Ethoxy­carbonyl­methyl 3-(2-chloro­benzyl­idene)dithio­carbazate

The title compound, C₁₂H₁₃ClN₂O₂S₂, is a new Schiff base derived from ring opening of N-amino­rhodanine. It is prepared by reaction of N-amino­rhodanine and 2-chloro­benzaldehyde in an ethanol solution in the presence of HCl. In the solid state, inter­molecular N—H...O hydrogen bonds link the mol­ecules into chains.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.029
• wR factor = 0.067
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  O1      ..       3.12 Ang.

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           26.75
           From the CIF: _reflns_number_total               3029
           From the CIF: _diffrn_reflns_limit_ max hkl   10.   21.   13.
           From the CIF: _diffrn_reflns_limit_ min hkl  -10.  -21.  -13.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   13.   21.   10.
           Calculated minimum hkl  -13.  -21.  -10.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-RED32 (Stoe & Cie, 2005); data reduction: X-RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-STEP32 (Stoe & Cie, 2000); software used to prepare material for publication: SHELXL97.

Ethoxycarbonylmethyl 3-(2-chlorobenzylidene)dithiocarbazate

Crystal data

C12H13ClN2O2S2	F(000) = 656
Mr = 316.81	Dx = 1.468 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2876 reflections
a = 10.5613 (18) Å	θ = 1.9–26.8°
b = 16.856 (3) Å	µ = 0.56 mm^−1
c = 8.1013 (14) Å	T = 150 K
β = 96.409 (14)°	Prism, yellow
V = 1433.2 (4) Å^3	0.20 × 0.15 × 0.10 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	3029 independent reflections
Radiation source: fine-focus sealed tube	2808 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ scans	θmax = 26.8°, θmin = 1.9°
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005)	h = −10→10
Tmin = 0.905, Tmax = 0.946	k = −21→21
10851 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0242P)^2 + 0.6651P] where P = (Fo^2 + 2Fc^2)/3
3029 reflections	(Δ/σ)max = 0.001
177 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.19215 (4)	0.37074 (2)	−0.21139 (5)	0.03234 (11)
S1	0.55752 (4)	0.07535 (2)	0.24980 (4)	0.02360 (10)
S2	0.74170 (4)	0.21023 (2)	0.35123 (5)	0.02987 (11)
O1	0.73663 (10)	0.05070 (6)	0.70072 (12)	0.0257 (2)
O2	0.54516 (10)	0.10337 (6)	0.61500 (13)	0.0273 (2)
N1	0.53817 (12)	0.21977 (8)	0.13526 (16)	0.0247 (3)
N2	0.43309 (12)	0.18889 (7)	0.04096 (15)	0.0228 (3)
C1	0.84343 (17)	0.06280 (11)	0.9754 (2)	0.0351 (4)
H1A	0.8336	0.0744	1.0919	0.053*
H1B	0.9026	0.1010	0.9347	0.053*
H1C	0.8771	0.0090	0.9666	0.053*
C2	0.71688 (16)	0.06898 (10)	0.87355 (19)	0.0294 (3)
H2A	0.6560	0.0309	0.9140	0.035*
H2B	0.6820	0.1232	0.8812	0.035*
C3	0.64099 (14)	0.06909 (8)	0.58654 (18)	0.0224 (3)
C4	0.66694 (14)	0.03795 (9)	0.41802 (18)	0.0243 (3)
H4A	0.6619	−0.0207	0.4188	0.029*
H4B	0.7547	0.0527	0.3984	0.029*
C5	0.61254 (14)	0.17403 (9)	0.24154 (18)	0.0225 (3)
C6	0.36527 (14)	0.23983 (9)	−0.04762 (18)	0.0236 (3)
H6A	0.3897	0.2941	−0.0452	0.028*
C7	0.25025 (14)	0.21433 (9)	−0.15245 (17)	0.0224 (3)
C8	0.22164 (15)	0.13371 (9)	−0.17439 (19)	0.0261 (3)
H8A	0.2787	0.0951	−0.1232	0.031*
C9	0.11149 (15)	0.10936 (10)	−0.2695 (2)	0.0299 (3)
H9A	0.0934	0.0544	−0.2826	0.036*
C10	0.02749 (15)	0.16489 (10)	−0.3458 (2)	0.0322 (4)
H10A	−0.0481	0.1479	−0.4109	0.039*
C11	0.05374 (15)	0.24510 (10)	−0.3270 (2)	0.0296 (3)
H11A	−0.0035	0.2834	−0.3791	0.036*
C12	0.16438 (14)	0.26910 (9)	−0.23166 (18)	0.0240 (3)
H1	0.5571 (19)	0.2683 (13)	0.124 (2)	0.036 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0377 (2)	0.02304 (19)	0.0355 (2)	0.00344 (15)	0.00031 (16)	0.00507 (15)
S1	0.02555 (19)	0.02189 (18)	0.02214 (17)	−0.00269 (13)	−0.00269 (13)	0.00131 (14)
S2	0.02541 (19)	0.0288 (2)	0.0330 (2)	−0.00513 (15)	−0.00746 (15)	0.00152 (16)
O1	0.0295 (6)	0.0253 (5)	0.0214 (5)	0.0049 (4)	−0.0019 (4)	0.0005 (4)
O2	0.0282 (6)	0.0255 (5)	0.0279 (5)	0.0053 (4)	0.0022 (4)	0.0016 (4)
N1	0.0242 (6)	0.0227 (6)	0.0258 (6)	−0.0049 (5)	−0.0031 (5)	0.0047 (5)
N2	0.0207 (6)	0.0267 (6)	0.0201 (6)	−0.0022 (5)	−0.0012 (5)	0.0017 (5)
C1	0.0372 (9)	0.0412 (9)	0.0256 (8)	−0.0041 (7)	−0.0019 (7)	−0.0022 (7)
C2	0.0355 (9)	0.0311 (8)	0.0213 (7)	0.0041 (7)	0.0021 (6)	−0.0002 (6)
C3	0.0272 (7)	0.0150 (6)	0.0242 (7)	−0.0008 (5)	−0.0008 (6)	0.0032 (5)
C4	0.0265 (7)	0.0211 (7)	0.0245 (7)	0.0040 (6)	−0.0014 (6)	0.0012 (6)
C5	0.0215 (7)	0.0252 (7)	0.0207 (7)	−0.0014 (6)	0.0023 (5)	0.0007 (6)
C6	0.0252 (7)	0.0232 (7)	0.0222 (7)	−0.0016 (6)	0.0019 (6)	0.0023 (6)
C7	0.0225 (7)	0.0254 (7)	0.0194 (6)	0.0009 (6)	0.0024 (5)	0.0026 (6)
C8	0.0263 (7)	0.0253 (7)	0.0259 (7)	0.0029 (6)	−0.0012 (6)	0.0030 (6)
C9	0.0302 (8)	0.0267 (8)	0.0319 (8)	−0.0018 (6)	−0.0013 (6)	−0.0013 (7)
C10	0.0255 (8)	0.0395 (9)	0.0298 (8)	−0.0028 (7)	−0.0044 (6)	0.0018 (7)
C11	0.0254 (8)	0.0349 (9)	0.0276 (8)	0.0056 (6)	−0.0017 (6)	0.0080 (7)
C12	0.0269 (7)	0.0242 (7)	0.0212 (7)	0.0018 (6)	0.0038 (6)	0.0039 (6)

Geometric parameters (Å, º)

Cl1—C12	1.7428 (16)	C2—H2B	0.990
S1—C5	1.7655 (15)	C3—C4	1.516 (2)
S1—C4	1.7995 (15)	C4—H4A	0.990
S2—C5	1.6589 (15)	C4—H4B	0.990
O1—C3	1.3280 (18)	C6—C7	1.467 (2)
O1—C2	1.4711 (18)	C6—H6A	0.950
O2—C3	1.2097 (18)	C7—C12	1.399 (2)
N1—C5	1.3424 (19)	C7—C8	1.399 (2)
N1—N2	1.3772 (17)	C8—C9	1.384 (2)
N1—H1	0.85 (2)	C8—H8A	0.950
N2—C6	1.2847 (19)	C9—C10	1.386 (2)
C1—C2	1.494 (2)	C9—H9A	0.950
C1—H1A	0.980	C10—C11	1.385 (2)
C1—H1B	0.980	C10—H10A	0.950
C1—H1C	0.980	C11—C12	1.387 (2)
C2—H2A	0.990	C11—H11A	0.950
C5—S1—C4	99.93 (7)	H4A—C4—H4B	107.7
C3—O1—C2	115.87 (12)	N1—C5—S2	121.30 (11)
C5—N1—N2	121.08 (13)	N1—C5—S1	113.20 (11)
C5—N1—H1	119.6 (14)	S2—C5—S1	125.50 (9)
N2—N1—H1	119.3 (14)	N2—C6—C7	120.11 (13)
C6—N2—N1	114.94 (13)	N2—C6—H6A	119.9
C2—C1—H1A	109.5	C7—C6—H6A	119.9
C2—C1—H1B	109.5	C12—C7—C8	117.58 (14)
H1A—C1—H1B	109.5	C12—C7—C6	121.65 (14)
C2—C1—H1C	109.5	C8—C7—C6	120.75 (13)
H1A—C1—H1C	109.5	C9—C8—C7	120.99 (14)
H1B—C1—H1C	109.5	C9—C8—H8A	119.5
O1—C2—C1	107.34 (13)	C7—C8—H8A	119.5
O1—C2—H2A	110.2	C8—C9—C10	120.28 (15)
C1—C2—H2A	110.2	C8—C9—H9A	119.9
O1—C2—H2B	110.2	C10—C9—H9A	119.9
C1—C2—H2B	110.2	C11—C10—C9	119.99 (15)
H2A—C2—H2B	108.5	C11—C10—H10A	120.0
O2—C3—O1	124.49 (14)	C9—C10—H10A	120.0
O2—C3—C4	125.19 (13)	C10—C11—C12	119.45 (14)
O1—C3—C4	110.28 (12)	C10—C11—H11A	120.3
C3—C4—S1	113.29 (10)	C12—C11—H11A	120.3
C3—C4—H4A	108.9	C11—C12—C7	121.71 (14)
S1—C4—H4A	108.9	C11—C12—Cl1	117.49 (12)
C3—C4—H4B	108.9	C7—C12—Cl1	120.79 (12)
S1—C4—H4B	108.9
C5—N1—N2—C6	175.65 (14)	N2—C6—C7—C8	−8.3 (2)
C3—O1—C2—C1	−166.47 (13)	C12—C7—C8—C9	−0.7 (2)
C2—O1—C3—O2	4.7 (2)	C6—C7—C8—C9	178.23 (14)
C2—O1—C3—C4	−172.93 (12)	C7—C8—C9—C10	0.3 (2)
O2—C3—C4—S1	13.15 (19)	C8—C9—C10—C11	0.1 (3)
O1—C3—C4—S1	−169.25 (10)	C9—C10—C11—C12	0.0 (3)
C5—S1—C4—C3	72.85 (12)	C10—C11—C12—C7	−0.5 (2)
N2—N1—C5—S2	178.12 (11)	C10—C11—C12—Cl1	−179.65 (13)
N2—N1—C5—S1	−2.13 (18)	C8—C7—C12—C11	0.8 (2)
C4—S1—C5—N1	−173.39 (11)	C6—C7—C12—C11	−178.15 (14)
C4—S1—C5—S2	6.35 (12)	C8—C7—C12—Cl1	179.99 (11)
N1—N2—C6—C7	−179.51 (13)	C6—C7—C12—Cl1	1.0 (2)
N2—C6—C7—C12	170.64 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.85 (2)	2.17 (2)	2.9870 (18)	162.0 (19)

Symmetry code: (i) x, −y+1/2, z−1/2.