N-(4-Chloro­phen­yl)-N′-(4-nitro­benzo­yl)urea

The title compound, C₁₄H₁₀ClN₃O₄, was obtained by the reaction of N-(4-chloro­phen­yl)-N′-(4-nitro­benzo­yl)thio­urea with cupric chloride dihydrate. Inter­molecular N—H...O hydrogen bonds link the mol­ecules into centrosymmetric dimers. The crystal packing is further stabilized by weak C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.033
• wR factor = 0.088
• Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N3

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Thiourea derivatives have been studied intensively in recent years (Koch, 2001; Foss et al., 2004; Bombicz et al., 2004). Acyl thiourea derivatives are known to form various coordination compounds with transition metals. They can act as reducing agents to reduce the oxidation state of transition metal ions. They may also produce unexpected compounds in ordinary coordination reactions. Recently, (Zhang et al. (2003) reported that an oxazoline ring was formed in the coordination reaction of dihydrate cupric chloride with N-benzoyl-N'-(2-hydroxyethyl)thiourea. In this reaction, desulfurization and cyclization have occurred, and two oxazoline rings were formed in the resulting coordination compound. In the coordination reaction of N-ethoxycarbonyl-N'-o-chlorophenylthiourea with dihydrate cupric chloride in ethanol solution (Su, Xian et al., 2005), an unusual compound was obtained, containing the Cu₆ cluster unit, where the copper(I) ions form a hexagonal ring structure via Cu—Cu bonds.

The title compound, (I) (Fig. 1), was obtained by the reaction of N-p-nitrobenzoyl-N'-p-chlorophenylthiourea with dihydrate cupric chloride, in which the S atom on the thiocarbonyl group of the thiourea ligand was replaced by an O atom. The bond lengths and angles in (I) (Table 1) are normal (Allen et al., 1987). The intramolecular N1—H1···O2 hydrogen bond (Table 2) defines a molecular conformation. The intermolecular N—H···O hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers. The crystal packing (Fig. 2) is further stabilized by weak C—H···O interactions (Table 2).

The title compound was obtained unexpectedly in the coordination reaction of thiourea with copper(II). To validate the results of the structural analysis, IR and ¹H NMR measurements have been carried out. The IR and ¹H NMR data indicated that the thiocarbonyl group was replaced by the carbonyl group, viz. that the S atom was replaced by the O atom in air when the solution was heated. We suppose that in this process the copper(II) ion acts as an electron transferring unit, allowing the replacement of the S atom by an O atom in air. This reaction is distinct from other coordination reactions, which commonly form the 1:2 thiourea coordination compounds in triangle central structure (Su et al., 2004), and the reasons for this distinction are still unknown.

S2. Experimental

All chemicals used for the preparation of compound (I) were of reagent grade quality. N-(4-Chlorophenyl)-N'-(4-nitrobenzoyl)thiourea was obtained in CH₂Cl₂ using the known method (Su, Liu et al., 2005). The thiourea ligand and cupric chloride were dissolved in ethanol. The two solutions were mixed and heated for a while with stirring, and a yellow product was obtained as deposition. Single crystals were obtained after one week by slow evaporation of a mixed solution of dimethyl sulphoxide with acetone in a 1:1 ratio heated for 10 min. Yield 28%. Analysis required for C₁₄H₁₀ClN₃O₄: C 52.55, H 3.13, N 13.15%; found: C 50.04, H 2.59, N 13.13%. IR (cm⁻¹): 3131 (NH), 1701 (C═O), 1596, 1525, 1499 (C═C), 1346, 1270, 1227, 1091, 831, 723, 511. ¹H NMR: 7.38–7.70 (m, 4H, Cl—C₆H₄), 8.14–8.34 (m, 4H, NO₂—C₆H₄), 10.64 (s, 1H, NH), 11.39 (s, 1H, NH).

S3. Refinement

The C-bound H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The amine atoms H1 and H2 were located in a difference Fourier map and refined isotropically with a restrained N—H distance of 0.87 (1) Å.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of (I), with displacement ellipsoids at the 50% probability level. The intramolecular hydrogen bond is indicated by a dashed line.
	Fig. 2. The crystal packing viewed approximately along the b axis. Intermolecular hydrogen bonds are indicated by dashed lines.

N-(4-Chlorophenyl)-N'-(4-nitrobenzoyl)urea

Crystal data

C14H10ClN3O4	Z = 2
Mr = 319.70	F(000) = 328
Triclinic, P1	Dx = 1.558 Mg m^−3
a = 7.1737 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2486 (12) Å	Cell parameters from 1727 reflections
c = 12.1873 (17) Å	θ = 2.5–27.7°
α = 91.418 (2)°	µ = 0.30 mm^−1
β = 106.157 (2)°	T = 293 K
γ = 99.400 (2)°	Block, yellow
V = 681.50 (17) Å^3	0.26 × 0.24 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2368 independent reflections
Radiation source: fine-focus sealed tube	1941 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.009
ϕ and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.911, Tmax = 0.947	k = −9→8
3693 measured reflections	l = −10→14

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0423P)^2 + 0.161P] where P = (Fo^2 + 2Fc^2)/3
2368 reflections	(Δ/σ)max < 0.001
207 parameters	Δρmax = 0.26 e Å^−3
2 restraints	Δρmin = −0.21 e Å^−3

Special details

Experimental. The IR spectrum was recorded on a Nicolet NEXUS 670 F T–IR spectrophotometer using KBr discs. 1H NMR spectra were recorded on an Advance 300 Bruker spectrometer with DMSO-d6 as solvent.

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
Cl1	1.28679 (9)	−0.00089 (7)	0.27008 (5)	0.0716 (2)
N1	0.9143 (2)	0.32409 (17)	0.56999 (12)	0.0412 (3)
H1	0.984 (2)	0.337 (2)	0.6415 (9)	0.050 (5)*
N2	0.70475 (19)	0.46082 (17)	0.63786 (11)	0.0395 (3)
H2	0.5996 (18)	0.5037 (19)	0.6185 (14)	0.044 (5)*
N3	0.5108 (2)	0.8111 (2)	1.06294 (14)	0.0567 (4)
O1	0.64018 (16)	0.39301 (16)	0.44858 (9)	0.0496 (3)
O2	0.97614 (18)	0.44473 (16)	0.78491 (10)	0.0534 (3)
O3	0.3401 (2)	0.8288 (2)	1.03227 (15)	0.0918 (6)
O4	0.6206 (3)	0.8557 (2)	1.15750 (13)	0.0884 (5)
C1	0.7506 (2)	0.39051 (19)	0.54468 (14)	0.0367 (4)
C2	0.8153 (2)	0.4858 (2)	0.74984 (14)	0.0399 (4)
C3	0.9940 (2)	0.24722 (19)	0.49319 (14)	0.0377 (4)
C4	1.1752 (2)	0.2006 (2)	0.54013 (15)	0.0436 (4)
H4	1.2364	0.2206	0.6184	0.052*
C5	1.2654 (3)	0.1254 (2)	0.47245 (17)	0.0494 (4)
H5	1.3874	0.0954	0.5045	0.059*
C6	1.1737 (3)	0.0946 (2)	0.35684 (16)	0.0488 (4)
C7	0.9928 (3)	0.1375 (2)	0.30907 (16)	0.0490 (4)
H7	0.9313	0.1149	0.2310	0.059*
C8	0.9018 (3)	0.2141 (2)	0.37664 (15)	0.0452 (4)
H8	0.7795	0.2432	0.3442	0.054*
C9	0.7284 (2)	0.5695 (2)	0.82916 (13)	0.0385 (4)
C10	0.8574 (2)	0.6555 (2)	0.92800 (14)	0.0466 (4)
H10	0.9923	0.6585	0.9426	0.056*
C11	0.7882 (3)	0.7360 (2)	1.00432 (15)	0.0481 (4)
H11	0.8744	0.7947	1.0700	0.058*
C12	0.5877 (3)	0.7274 (2)	0.98081 (14)	0.0423 (4)
C13	0.4555 (2)	0.6416 (2)	0.88505 (14)	0.0456 (4)
H13	0.3206	0.6373	0.8718	0.055*
C14	0.5269 (2)	0.5619 (2)	0.80906 (14)	0.0433 (4)
H14	0.4396	0.5028	0.7439	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0941 (4)	0.0647 (3)	0.0800 (4)	0.0300 (3)	0.0551 (3)	0.0010 (3)
N1	0.0419 (8)	0.0512 (8)	0.0315 (8)	0.0163 (6)	0.0081 (6)	−0.0021 (6)
N2	0.0354 (7)	0.0516 (8)	0.0326 (7)	0.0155 (6)	0.0076 (6)	−0.0017 (6)
N3	0.0609 (10)	0.0644 (10)	0.0475 (10)	0.0091 (8)	0.0221 (8)	−0.0095 (8)
O1	0.0422 (6)	0.0732 (8)	0.0343 (7)	0.0217 (6)	0.0069 (5)	−0.0051 (6)
O2	0.0470 (7)	0.0749 (9)	0.0390 (7)	0.0286 (6)	0.0038 (5)	−0.0030 (6)
O3	0.0607 (10)	0.1333 (15)	0.0851 (12)	0.0265 (10)	0.0255 (8)	−0.0387 (10)
O4	0.0854 (11)	0.1217 (14)	0.0521 (9)	0.0138 (10)	0.0162 (8)	−0.0392 (9)
C1	0.0343 (8)	0.0402 (9)	0.0352 (9)	0.0058 (7)	0.0103 (7)	−0.0012 (7)
C2	0.0394 (9)	0.0438 (9)	0.0360 (9)	0.0100 (7)	0.0087 (7)	0.0012 (7)
C3	0.0404 (8)	0.0351 (8)	0.0393 (9)	0.0057 (7)	0.0150 (7)	0.0016 (7)
C4	0.0434 (9)	0.0431 (9)	0.0446 (10)	0.0119 (7)	0.0110 (7)	0.0001 (7)
C5	0.0471 (10)	0.0448 (10)	0.0621 (12)	0.0162 (8)	0.0204 (9)	0.0038 (9)
C6	0.0612 (11)	0.0380 (9)	0.0586 (12)	0.0112 (8)	0.0347 (9)	0.0022 (8)
C7	0.0591 (11)	0.0492 (10)	0.0407 (10)	0.0068 (9)	0.0194 (8)	−0.0024 (8)
C8	0.0445 (9)	0.0506 (10)	0.0427 (10)	0.0121 (8)	0.0140 (8)	0.0005 (8)
C9	0.0411 (9)	0.0433 (9)	0.0311 (8)	0.0100 (7)	0.0090 (7)	0.0033 (7)
C10	0.0390 (9)	0.0609 (11)	0.0372 (9)	0.0126 (8)	0.0050 (7)	−0.0026 (8)
C11	0.0473 (10)	0.0578 (11)	0.0335 (9)	0.0088 (8)	0.0037 (7)	−0.0076 (8)
C12	0.0495 (10)	0.0474 (9)	0.0328 (9)	0.0109 (8)	0.0150 (7)	0.0005 (7)
C13	0.0377 (9)	0.0621 (11)	0.0376 (9)	0.0098 (8)	0.0114 (7)	0.0005 (8)
C14	0.0414 (9)	0.0551 (10)	0.0304 (9)	0.0051 (8)	0.0079 (7)	−0.0033 (7)

Geometric parameters (Å, º)

Cl1—C6	1.7442 (17)	C5—C6	1.376 (3)
N1—C1	1.338 (2)	C5—H5	0.9300
N1—C3	1.412 (2)	C6—C7	1.374 (3)
N1—H1	0.871 (9)	C7—C8	1.382 (2)
N2—C2	1.365 (2)	C7—H7	0.9300
N2—C1	1.404 (2)	C8—H8	0.9300
N2—H2	0.861 (9)	C9—C14	1.388 (2)
N3—O4	1.210 (2)	C9—C10	1.391 (2)
N3—O3	1.212 (2)	C10—C11	1.374 (2)
N3—C12	1.477 (2)	C10—H10	0.9300
O1—C1	1.2207 (19)	C11—C12	1.375 (2)
O2—C2	1.2204 (19)	C11—H11	0.9300
C2—C9	1.498 (2)	C12—C13	1.374 (2)
C3—C4	1.387 (2)	C13—C14	1.376 (2)
C3—C8	1.389 (2)	C13—H13	0.9300
C4—C5	1.374 (2)	C14—H14	0.9300
C4—H4	0.9300
C1—N1—C3	127.58 (14)	C5—C6—Cl1	119.86 (14)
C1—N1—H1	115.7 (12)	C6—C7—C8	120.21 (17)
C3—N1—H1	116.5 (12)	C6—C7—H7	119.9
C2—N2—C1	128.49 (13)	C8—C7—H7	119.9
C2—N2—H2	117.3 (12)	C7—C8—C3	119.68 (16)
C1—N2—H2	113.7 (12)	C7—C8—H8	120.2
O4—N3—O3	123.72 (17)	C3—C8—H8	120.2
O4—N3—C12	118.26 (17)	C14—C9—C10	119.38 (15)
O3—N3—C12	118.01 (16)	C14—C9—C2	122.93 (15)
O1—C1—N1	125.27 (15)	C10—C9—C2	117.68 (15)
O1—C1—N2	118.64 (14)	C11—C10—C9	120.85 (16)
N1—C1—N2	116.09 (14)	C11—C10—H10	119.6
O2—C2—N2	123.12 (15)	C9—C10—H10	119.6
O2—C2—C9	120.95 (15)	C10—C11—C12	118.09 (16)
N2—C2—C9	115.93 (14)	C10—C11—H11	121.0
C4—C3—C8	119.24 (15)	C12—C11—H11	121.0
C4—C3—N1	116.38 (15)	C13—C12—C11	122.74 (15)
C8—C3—N1	124.37 (15)	C13—C12—N3	118.50 (15)
C5—C4—C3	120.81 (17)	C11—C12—N3	118.74 (15)
C5—C4—H4	119.6	C12—C13—C14	118.57 (15)
C3—C4—H4	119.6	C12—C13—H13	120.7
C4—C5—C6	119.46 (16)	C14—C13—H13	120.7
C4—C5—H5	120.3	C13—C14—C9	120.35 (15)
C6—C5—H5	120.3	C13—C14—H14	119.8
C7—C6—C5	120.58 (16)	C9—C14—H14	119.8
C7—C6—Cl1	119.56 (15)
C3—N1—C1—O1	1.1 (3)	O2—C2—C9—C14	−154.16 (17)
C3—N1—C1—N2	−179.51 (15)	N2—C2—C9—C14	26.5 (2)
C2—N2—C1—O1	−173.13 (16)	O2—C2—C9—C10	24.6 (3)
C2—N2—C1—N1	7.4 (3)	N2—C2—C9—C10	−154.76 (15)
C1—N2—C2—O2	−1.4 (3)	C14—C9—C10—C11	−1.5 (3)
C1—N2—C2—C9	178.00 (15)	C2—C9—C10—C11	179.64 (16)
C1—N1—C3—C4	174.64 (16)	C9—C10—C11—C12	0.8 (3)
C1—N1—C3—C8	−6.5 (3)	C10—C11—C12—C13	0.3 (3)
C8—C3—C4—C5	1.3 (3)	C10—C11—C12—N3	179.05 (16)
N1—C3—C4—C5	−179.81 (15)	O4—N3—C12—C13	164.33 (18)
C3—C4—C5—C6	−0.6 (3)	O3—N3—C12—C13	−14.5 (3)
C4—C5—C6—C7	−0.4 (3)	O4—N3—C12—C11	−14.5 (3)
C4—C5—C6—Cl1	180.00 (13)	O3—N3—C12—C11	166.71 (19)
C5—C6—C7—C8	0.8 (3)	C11—C12—C13—C14	−0.5 (3)
Cl1—C6—C7—C8	−179.65 (14)	N3—C12—C13—C14	−179.30 (16)
C6—C7—C8—C3	−0.1 (3)	C12—C13—C14—C9	−0.3 (3)
C4—C3—C8—C7	−0.9 (3)	C10—C9—C14—C13	1.3 (3)
N1—C3—C8—C7	−179.74 (16)	C2—C9—C14—C13	−179.96 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.87 (1)	1.96 (1)	2.6699 (18)	138 (2)
C8—H8···O1	0.93	2.28	2.868 (2)	121
N2—H2···O1^i	0.86 (1)	2.02 (1)	2.8763 (17)	172 (2)
C10—H10···O3^ii	0.93	2.58	3.390 (2)	146
C14—H14···O1^i	0.93	2.47	3.089 (2)	124

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