon et al., 2007) are illustrated in Fig. 6b–i, respectively; the relative contributions from different inter-atomic contacts to the Hirshfeld surfaces are summarized in Table 4. The pair of adjacent short spikes at Figure 4 Figure 3 Two views of the Hirshfeld surface for (I) mapped over dnorm in the range 0.400 to 1.552 au. Acta Cryst. (2017). E73, 1458–1464 Two views of the Hirshfeld surface for (I) mapped over the electrostatic potential in the range 0.151 au. The red and blue regions represent negative and positive electrostatic potentials, respectively. Broker et al.  [Zn(C4H8NOS2)2C12H10N4)] 1461 research communications Figure 5 Views of Hirshfeld surface mapped over dnorm about a reference molecule showing (a) intermolecular O—H  O, O—H  N and C—H  O interactions as black dashed lines, (b) short inter-atomic S  C/C  S contacts and — stacking interactions as black and red lines, respectively (H atoms are omitted) and (c) C—H  (chelate) interactions through short inter-atomic contacts involving the methylene-H6B atom with the Zn, S1 and C1 atoms of the chelate ring as black dashed lines. Figure 6 The full two-dimensional fingerprint plot for (I) and fingerprint plots delineated into (b) H  H, (c) C  H/H  C, (d) N  H/H  N, (e) S  H/H  S, (f) O  H/H  O, (g) C  C, (h) C  S/S  C and (i) Zn  H/H  Zn contacts. 1462 Broker et al.  [Zn(C4H8NOS2)2C12H10N4)] Acta Cryst. (2017). E73, 1458–1464 research communications 5. Database survey Figure 7 Two views of Hirshfeld surface mapped over curvedness showing flat regions over pyridyl-(N3,C9–C13) and (N6, C15–C20) rings with labels 1 and 2, respectively. de + di  2.2 Å flanked by the broad spikes with tips at de + di  2.3 Å in the fingerprint plot delineated into H  H contacts are due to short inter-atomic H  H contacts, Fig. 6b. The forceps-like tips at de + di  2.8 Å in the fingerprint plot delineated into C  H/H  C contacts, Fig. 6c, are due to the presence of some short inter-atomic contacts involving these atoms, Table 3. The effect of the intermolecular C— H  (chelate) interactions is also reflected by the short interatomic contacts formed by the methylene-C6 with the Zn atom, and methylene-H6B with the Zn, S1 and C1 atoms of the chelate ring, Fig. 6c, 6e, 6i, and Table 2. The two pairs of adjacent long spikes on the fingerprint plots delineated into N  H/H  N and O  H/H  O contacts, Fig. 6d and 6f, with the pair of tips at de + di  2.0 Å and de + di  1.9 Å, respectively, indicate the presence of conventional O—H  O and O—H  N hydrogen-bonds in the structure. The points corresponding to short inter-atomic N  H/H  N contacts, Table 3, are merged within the plot in Fig. 6d. The pattern of aligned green points superimposed on the forceps-like distribution of blue points in the S  H/H  S delineated fingerprint plot in Fig. 6e characterize the presence of short interatomic S  H/H  S contacts, Table 3, and C—H   (chelate) interactions, Fig. 5c. The C—H  O interactions appear as the distribution of points in the short parabolic form attached to each of the spikes on the outer side of fingerprint plot delineated into O  H/H  O contacts, Fig. 6f, with (de + di)min  2.3 Å. The parabolic distribution of points in the (de = di)  1.8–2.0 Å range in the fingerprint plot delineated into C  C contacts, Fig. 6g, indicate the existence of weak – stacking interactions between the pyridyl-(N3,C9–C13) and (N6, C15– C20)i rings [Cg  Cgi = 3.901 (3) Å; symmetry code: (i) = x, 1 + y, z]. This observation is also viewed as the flat region around these rings in the Hirshfeld surfaces mapped over curvedness in Fig. 7. Both the C  S/S  C and Zn  H/ H  Zn contacts make small but discernible contributions of 1.2 and 0.6% to the Hirshfeld surface, respectively, which are manifested as the pair of the short spikes in the centre of Fig. 6h, with their tips at de + di  3.2 Å, and wings in Fig. 6i. The low contribution from other contacts summarized in Table 4 have no significant influence on the molecular packing owing to their long separations. Acta Cryst. (2017). E73, 1458–1464 A search of the Cambridge Structural Database (Version 5.38, May 2017 update; Groom et al., 2016) showed there were over 145 examples of metal complexes/main-group element compounds containing the 4-pyridinealdazine molecule. Bridging modes were observed in both cadmium(II) (Lai & Tiekink, 2006) and nickel(II) (e.g. Berdugo & Tiekink, 2009) dithiophosphate [S2P(OR)2] derivatives, indicating bridging modes are possible in the presence of 1,1-dithiolate co-ligands. There were six examples of structures where 4-pyridinealdazine was present in the crystal but was non-coordinating, and two where the ligand was terminally bound as in (I), i.e. the cadmium analogue of (I) and in a structure particularly worth highlighting as both a terminally bound ligand as well as a non-coordinating molecule of 4-pyridinealdazine are present, namely [Zn(OH2)2[O(H)Me]2(4-pyridinealdazine)2](ClO4)24-pyridinealdazine, 1.72MeOH, 1.28H2O (Shoshnik et al., 2005). In summary, the 4-pyridinealdazine molecule is usually found to be bridging, a conclusion vindicated by this mode of coordination being observed in about 95% of structures having 4-pyridinealdazine. While one might be tempted to ascribe the unusual behaviour of 4-pyridinealdazine in (I) and the cadmium(II) analogue to the influence of hydrogen-bonding associated with the dithiocarbamate ligand, it is salutatory to recall that the sole example of a monodentate bipyridyl ligand is found in the structure of Zn[S2CN(n-Pr)2]2(4,40 -bipyridyl) (Klevtsova et al., 2001), where there is no possibility of conventional hydrogenbonding interactions; the binuclear species, {Zn[S2CN(nPr)2]2}2(4,40 -bipyridyl), was characterized in the same study. 6. Synthesis and crystallization Compound (I) was prepared following the standard literature procedure whereby the 1:1 reaction of Zn[S2CN(Me)CH2CH2OH]2 (Howie et al., 2008) and 4-pyridinealdazine (Sigma Aldrich). Yellow crystals of (I) were obtained from the slow evaporation of a chloroform/acetonitrile (3/1) solution. 7. Refinement details Crystal data, data collection and structure refinement details are summarized in Table 5. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.99 Å) and were included in the refinement in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The O-bound H atoms were located in a difference-Fourier map but were refined with distance restraint of O—H = 0.840.01 Å, and with Uiso(H) set to 1.5Ueq(O). Acknowledgements We thank Sunway University for support of biological and crystal engineering studies of metal dithiocarbamates. Broker et al.  [Zn(C4H8NOS2)2C12H10N4)] 1463 research communications Table 5 Experimental details. Crystal data Chemical formula Mr Crystal system, space group Temperature (K) a, b, c (Å) ( ) V (Å3) Z Radiation type  (mm1) Crystal size (mm) [Zn(C4H8NOS2)2C12H10N4)] 576.08 Monoclinic, P21/c 153 11.499 (4), 8.5710 (19), 25.945 (7) 95.515 (8) 2545.3 (13) 4 Mo K 1.32 0.40  0.18  0.15 Data collection Diffractometer Absorption correction Tmin, Tmax No. of measured, independent and observed [I > 2(I)] reflections Rint (sin /)max (Å1) Refinement R[F 2 > 2(F 2)], wR(F 2), S No. of reflections No. of parameters No. of restraints H-atom treatment
max,
min (e Å3) Rigaku AFC12K/SATURN724 Multi-scan (ABSCOR; Higashi, 1995) 0.575, 1 25373, 4485, 4180 0.044 0.595 0.050, 0.132, 1.13 4485 306 2 H atoms treated by a mixture of independent and constrained refinement 0.72, 0.44 Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2005), SHELXS (Sheldrick, 2008), SHELXL2014/7 (Sheldrick, 2015), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010). References Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. Arman, H. D., Poplaukhin, P. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1234–1238. Avila, V., Benson, R. E., Broker, G. A., Daniels, L. M. & Tiekink, E. R. T. (2006). Acta Cryst. E62, m1425–m1427. 1464 Broker et al.  [Zn(C4H8NOS2)2C12H10N4)] Benson, R. E., Ellis, C. A., Lewis, C. E. & Tiekink, E. R. T. (2007). CrystEngComm, 9, 930–940. Berdugo, E. & Tiekink, E. R. T. (2009). Acta Cryst. E65, m1444– m1445. Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Broker, G. A. & Tiekink, E. R. T. (2011). Acta Cryst. E67, m320– m321. Chai, J., Lai, C. S., Yan, J. & Tiekink, E. R. T. (2003). Appl. Organomet. Chem. 17, 249–250. Fan, J., Wei, F.-X., Zhang, W.-G., Yin, X., Lai, C. S. & Tiekink, E. R. T. (2007). Acta Chim. Sinica, 65, 2014–2018. Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Howie, R. A., de Lima, G. M., Menezes, D. C., Wardell, J. L., Wardell, S. M. S. V., Young, D. J. & Tiekink, E. R. T. (2008). CrystEngComm, 10, 1626–1637. Jotani, M. M., Poplaukhin, P., Arman, H. D. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1085–1092. Jotani, M. M., Poplaukhin, P., Arman, H. D. & Tiekink, E. R. T. (2017). Z. Kristallogr. 232, 287–298. Klevtsova, R. F., Glinskaya, L. A., Berus, E. I. & Larionov, S. V. (2001). J. Struct. Chem. 42, 639–647. Lai, C. S. & Tiekink, E. R. T. (2003). Appl. Organomet. Chem. 17, 251–252. Lai, C. S. & Tiekink, E. R. T. (2006). Z. Kristallogr. 221, 288–293. McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Molecular Structure Corporation & Rigaku (2005). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Poplaukhin, P., Arman, H. D. & Tiekink, E. R. T. (2012). Z. Kristallogr. 227, 363–368. Poplaukhin, P. & Tiekink, E. R. T. (2010). CrystEngComm, 12, 1302– 1306. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Shoshnik, R., Elengoz, H. & Goldberg, I. (2005). Acta Cryst. C61, m187–m189. Tiekink, E. R. T. (2003). CrystEngComm, 5, 101–113. Tiekink, E. R. T. (2017). Coord. Chem. Rev. 345, 209–228. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Acta Cryst. (2017). E73, 1458–1464 supporting information supporting information Acta Cryst. (2017). E73, 1458-1464 [https://doi.org/10.1107/S2056989017012725] Bis[N-2-hydroxyethyl,N-methyldithiocarbamato-κ2S,S)′-4-{[(pyridin-4-ylmethylidene)hydrazinylidene}methyl]pyridine-κN1)zinc(II): crystal structure and Hirshfeld surface analysis Grant A. Broker, Mukesh M. Jotani and Edward R. T. Tiekink Computing details Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); cell refinement: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2005); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010). Bis[N-2-hydroxyethyl,N-methyldithiocarbamato-κ2S,S)′-4-{[(pyridin-4ylmethylidene)hydrazinylidene}methyl]pyridine-κN1)zinc(II) Crystal data [Zn(C4H8NOS2)2C12H10N4)] Mr = 576.08 Monoclinic, P21/c a = 11.499 (4) Å b = 8.5710 (19) Å c = 25.945 (7) Å β = 95.515 (8)° V = 2545.3 (13) Å3 Z=4 F(000) = 1192 Dx = 1.503 Mg m−3 Mo Kα radiation, λ = 0.71069 Å Cell parameters from 1535 reflections θ = 3.1–30.3° µ = 1.32 mm−1 T = 153 K Prism, yellow 0.40 × 0.18 × 0.15 mm Data collection Rigaku AFC12K/SATURN724 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.575, Tmax = 1 25373 measured reflections 4485 independent reflections 4180 reflections with I > 2σ(I) Rint = 0.044 θmax = 25.0°, θmin = 2.3° h = −13→13 k = −10→8 l = −30→30 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.050 wR(F2) = 0.132 S = 1.13 Acta Cryst. (2017). E73, 1458-1464 4485 reflections 306 parameters 2 restraints Hydrogen site location: mixed sup-1 supporting information H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0663P)2 + 3.198P] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001 Δρmax = 0.72 e Å−3 Δρmin = −0.44 e Å−3 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) Zn S1 S2 S3 S4 O1 H1O O2 H2O N1 N2 N3 N4 N5 N6 C1 C2 H2A H2B C3 H3A H3B C4 H4A H4B H4C C5 C6 H6A H6B C7 H7A H7B C8 H8A x y z Uiso*/Ueq 0.13806 (4) 0.13958 (8) −0.04566 (8) 0.04838 (8) 0.26964 (8) −0.2678 (3) −0.225 (4) 0.1675 (3) 0.230 (3) −0.0546 (3) 0.1419 (3) 0.2411 (3) 0.4206 (3) 0.4931 (3) 0.6562 (3) 0.0057 (3) −0.1697 (3) −0.1744 −0.1786 −0.2681 (4) −0.3435 −0.2612 −0.0090 (4) 0.0029 −0.0650 0.0656 0.1526 (3) 0.0441 (3) −0.0271 0.0304 0.0636 (3) −0.0042 0.0682 0.2286 (4) 0.2938 0.15577 (5) 0.27822 (11) 0.07162 (11) 0.20445 (11) 0.34274 (11) 0.3986 (4) 0.462 (5) 0.4188 (3) 0.373 (6) 0.2180 (4) 0.4612 (3) −0.0416 (4) −0.5525 (4) −0.6843 (4) −1.2152 (4) 0.1899 (4) 0.1479 (5) 0.0463 0.1282 0.2508 (5) 0.1979 0.2670 0.3239 (6) 0.4277 0.3308 0.2837 0.3476 (4) 0.4690 (4) 0.4303 0.5793 0.3757 (4) 0.3895 0.2638 0.5857 (5) 0.5502 0.42882 (2) 0.34505 (4) 0.37564 (4) 0.50658 (4) 0.48156 (4) 0.25882 (13) 0.277 (2) 0.66339 (11) 0.658 (2) 0.28469 (12) 0.55174 (11) 0.42704 (12) 0.38299 (13) 0.38951 (13) 0.35773 (14) 0.33010 (14) 0.27017 (16) 0.2880 0.2324 0.28404 (17) 0.2741 0.3220 0.24694 (16) 0.2624 0.2161 0.2372 0.51757 (14) 0.58335 (14) 0.5628 0.5924 0.63208 (14) 0.6524 0.6230 0.55967 (17) 0.5840 0.03058 (16) 0.0337 (2) 0.0327 (2) 0.0332 (2) 0.0349 (2) 0.0546 (8) 0.082* 0.0447 (7) 0.067* 0.0346 (7) 0.0305 (7) 0.0325 (7) 0.0377 (8) 0.0363 (7) 0.0437 (8) 0.0291 (8) 0.0396 (9) 0.048* 0.048* 0.0472 (10) 0.057* 0.057* 0.0473 (11) 0.071* 0.071* 0.071* 0.0293 (8) 0.0329 (8) 0.040* 0.040* 0.0348 (8) 0.042* 0.042* 0.0424 (10) 0.064* Acta Cryst. (2017). E73, 1458-1464 sup-2 supporting information H8B H8C C9 H9 C10 H10 C11 C12 H12 C13 H13 C14 H14 C15 H15 C16 C17 H17 C18 H18 C19 H19 C20 H20 0.1926 0.2577 0.3348 (3) 0.3551 0.4029 (3) 0.4690 0.3752 (3) 0.2771 (4) 0.2538 0.2146 (4) 0.1477 0.4440 (3) 0.5072 0.4595 (3) 0.3919 0.5253 (3) 0.6222 (3) 0.6453 0.6836 (3) 0.7498 0.5620 (4) 0.5398 0.4943 (4) 0.4281 0.6778 0.6125 −0.0675 (4) 0.0079 −0.1992 (5) −0.2131 −0.3110 (4) −0.2850 (6) −0.3591 −0.1507 (5) −0.1343 −0.4535 (4) −0.4724 −0.7935 (4) −0.7803 −0.9406 (4) −0.9662 (4) −0.8902 −1.1017 (4) −1.1169 −1.1910 (5) −1.2707 −1.0576 (5) −1.0462 0.5739 0.5265 0.46063 (15) 0.4868 0.45873 (15) 0.4832 0.42118 (14) 0.38681 (19) 0.3606 0.39140 (19) 0.3675 0.41878 (15) 0.4444 0.35868 (15) 0.3350 0.35960 (14) 0.39506 (15) 0.4207 0.39256 (15) 0.4169 0.32486 (18) 0.3004 0.32386 (18) 0.2993 0.064* 0.064* 0.0366 (9) 0.044* 0.0364 (9) 0.044* 0.0320 (8) 0.0553 (13) 0.066* 0.0557 (13) 0.067* 0.0341 (8) 0.041* 0.0328 (8) 0.039* 0.0315 (8) 0.0329 (8) 0.039* 0.0349 (8) 0.042* 0.0481 (11) 0.058* 0.0447 (10) 0.054* Atomic displacement parameters (Å2) Zn S1 S2 S3 S4 O1 O2 N1 N2 N3 N4 N5 N6 C1 C2 C3 C4 C5 C6 C7 U11 U22 U33 U12 U13 U23 0.0318 (3) 0.0302 (5) 0.0322 (5) 0.0317 (5) 0.0351 (5) 0.055 (2) 0.0492 (17) 0.0365 (17) 0.0322 (16) 0.0324 (16) 0.0312 (17) 0.0290 (16) 0.0402 (19) 0.0294 (18) 0.036 (2) 0.037 (2) 0.055 (3) 0.0303 (19) 0.0304 (18) 0.043 (2) 0.0277 (3) 0.0343 (5) 0.0286 (5) 0.0317 (5) 0.0321 (5) 0.0464 (18) 0.0422 (17) 0.0351 (17) 0.0243 (15) 0.0309 (16) 0.0334 (18) 0.0309 (17) 0.0330 (18) 0.0252 (17) 0.038 (2) 0.053 (3) 0.055 (3) 0.0264 (18) 0.0319 (19) 0.0253 (18) 0.0314 (3) 0.0365 (5) 0.0366 (5) 0.0360 (5) 0.0381 (5) 0.0575 (19) 0.0404 (15) 0.0314 (16) 0.0347 (16) 0.0332 (16) 0.0484 (19) 0.0480 (19) 0.056 (2) 0.0321 (19) 0.042 (2) 0.049 (2) 0.031 (2) 0.0300 (18) 0.0366 (19) 0.037 (2) 0.00704 (16) 0.0010 (4) 0.0015 (4) −0.0020 (4) −0.0023 (4) 0.0100 (15) 0.0154 (13) 0.0016 (14) 0.0031 (12) 0.0054 (13) 0.0091 (14) 0.0063 (13) 0.0101 (15) 0.0043 (14) −0.0015 (17) −0.0003 (19) −0.002 (2) 0.0070 (14) 0.0075 (15) 0.0048 (16) −0.00087 (18) 0.0022 (4) −0.0014 (4) 0.0025 (4) 0.0063 (4) −0.0213 (15) −0.0074 (13) −0.0011 (13) 0.0012 (13) −0.0014 (13) 0.0029 (14) −0.0007 (14) −0.0052 (16) 0.0007 (15) −0.0091 (18) −0.0100 (19) 0.0009 (19) −0.0034 (15) 0.0035 (15) 0.0075 (17) −0.00366 (16) −0.0003 (4) 0.0018 (4) −0.0042 (4) −0.0061 (4) 0.0022 (15) −0.0085 (13) 0.0012 (13) −0.0011 (13) −0.0044 (13) −0.0042 (15) −0.0040 (15) −0.0051 (16) −0.0046 (15) −0.0033 (17) 0.003 (2) 0.0096 (19) 0.0004 (14) −0.0026 (16) −0.0026 (16) Acta Cryst. (2017). E73, 1458-1464 sup-3 supporting information C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 0.042 (2) 0.040 (2) 0.033 (2) 0.0304 (19) 0.049 (3) 0.052 (3) 0.0252 (18) 0.0259 (18) 0.0267 (18) 0.0304 (19) 0.0301 (19) 0.046 (2) 0.034 (2) 0.033 (2) 0.033 (2) 0.033 (2) 0.0296 (19) 0.051 (3) 0.049 (3) 0.033 (2) 0.034 (2) 0.0282 (19) 0.0283 (19) 0.034 (2) 0.038 (2) 0.038 (2) 0.054 (2) 0.035 (2) 0.041 (2) 0.0359 (19) 0.060 (3) 0.060 (3) 0.044 (2) 0.038 (2) 0.040 (2) 0.039 (2) 0.040 (2) 0.058 (3) 0.059 (3) −0.0107 (17) 0.0047 (17) 0.0076 (16) 0.0018 (15) 0.022 (2) 0.025 (2) 0.0046 (15) 0.0058 (15) 0.0012 (15) −0.0001 (15) 0.0022 (16) 0.0056 (19) 0.0025 (17) 0.0106 (19) −0.0052 (17) −0.0083 (17) 0.0028 (16) −0.022 (2) −0.027 (2) 0.0017 (16) 0.0007 (15) 0.0032 (15) 0.0001 (16) −0.0017 (16) −0.007 (2) −0.0106 (19) −0.0143 (19) −0.0039 (16) 0.0012 (17) −0.0006 (16) −0.030 (2) −0.021 (2) 0.0054 (17) 0.0005 (17) −0.0001 (16) −0.0018 (16) 0.0025 (17) −0.013 (2) −0.010 (2) Geometric parameters (Å, º) Zn—S1 Zn—S2 Zn—S3 Zn—S4 Zn—N3 S1—C1 S2—C1 S3—C5 S4—C5 O1—C3 O1—H1O O2—C7 O2—H2O N1—C1 N1—C4 N1—C2 N2—C5 N2—C6 N2—C8 N3—C13 N3—C9 N4—C14 N4—N5 N5—C15 N6—C19 N6—C18 C2—C3 C2—H2A C2—H2B C3—H3A C3—H3B Acta Cryst. (2017). E73, 1458-1464 2.4152 (12) 2.5152 (11) 2.3890 (12) 2.5162 (11) 2.068 (3) 1.726 (4) 1.705 (4) 1.720 (4) 1.711 (4) 1.426 (5) 0.841 (10) 1.428 (5) 0.838 (10) 1.331 (5) 1.468 (5) 1.469 (5) 1.331 (5) 1.456 (5) 1.461 (5) 1.330 (5) 1.337 (5) 1.267 (5) 1.405 (4) 1.267 (5) 1.329 (5) 1.344 (5) 1.506 (6) 0.9900 0.9900 0.9900 0.9900 C4—H4A C4—H4B C4—H4C C6—C7 C6—H6A C6—H6B C7—H7A C7—H7B C8—H8A C8—H8B C8—H8C C9—C10 C9—H9 C10—C11 C10—H10 C11—C12 C11—C14 C12—C13 C12—H12 C13—H13 C14—H14 C15—C16 C15—H15 C16—C20 C16—C17 C17—C18 C17—H17 C18—H18 C19—C20 C19—H19 C20—H20 0.9800 0.9800 0.9800 1.495 (5) 0.9900 0.9900 0.9900 0.9900 0.9800 0.9800 0.9800 1.378 (5) 0.9500 1.382 (5) 0.9500 1.387 (5) 1.460 (5) 1.369 (6) 0.9500 0.9500 0.9500 1.470 (5) 0.9500 1.389 (5) 1.393 (5) 1.364 (5) 0.9500 0.9500 1.383 (6) 0.9500 0.9500 sup-4 supporting information N3—Zn—S3 N3—Zn—S1 S1—Zn—S3 N3—Zn—S2 S3—Zn—S2 S1—Zn—S2 N3—Zn—S4 S3—Zn—S4 S1—Zn—S4 S2—Zn—S4 C1—S1—Zn C1—S2—Zn C5—S3—Zn C5—S4—Zn C3—O1—H1O C7—O2—H2O C1—N1—C4 C1—N1—C2 C4—N1—C2 C5—N2—C6 C5—N2—C8 C6—N2—C8 C13—N3—C9 C13—N3—Zn C9—N3—Zn C14—N4—N5 C15—N5—N4 C19—N6—C18 N1—C1—S2 N1—C1—S1 S2—C1—S1 N1—C2—C3 N1—C2—H2A C3—C2—H2A N1—C2—H2B C3—C2—H2B H2A—C2—H2B O1—C3—C2 O1—C3—H3A C2—C3—H3A O1—C3—H3B C2—C3—H3B H3A—C3—H3B N1—C4—H4A N1—C4—H4B H4A—C4—H4B N1—C4—H4C H4A—C4—H4C Acta Cryst. (2017). E73, 1458-1464 117.15 (9) 106.36 (9) 136.48 (4) 101.88 (9) 96.05 (4) 73.10 (4) 102.55 (9) 73.47 (4) 99.01 (4) 155.56 (4) 85.88 (13) 83.17 (12) 85.07 (13) 81.33 (12) 111 (4) 118 (4) 120.9 (3) 122.2 (3) 116.9 (3) 122.3 (3) 121.5 (3) 116.2 (3) 116.9 (3) 119.8 (3) 123.3 (2) 111.6 (3) 112.1 (3) 116.3 (3) 122.4 (3) 119.8 (3) 117.8 (2) 112.3 (3) 109.2 109.2 109.2 109.2 107.9 112.1 (4) 109.2 109.2 109.2 109.2 107.9 109.5 109.5 109.5 109.5 109.5 N2—C6—H6A C7—C6—H6A N2—C6—H6B C7—C6—H6B H6A—C6—H6B O2—C7—C6 O2—C7—H7A C6—C7—H7A O2—C7—H7B C6—C7—H7B H7A—C7—H7B N2—C8—H8A N2—C8—H8B H8A—C8—H8B N2—C8—H8C H8A—C8—H8C H8B—C8—H8C N3—C9—C10 N3—C9—H9 C10—C9—H9 C9—C10—C11 C9—C10—H10 C11—C10—H10 C10—C11—C12 C10—C11—C14 C12—C11—C14 C13—C12—C11 C13—C12—H12 C11—C12—H12 N3—C13—C12 N3—C13—H13 C12—C13—H13 N4—C14—C11 N4—C14—H14 C11—C14—H14 N5—C15—C16 N5—C15—H15 C16—C15—H15 C20—C16—C17 C20—C16—C15 C17—C16—C15 C18—C17—C16 C18—C17—H17 C16—C17—H17 N6—C18—C17 N6—C18—H18 C17—C18—H18 N6—C19—C20 109.0 109.0 109.0 109.0 107.8 113.1 (3) 109.0 109.0 109.0 109.0 107.8 109.5 109.5 109.5 109.5 109.5 109.5 122.5 (3) 118.7 118.7 120.0 (3) 120.0 120.0 117.4 (3) 121.4 (3) 121.2 (3) 118.8 (4) 120.6 120.6 124.4 (4) 117.8 117.8 120.9 (3) 119.5 119.5 119.9 (3) 120.1 120.1 117.7 (3) 120.7 (3) 121.6 (3) 119.2 (3) 120.4 120.4 124.0 (3) 118.0 118.0 124.3 (4) sup-5 supporting information H4B—C4—H4C N2—C5—S4 N2—C5—S3 S4—C5—S3 N2—C6—C7 109.5 120.7 (3) 121.7 (3) 117.7 (2) 113.0 (3) N6—C19—H19 C20—C19—H19 C19—C20—C16 C19—C20—H20 C16—C20—H20 117.8 117.8 118.5 (4) 120.8 120.8 C14—N4—N5—C15 C4—N1—C1—S2 C2—N1—C1—S2 C4—N1—C1—S1 C2—N1—C1—S1 Zn—S2—C1—N1 Zn—S2—C1—S1 Zn—S1—C1—N1 Zn—S1—C1—S2 C1—N1—C2—C3 C4—N1—C2—C3 N1—C2—C3—O1 C6—N2—C5—S4 C8—N2—C5—S4 C6—N2—C5—S3 C8—N2—C5—S3 Zn—S4—C5—N2 Zn—S4—C5—S3 Zn—S3—C5—N2 Zn—S3—C5—S4 C5—N2—C6—C7 C8—N2—C6—C7 N2—C6—C7—O2 C13—N3—C9—C10 170.1 (4) 178.3 (3) −0.6 (5) −0.1 (5) −179.1 (3) −175.9 (3) 2.55 (18) 175.9 (3) −2.64 (19) 92.4 (4) −86.6 (4) 59.9 (4) −179.6 (2) 0.3 (5) 2.3 (5) −177.8 (3) −163.6 (3) 14.54 (17) 162.9 (3) −15.21 (18) 86.1 (4) −93.8 (4) 56.2 (4) 0.8 (6) Zn—N3—C9—C10 N3—C9—C10—C11 C9—C10—C11—C12 C9—C10—C11—C14 C10—C11—C12—C13 C14—C11—C12—C13 C9—N3—C13—C12 Zn—N3—C13—C12 C11—C12—C13—N3 N5—N4—C14—C11 C10—C11—C14—N4 C12—C11—C14—N4 N4—N5—C15—C16 N5—C15—C16—C20 N5—C15—C16—C17 C20—C16—C17—C18 C15—C16—C17—C18 C19—N6—C18—C17 C16—C17—C18—N6 C18—N6—C19—C20 N6—C19—C20—C16 C17—C16—C20—C19 C15—C16—C20—C19 −179.6 (3) −0.2 (6) −0.7 (6) −178.6 (4) 0.8 (7) 178.8 (5) −0.6 (8) 179.8 (4) −0.2 (9) −176.8 (3) −177.2 (4) 4.9 (6) 179.5 (3) −175.7 (4) 2.4 (6) 1.4 (6) −176.8 (3) −1.1 (6) −0.4 (6) 1.5 (7) −0.5 (7) −1.0 (6) 177.2 (4) Hydrogen-bond geometry (Å, º) Cg1 is the centroid of the Zn/S1/S2/C1 ring. D—H···A i O1—H1O···O2 O2—H2O···N6ii C20—H20···O1iii C6—H6B···Cg1i D—H H···A D···A D—H···A 0.85 (5) 0.84 (4) 0.95 0.99 1.92 (5) 1.95 (4) 2.32 2.59 2.721 (5) 2.769 (5) 3.233 (6) 3.540 (4) 158 (5) 163 (5) 162 162 Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y−1, −z+1; (iii) −x, y−3/2, −z+1/2. Acta Cryst. (2017). E73, 1458-1464 sup-6