4-(Methyl­sulfan­yl)benzaldehyde thio­semicarbazone

The title compound, C₉H₁₁N₃S₂, crystallizes with two mol­ecules in the asymmetric unit, which differ mainly in the degree of planarity. The C=N double bonds are trans configured. Geometric parameters are in the usual ranges. The crystal structure is characterized by N—H...N and N—H...S hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.031
• wR factor = 0.084
• Data-to-parameter ratio = 22.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    S1     -   C1      ..       7.28 su

Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1A    -   C1A     ..       5.68 su
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 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, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PLATON.

4-(Methylsulfanyl)benzaldehyde thiosemicarbazone

Crystal data

C9H11N3S2	Z = 4
Mr = 225.33	F(000) = 472
Triclinic, P1	Dx = 1.373 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2052 (4) Å	Cell parameters from 35812 reflections
b = 9.1947 (5) Å	θ = 2.6–30.3°
c = 15.5994 (8) Å	µ = 0.45 mm^−1
α = 106.558 (5)°	T = 173 K
β = 97.573 (3)°	Block, light orange
γ = 100.110 (4)°	0.38 × 0.36 × 0.33 mm
V = 1089.76 (10) Å^3

Data collection

Stoe IPDS-II two-circle diffractometer	6421 independent reflections
Radiation source: fine-focus sealed tube	6026 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
ω scans	θmax = 30.2°, θmin = 2.6°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −11→11
Tmin = 0.847, Tmax = 0.865	k = −12→12
36432 measured reflections	l = −22→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.084	w = 1/[σ^2(Fo^2) + (0.0409P)^2 + 0.3428P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
6421 reflections	Δρmax = 0.38 e Å^−3
280 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.048 (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	0.67198 (3)	0.07742 (3)	0.631875 (17)	0.02549 (7)
S2	−0.25814 (4)	0.65923 (4)	0.88918 (2)	0.03788 (9)
N1	0.39725 (14)	0.17237 (13)	0.57770 (7)	0.0312 (2)
H1A	0.390 (2)	0.109 (2)	0.5230 (12)	0.038 (4)*
H1B	0.310 (2)	0.2118 (19)	0.5896 (11)	0.038 (4)*
N2	0.48514 (12)	0.23271 (11)	0.73196 (6)	0.02565 (18)
H2	0.547 (2)	0.222 (2)	0.7774 (12)	0.041 (4)*
N3	0.34361 (12)	0.29195 (11)	0.74363 (6)	0.02462 (17)
C1	0.50545 (13)	0.16371 (12)	0.64601 (7)	0.02302 (18)
C2	0.33505 (13)	0.36393 (12)	0.82623 (7)	0.02456 (19)
H2B	0.4232	0.3739	0.8750	0.029*
C3	−0.19202 (19)	0.81155 (15)	0.99705 (10)	0.0397 (3)
H3A	−0.1606	0.7667	1.0451	0.059*
H3B	−0.2848	0.8631	1.0104	0.059*
H3C	−0.0946	0.8877	0.9944	0.059*
C11	0.18868 (13)	0.43033 (12)	0.84461 (7)	0.02277 (18)
C12	0.03851 (14)	0.38485 (13)	0.77929 (7)	0.0264 (2)
H12	0.0276	0.3037	0.7238	0.032*
C13	−0.09340 (14)	0.45763 (14)	0.79535 (8)	0.0289 (2)
H13	−0.1937	0.4270	0.7504	0.035*
C14	−0.08065 (13)	0.57645 (13)	0.87757 (8)	0.0262 (2)
C15	0.06585 (14)	0.61834 (12)	0.94438 (7)	0.0268 (2)
H15	0.0748	0.6965	1.0009	0.032*
C16	0.19843 (13)	0.54492 (12)	0.92766 (7)	0.02488 (19)
H16	0.2973	0.5731	0.9734	0.030*
S1A	0.38986 (4)	−0.08951 (3)	0.102549 (17)	0.02913 (8)
S2A	1.06187 (4)	0.93546 (3)	0.64566 (2)	0.03645 (9)
N1A	0.61386 (14)	0.17483 (12)	0.12934 (7)	0.0318 (2)
H1C	0.609 (2)	0.147 (2)	0.0708 (13)	0.048 (5)*
H1D	0.677 (2)	0.262 (2)	0.1625 (11)	0.039 (4)*
N2A	0.52121 (13)	0.14129 (11)	0.25613 (6)	0.02653 (18)
H2A	0.456 (2)	0.0849 (19)	0.2834 (11)	0.035 (4)*
N3A	0.62678 (12)	0.28349 (10)	0.30691 (6)	0.02564 (18)
C1A	0.51689 (14)	0.08655 (12)	0.16569 (7)	0.02419 (19)
C2A	0.62789 (14)	0.32367 (12)	0.39316 (7)	0.0256 (2)
H2A1	0.5585	0.2567	0.4169	0.031*
C3A	1.0228 (2)	0.94995 (18)	0.75830 (10)	0.0495 (4)
H3A1	0.9063	0.9599	0.7607	0.074*
H3A2	1.1007	1.0417	0.8026	0.074*
H3A3	1.0400	0.8562	0.7729	0.074*
C11A	0.73408 (13)	0.47062 (12)	0.45536 (7)	0.02366 (19)
C12A	0.85520 (14)	0.56411 (12)	0.42608 (7)	0.0258 (2)
H12A	0.8702	0.5312	0.3647	0.031*
C13A	0.95270 (14)	0.70357 (13)	0.48588 (8)	0.0280 (2)
H13A	1.0343	0.7654	0.4652	0.034*
C14A	0.93201 (13)	0.75450 (12)	0.57704 (8)	0.0272 (2)
C15A	0.81326 (15)	0.66133 (14)	0.60712 (8)	0.0296 (2)
H15A	0.7987	0.6939	0.6686	0.036*
C16A	0.71637 (14)	0.52038 (13)	0.54644 (7)	0.0282 (2)
H16A	0.6369	0.4571	0.5674	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.02376 (12)	0.02918 (13)	0.02258 (12)	0.00799 (9)	0.00616 (9)	0.00470 (9)
S2	0.03053 (15)	0.04077 (17)	0.03995 (17)	0.01490 (12)	0.00683 (12)	0.00491 (13)
N1	0.0350 (5)	0.0402 (5)	0.0211 (4)	0.0189 (4)	0.0066 (4)	0.0072 (4)
N2	0.0260 (4)	0.0306 (4)	0.0204 (4)	0.0103 (3)	0.0052 (3)	0.0053 (3)
N3	0.0252 (4)	0.0254 (4)	0.0234 (4)	0.0073 (3)	0.0074 (3)	0.0057 (3)
C1	0.0248 (4)	0.0222 (4)	0.0213 (4)	0.0040 (3)	0.0064 (4)	0.0057 (3)
C2	0.0250 (5)	0.0244 (4)	0.0221 (4)	0.0040 (4)	0.0050 (4)	0.0047 (4)
C3	0.0463 (7)	0.0324 (6)	0.0421 (7)	0.0164 (5)	0.0146 (6)	0.0073 (5)
C11	0.0245 (4)	0.0213 (4)	0.0210 (4)	0.0029 (3)	0.0062 (3)	0.0050 (3)
C12	0.0265 (5)	0.0263 (5)	0.0216 (4)	0.0025 (4)	0.0050 (4)	0.0019 (4)
C13	0.0245 (5)	0.0317 (5)	0.0253 (5)	0.0036 (4)	0.0027 (4)	0.0036 (4)
C14	0.0242 (5)	0.0255 (5)	0.0280 (5)	0.0046 (4)	0.0077 (4)	0.0066 (4)
C15	0.0267 (5)	0.0249 (5)	0.0240 (5)	0.0031 (4)	0.0065 (4)	0.0013 (4)
C16	0.0236 (5)	0.0252 (5)	0.0217 (4)	0.0027 (4)	0.0038 (4)	0.0030 (4)
S1A	0.03812 (15)	0.02424 (13)	0.01908 (12)	0.00001 (10)	0.00147 (10)	0.00366 (9)
S2A	0.03119 (15)	0.02522 (14)	0.04128 (17)	0.00205 (11)	−0.00131 (12)	−0.00120 (11)
N1A	0.0401 (5)	0.0288 (5)	0.0220 (4)	−0.0014 (4)	0.0068 (4)	0.0061 (4)
N2A	0.0329 (5)	0.0224 (4)	0.0194 (4)	−0.0003 (3)	0.0039 (3)	0.0033 (3)
N3A	0.0289 (4)	0.0211 (4)	0.0227 (4)	0.0025 (3)	0.0023 (3)	0.0035 (3)
C1A	0.0282 (5)	0.0235 (4)	0.0201 (4)	0.0062 (4)	0.0033 (4)	0.0061 (3)
C2A	0.0279 (5)	0.0231 (4)	0.0229 (5)	0.0036 (4)	0.0043 (4)	0.0041 (4)
C3A	0.0577 (9)	0.0387 (7)	0.0343 (7)	0.0024 (6)	−0.0097 (6)	−0.0026 (5)
C11A	0.0239 (4)	0.0224 (4)	0.0224 (4)	0.0058 (3)	0.0026 (4)	0.0042 (3)
C12A	0.0273 (5)	0.0259 (5)	0.0241 (5)	0.0073 (4)	0.0050 (4)	0.0070 (4)
C13A	0.0252 (5)	0.0254 (5)	0.0323 (5)	0.0050 (4)	0.0044 (4)	0.0085 (4)
C14A	0.0232 (5)	0.0227 (4)	0.0301 (5)	0.0063 (4)	−0.0008 (4)	0.0018 (4)
C15A	0.0291 (5)	0.0295 (5)	0.0244 (5)	0.0054 (4)	0.0041 (4)	0.0007 (4)
C16A	0.0274 (5)	0.0281 (5)	0.0244 (5)	0.0026 (4)	0.0052 (4)	0.0032 (4)

Geometric parameters (Å, º)

S1—C1	1.7045 (11)	S1A—C1A	1.7045 (11)
S2—C14	1.7645 (11)	S2A—C14A	1.7640 (11)
S2—C3	1.7991 (14)	S2A—C3A	1.7995 (17)
N1—C1	1.3244 (14)	N1A—C1A	1.3297 (14)
N1—H1A	0.873 (17)	N1A—H1C	0.869 (19)
N1—H1B	0.875 (17)	N1A—H1D	0.852 (17)
N2—C1	1.3561 (13)	N2A—C1A	1.3493 (13)
N2—N3	1.3783 (12)	N2A—N3A	1.3851 (12)
N2—H2	0.854 (17)	N2A—H2A	0.906 (17)
N3—C2	1.2874 (13)	N3A—C2A	1.2880 (14)
C2—C11	1.4649 (15)	C2A—C11A	1.4639 (14)
C2—H2B	0.9500	C2A—H2A1	0.9500
C3—H3A	0.9800	C3A—H3A1	0.9800
C3—H3B	0.9800	C3A—H3A2	0.9800
C3—H3C	0.9800	C3A—H3A3	0.9800
C11—C16	1.3999 (14)	C11A—C16A	1.3987 (15)
C11—C12	1.4060 (15)	C11A—C12A	1.4067 (15)
C12—C13	1.3829 (16)	C12A—C13A	1.3842 (15)
C12—H12	0.9500	C12A—H12A	0.9500
C13—C14	1.4055 (15)	C13A—C14A	1.4079 (16)
C13—H13	0.9500	C13A—H13A	0.9500
C14—C15	1.3992 (15)	C14A—C15A	1.4000 (17)
C15—C16	1.3926 (15)	C15A—C16A	1.3958 (15)
C15—H15	0.9500	C15A—H15A	0.9500
C16—H16	0.9500	C16A—H16A	0.9500
C14—S2—C3	103.46 (6)	C14A—S2A—C3A	103.74 (7)
C1—N1—H1A	118.9 (11)	C1A—N1A—H1C	120.3 (13)
C1—N1—H1B	118.9 (11)	C1A—N1A—H1D	120.6 (11)
H1A—N1—H1B	117.9 (15)	H1C—N1A—H1D	118.9 (17)
C1—N2—N3	118.67 (9)	C1A—N2A—N3A	119.41 (9)
C1—N2—H2	120.0 (11)	C1A—N2A—H2A	120.2 (10)
N3—N2—H2	119.9 (11)	N3A—N2A—H2A	120.4 (10)
C2—N3—N2	116.18 (9)	C2A—N3A—N2A	115.19 (9)
N1—C1—N2	117.64 (10)	N1A—C1A—N2A	117.52 (10)
N1—C1—S1	123.74 (8)	N1A—C1A—S1A	122.52 (8)
N2—C1—S1	118.57 (8)	N2A—C1A—S1A	119.96 (8)
N3—C2—C11	119.66 (10)	N3A—C2A—C11A	121.25 (10)
N3—C2—H2B	120.2	N3A—C2A—H2A1	119.4
C11—C2—H2B	120.2	C11A—C2A—H2A1	119.4
S2—C3—H3A	109.5	S2A—C3A—H3A1	109.5
S2—C3—H3B	109.5	S2A—C3A—H3A2	109.5
H3A—C3—H3B	109.5	H3A1—C3A—H3A2	109.5
S2—C3—H3C	109.5	S2A—C3A—H3A3	109.5
H3A—C3—H3C	109.5	H3A1—C3A—H3A3	109.5
H3B—C3—H3C	109.5	H3A2—C3A—H3A3	109.5
C16—C11—C12	118.67 (10)	C16A—C11A—C12A	118.58 (10)
C16—C11—C2	119.91 (9)	C16A—C11A—C2A	119.77 (10)
C12—C11—C2	121.39 (9)	C12A—C11A—C2A	121.65 (9)
C13—C12—C11	120.38 (10)	C13A—C12A—C11A	120.60 (10)
C13—C12—H12	119.8	C13A—C12A—H12A	119.7
C11—C12—H12	119.8	C11A—C12A—H12A	119.7
C12—C13—C14	120.67 (10)	C12A—C13A—C14A	120.55 (10)
C12—C13—H13	119.7	C12A—C13A—H13A	119.7
C14—C13—H13	119.7	C14A—C13A—H13A	119.7
C15—C14—C13	119.32 (10)	C15A—C14A—C13A	119.27 (10)
C15—C14—S2	124.70 (8)	C15A—C14A—S2A	124.71 (9)
C13—C14—S2	115.97 (8)	C13A—C14A—S2A	116.02 (9)
C16—C15—C14	119.71 (10)	C16A—C15A—C14A	119.74 (10)
C16—C15—H15	120.1	C16A—C15A—H15A	120.1
C14—C15—H15	120.1	C14A—C15A—H15A	120.1
C15—C16—C11	121.17 (10)	C15A—C16A—C11A	121.24 (10)
C15—C16—H16	119.4	C15A—C16A—H16A	119.4
C11—C16—H16	119.4	C11A—C16A—H16A	119.4
C1—N2—N3—C2	−176.22 (10)	C1A—N2A—N3A—C2A	−177.30 (10)
N3—N2—C1—N1	7.31 (15)	N3A—N2A—C1A—N1A	−1.10 (16)
N3—N2—C1—S1	−175.05 (8)	N3A—N2A—C1A—S1A	179.07 (8)
N2—N3—C2—C11	−179.95 (9)	N2A—N3A—C2A—C11A	179.70 (9)
N3—C2—C11—C16	−161.46 (10)	N3A—C2A—C11A—C16A	171.71 (11)
N3—C2—C11—C12	16.63 (16)	N3A—C2A—C11A—C12A	−8.53 (16)
C16—C11—C12—C13	3.11 (16)	C16A—C11A—C12A—C13A	−1.04 (16)
C2—C11—C12—C13	−175.00 (10)	C2A—C11A—C12A—C13A	179.19 (10)
C11—C12—C13—C14	−0.92 (17)	C11A—C12A—C13A—C14A	−0.17 (16)
C12—C13—C14—C15	−1.51 (17)	C12A—C13A—C14A—C15A	0.96 (17)
C12—C13—C14—S2	−179.97 (9)	C12A—C13A—C14A—S2A	−179.10 (8)
C3—S2—C14—C15	5.08 (12)	C3A—S2A—C14A—C15A	7.41 (12)
C3—S2—C14—C13	−176.55 (9)	C3A—S2A—C14A—C13A	−172.52 (9)
C13—C14—C15—C16	1.69 (17)	C13A—C14A—C15A—C16A	−0.52 (17)
S2—C14—C15—C16	−179.99 (9)	S2A—C14A—C15A—C16A	179.55 (9)
C14—C15—C16—C11	0.54 (17)	C14A—C15A—C16A—C11A	−0.72 (18)
C12—C11—C16—C15	−2.94 (16)	C12A—C11A—C16A—C15A	1.50 (17)
C2—C11—C16—C15	175.20 (10)	C2A—C11A—C16A—C15A	−178.74 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1^i	0.873 (17)	2.459 (17)	3.3254 (11)	172.1 (15)
N1—H1B···N3	0.875 (17)	2.266 (16)	2.6364 (13)	105.4 (12)
N2—H2···S1A^i	0.854 (17)	2.555 (18)	3.3412 (10)	153.5 (15)
N1A—H1C···S1A^ii	0.869 (19)	2.604 (19)	3.4707 (11)	174.7 (17)
N2A—H2A···S1^i	0.906 (17)	2.454 (17)	3.3499 (10)	169.8 (14)
N1A—H1D···N3A	0.852 (17)	2.302 (16)	2.6440 (14)	104.2 (13)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z.