N-(Diethyl­carbamothio­yl)-4-nitro­benzamide

In the title compound, C₁₂H₁₅N₃O₃S, the 4-nitro and carbonyl groups are nearly coplanar with the benzene ring [C—C—N—O = −175.72 (14) and C—C—C—O = 172.75 (14)°]. The diethyl­carbamothioyl group is twisted significantly from the plane of the benzene ring [C—N—C—N = −89.79 (15)°] with the S atom pointing away from each of these groups [C—N—C—S = 91.12 (14)°]. In the crystal, an inter­molecular N—H...O hydrogen bond, which forms an infinite polymeric chain along the c axis, and weak C—H...O and C—H...S hydrogen bonds are observed.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.040
• wR factor = 0.115
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         11
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          6
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        500 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H6A    ..  S1      ..       2.98 Ang.
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         49

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 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
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Thioureas are of significant interest in medicinal chemistry due to their biological activity as fungicides (Saeed et al., 2010a), anticancer (Saeed et al., 2010b), herbicides, rodenticides and phenoloxidase enzymatic inhibitors (Maddani et al., 2010). Recently, thiourea derivatives have found use in organocatalysis (Jung et al., 2008) and amino-thiourea derivatives as curing agents for epoxy resins (Saeed et al., 2009). Thioureas have a long history as ligand in coordination chemistry and coordinate to a metal via sulfur (Burrows et al., 1999). These hard and soft donor atoms provide a multitude of bonding possibilities (Henderson et al., 2002). Hydrogen bonding behavior of some acyl thioureas has been investigated and it is found that intramolecular hydrogen bonds between the carbonyl oxygen and a hydrogen atom on N' is common. The complexing capacity of thiourea derivatives has been reported in several papers (Schuster et al., 1990). Some acyl thioureas possess pesticidal activities and promote plant growth while some have a notable positive effect on the germination of maize seeds as well as on the chlorophyll contents in seedling leaves (Che et al., 1999). With the simultaneous presence of S, N and O electron donors, the versalitility and interesting behavior of acyl thioureas as building blocks in polydentate ligands for metal ions have become a topic of interest in the last few years. It has been reported that substituted acyl thiourea ligands might act as monodentate sulfur donors, bidentate oxygen and nitrogen donors. In continuation of our research on the structural modification of certain biologically active thiourea derivatives and their transition metal complexes with the purpose of enhancing their biological activity, we aimed to incorporate aliphatic and aromatic moieties in the substituted phenyl nucleus with thiourea functionality to obtain new functions with improved antimicrobial profile. In view of the importance of thiourea derivatives, the crystal structure of the title compound is reported.

In the title compound, C₁₂H₁₅N₃O₃S the 4-nitro (C3/C4/N1/O2 = -175.72 (14)°) and carbonyl (C2/C1/C7/O3 = 172.75 (14)°) groups are nearly co-planar to the benzene ring. The N-(diethylcarbamothioyl) group is significantly twisted from the plane of the benzene ring (C7/N2/C8/N3 = -89.79 (15)°) with the S1 atom pointing away from each of these moieties (C7/N2/C8/S1 = 91.12 (14)°). Bond distances (Allen et al., 1987) and angles are in normal ranges. An N—H···O hydrogen bond which forms an infinite polymeric chain along the c axis and weak C—H···O and C—H···S hydrogen bond intermolecular interactions are observed (Table 1) and contribute to crystal packing (Fig. 1).

Related literature

For background to the use of thioureas in coordination chemistry, see: Burrows et al. (1999); Henderson et al. (2002), Schuster et al. (1990); Che et al. (1999); For their biological and catalytic activity, see: Saeed et al. (2009, 2010a,b); Maddani et al. (2010); Jung et al. (2008); For related literature [on what subject?], see: Zhang et al. (2004). For bond-length data, see: Allen et al. (1987).

S2. Experimental

A solution of 4-nitrobenzoyl chloride (0.01 mol) in anhydrous acetone (80 ml) and 3% tetrabutylammonium bromide (TBAB) as a phase-transfer catalyst (PTC) in anhydrous acetone was added dropwise to a suspension of dry ammonium thiocyanate (0.01 mol) in acetone (50 ml) and the reaction mixture was refluxed for 45 min. After cooling to room temperature, a solution of diethylamine (0.01 mol) in anhydrous acetone (25 ml) was added dropwise and the resulting mixture refluxed for 2.5 h. Hydrochloric acid (0.1 N, 300 ml) was added, and the solution was filtered. The solid product was washed with water and purified by re-crystallization from ethyl acetate.

S3. Refinement

The N–H atom length was set to 0.85Å (NH) and the H atom refined isotropically. All of the other H atoms were placed in their calculated positions and then refined using the riding model with Atom–H lengths of 0.93Å (CH), 0.97Å (CH₂), or 0.97Å (CH₃). Isotropic displacement parameters for these atoms were set to 1.18–1.20 (CH), 1.20 (CH₂) or 1.50 (CH₃)times U_eq of the parent atom.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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: PLATON (Spek, 2009).

Figures

	Fig. 1. Molecular structure of C12H15N3O3S showing the atom labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound C12H15N3O3S viewed down the a axis. Dashed lines indicate N—H···O and weak C—H···O hydrogen bonds.

N-(Diethylcarbamothioyl)-4-nitrobenzamide

Crystal data

C12H15N3O3S	F(000) = 592
Mr = 281.33	Dx = 1.393 Mg m^−3
Monoclinic, P21/c	Melting point: 434 K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.54178 Å
a = 6.884 (5) Å	Cell parameters from 4133 reflections
b = 19.237 (5) Å	θ = 4.6–77.2°
c = 10.146 (5) Å	µ = 2.23 mm^−1
β = 92.983 (5)°	T = 295 K
V = 1341.8 (12) Å^3	Block, pale yellow
Z = 4	0.52 × 0.41 × 0.35 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini Cu diffractometer	2790 independent reflections
Radiation source: Enhance (Cu) X-ray Source	2507 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
Detector resolution: 10.5081 pixels mm^-1	θmax = 77.4°, θmin = 4.9°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −17→24
Tmin = 0.769, Tmax = 1.000	l = −12→12
5616 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.078P)^2 + 0.1589P] where P = (Fo^2 + 2Fc^2)/3
2790 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.30 e Å^−3

Special details

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

	x	y	z	Uiso*/Ueq
S1	0.38042 (6)	0.89794 (2)	0.52976 (4)	0.05321 (16)
O1	0.2051 (3)	0.42290 (7)	0.69201 (14)	0.0818 (5)
O2	0.1805 (2)	0.40370 (6)	0.48459 (14)	0.0627 (3)
O3	0.4507 (2)	0.73790 (6)	0.35424 (9)	0.0547 (3)
N1	0.21185 (19)	0.44183 (6)	0.57929 (14)	0.0461 (3)
N2	0.48161 (17)	0.76526 (6)	0.56885 (10)	0.0364 (3)
H2B	0.465 (3)	0.7568 (10)	0.650 (2)	0.054 (5)*
N3	0.73455 (16)	0.84093 (5)	0.53139 (10)	0.0350 (2)
C1	0.36465 (18)	0.65019 (7)	0.50551 (12)	0.0337 (3)
C2	0.3617 (2)	0.62603 (7)	0.63527 (12)	0.0387 (3)
H2A	0.3946	0.6558	0.7051	0.046*
C3	0.3098 (2)	0.55777 (7)	0.66026 (13)	0.0404 (3)
H3A	0.3079	0.5412	0.7463	0.048*
C4	0.26114 (19)	0.51499 (7)	0.55432 (13)	0.0366 (3)
C5	0.2607 (2)	0.53744 (7)	0.42543 (13)	0.0417 (3)
H5A	0.2265	0.5075	0.3561	0.050*
C6	0.3125 (2)	0.60570 (7)	0.40138 (13)	0.0398 (3)
H6A	0.3124	0.6219	0.3150	0.048*
C7	0.43282 (19)	0.72156 (7)	0.46945 (12)	0.0358 (3)
C8	0.54477 (19)	0.83458 (6)	0.54204 (11)	0.0343 (3)
C9	0.8723 (2)	0.78196 (7)	0.54253 (14)	0.0419 (3)
H9A	0.9859	0.7928	0.4937	0.050*
H9B	0.8111	0.7411	0.5029	0.050*
C10	0.9359 (3)	0.76598 (10)	0.68374 (18)	0.0599 (4)
H10A	1.0291	0.7288	0.6858	0.090*
H10B	0.8251	0.7523	0.7312	0.090*
H10C	0.9941	0.8066	0.7241	0.090*
C11	0.8218 (2)	0.90929 (7)	0.50932 (14)	0.0424 (3)
H11A	0.9462	0.9121	0.5585	0.051*
H11B	0.7380	0.9451	0.5423	0.051*
C12	0.8516 (3)	0.92242 (10)	0.36548 (17)	0.0626 (5)
H12A	0.9112	0.9671	0.3555	0.094*
H12B	0.7282	0.9215	0.3169	0.094*
H12C	0.9343	0.8870	0.3324	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0504 (2)	0.0454 (2)	0.0645 (3)	0.01207 (15)	0.00856 (18)	0.01556 (17)
O1	0.1340 (14)	0.0535 (7)	0.0571 (8)	−0.0315 (8)	−0.0022 (8)	0.0155 (6)
O2	0.0811 (9)	0.0375 (6)	0.0697 (8)	−0.0083 (5)	0.0065 (6)	−0.0115 (5)
O3	0.0924 (9)	0.0461 (6)	0.0260 (5)	−0.0114 (5)	0.0046 (5)	0.0040 (4)
N1	0.0475 (6)	0.0360 (6)	0.0549 (7)	−0.0035 (5)	0.0026 (5)	0.0004 (5)
N2	0.0496 (6)	0.0339 (5)	0.0258 (5)	−0.0056 (4)	0.0048 (4)	0.0039 (4)
N3	0.0428 (6)	0.0290 (5)	0.0333 (5)	−0.0008 (4)	0.0032 (4)	0.0024 (4)
C1	0.0386 (6)	0.0338 (6)	0.0288 (6)	0.0001 (5)	0.0030 (4)	−0.0007 (5)
C2	0.0521 (7)	0.0360 (6)	0.0282 (6)	−0.0042 (5)	0.0035 (5)	−0.0018 (5)
C3	0.0515 (7)	0.0386 (7)	0.0313 (6)	−0.0024 (5)	0.0050 (5)	0.0034 (5)
C4	0.0364 (6)	0.0324 (6)	0.0413 (6)	−0.0001 (5)	0.0043 (5)	−0.0002 (5)
C5	0.0494 (7)	0.0400 (7)	0.0354 (6)	−0.0023 (6)	0.0004 (5)	−0.0084 (5)
C6	0.0510 (7)	0.0406 (7)	0.0277 (6)	−0.0011 (5)	0.0007 (5)	−0.0010 (5)
C7	0.0442 (6)	0.0351 (6)	0.0282 (6)	0.0001 (5)	0.0033 (5)	0.0035 (5)
C8	0.0460 (7)	0.0311 (6)	0.0259 (5)	−0.0003 (5)	0.0034 (5)	0.0032 (4)
C9	0.0457 (7)	0.0342 (6)	0.0463 (7)	0.0043 (5)	0.0085 (6)	0.0004 (5)
C10	0.0665 (10)	0.0546 (9)	0.0576 (10)	0.0181 (8)	−0.0072 (8)	0.0076 (8)
C11	0.0503 (8)	0.0336 (6)	0.0433 (7)	−0.0077 (5)	0.0013 (6)	0.0024 (5)
C12	0.0816 (12)	0.0578 (10)	0.0486 (9)	−0.0237 (9)	0.0034 (8)	0.0158 (7)

Geometric parameters (Å, º)

S1—C8	1.6632 (14)	C3—H3A	0.9300
O1—N1	1.203 (2)	C4—C5	1.377 (2)
O2—N1	1.2191 (19)	C5—C6	1.386 (2)
O3—C7	1.2228 (17)	C5—H5A	0.9300
N1—C4	1.4727 (17)	C6—H6A	0.9300
N2—C7	1.3423 (17)	C9—C10	1.508 (2)
N2—C8	1.4331 (16)	C9—H9A	0.9700
N2—H2B	0.85 (2)	C9—H9B	0.9700
N3—C8	1.322 (2)	C10—H10A	0.9600
N3—C11	1.4678 (17)	C10—H10B	0.9600
N3—C9	1.4792 (17)	C10—H10C	0.9600
C1—C6	1.3921 (18)	C11—C12	1.506 (2)
C1—C2	1.3973 (18)	C11—H11A	0.9700
C1—C7	1.5022 (18)	C11—H11B	0.9700
C2—C3	1.3877 (19)	C12—H12A	0.9600
C2—H2A	0.9300	C12—H12B	0.9600
C3—C4	1.3810 (19)	C12—H12C	0.9600
O1—N1—O2	123.58 (14)	N2—C7—C1	117.30 (11)
O1—N1—C4	118.24 (13)	N3—C8—N2	114.35 (11)
O2—N1—C4	118.18 (13)	N3—C8—S1	126.68 (10)
C7—N2—C8	120.45 (10)	N2—C8—S1	118.96 (10)
C7—N2—H2B	124.5 (14)	N3—C9—C10	112.48 (12)
C8—N2—H2B	114.6 (14)	N3—C9—H9A	109.1
C8—N3—C11	120.62 (11)	C10—C9—H9A	109.1
C8—N3—C9	123.73 (11)	N3—C9—H9B	109.1
C11—N3—C9	115.64 (12)	C10—C9—H9B	109.1
C6—C1—C2	119.65 (13)	H9A—C9—H9B	107.8
C6—C1—C7	116.65 (12)	C9—C10—H10A	109.5
C2—C1—C7	123.60 (11)	C9—C10—H10B	109.5
C3—C2—C1	120.22 (12)	H10A—C10—H10B	109.5
C3—C2—H2A	119.9	C9—C10—H10C	109.5
C1—C2—H2A	119.9	H10A—C10—H10C	109.5
C4—C3—C2	118.43 (12)	H10B—C10—H10C	109.5
C4—C3—H3A	120.8	N3—C11—C12	112.06 (12)
C2—C3—H3A	120.8	N3—C11—H11A	109.2
C5—C4—C3	122.73 (13)	C12—C11—H11A	109.2
C5—C4—N1	118.29 (12)	N3—C11—H11B	109.2
C3—C4—N1	118.97 (12)	C12—C11—H11B	109.2
C4—C5—C6	118.46 (12)	H11A—C11—H11B	107.9
C4—C5—H5A	120.8	C11—C12—H12A	109.5
C6—C5—H5A	120.8	C11—C12—H12B	109.5
C5—C6—C1	120.50 (12)	H12A—C12—H12B	109.5
C5—C6—H6A	119.8	C11—C12—H12C	109.5
C1—C6—H6A	119.8	H12A—C12—H12C	109.5
O3—C7—N2	121.57 (13)	H12B—C12—H12C	109.5
O3—C7—C1	121.07 (12)
C6—C1—C2—C3	0.9 (2)	C8—N2—C7—C1	−178.94 (11)
C7—C1—C2—C3	−175.39 (13)	C6—C1—C7—O3	−3.7 (2)
C1—C2—C3—C4	−0.2 (2)	C2—C1—C7—O3	172.75 (14)
C2—C3—C4—C5	−0.5 (2)	C6—C1—C7—N2	179.30 (12)
C2—C3—C4—N1	178.08 (12)	C2—C1—C7—N2	−4.3 (2)
O1—N1—C4—C5	−177.27 (16)	C11—N3—C8—N2	−177.53 (11)
O2—N1—C4—C5	2.9 (2)	C9—N3—C8—N2	1.45 (17)
O1—N1—C4—C3	4.1 (2)	C11—N3—C8—S1	1.47 (17)
O2—N1—C4—C3	−175.72 (14)	C9—N3—C8—S1	−179.55 (10)
C3—C4—C5—C6	0.4 (2)	C7—N2—C8—N3	−89.79 (15)
N1—C4—C5—C6	−178.16 (13)	C7—N2—C8—S1	91.12 (14)
C4—C5—C6—C1	0.4 (2)	C8—N3—C9—C10	−84.81 (17)
C2—C1—C6—C5	−1.0 (2)	C11—N3—C9—C10	94.21 (15)
C7—C1—C6—C5	175.56 (13)	C8—N3—C11—C12	−96.35 (16)
C8—N2—C7—O3	4.1 (2)	C9—N3—C11—C12	84.59 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3^i	0.85 (2)	2.08 (2)	2.915 (2)	165.4 (19)
C2—H2A···O3^i	0.93	2.56	3.4671 (19)	165
C6—H6A···S1^ii	0.93	2.98	3.824 (2)	152

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