1-Benzoyl-4-methyl­thio­semicarbazide

In the title compound, C₉H₁₁N₃OS, the OCN group makes dihedral angles of 30.48 (16) and 74.41 (14)°, respectively, with the phenyl and methyl­thio­urea groups. The crystal structure is stabilized by weak inter­molecular N—H...S, N—H...O and C—H...O hydrogen bonds, to form a two-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.064
• wR factor = 0.155
• Data-to-parameter ratio = 15.9

checkCIF/PLATON results

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Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          5

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 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
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
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S1. Comment

The continuing efforts to synthesize new thiosemicarbazide derivatives are driven by their ability to form complexes with metal ions and also their biological activities. As an example, 4-(2-methylprop-2-enyl)-1-[3-(trifluoromethyl)phenyl]thiosemicarbazide has been found to exhibit anti-implantation activity (Nagarajan et al., 1984).

The title molecule, (I), adopts a cis–trans configuration with respect to the position of the methyl and benzoylamine groups, respectively, against the thiono across the N3—C8 and N2—C8 bonds (Fig. 1), as observed in the related compounds 1-methyl-4-salicyloyl-thiosemicarbazide (Gors et al., 1979) and 4-phenyl-1-(propan-2-ylidene)thiosemicarbazide (Jian et al., 2005). The bond lengths and angles in (I) are in normal ranges (Allen et al., 1987) and comparable to those in the above-cited compounds.

The methylthiourea (S1/N2/N3/C8/C9), phenyl (C1–C6) and O1/C7/N1 fragments are each planar. The maximum deviation is 0.011 (3) Å for atom C1 in the phenyl group. The O1/C7/N1 fragment makes dihedral angles of 30.48 (16) and 74.41 (14)° with the phenyl and methylthiourea fragments. The phenyl and methylthiourea fragments bisect each other by 75.12 (14)°. In the crystal structure, the molecules are linked by weak intermolecular N—H···S, N—H···O and C—H···O hydrogen bonds (Table 2) to form a two-dimensional network (Fig.2).

S2. Experimental

A solution of 4-methyl-thiosemicarbazide (1.05 g, 0.01 mol) in acetone (50 ml) was added dropwise into an acetone solution (50 ml) containing an equimolar amount of benzoylchloride and ammonium thiocyanate in a two-necked round-bottomed flask. The mixture was refluxed for about 2 h. The light-yellow solution was filtered off and colourless crystals were obtained after five days of evaporation (yield 85%, m.p. 185.3–188.8 K).

S3. Refinement

All H atoms were placed in idealized positions and allowed to ride on their parent C and N atoms with distances constrained to 0.93 (aromatic C—H), 0.96 (methyl C—H) or 0.86 Å (N—H). U_iso(H) values were set at 1.2U_eq(carrier atom) for aromatic CH and NH groups, and 1.5U_eq(carrier atom) for the methyl CH₃ group.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. : Molecular structure of (I), with 50% probability displacement ellipsoids.
	Fig. 2. : Packing diagram of (I), viewed down the b axis. The dashed lines denote the N—H···O and N—H···S hydrogen bonds.

1-Benzoyl-4-methylthiosemicarbazide

Crystal data

C9H11N3OS	F(000) = 440
Mr = 209.27	Dx = 1.349 Mg m^−3
Monoclinic, P21/c	Melting point = 185.3–188.8 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.110 (14) Å	Cell parameters from 2263 reflections
b = 9.958 (11) Å	θ = 1.7–26.0°
c = 8.758 (10) Å	µ = 0.29 mm^−1
β = 102.69 (2)°	T = 298 K
V = 1030 (2) Å^3	Block, colourless
Z = 4	0.49 × 0.20 × 0.19 mm

Data collection

Bruker AXS CCD area-detector diffractometer	2014 independent reflections
Radiation source: fine-focus sealed tube	1807 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
Detector resolution: 83.66 pixels mm^-1	θmax = 26.0°, θmin = 1.7°
ω scans	h = −13→14
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −12→11
Tmin = 0.873, Tmax = 0.947	l = −10→10
5555 measured reflections

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.23	w = 1/[σ^2(Fo^2) + (0.0526P)^2 + 0.5802P] where P = (Fo^2 + 2Fc^2)/3
2014 reflections	(Δ/σ)max < 0.001
127 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

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

	x	y	z	Uiso*/Ueq
S1	0.48871 (7)	0.57819 (8)	0.19465 (10)	0.0508 (3)
O1	0.20052 (19)	0.8871 (2)	0.1134 (3)	0.0571 (6)
N1	0.3140 (2)	0.8563 (2)	0.3521 (3)	0.0447 (6)
H1A	0.3219	0.8627	0.4518	0.054*
N2	0.3912 (2)	0.7853 (2)	0.2877 (3)	0.0490 (7)
H2A	0.4358	0.8291	0.2418	0.059*
N3	0.3364 (2)	0.5854 (2)	0.3757 (3)	0.0438 (6)
H3A	0.2946	0.6323	0.4231	0.053*
C1	0.0452 (3)	1.0291 (3)	0.2587 (4)	0.0526 (8)
H1B	0.0119	0.9795	0.1706	0.063*
C2	−0.0190 (3)	1.1178 (4)	0.3228 (5)	0.0622 (9)
H2B	−0.0959	1.1263	0.2787	0.075*
C3	0.0284 (3)	1.1936 (3)	0.4500 (4)	0.0584 (9)
H3B	−0.0160	1.2525	0.4930	0.070*
C4	0.1421 (3)	1.1823 (3)	0.5142 (4)	0.0606 (9)
H4A	0.1751	1.2356	0.5991	0.073*
C5	0.2076 (3)	1.0920 (3)	0.4531 (4)	0.0502 (8)
H5A	0.2844	1.0837	0.4979	0.060*
C6	0.1591 (2)	1.0137 (3)	0.3249 (3)	0.0398 (6)
C7	0.2254 (2)	0.9155 (3)	0.2522 (3)	0.0414 (7)
C8	0.3992 (2)	0.6504 (3)	0.2943 (3)	0.0375 (6)
C9	0.3328 (3)	0.4408 (3)	0.3908 (4)	0.0608 (9)
H9A	0.2818	0.4172	0.4563	0.091*
H9B	0.4072	0.4079	0.4368	0.091*
H9C	0.3071	0.4012	0.2892	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0543 (5)	0.0487 (5)	0.0549 (5)	0.0154 (3)	0.0240 (4)	−0.0014 (3)
O1	0.0566 (13)	0.0728 (15)	0.0462 (13)	−0.0129 (11)	0.0208 (11)	−0.0172 (11)
N1	0.0556 (15)	0.0357 (12)	0.0490 (14)	0.0036 (11)	0.0248 (12)	−0.0056 (10)
N2	0.0540 (15)	0.0353 (12)	0.0686 (17)	−0.0030 (10)	0.0374 (14)	−0.0085 (11)
N3	0.0485 (14)	0.0387 (12)	0.0478 (14)	0.0008 (10)	0.0185 (12)	−0.0013 (10)
C1	0.0494 (18)	0.0490 (17)	0.058 (2)	−0.0024 (14)	0.0080 (15)	−0.0005 (15)
C2	0.0503 (19)	0.060 (2)	0.077 (2)	0.0139 (16)	0.0146 (18)	0.0080 (18)
C3	0.066 (2)	0.0471 (17)	0.068 (2)	0.0222 (16)	0.0282 (18)	0.0079 (16)
C4	0.079 (3)	0.0481 (18)	0.054 (2)	0.0162 (16)	0.0124 (18)	−0.0083 (15)
C5	0.0519 (18)	0.0456 (16)	0.0519 (18)	0.0083 (13)	0.0092 (15)	−0.0067 (14)
C6	0.0453 (16)	0.0355 (13)	0.0421 (16)	−0.0013 (12)	0.0170 (13)	0.0032 (11)
C7	0.0442 (16)	0.0393 (15)	0.0457 (17)	−0.0126 (12)	0.0204 (13)	−0.0041 (12)
C8	0.0354 (14)	0.0399 (15)	0.0361 (14)	0.0018 (11)	0.0055 (11)	−0.0060 (11)
C9	0.083 (3)	0.0408 (16)	0.061 (2)	−0.0032 (16)	0.0209 (19)	0.0048 (14)

Geometric parameters (Å, º)

S1—C8	1.694 (3)	C2—C3	1.363 (5)
O1—C7	1.220 (4)	C2—H2B	0.9300
N1—C7	1.361 (4)	C3—C4	1.373 (5)
N1—N2	1.387 (3)	C3—H3B	0.9300
N1—H1A	0.8600	C4—C5	1.383 (4)
N2—C8	1.347 (4)	C4—H4A	0.9300
N2—H2A	0.8600	C5—C6	1.387 (4)
N3—C8	1.320 (4)	C5—H5A	0.9300
N3—C9	1.448 (4)	C6—C7	1.494 (4)
N3—H3A	0.8600	C9—H9A	0.9600
C1—C2	1.375 (5)	C9—H9B	0.9600
C1—C6	1.383 (5)	C9—H9C	0.9600
C1—H1B	0.9300
C7—N1—N2	117.8 (3)	C5—C4—H4A	119.9
C7—N1—H1A	121.1	C4—C5—C6	120.1 (3)
N2—N1—H1A	121.1	C4—C5—H5A	120.0
C8—N2—N1	122.7 (2)	C6—C5—H5A	120.0
C8—N2—H2A	118.7	C1—C6—C5	118.9 (3)
N1—N2—H2A	118.7	C1—C6—C7	118.3 (3)
C8—N3—C9	124.7 (3)	C5—C6—C7	122.7 (3)
C8—N3—H3A	117.6	O1—C7—N1	121.8 (3)
C9—N3—H3A	117.6	O1—C7—C6	122.6 (3)
C2—C1—C6	120.1 (3)	N1—C7—C6	115.6 (3)
C2—C1—H1B	120.0	N3—C8—N2	117.9 (2)
C6—C1—H1B	120.0	N3—C8—S1	125.4 (2)
C3—C2—C1	121.0 (3)	N2—C8—S1	116.7 (2)
C3—C2—H2B	119.5	N3—C9—H9A	109.5
C1—C2—H2B	119.5	N3—C9—H9B	109.5
C2—C3—C4	119.6 (3)	H9A—C9—H9B	109.5
C2—C3—H3B	120.2	N3—C9—H9C	109.5
C4—C3—H3B	120.2	H9A—C9—H9C	109.5
C3—C4—C5	120.3 (3)	H9B—C9—H9C	109.5
C3—C4—H4A	119.9
C7—N1—N2—C8	−109.4 (3)	N2—N1—C7—C6	−167.6 (2)
C6—C1—C2—C3	1.3 (5)	C1—C6—C7—O1	28.3 (4)
C1—C2—C3—C4	0.7 (5)	C5—C6—C7—O1	−150.0 (3)
C2—C3—C4—C5	−1.8 (5)	C1—C6—C7—N1	−149.8 (3)
C3—C4—C5—C6	0.9 (5)	C5—C6—C7—N1	31.9 (4)
C2—C1—C6—C5	−2.1 (5)	C9—N3—C8—N2	178.3 (3)
C2—C1—C6—C7	179.6 (3)	C9—N3—C8—S1	−1.0 (4)
C4—C5—C6—C1	1.0 (5)	N1—N2—C8—N3	−5.2 (4)
C4—C5—C6—C7	179.3 (3)	N1—N2—C8—S1	174.1 (2)
N2—N1—C7—O1	14.3 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N1	0.86	2.34	2.715 (4)	107
N1—H1A···S1^i	0.86	2.66	3.334 (5)	136
N2—H2A···S1^ii	0.86	2.66	3.248 (4)	127
N3—H3A···O1^i	0.86	2.22	2.936 (5)	140
C3—H3B···O1^iii	0.93	2.60	3.321 (6)	135

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x, y+1/2, −z+1/2.