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

Gomes, L.R.; Santos, L.M.N.B.F.; Coutinho, J.A.P.; Schröder, B.; Low, J.N.

doi:10.1107/S1600536810009578

organic compounds

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Volume 66| Part 4| April 2010| Page o870

doi:10.1107/S1600536810009578

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

Ligia R. Gomes,^a Luís M. N. B. F. Santos,^b João A. P. Coutinho,^c Bernd Schröder ^c and John Nicolson Low ^d ^*

^aREQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, P-4169_007 Porto, Portugal, ^bCentro de Investigação em Química, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre 687, P-4169_007 Porto, Portugal, ^cCICECO, Departamento de Química, Universidade de Aveiro, 3810-193 Aveiro, Portugal, and ^dDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen, AB24 3UE, Scotland
^*Correspondence e-mail: jnlow111@googlemail.com

(Received 12 March 2010; accepted 13 March 2010; online 20 March 2010)

In the crystal of the title compound, C₁₂H₁₆N₂OS, inversion dimers linked by pairs of N—H⋯S hydrogen bonds occur, generating R₂²(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 ). 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_r = 236.33
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.096
S = 1.04
3704 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −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.

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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 this 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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 (Sheldrick, 2008).

Figures top

	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.

N'-benzoyl-N,N-diethylthiourea top

Crystal data top

C₁₂H₁₆N₂OS	F(000) = 1008
M_r = 236.33	D_x = 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

Data collection top

Bruker SMART APEXII diffractometer	3704 independent reflections
Radiation source: fine-focus sealed tube	2940 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 30.5°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −28→28
T_min = 0.939, T_max = 0.995	k = −12→12
18425 measured reflections	l = −20→21

Refinement top

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(F_o²) + (0.041P)² + 1.4589P] where P = (F_o² + 2F_c²)/3
3704 reflections	(Δ/σ)_max < 0.001
147 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₆N₂OS	V = 2430.11 (16) Å³
M_r = 236.33	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.1727 (7) Å	µ = 0.25 mm⁻¹
b = 8.4717 (3) Å	T = 150 K
c = 14.8345 (6) Å	0.26 × 0.20 × 0.02 mm
β = 106.553 (2)°

Data collection top

Bruker SMART APEXII diffractometer	3704 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	2940 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.995	R_int = 0.038
18425 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.04	Δρ_max = 0.41 e Å⁻³
3704 reflections	Δρ_min = −0.21 e Å⁻³
147 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₂OS
M_r	236.33
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	150
a, b, c (Å)	20.1727 (7), 8.4717 (3), 14.8345 (6)
β (°)	106.553 (2)
V (Å³)	2430.11 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.25
Crystal size (mm)	0.26 × 0.20 × 0.02

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.939, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	18425, 3704, 2940
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.096, 1.04
No. of reflections	3704
No. of parameters	147
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.21

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and PLATON (Spek, 2009).

Acknowledgements

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

References

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