N'-Benzoyl-N,N-diethyl-thio-urea: a monoclinic polymorph.

In the crystal of the title compound, C(12)H(16)N(2)OS, inversion dimers linked by pairs of N-H⋯S hydrogen bonds occur, generating R(2) (2)(8) loops. The mol-ecules are also linked by weak C-H⋯O hydrogen bonds. The structure is isostructural with that of N'-benzoyl-N,N-diethyl-seleno-urea [Bruce et al. (2007 ▶). New J. Chem.31, 1647-1653].

Related literature

For graph-set notation, see: Bernstein et al. (1995 ▶). For the structure of the isomorphous compound N,N-diethyl-N′-benzoyl­seleno­urea, see: Bruce et al. (2007 ▶). For a triclinic polymorph of the title compound, see: Bolte & Fink (2003 ▶). For related thio­ureas, see: Braun et al. (1987 ▶). For the preparation of the title compound, see: Beyer et al. (1975 ▶); Hartmann & Reuther (1973 ▶).

Experimental

Crystal data

C12H16N2OS

M = 236.33

Monoclinic,

a = 20.1727 (7) Å

b = 8.4717 (3) Å

c = 14.8345 (6) Å

β = 106.553 (2)°

V = 2430.11 (16) Å3

Z = 8

Mo Kα radiation

μ = 0.25 mm−1

T = 150 K

0.26 × 0.20 × 0.02 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.939, T max = 0.995

18425 measured reflections

3704 independent reflections

2940 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.096

S = 1.04

3704 reflections

147 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810009578/hb5361sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810009578/hb5361Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H16N2OS	F(000) = 1008
Mr = 236.33	Dx = 1.292 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.1727 (7) Å	Cell parameters from 173 reflections
b = 8.4717 (3) Å	θ = 2.0–28.2°
c = 14.8345 (6) Å	µ = 0.25 mm−1
β = 106.553 (2)°	T = 150 K
V = 2430.11 (16) Å3	Plate, yellow
Z = 8	0.26 × 0.20 × 0.02 mm

Bruker SMART APEXII diffractometer	3704 independent reflections
Radiation source: fine-focus sealed tube	2940 reflections with I > 2σ(I)
graphite	Rint = 0.038
ω scans	θmax = 30.5°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −28→28
Tmin = 0.939, Tmax = 0.995	k = −12→12
18425 measured reflections	l = −20→21

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.041P)2 + 1.4589P] where P = (Fo2 + 2Fc2)/3
3704 reflections	(Δ/σ)max < 0.001
147 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

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

	x	y	z	Uiso*/Ueq
S2	0.533573 (16)	0.44430 (4)	0.64948 (2)	0.02564 (9)
O4	0.64408 (5)	0.83285 (11)	0.66081 (6)	0.0268 (2)
N1	0.66786 (5)	0.47946 (12)	0.66756 (7)	0.0196 (2)
N3	0.59450 (5)	0.64040 (11)	0.55563 (7)	0.0195 (2)
H3	0.5563	0.6221	0.5060	0.023*
C2	0.60315 (6)	0.52200 (13)	0.62564 (8)	0.0187 (2)
C4	0.61335 (6)	0.79534 (14)	0.58044 (9)	0.0197 (2)
C11	0.72802 (6)	0.52699 (14)	0.63579 (9)	0.0219 (2)
H11A	0.7689	0.5404	0.6910	0.026*
H11B	0.7183	0.6295	0.6026	0.026*
C12	0.74337 (7)	0.40383 (16)	0.57050 (10)	0.0281 (3)
H12A	0.7556	0.3039	0.6045	0.042*
H12B	0.7821	0.4395	0.5480	0.042*
H12C	0.7024	0.3884	0.5168	0.042*
C13	0.68400 (7)	0.36738 (14)	0.74658 (9)	0.0233 (2)
H13A	0.7264	0.3079	0.7474	0.028*
H13B	0.6456	0.2908	0.7380	0.028*
C14	0.69465 (8)	0.45271 (17)	0.83921 (10)	0.0320 (3)
H14A	0.7331	0.5274	0.8481	0.048*
H14B	0.7054	0.3759	0.8907	0.048*
H14C	0.6524	0.5101	0.8388	0.048*
C41	0.59558 (6)	0.91116 (14)	0.50117 (9)	0.0193 (2)
C42	0.58864 (6)	0.86700 (15)	0.40819 (9)	0.0226 (2)
H42	0.5927	0.7592	0.3930	0.027*
C43	0.57585 (7)	0.98072 (17)	0.33807 (10)	0.0281 (3)
H43	0.5724	0.9510	0.2751	0.034*
C44	0.56814 (7)	1.13787 (16)	0.35958 (10)	0.0297 (3)
H44	0.5589	1.2153	0.3113	0.036*
C45	0.57385 (6)	1.18181 (15)	0.45143 (10)	0.0275 (3)
H45	0.5678	1.2892	0.4658	0.033*
C46	0.58840 (6)	1.06976 (14)	0.52255 (9)	0.0234 (2)
H46	0.5935	1.1008	0.5857	0.028*

	U11	U22	U33	U12	U13	U23
S2	0.02011 (15)	0.03108 (17)	0.02609 (17)	−0.00359 (12)	0.00715 (12)	0.00515 (13)
O4	0.0307 (5)	0.0238 (4)	0.0221 (4)	−0.0002 (4)	0.0016 (4)	−0.0030 (4)
N1	0.0191 (5)	0.0180 (5)	0.0211 (5)	0.0003 (4)	0.0047 (4)	0.0009 (4)
N3	0.0189 (5)	0.0180 (5)	0.0192 (5)	−0.0019 (4)	0.0016 (4)	0.0018 (4)
C2	0.0202 (5)	0.0171 (5)	0.0179 (5)	−0.0012 (4)	0.0043 (4)	−0.0013 (4)
C4	0.0169 (5)	0.0191 (5)	0.0232 (6)	0.0005 (4)	0.0057 (4)	−0.0003 (4)
C11	0.0170 (5)	0.0203 (6)	0.0276 (6)	−0.0017 (4)	0.0051 (5)	−0.0005 (5)
C12	0.0293 (6)	0.0278 (6)	0.0292 (7)	−0.0031 (5)	0.0117 (5)	−0.0042 (5)
C13	0.0250 (6)	0.0195 (5)	0.0228 (6)	0.0013 (4)	0.0028 (5)	0.0037 (5)
C14	0.0407 (8)	0.0303 (7)	0.0235 (6)	0.0024 (6)	0.0070 (6)	0.0005 (5)
C41	0.0146 (5)	0.0191 (5)	0.0234 (6)	−0.0005 (4)	0.0041 (4)	0.0010 (4)
C42	0.0215 (5)	0.0210 (6)	0.0247 (6)	−0.0016 (4)	0.0056 (5)	0.0004 (5)
C43	0.0264 (6)	0.0322 (7)	0.0231 (6)	−0.0027 (5)	0.0027 (5)	0.0032 (5)
C44	0.0242 (6)	0.0278 (7)	0.0328 (7)	−0.0012 (5)	0.0011 (5)	0.0097 (5)
C45	0.0210 (6)	0.0195 (6)	0.0393 (7)	0.0012 (5)	0.0040 (5)	0.0030 (5)
C46	0.0205 (5)	0.0202 (6)	0.0282 (6)	0.0005 (4)	0.0050 (5)	−0.0011 (5)

S2—C2	1.6767 (12)	C13—H13A	0.9900
O4—C4	1.2188 (15)	C13—H13B	0.9900
N1—C2	1.3258 (15)	C14—H14A	0.9800
N1—C13	1.4712 (15)	C14—H14B	0.9800
N1—C11	1.4774 (15)	C14—H14C	0.9800
N3—C4	1.3869 (15)	C41—C42	1.3971 (17)
N3—C2	1.4183 (15)	C41—C46	1.3975 (16)
N3—H3	0.9138	C42—C43	1.3871 (18)
C4—C41	1.4946 (17)	C42—H42	0.9500
C11—C12	1.5145 (17)	C43—C44	1.388 (2)
C11—H11A	0.9900	C43—H43	0.9500
C11—H11B	0.9900	C44—C45	1.385 (2)
C12—H12A	0.9800	C44—H44	0.9500
C12—H12B	0.9800	C45—C46	1.3870 (18)
C12—H12C	0.9800	C45—H45	0.9500
C13—C14	1.5129 (18)	C46—H46	0.9500
C2—N1—C13	120.93 (10)	N1—C13—H13B	109.5
C2—N1—C11	124.38 (10)	C14—C13—H13B	109.5
C13—N1—C11	114.50 (10)	H13A—C13—H13B	108.0
C4—N3—C2	120.52 (10)	C13—C14—H14A	109.5
C4—N3—H3	118.6	C13—C14—H14B	109.5
C2—N3—H3	111.7	H14A—C14—H14B	109.5
N1—C2—N3	115.79 (10)	C13—C14—H14C	109.5
N1—C2—S2	124.46 (9)	H14A—C14—H14C	109.5
N3—C2—S2	119.75 (8)	H14B—C14—H14C	109.5
O4—C4—N3	122.07 (11)	C42—C41—C46	119.59 (11)
O4—C4—C41	122.66 (11)	C42—C41—C4	122.35 (11)
N3—C4—C41	115.24 (10)	C46—C41—C4	118.02 (11)
N1—C11—C12	110.64 (10)	C43—C42—C41	119.96 (12)
N1—C11—H11A	109.5	C43—C42—H42	120.0
C12—C11—H11A	109.5	C41—C42—H42	120.0
N1—C11—H11B	109.5	C42—C43—C44	120.19 (13)
C12—C11—H11B	109.5	C42—C43—H43	119.9
H11A—C11—H11B	108.1	C44—C43—H43	119.9
C11—C12—H12A	109.5	C45—C44—C43	120.03 (13)
C11—C12—H12B	109.5	C45—C44—H44	120.0
H12A—C12—H12B	109.5	C43—C44—H44	120.0
C11—C12—H12C	109.5	C44—C45—C46	120.30 (12)
H12A—C12—H12C	109.5	C44—C45—H45	119.9
H12B—C12—H12C	109.5	C46—C45—H45	119.9
N1—C13—C14	110.93 (10)	C45—C46—C41	119.90 (12)
N1—C13—H13A	109.5	C45—C46—H46	120.0
C14—C13—H13A	109.5	C41—C46—H46	120.0
C13—N1—C2—N3	174.96 (10)	O4—C4—C41—C42	151.78 (12)
C11—N1—C2—N3	−10.38 (16)	N3—C4—C41—C42	−26.09 (16)
C13—N1—C2—S2	−5.74 (16)	O4—C4—C41—C46	−25.75 (17)
C11—N1—C2—S2	168.92 (9)	N3—C4—C41—C46	156.38 (10)
C4—N3—C2—N1	−71.43 (14)	C46—C41—C42—C43	1.06 (17)
C4—N3—C2—S2	109.23 (11)	C4—C41—C42—C43	−176.44 (11)
C2—N3—C4—O4	7.58 (17)	C41—C42—C43—C44	−1.66 (19)
C2—N3—C4—C41	−174.54 (10)	C42—C43—C44—C45	0.60 (19)
C2—N1—C11—C12	−93.09 (14)	C43—C44—C45—C46	1.07 (19)
C13—N1—C11—C12	81.88 (13)	C44—C45—C46—C41	−1.66 (18)
C2—N1—C13—C14	−88.47 (14)	C42—C41—C46—C45	0.59 (17)
C11—N1—C13—C14	96.37 (13)	C4—C41—C46—C45	178.19 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S2i	0.91	2.56	3.4595 (11)	169
C13—H13A···O4ii	0.99	2.59	3.3594 (18)	135