Chlorobis[N′-ethoxycarbonyl-N-(4-methylphenyl)thiourea-κS]copper(I)

The title complex, chloro­bis{ethyl N-[(4-methyl­anilino)­thio­carbonyl]­carbamate-κS}copper(I), [CuCl(C₁₁H₁₄N₂O₂S)₂], was synthesized by the reaction of cupric chloride with the corresponding thio­urea derivative. The complex has imposed crystallographic m symmetry and the Cu^I coordination environment is trigonal planar, formed by two S atoms and one Cl atom. The formation of intramolecular hydrogen bonds promotes the stability of the complex.

S1. Comment

In recent years, many transition metal complexes with thiourea derivatives have been reported (Guillon et al., 1996, 1998) and they have been popularly used in organic syntheses, such as metal-catalyzed asymmetric reduction of carbonyl compounds and carbonylative cyclization of o-hydroxylarylacetylenes etc. (Touchard et al., 1997; Nan et al., 2000). N-substituted-N'-acylthiourea has received greater attention because the existence of acyl and thiocarbonyl groups in the molecule enhances its coordination ability. As a part of our research into thiourea derivatives (Zhang et al., 2001, 2003), we have synthesized the title complex, (I), and the crystal structure is reported herein. \sch

In many cases of the synthesis of copper complexes, irreversible Cu^II/Cu^I systems were observed (Guillon et al., 1996, 1998), and much research work has been reported on the reduction of Cu^II in the presence of thione derivatives (Jeannin et al., 1979; Raper, 1985; Karagiannidis et al., 1990). In our process to synthesize complex (I), the cuprous complex was obtained from the reaction of cupric ions with thiourea. The reducing agent in this reaction is probably carbonylthiourea, according to previous publications (Jeannin et al., 1979). This reaction is similar to that reported by Shen et al. (1997).

In the molecular structure of (I), the two acylthiourea molecules adopt a cis-structure relative to the central Cu^I ion (Fig. 1). The Cu^I ion in (I) has trigonal geometry, made up of two S atoms from two ligands and one Cl atom, with Cl1—Cu1—S1 120.66 (7), Cl1—Cu1—S2 120.58 (7) and S1—Cu1—S2 118.77 (7)°. A very interesting phenomenon is that almost all the atoms in the molecule are in the same plane; the mean deviation from the plane is 0 Å, except for one benzene ring which is nearly perpendicular to this plane, at an angle of 92.4°. The molecules of (I) are packed in layers vertical to the b axis, with a distance between these molecular layers of 3.485 Å.

The existence of intramolecular hydrogen bonds in carbonylthiourea evidently influences its coordination properties and promotes the stability of the complexes it forms. In the coordination compound reported by Bourne & Koch (1993), namely cis-bis(N-Benzoyl-N'-propylthiourea)dichloroplatinum(II), the two ligand molecules bind to Pt^II via the S atoms only, the carbonyl O atoms being locked into position by hydrogen bonds similar to those in the free ligand. The same observation was reported for a Cu^I complex by Shen et al. (1997). By comparison, in N,N-disubstituted carbonylthiourea complexes, the carbonyl O atom commonly participates in coordination with the central metal ion, e.g. in Pt^II and Cu^II complexes (Koch et al., 1994; Richter et al., 1980). This is due to the absence of a thioamide H atom in N,N-disubstituted carbonylthiourea, and thus no hydrogen bonds form. This is also confirmed in complex (I). Here, there are four intramolecular hydrogen bonds in the molecule (Table 1). The acyl atoms O1 and O3 form hydrogen bonds with the H atoms on atoms N1 and N3, and atom Cl1 forms hydrogen bonds with the H atoms on atoms N2 and N4. Since they are locked into the planar six-membered ring formed by these hydrogen bonds, the acyl O atoms in the ligands cannot take part in the coordination with Cu^I in the same way as the S atoms.

S2. Experimental

The N-p-methylphenyl-N'-ethoxycarbonylthiourea ligand was synthesized according to the method reported in our previous work (Zhang et al., 2003). To ethanol (30 ml) containing the ligand (2 mmol) was added an ethanol solution of cupric chloride (1 mmol). After stirring the solution at room temperature for 2 h, the mixture was filtered to obtain a white solid, which was then dried in air. Single crystals of (I) were obtained, after one week, by slow evaporation of a chloroform solution. Elemental analysis (C₂₂H₂₈ClCuN₄O₄S₂, 575.59), calculated: C 45.87, H 4.86, N 9.73%; found: C 45.78, H 5.08, N 9.62%.

S3. Refinement

The structure was solved by direct methods (Sheldrick, 1990) and successive difference Fourier syntheses. The positions of all H atoms were fixed geometrically and C—H and N—H distances were as set by the program, with C—H distances in the range 0.93–0.97 Å and N—H distances of 0.86 Å. U_iso(H) values were fixed at 1.2U_eq(N,C). Please check added text.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the molecule of (I), showing the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Intramolecular hydrogen bonds are indicated by dashed lines.

Chlorobis[N'-ethoxycarbonyl-N-(4-methylphenyl)thiourea-κS]copper(I)

Crystal data

[CuCl(C11H14N2O2S)2]	Dx = 1.448 Mg m^−3
Mr = 575.59	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 998 reflections
a = 22.826 (7) Å	θ = 3.0–22.6°
b = 6.971 (2) Å	µ = 1.12 mm^−1
c = 16.593 (5) Å	T = 293 K
V = 2640.1 (14) Å^3	Block, colourless
Z = 4	0.30 × 0.20 × 0.16 mm
F(000) = 1192

Data collection

Make Model CCD area-detector diffractometer	2943 independent reflections
Radiation source: fine-focus sealed tube	1757 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.068
ϕ and ω scans	θmax = 26.4°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −27→28
Tmin = 0.542, Tmax = 0.836	k = −8→7
14770 measured reflections	l = −20→20

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0741P)^2 + 0.2626P] where P = (Fo^2 + 2Fc^2)/3
2943 reflections	(Δ/σ)max < 0.001
202 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.32 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	Occ. (<1)
Cu1	0.47544 (3)	0.7500	0.32174 (4)	0.0580 (3)
S1	0.45043 (8)	0.7500	0.19262 (9)	0.0654 (6)
S2	0.40543 (6)	0.7500	0.41373 (9)	0.0538 (5)
Cl1	0.57008 (7)	0.7500	0.35843 (10)	0.0833 (7)
N1	0.5099 (2)	0.7500	0.0544 (3)	0.0569 (15)
H1	0.5446	0.7500	0.0343	0.068*
N2	0.5649 (2)	0.7500	0.1683 (3)	0.0551 (14)
H2A	0.5659	0.7500	0.2201	0.066*
N3	0.4010 (2)	0.7500	0.5717 (3)	0.080 (2)
H3A	0.4190	0.7500	0.6172	0.096*
N4	0.4939 (2)	0.7500	0.5183 (3)	0.0460 (13)
H4	0.5154	0.7500	0.4757	0.055*
O1	0.6249 (2)	0.7500	0.0579 (3)	0.0832 (16)
O2	0.66131 (19)	0.7500	0.1832 (3)	0.0757 (15)
O3	0.4993 (2)	0.7500	0.6561 (3)	0.0928 (19)
O4	0.57942 (16)	0.7500	0.5785 (2)	0.0540 (11)
C1	0.4664 (3)	0.7500	−0.0052 (4)	0.0552 (17)
C2	0.4069 (3)	0.7500	0.0070 (4)	0.070 (2)
H2	0.3921	0.7500	0.0591	0.085*
C3	0.3692 (3)	0.7500	−0.0577 (4)	0.088 (3)
H3	0.3290	0.7500	−0.0482	0.106*
C4	0.3894 (3)	0.7500	−0.1367 (4)	0.0641 (19)
C5	0.4478 (3)	0.7500	−0.1477 (4)	0.072 (2)
H5	0.4628	0.7500	−0.1998	0.086*
C6	0.4857 (3)	0.7500	−0.0837 (4)	0.069 (2)
H6	0.5257	0.7500	−0.0937	0.082*
C7	0.3486 (4)	0.7500	−0.2076 (5)	0.092 (3)
H7A	0.3452	0.8779	−0.2285	0.138*	0.50
H7B	0.3107	0.7053	−0.1909	0.138*	0.50
H7C	0.3638	0.6667	−0.2487	0.138*	0.50
C8	0.5105 (2)	0.7500	0.1331 (4)	0.0509 (16)
C9	0.6179 (3)	0.7500	0.1292 (4)	0.0649 (19)
C10	0.7200 (3)	0.7500	0.1477 (5)	0.099 (3)
H10A	0.7258	0.8631	0.1146	0.119*	0.50
H10B	0.7258	0.6369	0.1146	0.119*	0.50
C11	0.7608 (3)	0.7500	0.2167 (5)	0.129 (4)
H11A	0.8004	0.7500	0.1972	0.193*
H11B	0.7542	0.6376	0.2488	0.193*	0.50
H11C	0.7542	0.8624	0.2488	0.193*	0.50
C12	0.3383 (3)	0.7500	0.5751 (4)	0.061 (2)
C13	0.3094 (2)	0.5825 (10)	0.5800 (3)	0.0831 (17)
H13	0.3293	0.4668	0.5745	0.100*
C14	0.2490 (2)	0.5846 (11)	0.5936 (3)	0.0909 (19)
H14	0.2289	0.4687	0.5962	0.109*
C15	0.2190 (3)	0.7500	0.6028 (4)	0.075 (3)
C16	0.1543 (3)	0.7500	0.6234 (5)	0.119 (4)
H16A	0.1477	0.8278	0.6703	0.178*	0.50
H16B	0.1417	0.6211	0.6340	0.178*	0.50
H16C	0.1324	0.8012	0.5789	0.178*	0.50
C17	0.4342 (2)	0.7500	0.5071 (3)	0.0454 (15)
C18	0.5224 (3)	0.7500	0.5916 (4)	0.0518 (16)
C19	0.6155 (3)	0.7500	0.6510 (4)	0.0623 (19)
H19A	0.6075	0.6370	0.6833	0.075*	0.50
H19B	0.6075	0.8630	0.6833	0.075*	0.50
C20	0.6773 (3)	0.7500	0.6239 (5)	0.093 (3)
H20A	0.6837	0.8562	0.5881	0.139*	0.50
H20B	0.6855	0.6322	0.5962	0.139*	0.50
H20C	0.7026	0.7616	0.6698	0.139*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0484 (5)	0.0897 (7)	0.0359 (4)	0.000	−0.0006 (3)	0.000
S1	0.0477 (9)	0.1125 (16)	0.0360 (9)	0.000	0.0022 (7)	0.000
S2	0.0384 (8)	0.0879 (13)	0.0352 (8)	0.000	−0.0065 (6)	0.000
Cl1	0.0433 (9)	0.161 (2)	0.0451 (9)	0.000	0.0001 (7)	0.000
N1	0.045 (3)	0.088 (4)	0.037 (3)	0.000	0.002 (2)	0.000
N2	0.055 (3)	0.077 (4)	0.033 (3)	0.000	0.001 (2)	0.000
N3	0.037 (3)	0.176 (7)	0.028 (3)	0.000	−0.001 (2)	0.000
N4	0.038 (3)	0.067 (4)	0.033 (3)	0.000	−0.007 (2)	0.000
O1	0.058 (3)	0.153 (5)	0.039 (3)	0.000	0.005 (2)	0.000
O2	0.044 (2)	0.131 (5)	0.052 (3)	0.000	0.007 (2)	0.000
O3	0.051 (3)	0.191 (6)	0.037 (3)	0.000	−0.007 (2)	0.000
O4	0.036 (2)	0.081 (3)	0.046 (2)	0.000	−0.0133 (19)	0.000
C1	0.054 (4)	0.078 (5)	0.034 (3)	0.000	−0.001 (3)	0.000
C2	0.059 (4)	0.115 (6)	0.038 (4)	0.000	0.007 (3)	0.000
C3	0.060 (5)	0.160 (8)	0.045 (4)	0.000	0.002 (3)	0.000
C4	0.072 (5)	0.076 (5)	0.044 (4)	0.000	−0.008 (3)	0.000
C5	0.063 (5)	0.115 (7)	0.038 (4)	0.000	0.006 (3)	0.000
C6	0.058 (4)	0.106 (6)	0.042 (4)	0.000	0.006 (3)	0.000
C7	0.079 (5)	0.139 (8)	0.057 (5)	0.000	−0.020 (4)	0.000
C8	0.044 (4)	0.067 (5)	0.042 (3)	0.000	0.003 (3)	0.000
C9	0.048 (4)	0.098 (6)	0.048 (4)	0.000	0.006 (3)	0.000
C10	0.048 (4)	0.182 (10)	0.068 (5)	0.000	0.009 (4)	0.000
C11	0.053 (5)	0.249 (14)	0.084 (6)	0.000	0.009 (4)	0.000
C12	0.038 (4)	0.108 (7)	0.037 (3)	0.000	−0.009 (3)	0.000
C13	0.059 (3)	0.102 (5)	0.088 (4)	0.008 (3)	−0.018 (3)	−0.009 (3)
C14	0.056 (3)	0.126 (6)	0.090 (4)	−0.026 (4)	−0.011 (3)	0.016 (4)
C15	0.041 (4)	0.147 (9)	0.038 (4)	0.000	−0.001 (3)	0.000
C16	0.045 (4)	0.253 (13)	0.057 (5)	0.000	0.006 (4)	0.000
C17	0.034 (3)	0.058 (4)	0.044 (3)	0.000	−0.010 (3)	0.000
C18	0.044 (4)	0.076 (5)	0.035 (3)	0.000	−0.012 (3)	0.000
C19	0.050 (4)	0.082 (5)	0.054 (4)	0.000	−0.022 (3)	0.000
C20	0.046 (4)	0.127 (8)	0.105 (7)	0.000	−0.025 (4)	0.000

Geometric parameters (Å, º)

Cu1—S2	2.2099 (17)	C4—C7	1.500 (9)
Cu1—S1	2.2171 (18)	C5—C6	1.369 (9)
Cu1—Cl1	2.2445 (19)	C5—H5	0.9300
S1—C8	1.689 (6)	C6—H6	0.9300
S2—C17	1.683 (6)	C7—H7A	0.9600
N1—C8	1.306 (8)	C7—H7B	0.9600
N1—C1	1.400 (7)	C7—H7C	0.9600
N1—H1	0.8600	C10—C11	1.475 (11)
N2—C8	1.373 (7)	C10—H10A	0.9700
N2—C9	1.373 (8)	C10—H10B	0.9700
N2—H2A	0.8600	C11—H11A	0.9600
N3—C17	1.312 (8)	C11—H11B	0.9600
N3—C12	1.434 (8)	C11—H11C	0.9600
N3—H3A	0.8600	C12—C13^i	1.343 (7)
N4—C17	1.374 (7)	C12—C13	1.343 (7)
N4—C18	1.380 (7)	C13—C14	1.397 (7)
N4—H4	0.8600	C13—H13	0.9300
O1—C9	1.192 (8)	C14—C15	1.351 (7)
O2—C9	1.337 (8)	C14—H14	0.9300
O2—C10	1.464 (8)	C15—C14^i	1.351 (7)
O3—C18	1.193 (7)	C15—C16	1.515 (9)
O4—C18	1.319 (7)	C16—H16A	0.9600
O4—C19	1.458 (7)	C16—H16B	0.9600
C1—C2	1.373 (9)	C16—H16C	0.9600
C1—C6	1.375 (9)	C19—C20	1.480 (9)
C2—C3	1.376 (9)	C19—H19A	0.9700
C2—H2	0.9300	C19—H19B	0.9700
C3—C4	1.391 (9)	C20—H20A	0.9600
C3—H3	0.9300	C20—H20B	0.9600
C4—C5	1.345 (10)	C20—H20C	0.9600
S2—Cu1—S1	118.77 (7)	O2—C10—C11	105.4 (6)
S2—Cu1—Cl1	120.58 (7)	O2—C10—H10A	110.7
S1—Cu1—Cl1	120.66 (7)	C11—C10—H10A	110.7
C8—S1—Cu1	110.9 (2)	O2—C10—H10B	110.7
C17—S2—Cu1	110.7 (2)	C11—C10—H10B	110.7
C8—N1—C1	135.5 (5)	H10A—C10—H10B	108.8
C8—N1—H1	112.2	C10—C11—H11A	109.5
C1—N1—H1	112.2	C10—C11—H11B	109.5
C8—N2—C9	126.6 (5)	H11A—C11—H11B	109.5
C8—N2—H2A	116.7	C10—C11—H11C	109.5
C9—N2—H2A	116.7	H11A—C11—H11C	109.5
C17—N3—C12	127.6 (5)	H11B—C11—H11C	109.5
C17—N3—H3A	116.2	C13^i—C12—C13	120.8 (7)
C12—N3—H3A	116.2	C13^i—C12—N3	119.5 (3)
C17—N4—C18	125.9 (5)	C13—C12—N3	119.5 (3)
C17—N4—H4	117.0	C12—C13—C14	119.0 (6)
C18—N4—H4	117.0	C12—C13—H13	120.5
C9—O2—C10	114.1 (5)	C14—C13—H13	120.5
C18—O4—C19	114.9 (5)	C15—C14—C13	121.9 (6)
C2—C1—C6	117.0 (6)	C15—C14—H14	119.0
C2—C1—N1	126.7 (6)	C13—C14—H14	119.0
C6—C1—N1	116.3 (6)	C14^i—C15—C14	117.2 (7)
C1—C2—C3	120.4 (6)	C14^i—C15—C16	121.4 (4)
C1—C2—H2	119.8	C14—C15—C16	121.4 (4)
C3—C2—H2	119.8	C15—C16—H16A	109.5
C2—C3—C4	121.8 (7)	C15—C16—H16B	109.5
C2—C3—H3	119.1	H16A—C16—H16B	109.5
C4—C3—H3	119.1	C15—C16—H16C	109.5
C5—C4—C3	117.2 (6)	H16A—C16—H16C	109.5
C5—C4—C7	120.6 (7)	H16B—C16—H16C	109.5
C3—C4—C7	122.2 (7)	N3—C17—N4	117.5 (5)
C4—C5—C6	121.3 (7)	N3—C17—S2	121.7 (4)
C4—C5—H5	119.3	N4—C17—S2	120.8 (4)
C6—C5—H5	119.3	O3—C18—O4	125.7 (5)
C5—C6—C1	122.3 (6)	O3—C18—N4	125.6 (6)
C5—C6—H6	118.9	O4—C18—N4	108.7 (5)
C1—C6—H6	118.9	O4—C19—C20	106.7 (6)
C4—C7—H7A	109.5	O4—C19—H19A	110.4
C4—C7—H7B	109.5	C20—C19—H19A	110.4
H7A—C7—H7B	109.5	O4—C19—H19B	110.4
C4—C7—H7C	109.5	C20—C19—H19B	110.4
H7A—C7—H7C	109.5	H19A—C19—H19B	108.6
H7B—C7—H7C	109.5	C19—C20—H20A	109.5
N1—C8—N2	115.8 (5)	C19—C20—H20B	109.5
N1—C8—S1	125.2 (5)	H20A—C20—H20B	109.5
N2—C8—S1	119.0 (4)	C19—C20—H20C	109.5
O1—C9—O2	124.5 (6)	H20A—C20—H20C	109.5
O1—C9—N2	125.9 (6)	H20B—C20—H20C	109.5
O2—C9—N2	109.6 (5)
S2—Cu1—S1—C8	180.0	C10—O2—C9—N2	180.0
Cl1—Cu1—S1—C8	0.0	C8—N2—C9—O1	0.0
S1—Cu1—S2—C17	180.0	C8—N2—C9—O2	180.0
Cl1—Cu1—S2—C17	0.0	C9—O2—C10—C11	180.0
C8—N1—C1—C2	0.0	C17—N3—C12—C13^i	−92.7 (5)
C8—N1—C1—C6	180.0	C17—N3—C12—C13	92.7 (5)
C6—C1—C2—C3	0.0	C13^i—C12—C13—C14	−2.5 (10)
N1—C1—C2—C3	180.0	N3—C12—C13—C14	172.0 (5)
C1—C2—C3—C4	0.0	C12—C13—C14—C15	−0.8 (9)
C2—C3—C4—C5	0.0	C13—C14—C15—C14^i	4.0 (11)
C2—C3—C4—C7	180.0	C13—C14—C15—C16	−175.6 (6)
C3—C4—C5—C6	0.0	C12—N3—C17—N4	180.0
C7—C4—C5—C6	180.0	C12—N3—C17—S2	0.000 (1)
C4—C5—C6—C1	0.0	C18—N4—C17—N3	0.0
C2—C1—C6—C5	0.0	C18—N4—C17—S2	180.0
N1—C1—C6—C5	180.0	Cu1—S2—C17—N3	180.0
C1—N1—C8—N2	180.0	Cu1—S2—C17—N4	0.0
C1—N1—C8—S1	0.0	C19—O4—C18—O3	0.000 (1)
C9—N2—C8—N1	0.0	C19—O4—C18—N4	180.0
C9—N2—C8—S1	180.0	C17—N4—C18—O3	0.000 (1)
Cu1—S1—C8—N1	180.0	C17—N4—C18—O4	180.0
Cu1—S1—C8—N2	0.0	C18—O4—C19—C20	180.000 (1)
C10—O2—C9—O1	0.0

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.87	2.625	145
N2—H2A···Cl1	0.86	2.30	3.157	179
N3—H3A···O3	0.86	1.94	2.645	138
N4—H4···Cl1	0.86	2.31	3.172	178