N-[(Morpholin-4-yl)carbonothio-yl]-4-nitro-benzamide.

In the title compound, C(12)H(13)N(3)O(4)S, the nitro group is slightly twisted [6.58 (11)°] from the benzene ring plane. The morpholine ring adopts a chair form. In the crystal, inter-molecular N-H⋯O hydrogen bonds link the mol-ecules into chains along [110]. There are also π-π contacts [centroid-centroid distance = 3.8301 (11) Å] and C-H⋯π inter-actions to stack neighbouring benzene rings and link the chains into a three-dimensional network. C-H⋯O and C-H⋯S inter-actions are also observed.

Related literature

For the use of thio­urea derivatives in the analysis of transition metals, see: Arslan et al. (2003 ▶). For the biological and agrochemical activity of thio­ureas and their transition n class="Chemical">metal complexes, see: Saeed et al. (2008 ▶, 2009 ▶, 2010 ▶); Che et al. (1999 ▶); Saeed & Parvez (2005 ▶). For their catalytic properties, see: Gu et al. (2007 ▶). For thio­ureas as ligands in coordination chemistry, see: Burrows et al. (1999 ▶); Henderson et al. (2002 ▶); Schuster et al. (1990 ▶).

Experimental

Crystal data

C12H13N3O4S

M = 295.31

Triclinic,

a = 6.9867 (11) Å

b = 7.4047 (11) Å

c = 14.261 (2) Å

α = 88.654 (2)°

β = 82.805 (2)°

γ = 65.638 (2)°

V = 666.46 (18) Å3

Z = 2

Mo Kα radiation

μ = 0.26 mm−1

T = 298 K

0.23 × 0.20 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.943, T max = 0.980

4478 measured reflections

2916 independent reflections

2485 reflections with I > 2σ(I)

R int = 0.009

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.106

S = 1.09

2916 reflections

186 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.31 e Å−3

Data collection: SMART (Bruker, 1996 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAIn class="Chemical">NT and CrystalStructure (Rigaku/MSC and Rigaku, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018763/sj2785sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018763/sj2785Isup2.hkl

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

C12H13N3O4S	Z = 2
Mr = 295.31	F(000) = 308
Triclinic, P1	Dx = 1.472 Mg m−3
Hall symbol: -P 1	Melting point: 445 K
a = 6.9867 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.4047 (11) Å	Cell parameters from 4479 reflections
c = 14.261 (2) Å	θ = 2.9–27.5°
α = 88.654 (2)°	µ = 0.26 mm−1
β = 82.805 (2)°	T = 298 K
γ = 65.638 (2)°	Prism, yellow
V = 666.46 (18) Å3	0.23 × 0.20 × 0.08 mm

Bruker SMART 1000 CCD diffractometer	2916 independent reflections
Radiation source: fine-focus sealed tube	2485 reflections with I > 2σ(I)
graphite	Rint = 0.009
ω scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.943, Tmax = 0.980	k = −9→8
4478 measured reflections	l = −14→18

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0533P)2 + 0.1461P] where P = (Fo2 + 2Fc2)/3
2916 reflections	(Δ/σ)max < 0.001
186 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.31 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 > 2σ(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
S1	0.59857 (7)	0.73600 (6)	0.06951 (4)	0.05471 (16)
O1	−0.4619 (2)	0.8315 (2)	0.56951 (10)	0.0682 (4)
O2	−0.2725 (3)	0.8900 (3)	0.66055 (10)	0.0896 (6)
O3	0.58764 (17)	0.5059 (2)	0.32004 (8)	0.0563 (3)
O4	0.98995 (18)	−0.01437 (17)	0.15537 (9)	0.0531 (3)
N1	−0.2970 (2)	0.8351 (2)	0.58493 (10)	0.0491 (3)
N2	0.3781 (2)	0.6145 (2)	0.20248 (9)	0.0393 (3)
N3	0.67667 (19)	0.36725 (18)	0.12218 (9)	0.0385 (3)
C1	−0.1170 (2)	0.7713 (2)	0.50874 (10)	0.0392 (3)
C2	0.0756 (3)	0.7565 (3)	0.52983 (11)	0.0480 (4)
H2	0.0917	0.7861	0.5906	0.058*
C3	0.2441 (3)	0.6969 (3)	0.45888 (12)	0.0466 (4)
H3	0.3762	0.6839	0.4720	0.056*
C4	0.2183 (2)	0.6559 (2)	0.36783 (10)	0.0370 (3)
C5	0.0231 (2)	0.6692 (2)	0.34882 (11)	0.0404 (3)
H5	0.0064	0.6394	0.2882	0.049*
C6	−0.1473 (2)	0.7268 (2)	0.42000 (11)	0.0423 (3)
H6	−0.2785	0.7352	0.4081	0.051*
C7	0.4116 (2)	0.5862 (2)	0.29591 (11)	0.0404 (3)
C8	0.5562 (2)	0.5601 (2)	0.13166 (10)	0.0366 (3)
C9	0.8852 (3)	0.2872 (2)	0.06511 (12)	0.0491 (4)
H9A	0.9256	0.3943	0.0456	0.059*
H9B	0.8801	0.2192	0.0088	0.059*
C10	1.0458 (3)	0.1439 (3)	0.12361 (15)	0.0562 (5)
H10A	1.1839	0.0895	0.0860	0.067*
H10B	1.0554	0.2148	0.1779	0.067*
C11	0.7884 (3)	0.0630 (2)	0.21261 (12)	0.0484 (4)
H11B	0.7980	0.1283	0.2689	0.058*
H11A	0.7507	−0.0456	0.2325	0.058*
C12	0.6179 (2)	0.2085 (2)	0.16003 (12)	0.0428 (3)
H12B	0.5951	0.1395	0.1085	0.051*
H12A	0.4864	0.2658	0.2024	0.051*
H2N	0.275 (3)	0.715 (3)	0.1911 (13)	0.049 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.0490 (3)	0.0384 (2)	0.0673 (3)	−0.01365 (18)	0.0083 (2)	0.01329 (19)
O1	0.0487 (7)	0.0877 (10)	0.0656 (9)	−0.0304 (7)	0.0118 (6)	−0.0065 (7)
O2	0.0829 (11)	0.1409 (16)	0.0466 (8)	−0.0539 (11)	0.0186 (7)	−0.0273 (9)
O3	0.0357 (6)	0.0730 (8)	0.0458 (6)	−0.0071 (5)	−0.0071 (5)	−0.0031 (6)
O4	0.0470 (6)	0.0382 (6)	0.0582 (7)	−0.0045 (5)	0.0022 (5)	0.0077 (5)
N1	0.0521 (8)	0.0472 (8)	0.0425 (8)	−0.0190 (6)	0.0078 (6)	0.0018 (6)
N2	0.0313 (6)	0.0388 (7)	0.0378 (7)	−0.0060 (5)	−0.0005 (5)	0.0071 (5)
N3	0.0367 (6)	0.0339 (6)	0.0387 (7)	−0.0110 (5)	0.0033 (5)	0.0041 (5)
C1	0.0417 (8)	0.0345 (7)	0.0361 (7)	−0.0129 (6)	0.0034 (6)	0.0033 (6)
C2	0.0521 (9)	0.0562 (10)	0.0348 (8)	−0.0219 (8)	−0.0031 (7)	−0.0040 (7)
C3	0.0400 (8)	0.0562 (10)	0.0431 (9)	−0.0190 (7)	−0.0052 (6)	−0.0015 (7)
C4	0.0365 (7)	0.0335 (7)	0.0357 (7)	−0.0098 (6)	−0.0024 (6)	0.0040 (6)
C5	0.0405 (8)	0.0424 (8)	0.0350 (7)	−0.0136 (6)	−0.0055 (6)	0.0029 (6)
C6	0.0365 (7)	0.0452 (8)	0.0433 (8)	−0.0156 (6)	−0.0024 (6)	0.0030 (6)
C7	0.0361 (7)	0.0392 (8)	0.0404 (8)	−0.0108 (6)	−0.0026 (6)	0.0003 (6)
C8	0.0327 (7)	0.0374 (7)	0.0361 (7)	−0.0116 (6)	−0.0026 (5)	0.0037 (6)
C9	0.0453 (8)	0.0399 (8)	0.0475 (9)	−0.0086 (7)	0.0137 (7)	0.0034 (7)
C10	0.0402 (8)	0.0441 (9)	0.0723 (12)	−0.0089 (7)	0.0038 (8)	0.0069 (8)
C11	0.0491 (9)	0.0414 (8)	0.0457 (9)	−0.0117 (7)	−0.0005 (7)	0.0094 (7)
C12	0.0427 (8)	0.0367 (8)	0.0462 (8)	−0.0153 (6)	−0.0011 (6)	0.0061 (6)

S1—C8	1.6635 (15)	C3—C4	1.390 (2)
O1—N1	1.211 (2)	C3—H3	0.9300
O2—N1	1.217 (2)	C4—C5	1.387 (2)
O3—C7	1.2157 (19)	C4—C7	1.498 (2)
O4—C10	1.428 (2)	C5—C6	1.389 (2)
O4—C11	1.4302 (19)	C5—H5	0.9300
N1—C1	1.4753 (19)	C6—H6	0.9300
N2—C7	1.378 (2)	C9—C10	1.514 (3)
N2—C8	1.4219 (18)	C9—H9A	0.9700
N2—H2N	0.82 (2)	C9—H9B	0.9700
N3—C8	1.3249 (19)	C10—H10A	0.9700
N3—C9	1.4660 (19)	C10—H10B	0.9700
N3—C12	1.4682 (19)	C11—C12	1.506 (2)
C1—C2	1.375 (2)	C11—H11B	0.9700
C1—C6	1.378 (2)	C11—H11A	0.9700
C2—C3	1.378 (2)	C12—H12B	0.9700
C2—H2	0.9300	C12—H12A	0.9700
C10—O4—C11	110.05 (12)	O3—C7—C4	120.79 (14)
O1—N1—O2	123.01 (14)	N2—C7—C4	116.60 (13)
O1—N1—C1	118.84 (14)	N3—C8—N2	114.93 (13)
O2—N1—C1	118.15 (15)	N3—C8—S1	125.69 (11)
C7—N2—C8	118.86 (12)	N2—C8—S1	119.37 (11)
C7—N2—H2N	116.6 (13)	N3—C9—C10	108.91 (13)
C8—N2—H2N	114.2 (13)	N3—C9—H9A	109.9
C8—N3—C9	122.29 (13)	C10—C9—H9A	109.9
C8—N3—C12	126.02 (12)	N3—C9—H9B	109.9
C9—N3—C12	111.57 (12)	C10—C9—H9B	109.9
C2—C1—C6	122.68 (14)	H9A—C9—H9B	108.3
C2—C1—N1	118.30 (14)	O4—C10—C9	111.74 (15)
C6—C1—N1	119.02 (14)	O4—C10—H10A	109.3
C1—C2—C3	118.47 (14)	C9—C10—H10A	109.3
C1—C2—H2	120.8	O4—C10—H10B	109.3
C3—C2—H2	120.8	C9—C10—H10B	109.3
C2—C3—C4	120.54 (15)	H10A—C10—H10B	107.9
C2—C3—H3	119.7	O4—C11—C12	111.69 (13)
C4—C3—H3	119.7	O4—C11—H11B	109.3
C5—C4—C3	119.79 (14)	C12—C11—H11B	109.3
C5—C4—C7	123.23 (13)	O4—C11—H11A	109.3
C3—C4—C7	116.87 (13)	C12—C11—H11A	109.3
C4—C5—C6	120.20 (14)	H11B—C11—H11A	107.9
C4—C5—H5	119.9	N3—C12—C11	111.05 (13)
C6—C5—H5	119.9	N3—C12—H12B	109.4
C1—C6—C5	118.29 (14)	C11—C12—H12B	109.4
C1—C6—H6	120.9	N3—C12—H12A	109.4
C5—C6—H6	120.9	C11—C12—H12A	109.4
O3—C7—N2	122.60 (14)	H12B—C12—H12A	108.0
O1—N1—C1—C2	−173.39 (16)	C3—C4—C7—O3	24.2 (2)
O2—N1—C1—C2	6.9 (2)	C5—C4—C7—N2	27.0 (2)
O1—N1—C1—C6	5.8 (2)	C3—C4—C7—N2	−156.96 (15)
O2—N1—C1—C6	−173.87 (17)	C9—N3—C8—N2	−169.00 (14)
C6—C1—C2—C3	0.8 (3)	C12—N3—C8—N2	15.4 (2)
N1—C1—C2—C3	179.95 (15)	C9—N3—C8—S1	10.5 (2)
C1—C2—C3—C4	1.0 (3)	C12—N3—C8—S1	−165.17 (12)
C2—C3—C4—C5	−2.0 (2)	C7—N2—C8—N3	66.86 (18)
C2—C3—C4—C7	−178.23 (15)	C7—N2—C8—S1	−112.65 (14)
C3—C4—C5—C6	1.2 (2)	C8—N3—C9—C10	129.24 (16)
C7—C4—C5—C6	177.18 (14)	C12—N3—C9—C10	−54.55 (19)
C2—C1—C6—C5	−1.5 (2)	C11—O4—C10—C9	−60.10 (19)
N1—C1—C6—C5	179.29 (13)	N3—C9—C10—O4	58.40 (19)
C4—C5—C6—C1	0.5 (2)	C10—O4—C11—C12	57.60 (19)
C8—N2—C7—O3	−4.3 (2)	C8—N3—C12—C11	−130.55 (16)
C8—N2—C7—C4	176.88 (13)	C9—N3—C12—C11	53.41 (18)
C5—C4—C7—O3	−151.81 (16)	O4—C11—C12—N3	−54.50 (18)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O4i	0.82 (2)	2.27 (2)	3.0947 (17)	178.1 (18)
C3—H3···O1ii	0.93	2.43	3.206 (2)	141
C6—H6···O3iii	0.93	2.65	3.377 (2)	135
C9—H9B···O4iv	0.97	2.67	3.590 (2)	159
C10—H10A···S1v	0.97	2.98	3.7913 (18)	142
C12—H12B···S1vi	0.97	2.97	3.7196 (18)	135
C2—H2···Cg1vii	0.93	3.45	3.682 (2)	83

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O4i	0.82 (2)	2.27 (2)	3.0947 (17)	178.1 (18)
C3—H3⋯O1ii	0.93	2.43	3.206 (2)	141
C6—H6⋯O3iii	0.93	2.65	3.377 (2)	135
C9—H9B⋯O4iv	0.97	2.67	3.590 (2)	159
C10—H10A⋯S1v	0.97	2.98	3.7913 (18)	142
C12—H12B⋯S1vi	0.97	2.97	3.7196 (18)	135
C2—H2⋯Cg1vii	0.93	3.45	3.682 (2)	83

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .