A co-crystal of 3-(3,5-dinitro­benzo­yl)-1,1-dimethyl­thio­urea and N,N-dimethyl-3,5-dinitro­benzamide

Sohail Saeed; Naghmana Rashid; Ray J Butcher; Sema Öztürk Yildirim; Rizwan Hussain

doi:10.1107/S1600536812041864

. 2012 Oct 13;68(Pt 11):o3108. doi: 10.1107/S1600536812041864

A co-crystal of 3-(3,5-dinitrobenzoyl)-1,1-dimethylthiourea and N,N-dimethyl-3,5-dinitrobenzamide

Sohail Saeed ^a,^*, Naghmana Rashid ^a, Ray J Butcher ^b, Sema Öztürk Yildirim ^c, Rizwan Hussain ^d

PMCID: PMC3515214 PMID: 23284434

Abstract

In the title compound, C₁₀H₁₀N₄O₅S·C₉H₉N₃O₅, the amide groups of 3-(3,5-dinitro-benzoyl)-1,1-dimethyl-thiourea and N,N-dimethyl-3,5-dinitro-benzamide molecules are oriented at dihedral angles of 39.13 (8) and 55.97 (11)°, respectively, to the attached benzene rings. In the crystal, the two molecules are linked by an N—H⋯O hydrogen bond. Weak C—H⋯O link the molecules into a sheet parallel to the bc plane. C—H⋯S interactions also occur.

Related literature

For related structures, see: Saeed et al. (2010a ▶,b ▶, 2011 ▶, 2012 ▶).

Experimental

Crystal data

C₁₀H₁₀N₄O₅S·C₉H₉N₃O₅
M _r = 537.47
Triclinic,
a = 9.8457 (5) Å
b = 10.0057 (5) Å
c = 12.5185 (6) Å
α = 72.413 (5)°
β = 78.428 (4)°
γ = 89.129 (4)°
V = 1150.35 (10) Å³
Z = 2
Cu Kα radiation
μ = 1.90 mm⁻¹
T = 123 K
0.44 × 0.38 × 0.27 mm

Data collection

Agilent Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011 ▶) T _min = 0.488, T _max = 0.628
7591 measured reflections
4597 independent reflections
4099 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.113
S = 1.07
4597 reflections
342 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2011 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(32.4KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812041864/xu5627sup1.cif

e-68-o3108-sup1.cif^{(32.4KB, cif)}

Click here for additional data file.^{(225.2KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812041864/xu5627Isup2.hkl

e-68-o3108-Isup2.hkl^{(225.2KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812041864/xu5627Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3A—H1NA⋯O5B	0.84 (2)	2.07 (2)	2.888 (2)	163 (2)
C2B—H2BA⋯O1A ⁱ	0.95	2.51	3.390 (2)	155
C4B—H4BA⋯O3A ⁱⁱ	0.95	2.35	3.163 (2)	143
C6B—H6BA⋯S1A	0.95	2.76	3.6856 (16)	166
C9A—H9AB⋯O5B ⁱⁱⁱ	0.98	2.48	3.368 (2)	150
C9B—H9BB⋯O4B ^iv	0.98	2.46	3.439 (2)	175
C10A—H10B⋯O2A ^v	0.98	2.51	3.334 (2)	142

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

RJB acknowledges the NSF–MRI program (grant No. CHE-0619278) for funds to purchase the diffractometer.

supplementary crystallographic information

Comment

The crystal structure of the 1:1 adduct of 3-(3,5-dinitro-benzoyl)-1,1-dimethyl-thiourea and N,N-dimethyl-3,5-dinitro-benzamide is reported. It is related to our previous studies on the structural chemistry of heterocyclic compounds containing an N-substituted thiourea (Saeed et al., 2010a, 2010b, 2011) and amide (Saeed et al., 2012). Herein, as a continuation of these studies, the structure of the title compound, (I), is described.

In the crystal structure of the title compound (Fig. 1), C₁₀H₁₀N₄O₅S, C₉H₉N₃O₅, there are independent different molecules 3-(3,5-dinitro-benzoyl)-1,1-dimethyl-thiourea(A) and N, N-dimethyl-3,5-dinitro-benzamide(B) in the asymmetric unit. Both of the molecule the dinitro-benzene ring systems are planar, with a maximum deviation of 0.295 (1) Å for the O1A atom and 0.286 (2) Å for the O4B atom. In the molecular conformation of 3-(3,5-dinitro-benzoyl)-1,1-dimethyl-thiourea's the C7A=O5A and C8A=S1A bonds are anti to each other. The dihedral angle between the dinitro-benzene unit (C1A—C6A/N1A/N2A/O1A—O4A atoms) and thiourea group (N3A/C8A/N4A/S1A atoms) is 88.2 (1)°. In N-dimethyl-3,5-dinitro-benzamide, the dimethyl amide group is rotated by 59.8 (0.1)° out of the plane of the benzene ring.

The 3-(3,5-dinitro-benzoyl)-1,1-dimethyl-thiourea and N,N-dimethyl-3,5-dinitro-benzamide molecular structure is stabilized by intra- and inter molecular N—H···O and C—H···O hydrogen bonds (Fig. 1 and Table 1). The intermolecular C—H···O hydrogen bonds link the molecules into a sheet parallel to the bc plane (Fig. 2).

Experimental

To a 250 ml round flask fitted with a condenser was added dimethyl amine (0.01 mol), dichloromethane (15 ml) and triethylamine(0.5 ml) with magnetic stirring. 3,5-Dinitrobenzoyl chloride (0.01 mol) was added gradually. The reaction mixture was stirred at room temperature for 1 h and then refluxed for 1.5 h. The product precipitated as a colorless powder, which was washed three times with water and dichloromethane. Recrystallization from ethanol produced the crystals of the title compound.