organic compounds Acta Crystallographica Section E Experimental Structure Reports Online Crystal data ISSN 1600-5368 Ethyl (Z)-2-chloro-2-(2-phenylhydrazin1-ylidene)acetate Abdullah M. Asiri,a Mohie E. M. Zayeda and Seik Weng Ngb* a Chemistry Department, Faculty of Science, King Abdul Aziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia Correspondence e-mail: seikweng@um.edu.my Received 11 August 2010; accepted 13 August 2010 Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.002 Å; R factor = 0.026; wR factor = 0.076; data-to-parameter ratio = 17.1. The title compound, C10H11ClN2O2, features an almost planar Car—N(H)—N C(Cl) unit [torsion angle = 0.8 (1) whose phenyl substituent is almost coplanar with it [dihedral angle = 2.8 (2) ]; this unit is slightly twisted with respect to the carboxyl –CO2 fragment [dihedral angle = 10.3 (2) ]. In the crystal, the amino group acts as a hydrogen-bond donor to the carbonyl O atom of an adjacent molecule; the hydrogen bond generates a helical chain that runs along the b axis of the monoclinic unit cell. Related literature For a review of the reactions of hydrazonyl halides with heterocyclic thiones for heteroannulation, the synthesis of spiroheterocycles and heterocyclic ring formation, see: Shawali & Farghaly (2008). For related crystal structures, see: Xu (2006); Yin et al. (2006). V = 1048.41 (13) Å3 Z=4 Mo K radiation  = 0.35 mm1 T = 100 K 0.30  0.30  0.10 mm C10H11ClN2O2 Mr = 226.66 Monoclinic, P21 =c a = 10.5091 (7) Å b = 11.1813 (8) Å c = 10.1190 (7) Å = 118.148 (1) Data collection 6532 measured reflections 2399 independent reflections 2191 reflections with I > 2(I) Rint = 0.022 Bruker SMART APEX diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.904, Tmax = 0.966 Refinement R[F 2 > 2(F 2)] = 0.026 wR(F 2) = 0.076 S = 1.03 2399 reflections 140 parameters 1 restraint H atoms treated by a mixture of independent and constrained refinement
max = 0.31 e Å3
min = 0.21 e Å3 Table 1 Hydrogen-bond geometry (Å,  ). D—H  A D—H H  A D  A D—H  A N1—H1  O2i 0.85 (1) 2.18 (1) 2.969 (1) 153 (2) Symmetry code: (i) x þ 1; y þ 12; z þ 12. Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XSEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010). The authors thank King Abdul Aziz University and the University of Malaya for supporting this study. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NK2054). References Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Shawali, A. S. & Farghaly, T. A. (2008). ARKIVOC, i, 18–64. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Xu, J. (2006). Acta Cryst. E62, o5317–o5318. Yin, Z.-G., Du, Y.-J., Zhang, J.-S., Qian, H.-Y. & Wang, Q.-L. (2006). Acta Cryst. E62, o4807–o4808. o2374 Asiri et al. doi:10.1107/S1600536810032587 Acta Cryst. (2010). E66, o2374 supplementary materials supplementary materials Acta Cryst. (2010). E66, o2374 [ doi:10.1107/S1600536810032587 ] Ethyl (Z)-2-chloro-2-(2-phenylhydrazin-1-ylidene)acetate A. M. Asiri, M. E. M. Zayed and S. W. Ng Comment Ethyl 2-chloro(phenylhydrazono)acetate belongs to the class of of hydrazonyl halides that undergo heteroannulation, and are used for the synthesis of spiroheterocycles and other heterocyclic compounds. The utility in some aspects of heterocyclic chemistry has recently been reviewed (Shawali & Farghaly (2008). The central structural feature is an planar Caryl–NH–N═C unit, as noted in the crystal structures of other substituted derivatives (Xu, 2006; Yin et al., 2006). The parent compound (Scheme I) shows this characteristic linkage, whose torsion angle is 0.8 (1) °. The carbon-nitrogen double bond is of a Z-configuration (Fig. 1). Such a configuration allows the amino site to form a hydrogen bond to the double-bond carbonyl oxygen atom of an adjacent molecule, this hydrogen bond giving rise to a helical chain that runs along the b-axis of the unit cell (Fig. 2). Experimental The synthesis works with either 3-chloropentane-2,4-dione or ethyl 2-chloro-3-oxobutanoate. To a solution of either 3chloropentane-2,4-dione (1.34 g, 10 mmol) or ethyl 2-chloro-3-oxobutanoate (1.64 g, 10 mmol) in ethanol (100 ml) was added sodium acetate trihydrate (1.3 g, 10 mmol). The mixture was chilled to 273 K. To the mixture was added a cold solution of benzenediazonium chloride, prepared by diazotizing aniline (0.93 g, 10 mmol) dissolved in 6M hydrochloricacid (6 ml) with a solution of sodium nitrite (0.7 g, 10 mmol) dissolved in water (10 ml). The diazonium salt was added over a period of 20 min. The reaction mixture was stirred for another 15 min. and then left for 3 h in a refrigerator. The resulting solid was collected and washed with water. The crude product was recrystallized from ethanol to give the hydrazone in 80% yield; m.p. 352–353 K. Refinement Carbon-bound H-atoms were placed in calculated positions [C–H 0.95 to 0.99 Å, U(H) 1.2 to 1.5Ueq(C)] and were included in the refinement in the riding model approximation. The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint [N–H 0.86±0.01 Å]; its temperature factor was freely refined. Figures Fig. 1. Displacement ellipsoid plot of C10H11ClN2O2 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. sup-1 supplementary materials Fig. 2. Part of the hydrogen-bonded helical chain structure (red dashed lines) which runs along the b-axis. Ethyl (Z)-2-chloro-2-(2-phenylhydrazin-1-ylidene)acetate Crystal data C10H11ClN2O2 F(000) = 472 Mr = 226.66 Dx = 1.436 Mg m−3 Monoclinic, P21/c Mo Kα radiation, λ = 0.71073 Å Hall symbol: -P 2ybc a = 10.5091 (7) Å Cell parameters from 4259 reflections θ = 2.3–28.3° b = 11.1813 (8) Å µ = 0.35 mm−1 T = 100 K Irregular, yellow c = 10.1190 (7) Å β = 118.148 (1)° V = 1048.41 (13) Å3 Z=4 0.30 × 0.30 × 0.10 mm Data collection Bruker SMART APEX diffractometer Radiation source: fine-focus sealed tube 2399 independent reflections graphite 2191 reflections with I > 2σ(I) Rint = 0.022 ω scans θmax = 27.5°, θmin = 2.2° Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.904, Tmax = 0.966 6532 measured reflections h = −13→11 k = −14→12 l = −13→13 Refinement Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.026 wR(F2) = 0.076 S = 1.03 Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement w = 1/[σ2(Fo2) + (0.0409P)2 + 0.389P] where P = (Fo2 + 2Fc2)/3 2399 reflections (Δ/σ)max = 0.001 140 parameters Δρmax = 0.31 e Å−3 1 restraint Δρmin = −0.21 e Å−3 sup-2 supplementary materials Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) Cl1 O1 O2 N1 H1 N2 C1 C2 H2 C3 H3 C4 H4 C5 H5 C6 H6 C7 C8 C9 H9A H9B C10 H10A H10B H10C x y z Uiso*/Ueq 0.52913 (3) 0.67383 (8) 0.49929 (9) 0.70432 (10) 0.6608 (17) 0.68722 (10) 0.78999 (11) 0.81229 (12) 0.7691 0.89810 (12) 0.9140 0.96101 (13) 1.0194 0.93736 (12) 0.9796 0.85275 (12) 0.8378 0.61141 (12) 0.58682 (11) 0.66715 (12) 0.5698 0.6887 0.77830 (12) 0.7777 0.8740 0.7557 0.54445 (2) 0.38123 (7) 0.33068 (7) 0.70808 (8) 0.7284 (15) 0.59913 (8) 0.79127 (10) 0.90363 (10) 0.9232 0.98666 (11) 1.0629 0.95973 (11) 1.0170 0.84780 (11) 0.8289 0.76310 (10) 0.6866 0.52090 (10) 0.40102 (10) 0.26082 (10) 0.2446 0.2006 0.25572 (12) 0.1760 0.2719 0.3159 0.33899 (3) 0.09626 (9) 0.15554 (9) 0.26261 (10) 0.3121 (17) 0.20434 (10) 0.23651 (11) 0.30391 (12) 0.3651 0.28081 (13) 0.3273 0.19073 (14) 0.1753 0.12342 (13) 0.0612 0.14599 (12) 0.1001 0.22737 (12) 0.15624 (12) 0.03770 (13) −0.0461 0.1172 −0.01594 (13) −0.0566 0.0681 −0.0943 0.02076 (10) 0.01737 (18) 0.01943 (19) 0.0153 (2) 0.032 (4)* 0.01443 (19) 0.0143 (2) 0.0171 (2) 0.020* 0.0201 (2) 0.024* 0.0208 (2) 0.025* 0.0201 (2) 0.024* 0.0167 (2) 0.020* 0.0152 (2) 0.0147 (2) 0.0176 (2) 0.021* 0.021* 0.0213 (3) 0.032* 0.032* 0.032* Atomic displacement parameters (Å2) Cl1 O1 O2 N1 N2 C1 C2 C3 C4 C5 C6 C7 C8 C9 U11 0.02594 (16) 0.0184 (4) 0.0200 (4) 0.0167 (4) 0.0133 (4) 0.0109 (5) 0.0165 (5) 0.0187 (5) 0.0164 (5) 0.0172 (5) 0.0163 (5) 0.0144 (5) 0.0139 (5) 0.0184 (5) U22 0.01667 (16) 0.0141 (4) 0.0155 (4) 0.0138 (5) 0.0130 (5) 0.0151 (5) 0.0163 (6) 0.0144 (5) 0.0202 (6) 0.0250 (6) 0.0169 (5) 0.0162 (5) 0.0149 (5) 0.0151 (5) U33 0.02897 (16) 0.0232 (4) 0.0260 (4) 0.0185 (4) 0.0153 (4) 0.0148 (5) 0.0187 (5) 0.0249 (6) 0.0247 (6) 0.0201 (5) 0.0170 (5) 0.0166 (5) 0.0146 (5) 0.0200 (5) U12 −0.00155 (10) −0.0018 (3) −0.0020 (3) −0.0005 (4) 0.0013 (3) 0.0005 (4) 0.0016 (4) −0.0006 (4) −0.0026 (4) 0.0002 (5) −0.0002 (4) 0.0020 (4) 0.0018 (4) 0.0000 (4) U13 0.02060 (13) 0.0128 (3) 0.0136 (3) 0.0109 (4) 0.0053 (3) 0.0043 (4) 0.0087 (4) 0.0084 (5) 0.0090 (5) 0.0105 (4) 0.0078 (4) 0.0087 (4) 0.0061 (4) 0.0098 (4) U23 −0.00199 (10) −0.0032 (3) 0.0007 (3) −0.0015 (3) 0.0007 (3) 0.0024 (4) 0.0002 (4) 0.0001 (4) 0.0044 (4) 0.0017 (4) −0.0007 (4) 0.0011 (4) 0.0025 (4) −0.0022 (4) sup-3 supplementary materials C10 0.0189 (6) 0.0241 (6) 0.0221 (6) −0.0015 (5) 0.0107 (5) −0.0062 (5) Geometric parameters (Å, °) Cl1—C7 O1—C8 O1—C9 O2—C8 N1—N2 N1—C1 N1—H1 N2—C7 C1—C2 C1—C6 C2—C3 C2—H2 C3—C4 1.7361 (11) 1.3331 (13) 1.4593 (13) 1.2076 (14) 1.3282 (13) 1.4035 (14) 0.853 (13) 1.2765 (14) 1.3957 (16) 1.3939 (15) 1.3888 (16) 0.9500 1.3883 (17) C3—H3 C4—C5 C4—H4 C5—C6 C5—H5 C6—H6 C7—C8 C9—C10 C9—H9A C9—H9B C10—H10A C10—H10B C10—H10C 0.9500 1.3900 (17) 0.9500 1.3897 (16) 0.9500 0.9500 1.4853 (15) 1.5035 (15) 0.9900 0.9900 0.9800 0.9800 0.9800 C8—O1—C9 N2—N1—C1 N2—N1—H1 C1—N1—H1 C7—N2—N1 C2—C1—C6 C2—C1—N1 C6—C1—N1 C3—C2—C1 C3—C2—H2 C1—C2—H2 C4—C3—C2 C4—C3—H3 C2—C3—H3 C5—C4—C3 C5—C4—H4 C3—C4—H4 C4—C5—C6 C4—C5—H5 C6—C5—H5 C5—C6—C1 115.22 (8) 119.25 (9) 120.4 (11) 120.3 (11) 120.85 (9) 120.14 (10) 118.64 (10) 121.22 (10) 119.48 (10) 120.3 120.3 120.91 (11) 119.5 119.5 119.11 (11) 120.4 120.4 120.89 (11) 119.6 119.6 119.46 (11) C5—C6—H6 C1—C6—H6 N2—C7—C8 N2—C7—Cl1 C8—C7—Cl1 O2—C8—O1 O2—C8—C7 O1—C8—C7 O1—C9—C10 O1—C9—H9A C10—C9—H9A O1—C9—H9B C10—C9—H9B H9A—C9—H9B C9—C10—H10A C9—C10—H10B H10A—C10—H10B C9—C10—H10C H10A—C10—H10C H10B—C10—H10C 120.3 120.3 120.72 (10) 124.07 (9) 115.21 (8) 124.99 (10) 123.26 (10) 111.74 (9) 106.55 (9) 110.4 110.4 110.4 110.4 108.6 109.5 109.5 109.5 109.5 109.5 109.5 C1—N1—N2—C7 N2—N1—C1—C2 N2—N1—C1—C6 C6—C1—C2—C3 N1—C1—C2—C3 C1—C2—C3—C4 C2—C3—C4—C5 C3—C4—C5—C6 C4—C5—C6—C1 C2—C1—C6—C5 179.17 (10) −177.17 (9) 2.49 (15) −0.40 (16) 179.26 (10) 0.50 (17) −0.11 (17) −0.38 (17) 0.47 (17) −0.08 (16) N1—C1—C6—C5 N1—N2—C7—C8 N1—N2—C7—Cl1 C9—O1—C8—O2 C9—O1—C8—C7 N2—C7—C8—O2 Cl1—C7—C8—O2 N2—C7—C8—O1 Cl1—C7—C8—O1 C8—O1—C9—C10 −179.74 (10) 177.11 (9) −2.23 (15) −5.24 (15) 173.93 (9) −168.44 (10) 10.96 (14) 12.38 (14) −168.22 (7) −176.85 (9) sup-4 supplementary materials Hydrogen-bond geometry (Å, °) D—H···A i N1—H1···O2 Symmetry codes: (i) −x+1, y+1/2, −z+1/2. D—H H···A D···A D—H···A 0.85 (1) 2.18 (1) 2.969 (1) 153 (2) sup-5 supplementary materials Fig. 1 sup-6 supplementary materials Fig. 2 sup-7