1-(4-Chloro­benzyl­idene)-4-ethyl­thio­semicarbazide

In the title compound, C₁₀H₁₂ClN₃S, the dihedral angle between the benzene ring and the thio­urea unit is 2.35 (19)°. In the crystal, inversion dimers linked by pairs of N—H...S hydrogen bonds generate R₂²(8) loops.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.068
• wR factor = 0.272
• Data-to-parameter ratio = 20.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT934_ALERT_3_B Number of (Iobs-Icalc)/SigmaW .gt. 10 Outliers .          3

Alert level C
RFACR01_ALERT_3_C  The value of the weighted R factor is > 0.25
            Weighted R factor given   0.272
PLAT084_ALERT_2_C High wR2 Value .................................       0.27
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..          8
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C1     -   C2     ...       1.39 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          4

Alert level G
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT Unusually Large.       0.12
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K

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

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


checkCIF publication errors

Alert level G
PUBL013_ALERT_1_G The _publ_section_comment (discussion of study) is
            missing. This is required for a full paper submission (but is
            optional for an electronic paper).

   0 ALERT level A = Data missing that is essential or data in wrong format
   1 ALERT level G = General alerts. Data that may be required is missing

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Related literature

For related structures, see: Li & Jian (2010); Li & Meng (2010).

S1. Experimental

A mixture of 4-ethylthiosemicarbazide (0.1 mol) and 4-chlorobenzaldehyde (0.1 mol) was stirred in refluxing ethanol (20 mL) for 2 h to afford the title compound (0.089 mol, yield 89%). Colourless bars were obtained by recrystallization from ethanol at room temperature.

S2. Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances=0.97 Å, and with U_iso=1.2–1.5U_eq.

Structure description

For related structures, see: Li & Jian (2010); Li & Meng (2010).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids.

1-(4-Chlorobenzylidene)-4-ethylthiosemicarbazide

Crystal data

C10H12ClN3S	F(000) = 504
Mr = 241.75	Dx = 1.344 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2723 reflections
a = 4.6769 (10) Å	θ = 3.1–27.5°
b = 26.727 (6) Å	µ = 0.47 mm^−1
c = 9.791 (3) Å	T = 293 K
β = 102.59 (3)°	Bar, colorless
V = 1194.4 (5) Å^3	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	1388 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.066
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
phi and ω scans	h = −6→5
11437 measured reflections	k = −34→34
2723 independent reflections	l = −12→12

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.272	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.1156P)^2 + 1.1747P] where P = (Fo^2 + 2Fc^2)/3
2723 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.34 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
S1	1.2104 (3)	−0.01352 (5)	0.72223 (14)	0.0738 (5)
Cl1	−0.3450 (4)	0.27875 (6)	0.46099 (18)	0.1022 (6)
N2	0.7928 (8)	0.04912 (15)	0.6097 (4)	0.0637 (10)
H2A	0.7695	0.0311	0.5354	0.076*
N3	0.6207 (8)	0.09071 (14)	0.6128 (4)	0.0616 (10)
C5	0.2251 (9)	0.14199 (17)	0.4970 (5)	0.0576 (11)
C4	0.4166 (10)	0.09865 (18)	0.5041 (5)	0.0622 (11)
H4A	0.3907	0.0765	0.4291	0.075*
N1	1.0195 (10)	0.06662 (17)	0.8346 (4)	0.0789 (13)
H1A	0.8985	0.0912	0.8260	0.095*
C10	0.0157 (10)	0.15053 (19)	0.3771 (5)	0.0664 (12)
H10A	−0.0066	0.1281	0.3028	0.080*
C6	0.2528 (11)	0.1751 (2)	0.6072 (5)	0.0723 (13)
H6A	0.3933	0.1695	0.6889	0.087*
C9	−0.1627 (11)	0.1925 (2)	0.3665 (5)	0.0709 (13)
H9A	−0.3045	0.1983	0.2853	0.085*
C3	0.9998 (10)	0.03689 (17)	0.7250 (5)	0.0602 (11)
C8	−0.1287 (11)	0.22552 (19)	0.4764 (5)	0.0679 (12)
C7	0.0731 (14)	0.2164 (2)	0.5967 (6)	0.0836 (16)
H7A	0.0898	0.2382	0.6721	0.100*
C2	1.2242 (16)	0.0617 (2)	0.9669 (6)	0.096 (2)
H2B	1.1446	0.0383	1.0247	0.116*
H2C	1.4045	0.0475	0.9506	0.116*
C1	1.290 (2)	0.1061 (3)	1.0404 (9)	0.130 (3)
H1B	1.4287	0.0997	1.1264	0.196*
H1C	1.1142	0.1199	1.0606	0.196*
H1D	1.3723	0.1294	0.9851	0.196*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0781 (9)	0.0700 (8)	0.0700 (8)	0.0180 (6)	0.0089 (6)	0.0022 (6)
Cl1	0.1142 (13)	0.0852 (11)	0.1023 (12)	0.0396 (9)	0.0129 (9)	0.0139 (8)
N2	0.060 (2)	0.069 (2)	0.061 (2)	0.0125 (19)	0.0087 (17)	−0.0022 (18)
N3	0.060 (2)	0.062 (2)	0.063 (2)	0.0073 (19)	0.0145 (18)	0.0012 (17)
C5	0.054 (2)	0.062 (3)	0.055 (2)	−0.002 (2)	0.0104 (19)	0.0026 (19)
C4	0.057 (3)	0.069 (3)	0.059 (3)	0.008 (2)	0.010 (2)	−0.001 (2)
N1	0.087 (3)	0.079 (3)	0.063 (3)	0.025 (2)	0.000 (2)	−0.008 (2)
C10	0.063 (3)	0.070 (3)	0.062 (3)	0.002 (2)	0.006 (2)	−0.001 (2)
C6	0.072 (3)	0.077 (3)	0.060 (3)	0.014 (3)	−0.003 (2)	−0.004 (2)
C9	0.066 (3)	0.077 (3)	0.064 (3)	0.009 (3)	0.001 (2)	0.013 (2)
C3	0.057 (2)	0.063 (3)	0.062 (3)	0.006 (2)	0.013 (2)	0.005 (2)
C8	0.068 (3)	0.067 (3)	0.067 (3)	0.011 (2)	0.011 (2)	0.012 (2)
C7	0.098 (4)	0.079 (4)	0.068 (3)	0.025 (3)	0.005 (3)	−0.011 (3)
C2	0.111 (5)	0.085 (4)	0.077 (4)	0.012 (4)	−0.014 (3)	−0.005 (3)
C1	0.153 (7)	0.094 (5)	0.112 (6)	−0.002 (5)	−0.039 (5)	−0.022 (4)

Geometric parameters (Å, º)

S1—C3	1.673 (5)	C10—H10A	0.9300
Cl1—C8	1.733 (5)	C6—C7	1.379 (7)
N2—C3	1.357 (6)	C6—H6A	0.9300
N2—N3	1.377 (5)	C9—C8	1.373 (7)
N2—H2A	0.8600	C9—H9A	0.9300
N3—C4	1.283 (6)	C8—C7	1.361 (7)
C5—C10	1.374 (6)	C7—H7A	0.9300
C5—C6	1.379 (7)	C2—C1	1.386 (9)
C5—C4	1.457 (6)	C2—H2B	0.9700
C4—H4A	0.9300	C2—H2C	0.9700
N1—C3	1.322 (6)	C1—H1B	0.9600
N1—C2	1.439 (7)	C1—H1C	0.9600
N1—H1A	0.8600	C1—H1D	0.9600
C10—C9	1.389 (7)
C3—N2—N3	119.4 (4)	N1—C3—N2	116.2 (4)
C3—N2—H2A	120.3	N1—C3—S1	124.1 (4)
N3—N2—H2A	120.3	N2—C3—S1	119.7 (4)
C4—N3—N2	116.6 (4)	C7—C8—C9	120.3 (5)
C10—C5—C6	119.3 (4)	C7—C8—Cl1	120.2 (4)
C10—C5—C4	119.3 (4)	C9—C8—Cl1	119.5 (4)
C6—C5—C4	121.4 (4)	C8—C7—C6	120.2 (5)
N3—C4—C5	120.6 (4)	C8—C7—H7A	119.9
N3—C4—H4A	119.7	C6—C7—H7A	119.9
C5—C4—H4A	119.7	C1—C2—N1	114.7 (6)
C3—N1—C2	126.2 (5)	C1—C2—H2B	108.6
C3—N1—H1A	116.9	N1—C2—H2B	108.6
C2—N1—H1A	116.9	C1—C2—H2C	108.6
C5—C10—C9	120.2 (5)	N1—C2—H2C	108.6
C5—C10—H10A	119.9	H2B—C2—H2C	107.6
C9—C10—H10A	119.9	C2—C1—H1B	109.5
C5—C6—C7	120.3 (5)	C2—C1—H1C	109.5
C5—C6—H6A	119.9	H1B—C1—H1C	109.5
C7—C6—H6A	119.9	C2—C1—H1D	109.5
C8—C9—C10	119.7 (4)	H1B—C1—H1D	109.5
C8—C9—H9A	120.2	H1C—C1—H1D	109.5
C10—C9—H9A	120.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1^i	0.86	2.59	3.383 (4)	154

Symmetry code: (i) −x+2, −y, −z+1.