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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o870.
Published online 2010 March 20. doi:  10.1107/S1600536810009578
PMCID: PMC2983850

N′-Benzoyl-N,N-diethyl­thio­urea: a monoclinic polymorph

Abstract

In the crystal of the title compound, C12H16N2OS, inversion dimers linked by pairs of N—H(...)S hydrogen bonds occur, generating R 2 2(8) loops. The mol­ecules are also linked by weak C—H(...)O hydrogen bonds. The structure is isostructural with that of N′-benzoyl-N,N-diethyl­seleno­urea [Bruce et al. (2007 [triangle]). New J. Chem. 31, 1647–1653].

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-66-0o870-scheme1.jpg

Experimental

Crystal data

  • C12H16N2OS
  • M r = 236.33
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o870-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: APEX2 and SAINT (Bruker, 2004 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEPII (Johnson, 1976 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Supplementary Material

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

Acknowledgments

LRG thanks Fundação para o Ensino e Cultura Fernando Pessoa for support.

supplementary crystallographic information

Comment

The molecule of the title compound, (I) is shown in Fig.1, the bond lengths and angles show no unusual features. The structure is isostructural with that of N,N-diethyl-N'-benzoylselenourea, Bruce et al., 2007. An N3—H3···S2(1-x,1-y,1-z) hydrogen bond links the molecules into R22(8), Bernstein et al., 1995, centrosymetric dimers across the crystallographic centre of symmetry at (0.5, 0.5, 0.5). The bond lengths involved are N3—H3, 0.91 Å, H3···S2, 2.56Å and N3···S2, 3.4595 (11)Å and the angle at H3 is 169°, Fig. 2. The dimers are linked together to form sheets which lie parallel to (-101) by the weak C13—H13..O4(1.5-x,-0.5+y,1.5-z) hydrogen bond with C13—H13B, 0.99 Å, H13B···.O2, 2.59 Å, C13···.O4, 3.3594 (18)Å and an angle at H13B of 135°. This sheet is further re-inforced by a πi···πi interaction involving the phenyl rings at (x, y, z) and (1-x, 2-y, 1-z) which have a centre-to-centre distance of 4.3861 (8) Å, a perpendicular spacing of 3.5511 (6)Å and a slippage of 2.574 Å.

The structure of another polymorph of (1) is deposited as a private communication in the CCDC database, Bolte & Fink (2003). This is reported as crystallising in spacegroup P1 with four molecules in the asymmetric unit. In this compound the molecules are linked into two sets of C4 chains by N—H···O hydrogen bonds. These chains are formed by hydrogen bonded pairs of molecules in which the the N1—C2—N3—C4 torsion angles (our) numbering) are 78.6 (4)° and -80.8 (3)° in one pair and 78.7 (4)° and -81.9 (3)°. In these conformations the O atom is in a favourable position for forming N—H···O hydrogen bonds. In (1) the N1—C2—N3—C4 torsion angle is -71.43 (14)° and the S atom then becomes more accessible as an acceptor for a hydrogen bond and the O atom less so. Related thiourea structures are discussed in Braun et al., (1987).

Experimental

The title compound was prepared as described by Hartmann & Reuther (1973) and Beyer et al. (1975). The reaction as described in these papers produced yellow plates of (I), which after washing in ethanol at room temperature, were suitable for X-ray diffraction without recrystallisation.

Refinement

H atoms were treated as riding atoms with C—H(aromatic), 0.95 Å, C—H(CH2), 0.99 Å. The atom attached to N1 was located on a difference map at a distance of 0.9138Å and was fixed as a riding atom at this distance.

Figures

Fig. 1.
A view of (I) with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
A view of the R22(8) dimer lying across the centre-of symmetry at (0.5,0.5,0.5). Atoms marked with an asterisk,*, are in the molecule at (1-x,1-y,1-z). Hydrogen atoms not involved in the hydrogen bonding are omitted for the sake of clarity.

Crystal data

C12H16N2OSF(000) = 1008
Mr = 236.33Dx = 1.292 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 20.1727 (7) ÅCell parameters from 173 reflections
b = 8.4717 (3) Åθ = 2.0–28.2°
c = 14.8345 (6) ŵ = 0.25 mm1
β = 106.553 (2)°T = 150 K
V = 2430.11 (16) Å3Plate, yellow
Z = 80.26 × 0.20 × 0.02 mm

Data collection

Bruker SMART APEXII diffractometer3704 independent reflections
Radiation source: fine-focus sealed tube2940 reflections with I > 2σ(I)
graphiteRint = 0.038
ω scansθmax = 30.5°, θmin = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)h = −28→28
Tmin = 0.939, Tmax = 0.995k = −12→12
18425 measured reflectionsl = −20→21

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.041P)2 + 1.4589P] where P = (Fo2 + 2Fc2)/3
3704 reflections(Δ/σ)max < 0.001
147 parametersΔρmax = 0.41 e Å3
0 restraintsΔρmin = −0.21 e Å3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
S20.533573 (16)0.44430 (4)0.64948 (2)0.02564 (9)
O40.64408 (5)0.83285 (11)0.66081 (6)0.0268 (2)
N10.66786 (5)0.47946 (12)0.66756 (7)0.0196 (2)
N30.59450 (5)0.64040 (11)0.55563 (7)0.0195 (2)
H30.55630.62210.50600.023*
C20.60315 (6)0.52200 (13)0.62564 (8)0.0187 (2)
C40.61335 (6)0.79534 (14)0.58044 (9)0.0197 (2)
C110.72802 (6)0.52699 (14)0.63579 (9)0.0219 (2)
H11A0.76890.54040.69100.026*
H11B0.71830.62950.60260.026*
C120.74337 (7)0.40383 (16)0.57050 (10)0.0281 (3)
H12A0.75560.30390.60450.042*
H12B0.78210.43950.54800.042*
H12C0.70240.38840.51680.042*
C130.68400 (7)0.36738 (14)0.74658 (9)0.0233 (2)
H13A0.72640.30790.74740.028*
H13B0.64560.29080.73800.028*
C140.69465 (8)0.45271 (17)0.83921 (10)0.0320 (3)
H14A0.73310.52740.84810.048*
H14B0.70540.37590.89070.048*
H14C0.65240.51010.83880.048*
C410.59558 (6)0.91116 (14)0.50117 (9)0.0193 (2)
C420.58864 (6)0.86700 (15)0.40819 (9)0.0226 (2)
H420.59270.75920.39300.027*
C430.57585 (7)0.98072 (17)0.33807 (10)0.0281 (3)
H430.57240.95100.27510.034*
C440.56814 (7)1.13787 (16)0.35958 (10)0.0297 (3)
H440.55891.21530.31130.036*
C450.57385 (6)1.18181 (15)0.45143 (10)0.0275 (3)
H450.56781.28920.46580.033*
C460.58840 (6)1.06976 (14)0.52255 (9)0.0234 (2)
H460.59351.10080.58570.028*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S20.02011 (15)0.03108 (17)0.02609 (17)−0.00359 (12)0.00715 (12)0.00515 (13)
O40.0307 (5)0.0238 (4)0.0221 (4)−0.0002 (4)0.0016 (4)−0.0030 (4)
N10.0191 (5)0.0180 (5)0.0211 (5)0.0003 (4)0.0047 (4)0.0009 (4)
N30.0189 (5)0.0180 (5)0.0192 (5)−0.0019 (4)0.0016 (4)0.0018 (4)
C20.0202 (5)0.0171 (5)0.0179 (5)−0.0012 (4)0.0043 (4)−0.0013 (4)
C40.0169 (5)0.0191 (5)0.0232 (6)0.0005 (4)0.0057 (4)−0.0003 (4)
C110.0170 (5)0.0203 (6)0.0276 (6)−0.0017 (4)0.0051 (5)−0.0005 (5)
C120.0293 (6)0.0278 (6)0.0292 (7)−0.0031 (5)0.0117 (5)−0.0042 (5)
C130.0250 (6)0.0195 (5)0.0228 (6)0.0013 (4)0.0028 (5)0.0037 (5)
C140.0407 (8)0.0303 (7)0.0235 (6)0.0024 (6)0.0070 (6)0.0005 (5)
C410.0146 (5)0.0191 (5)0.0234 (6)−0.0005 (4)0.0041 (4)0.0010 (4)
C420.0215 (5)0.0210 (6)0.0247 (6)−0.0016 (4)0.0056 (5)0.0004 (5)
C430.0264 (6)0.0322 (7)0.0231 (6)−0.0027 (5)0.0027 (5)0.0032 (5)
C440.0242 (6)0.0278 (7)0.0328 (7)−0.0012 (5)0.0011 (5)0.0097 (5)
C450.0210 (6)0.0195 (6)0.0393 (7)0.0012 (5)0.0040 (5)0.0030 (5)
C460.0205 (5)0.0202 (6)0.0282 (6)0.0005 (4)0.0050 (5)−0.0011 (5)

Geometric parameters (Å, °)

S2—C21.6767 (12)C13—H13A0.9900
O4—C41.2188 (15)C13—H13B0.9900
N1—C21.3258 (15)C14—H14A0.9800
N1—C131.4712 (15)C14—H14B0.9800
N1—C111.4774 (15)C14—H14C0.9800
N3—C41.3869 (15)C41—C421.3971 (17)
N3—C21.4183 (15)C41—C461.3975 (16)
N3—H30.9138C42—C431.3871 (18)
C4—C411.4946 (17)C42—H420.9500
C11—C121.5145 (17)C43—C441.388 (2)
C11—H11A0.9900C43—H430.9500
C11—H11B0.9900C44—C451.385 (2)
C12—H12A0.9800C44—H440.9500
C12—H12B0.9800C45—C461.3870 (18)
C12—H12C0.9800C45—H450.9500
C13—C141.5129 (18)C46—H460.9500
C2—N1—C13120.93 (10)N1—C13—H13B109.5
C2—N1—C11124.38 (10)C14—C13—H13B109.5
C13—N1—C11114.50 (10)H13A—C13—H13B108.0
C4—N3—C2120.52 (10)C13—C14—H14A109.5
C4—N3—H3118.6C13—C14—H14B109.5
C2—N3—H3111.7H14A—C14—H14B109.5
N1—C2—N3115.79 (10)C13—C14—H14C109.5
N1—C2—S2124.46 (9)H14A—C14—H14C109.5
N3—C2—S2119.75 (8)H14B—C14—H14C109.5
O4—C4—N3122.07 (11)C42—C41—C46119.59 (11)
O4—C4—C41122.66 (11)C42—C41—C4122.35 (11)
N3—C4—C41115.24 (10)C46—C41—C4118.02 (11)
N1—C11—C12110.64 (10)C43—C42—C41119.96 (12)
N1—C11—H11A109.5C43—C42—H42120.0
C12—C11—H11A109.5C41—C42—H42120.0
N1—C11—H11B109.5C42—C43—C44120.19 (13)
C12—C11—H11B109.5C42—C43—H43119.9
H11A—C11—H11B108.1C44—C43—H43119.9
C11—C12—H12A109.5C45—C44—C43120.03 (13)
C11—C12—H12B109.5C45—C44—H44120.0
H12A—C12—H12B109.5C43—C44—H44120.0
C11—C12—H12C109.5C44—C45—C46120.30 (12)
H12A—C12—H12C109.5C44—C45—H45119.9
H12B—C12—H12C109.5C46—C45—H45119.9
N1—C13—C14110.93 (10)C45—C46—C41119.90 (12)
N1—C13—H13A109.5C45—C46—H46120.0
C14—C13—H13A109.5C41—C46—H46120.0
C13—N1—C2—N3174.96 (10)O4—C4—C41—C42151.78 (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—S2168.92 (9)N3—C4—C41—C46156.38 (10)
C4—N3—C2—N1−71.43 (14)C46—C41—C42—C431.06 (17)
C4—N3—C2—S2109.23 (11)C4—C41—C42—C43−176.44 (11)
C2—N3—C4—O47.58 (17)C41—C42—C43—C44−1.66 (19)
C2—N3—C4—C41−174.54 (10)C42—C43—C44—C450.60 (19)
C2—N1—C11—C12−93.09 (14)C43—C44—C45—C461.07 (19)
C13—N1—C11—C1281.88 (13)C44—C45—C46—C41−1.66 (18)
C2—N1—C13—C14−88.47 (14)C42—C41—C46—C450.59 (17)
C11—N1—C13—C1496.37 (13)C4—C41—C46—C45178.19 (11)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N3—H3···S2i0.912.563.4595 (11)169
C13—H13A···O4ii0.992.593.3594 (18)135

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5361).

References

  • Bernstein, J., Davis, R. E., Shimoni, I. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl.34, 1555–1573.
  • Beyer, L., Hoyer, E., Hennig, H., Kirmse, R. H., Hartmann, H. & Liebscher, J. (1975). J. Prakt. Chem.317, 829–839.
  • Bolte, M. & Fink, L. (2003). Private communication (refcode IJOQED). CCDC, Union Road, Cambridge, England.
  • Braun, U., Richter, R., Sieler, J., Beyer, L., Lindqvist, O., Yanovsky, A. I. & Struchkov, Yu. T. (1987). Acta Cryst. C43, 92–95.
  • Bruce, J. C., Revaprasadu, N. & Koch, K. R. (2007). New J. Chem.31, 1647–1653.
  • Bruker (2004). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Hartmann, H. & Reuther, I. (1973). J. Prakt. Chem.315, 144–148.
  • Johnson, C. K. (1976). ORTEPII Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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