Tetra­kis(di-4-pyridylsulfane)dinitratocopper(II)

Gao, R.-H.; Yang, L.-L.

doi:10.1107/S1600536810011414

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page m487

https://doi.org/10.1107/S1600536810011414

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Tetrakis(di-4-pyridylsulfane)dinitratocopper(II)

Rong-Hua Gao ^a and Li-Li Yang ^a ^*

^aWeihai Department of Biological and Chemical Engineering, Weihai Vocational College, Weihai 264210, People's Republic of China
^*Correspondence e-mail: wjoxxj@gmail.com

(Received 13 March 2010; accepted 25 March 2010; online 2 April 2010)

In the title complex, [Cu(NO₃)₂(C₁₀H₈N₂S)₄], the Cu^II atom (site symmetry $[\overline{1}]$ ) is coordinated by two monodentate nitrate ions and two monodentate di-4-pyridylsulfane ligands, resulting in a slightly distorted trans-arranged CuO₂N₄ octahedral geometry. Intramolecular C—H⋯O hydrogen bonds are present. In the crystal, adjacent molecules are linked via C—H⋯N hydrogen bonds into chains parallel to the a axis. Intermolecular C—H⋯O interactions also occur.

Related literature

For transition-metal complexes of di-4-pyridylsulfane, see: Wen et al. (2004 ); Muthu et al. (2005 ); Xu et al. (2007 ); Zhang et al. (2008 ).

Experimental

Crystal data

[Cu(NO₃)₂(C₁₀H₈N₂S)₄]
M_r = 940.59
Triclinic, $[P \overline 1]$
a = 9.299 (4) Å
b = 10.765 (5) Å
c = 10.978 (5) Å
α = 84.408 (6)°
β = 73.759 (6)°
γ = 79.180 (6)°
V = 1035.1 (8) Å³
Z = 1
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 296 K
0.21 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.847, T_max = 0.874
7479 measured reflections
3728 independent reflections
2392 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.100
S = 0.90
3679 reflections
277 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1ⁱ	0.93	2.52	3.063 (4)	118
C5—H5⋯O2ⁱ	0.93	2.49	3.419 (4)	174
C5—H5⋯O1ⁱ	0.93	2.51	3.193 (4)	130
C14—H14⋯N4ⁱⁱ	0.93	2.47	3.279 (5)	146
C1—H1⋯O1	0.93	2.27	3.008 (4)	135
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810011414/rz2428sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810011414/rz2428Isup2.hkl

checkCIF report

Comment top

Flexible ligands are interesting due to their smaller steric effects, which contribute to the construction of novel complexes. Compared to the widely investigated 4,4'-bipy, the dps (di-4-pyridylsulfane) ligand is more flexible and the two pyridine rings can rotate freely. There are only few complexes of metal-organic compounds with dps (Xu et al., 2007; Wen et al., 2004; Muthu et al., 2005; Zhang et al., 2008). Herein, we report the synthesis and structure of the title compound, dinitratotetrakis(di-4-pyridylsulfane)copper(II).

The title compound (Fig. 1) crystallizes in the monoclinic space group P1. The copper(II) ion lies on a crystallography inversion centre and adopts a slightly distorted octahedral provided by four N atoms from two dps ligands in the equatorial plane and two O atoms from two nitrate ions in the axial position. In the equatorial plane, the Cu1—N1 and Cu1—N3 bond lengths are 2.047 (3) and 2.023 (3) Å respectively, while the Cu1—O1 axial bond length is 2.558 (3) Å. The conformation of the complex molecule is stabilized by intramolecular C—H···O hydrogen bonds (Table 1). In the crystal structure (Fig. 2), intermolecular C—H···N hydrogen interactions link molecules into chains parallel to the a axis.

Related literature top

For transition-metal complexes of di-4-pyridylsulfane, see: Wen et al. (2004); Muthu et al. (2005); Xu et al. (2007); Zhang et al. (2008).

Experimental top

The title compound was prepared by adding a solution of copper(II) nitrate hexahydrate (0.1 mmol) in water (6 ml) to a solution of di-4-pyridylsulfane (0.2 mmol) in CH₃OH (5 ml) with gentle stirring. After several days, block-shaped blue crystals suitable for X-ray analysis were obtained on slow evaporation of the solvent (Yield 30 mg; 31.9%, based on Cu). Anal. calcd for C₄₀H₃₂CuN₁₀O₆S₄ (940.59): C 51.08, H 3.43, N 14.89%; found: C 51.23, H 3.45, N 14.93%.

Structure description top

For transition-metal complexes of di-4-pyridylsulfane, see: Wen et al. (2004); Muthu et al. (2005); Xu et al. (2007); Zhang et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with atomic labeling scheme and displacement ellipsoids drawn at the 50% probability level [symmetry code: (A) -x+1,-y+2,-z+1].
	Fig. 2. Crystal packing of the title compound viewed along the c axis. Hydrogen bonds are drawn as dashed lines.

Tetrakis(di-4-pyridylsulfane)dinitratocopper(II) top

Crystal data top

[Cu(NO₃)₂(C₁₀H₈N₂S)₄]	Z = 1
M_r = 940.59	F(000) = 483
Triclinic, P1	D_x = 1.509 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.299 (4) Å	Cell parameters from 4796 reflections
b = 10.765 (5) Å	θ = 2.3–28.2°
c = 10.978 (5) Å	µ = 0.79 mm⁻¹
α = 84.408 (6)°	T = 296 K
β = 73.759 (6)°	Block, blue
γ = 79.180 (6)°	0.21 × 0.19 × 0.17 mm
V = 1035.1 (8) Å³

Data collection top

Bruker SMART APEXII diffractometer	3728 independent reflections
Radiation source: fine-focus sealed tube	2392 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω scans	θ_max = 25.2°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.847, T_max = 0.874	k = −12→12
7479 measured reflections	l = −13→12

Refinement top

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.0391P)²] where P = (F_o² + 2F_c²)/3
3679 reflections	(Δ/σ)_max < 0.001
277 parameters	Δρ_max = 0.43 e Å⁻³
6 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Cu(NO₃)₂(C₁₀H₈N₂S)₄]	γ = 79.180 (6)°
M_r = 940.59	V = 1035.1 (8) Å³
Triclinic, P1	Z = 1
a = 9.299 (4) Å	Mo Kα radiation
b = 10.765 (5) Å	µ = 0.79 mm⁻¹
c = 10.978 (5) Å	T = 296 K
α = 84.408 (6)°	0.21 × 0.19 × 0.17 mm
β = 73.759 (6)°

Data collection top

Bruker SMART APEXII diffractometer	3728 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2392 reflections with I > 2σ(I)
T_min = 0.847, T_max = 0.874	R_int = 0.061
7479 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	6 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 0.90	Δρ_max = 0.43 e Å⁻³
3679 reflections	Δρ_min = −0.33 e Å⁻³
277 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.5000	1.0000	0.5000	0.03494 (19)
S1	0.46635 (10)	0.45645 (8)	0.29541 (10)	0.0526 (3)
S2	0.38860 (11)	1.20522 (11)	−0.05513 (9)	0.0609 (3)
O1	0.7889 (3)	0.9473 (2)	0.4138 (2)	0.0586 (7)
O2	0.9388 (3)	1.0613 (3)	0.2949 (3)	0.0869 (10)
O3	1.0298 (3)	0.8845 (3)	0.3704 (3)	0.1064 (12)
N1	0.4896 (3)	0.8203 (2)	0.4611 (2)	0.0337 (6)
N2	−0.0360 (3)	0.4563 (3)	0.3369 (3)	0.0556 (9)
N3	0.4666 (3)	1.0575 (2)	0.3276 (2)	0.0327 (6)
N4	−0.1253 (4)	1.2525 (3)	0.0096 (3)	0.0642 (9)
N5	0.9202 (4)	0.9628 (3)	0.3612 (3)	0.0538 (7)
C1	0.6125 (4)	0.7481 (3)	0.3889 (3)	0.0381 (8)
H1	0.7061	0.7748	0.3711	0.046*
C2	0.6058 (4)	0.6377 (3)	0.3409 (3)	0.0381 (8)
H2	0.6937	0.5908	0.2917	0.046*
C3	0.4684 (4)	0.5955 (3)	0.3654 (3)	0.0359 (8)
C4	0.3437 (4)	0.6656 (3)	0.4452 (3)	0.0433 (9)
H4	0.2500	0.6385	0.4682	0.052*
C5	0.3596 (4)	0.7753 (3)	0.4899 (3)	0.0413 (9)
H5	0.2746	0.8210	0.5436	0.050*
C6	0.2705 (3)	0.4599 (3)	0.3124 (3)	0.0385 (8)
C7	0.1802 (4)	0.5620 (3)	0.2676 (4)	0.0510 (10)
H7	0.2205	0.6326	0.2270	0.061*
C8	0.0298 (4)	0.5550 (4)	0.2851 (4)	0.0560 (10)
H8	−0.0309	0.6253	0.2586	0.067*
C9	0.0547 (4)	0.3585 (3)	0.3756 (4)	0.0556 (10)
H9	0.0133	0.2866	0.4105	0.067*
C10	0.2053 (4)	0.3570 (3)	0.3674 (3)	0.0453 (9)
H10	0.2621	0.2871	0.3987	0.054*
C11	0.3401 (4)	1.0425 (3)	0.2976 (3)	0.0365 (8)
H11	0.2705	1.0005	0.3569	0.044*
C12	0.3082 (4)	1.0855 (3)	0.1852 (3)	0.0386 (8)
H12	0.2191	1.0726	0.1693	0.046*
C13	0.4103 (4)	1.1485 (3)	0.0953 (3)	0.0389 (8)
C14	0.5424 (4)	1.1637 (3)	0.1250 (3)	0.0404 (9)
H14	0.6140	1.2051	0.0671	0.049*
C15	0.5658 (4)	1.1175 (3)	0.2396 (3)	0.0369 (8)
H15	0.6547	1.1281	0.2575	0.044*
C16	0.1889 (4)	1.2224 (3)	−0.0291 (3)	0.0415 (9)
C17	0.1259 (4)	1.1460 (3)	−0.0847 (3)	0.0504 (10)
H17	0.1873	1.0824	−0.1364	0.061*
C18	−0.0290 (5)	1.1645 (4)	−0.0632 (4)	0.0592 (11)
H18	−0.0694	1.1118	−0.1022	0.071*
C19	0.0927 (4)	1.3150 (4)	0.0459 (4)	0.0603 (11)
H19	0.1307	1.3701	0.0843	0.072*
C20	−0.0611 (5)	1.3244 (4)	0.0630 (4)	0.0725 (13)
H20	−0.1250	1.3859	0.1161	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0427 (4)	0.0243 (3)	0.0432 (4)	−0.0055 (2)	−0.0207 (3)	0.0000 (3)
S1	0.0416 (6)	0.0364 (5)	0.0856 (8)	−0.0001 (4)	−0.0239 (5)	−0.0226 (5)
S2	0.0406 (6)	0.0945 (8)	0.0442 (6)	−0.0093 (5)	−0.0137 (5)	0.0163 (6)
O1	0.0421 (14)	0.0601 (14)	0.0723 (17)	−0.0193 (12)	−0.0018 (13)	−0.0171 (13)
O2	0.073 (2)	0.064 (2)	0.107 (3)	−0.0221 (16)	0.0062 (18)	0.0106 (18)
O3	0.069 (2)	0.089 (2)	0.148 (3)	0.0266 (18)	−0.036 (2)	0.000 (2)
N1	0.0358 (16)	0.0265 (14)	0.0415 (17)	−0.0050 (12)	−0.0151 (14)	−0.0005 (12)
N2	0.0396 (18)	0.052 (2)	0.076 (2)	−0.0107 (16)	−0.0115 (17)	−0.0103 (18)
N3	0.0353 (16)	0.0287 (14)	0.0370 (17)	−0.0077 (12)	−0.0128 (14)	−0.0015 (12)
N4	0.045 (2)	0.073 (2)	0.072 (3)	−0.0104 (19)	−0.0154 (19)	0.006 (2)
N5	0.0412 (16)	0.0535 (16)	0.0649 (18)	−0.0102 (15)	−0.0065 (15)	−0.0127 (14)
C1	0.0317 (19)	0.0398 (19)	0.046 (2)	−0.0101 (16)	−0.0133 (17)	−0.0003 (17)
C2	0.035 (2)	0.0339 (19)	0.047 (2)	−0.0037 (15)	−0.0122 (17)	−0.0078 (16)
C3	0.040 (2)	0.0269 (17)	0.044 (2)	−0.0049 (15)	−0.0170 (17)	−0.0005 (15)
C4	0.0293 (19)	0.0364 (19)	0.065 (3)	−0.0094 (15)	−0.0092 (18)	−0.0096 (18)
C5	0.037 (2)	0.0347 (19)	0.051 (2)	−0.0030 (16)	−0.0087 (18)	−0.0083 (17)
C6	0.038 (2)	0.0345 (18)	0.048 (2)	−0.0056 (15)	−0.0179 (17)	−0.0093 (16)
C7	0.049 (2)	0.040 (2)	0.069 (3)	−0.0125 (17)	−0.023 (2)	0.0068 (19)
C8	0.050 (2)	0.046 (2)	0.077 (3)	−0.0013 (19)	−0.030 (2)	−0.001 (2)
C9	0.054 (3)	0.044 (2)	0.065 (3)	−0.0131 (19)	−0.006 (2)	−0.004 (2)
C10	0.047 (2)	0.0341 (19)	0.054 (2)	−0.0027 (17)	−0.0130 (19)	−0.0068 (17)
C11	0.0350 (19)	0.0340 (18)	0.042 (2)	−0.0104 (15)	−0.0114 (17)	0.0008 (16)
C12	0.0321 (19)	0.0406 (19)	0.045 (2)	−0.0078 (15)	−0.0133 (17)	0.0028 (17)
C13	0.0323 (19)	0.044 (2)	0.037 (2)	−0.0021 (16)	−0.0084 (17)	−0.0008 (16)
C14	0.034 (2)	0.043 (2)	0.042 (2)	−0.0099 (16)	−0.0081 (17)	0.0042 (17)
C15	0.0321 (19)	0.0322 (18)	0.049 (2)	−0.0054 (15)	−0.0136 (18)	−0.0035 (17)
C16	0.037 (2)	0.050 (2)	0.036 (2)	−0.0015 (17)	−0.0137 (17)	0.0079 (17)
C17	0.053 (2)	0.045 (2)	0.051 (3)	−0.0016 (18)	−0.015 (2)	−0.0030 (19)
C18	0.062 (3)	0.061 (3)	0.068 (3)	−0.024 (2)	−0.032 (2)	0.006 (2)
C19	0.053 (3)	0.068 (3)	0.065 (3)	−0.006 (2)	−0.021 (2)	−0.018 (2)
C20	0.053 (3)	0.079 (3)	0.080 (3)	0.008 (2)	−0.015 (3)	−0.024 (3)

Geometric parameters (Å, º) top

Cu1—N3ⁱ	2.023 (3)	C4—H4	0.9300
Cu1—N3	2.023 (3)	C5—H5	0.9300
Cu1—N1ⁱ	2.047 (3)	C6—C10	1.370 (4)
Cu1—N1	2.047 (3)	C6—C7	1.390 (4)
Cu1—O1	2.558 (3)	C7—C8	1.373 (5)
Cu1—O1ⁱ	2.558 (3)	C7—H7	0.9300
S1—C3	1.754 (3)	C8—H8	0.9300
S1—C6	1.772 (3)	C9—C10	1.375 (5)
S2—C13	1.757 (3)	C9—H9	0.9300
S2—C16	1.775 (3)	C10—H10	0.9300
O1—N5	1.231 (3)	C11—C12	1.366 (4)
O2—N5	1.238 (4)	C11—H11	0.9300
O3—N5	1.216 (4)	C12—C13	1.387 (4)
N1—C5	1.331 (4)	C12—H12	0.9300
N1—C1	1.348 (4)	C13—C14	1.397 (4)
N2—C8	1.326 (4)	C14—C15	1.367 (4)
N2—C9	1.334 (4)	C14—H14	0.9300
N3—C15	1.344 (4)	C15—H15	0.9300
N3—C11	1.347 (4)	C16—C17	1.367 (4)
N4—C20	1.326 (5)	C16—C19	1.374 (5)
N4—C18	1.329 (5)	C17—C18	1.372 (5)
C1—C2	1.365 (4)	C17—H17	0.9300
C1—H1	0.9300	C18—H18	0.9300
C2—C3	1.383 (4)	C19—C20	1.375 (5)
C2—H2	0.9300	C19—H19	0.9300
C3—C4	1.383 (4)	C20—H20	0.9300
C4—C5	1.370 (4)

N3ⁱ—Cu1—N3	180.000 (1)	C10—C6—S1	119.4 (3)
N3ⁱ—Cu1—N1ⁱ	87.75 (10)	C7—C6—S1	122.4 (3)
N3—Cu1—N1ⁱ	92.25 (10)	C8—C7—C6	117.8 (3)
N3ⁱ—Cu1—N1	92.25 (10)	C8—C7—H7	121.1
N3—Cu1—N1	87.75 (10)	C6—C7—H7	121.1
N1ⁱ—Cu1—N1	180.00 (14)	N2—C8—C7	125.3 (3)
N3ⁱ—Cu1—O1	86.21 (9)	N2—C8—H8	117.3
N3—Cu1—O1	93.79 (9)	C7—C8—H8	117.3
N1ⁱ—Cu1—O1	91.99 (9)	N2—C9—C10	124.3 (3)
N1—Cu1—O1	88.01 (9)	N2—C9—H9	117.9
N3ⁱ—Cu1—O1ⁱ	93.79 (9)	C10—C9—H9	117.9
N3—Cu1—O1ⁱ	86.21 (9)	C6—C10—C9	119.0 (3)
N1ⁱ—Cu1—O1ⁱ	88.01 (9)	C6—C10—H10	120.5
N1—Cu1—O1ⁱ	91.99 (9)	C9—C10—H10	120.5
O1—Cu1—O1ⁱ	180.000 (1)	N3—C11—C12	123.8 (3)
C3—S1—C6	103.18 (15)	N3—C11—H11	118.1
C13—S2—C16	101.57 (15)	C12—C11—H11	118.1
N5—O1—Cu1	159.3 (2)	C11—C12—C13	119.2 (3)
C5—N1—C1	116.5 (3)	C11—C12—H12	120.4
C5—N1—Cu1	122.5 (2)	C13—C12—H12	120.4
C1—N1—Cu1	120.4 (2)	C12—C13—C14	117.5 (3)
C8—N2—C9	115.3 (3)	C12—C13—S2	124.7 (3)
C15—N3—C11	116.8 (3)	C14—C13—S2	117.8 (3)
C15—N3—Cu1	121.7 (2)	C15—C14—C13	119.6 (3)
C11—N3—Cu1	121.4 (2)	C15—C14—H14	120.2
C20—N4—C18	115.0 (3)	C13—C14—H14	120.2
O3—N5—O1	122.4 (4)	N3—C15—C14	123.1 (3)
O3—N5—O2	119.9 (4)	N3—C15—H15	118.4
O1—N5—O2	117.7 (3)	C14—C15—H15	118.4
N1—C1—C2	122.9 (3)	C17—C16—C19	117.9 (3)
N1—C1—H1	118.5	C17—C16—S2	121.4 (3)
C2—C1—H1	118.5	C19—C16—S2	120.7 (3)
C1—C2—C3	120.0 (3)	C16—C17—C18	119.1 (4)
C1—C2—H2	120.0	C16—C17—H17	120.4
C3—C2—H2	120.0	C18—C17—H17	120.4
C4—C3—C2	117.2 (3)	N4—C18—C17	124.5 (4)
C4—C3—S1	125.1 (3)	N4—C18—H18	117.7
C2—C3—S1	117.7 (2)	C17—C18—H18	117.7
C5—C4—C3	119.3 (3)	C16—C19—C20	118.4 (4)
C5—C4—H4	120.4	C16—C19—H19	120.8
C3—C4—H4	120.4	C20—C19—H19	120.8
N1—C5—C4	123.9 (3)	N4—C20—C19	125.0 (4)
N1—C5—H5	118.1	N4—C20—H20	117.5
C4—C5—H5	118.1	C19—C20—H20	117.5
C10—C6—C7	118.1 (3)

N3ⁱ—Cu1—O1—N5	−120.2 (7)	C3—S1—C6—C10	−127.2 (3)
N3—Cu1—O1—N5	59.8 (7)	C3—S1—C6—C7	55.2 (3)
N1ⁱ—Cu1—O1—N5	−32.6 (7)	C10—C6—C7—C8	2.2 (5)
N1—Cu1—O1—N5	147.4 (7)	S1—C6—C7—C8	179.8 (3)
N3—Cu1—N1—C5	−89.3 (3)	C9—N2—C8—C7	1.1 (6)
O1—Cu1—N1—C5	176.8 (3)	C6—C7—C8—N2	−3.0 (6)
O1ⁱ—Cu1—N1—C5	−3.2 (3)	C8—N2—C9—C10	1.6 (6)
N3ⁱ—Cu1—N1—C1	−98.5 (2)	C7—C6—C10—C9	0.2 (5)
N3—Cu1—N1—C1	81.5 (2)	S1—C6—C10—C9	−177.4 (3)
O1—Cu1—N1—C1	−12.3 (2)	N2—C9—C10—C6	−2.3 (6)
O1ⁱ—Cu1—N1—C1	167.7 (2)	C15—N3—C11—C12	−0.6 (4)
N1ⁱ—Cu1—N3—C15	57.4 (2)	Cu1—N3—C11—C12	176.5 (2)
N1—Cu1—N3—C15	−122.6 (2)	N3—C11—C12—C13	0.0 (5)
O1—Cu1—N3—C15	−34.7 (2)	C11—C12—C13—C14	0.5 (5)
O1ⁱ—Cu1—N3—C15	145.3 (2)	C11—C12—C13—S2	178.0 (2)
N1ⁱ—Cu1—N3—C11	−119.5 (2)	C16—S2—C13—C12	23.8 (3)
N1—Cu1—N3—C11	60.5 (2)	C16—S2—C13—C14	−158.6 (3)
O1—Cu1—N3—C11	148.3 (2)	C12—C13—C14—C15	−0.3 (5)
O1ⁱ—Cu1—N3—C11	−31.7 (2)	S2—C13—C14—C15	−178.0 (2)
Cu1—O1—N5—O3	166.9 (5)	C11—N3—C15—C14	0.8 (4)
Cu1—O1—N5—O2	−14.5 (9)	Cu1—N3—C15—C14	−176.3 (2)
C5—N1—C1—C2	3.5 (5)	C13—C14—C15—N3	−0.4 (5)
Cu1—N1—C1—C2	−167.9 (2)	C13—S2—C16—C17	−111.6 (3)
N1—C1—C2—C3	0.1 (5)	C13—S2—C16—C19	69.8 (3)
C1—C2—C3—C4	−3.6 (5)	C19—C16—C17—C18	−0.2 (5)
C1—C2—C3—S1	177.4 (2)	S2—C16—C17—C18	−179.0 (3)
C6—S1—C3—C4	16.6 (3)	C20—N4—C18—C17	−0.3 (6)
C6—S1—C3—C2	−164.5 (3)	C16—C17—C18—N4	−0.3 (6)
C2—C3—C4—C5	3.5 (5)	C17—C16—C19—C20	1.2 (5)
S1—C3—C4—C5	−177.6 (3)	S2—C16—C19—C20	179.9 (3)
C1—N1—C5—C4	−3.6 (5)	C18—N4—C20—C19	1.4 (6)
Cu1—N1—C5—C4	167.5 (2)	C16—C19—C20—N4	−1.9 (7)
C3—C4—C5—N1	0.2 (5)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.93	2.52	3.063 (4)	118
C5—H5···O2ⁱ	0.93	2.49	3.419 (4)	174
C5—H5···O1ⁱ	0.93	2.51	3.193 (4)	130
C14—H14···N4ⁱⁱ	0.93	2.47	3.279 (5)	146
C1—H1···O1	0.93	2.27	3.008 (4)	135

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

Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₁₀H₈N₂S)₄]
M_r	940.59
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.299 (4), 10.765 (5), 10.978 (5)
α, β, γ (°)	84.408 (6), 73.759 (6), 79.180 (6)
V (Å³)	1035.1 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.21 × 0.19 × 0.17

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.847, 0.874
No. of measured, independent and observed [I > 2σ(I)] reflections	7479, 3728, 2392
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.100, 0.90
No. of reflections	3679
No. of parameters	277
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.33

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.93	2.52	3.063 (4)	117.7
C5—H5···O2ⁱ	0.93	2.49	3.419 (4)	174.0
C5—H5···O1ⁱ	0.93	2.51	3.193 (4)	130.3
C14—H14···N4ⁱⁱ	0.93	2.47	3.279 (5)	146.0
C1—H1···O1	0.93	2.27	3.008 (4)	135.4

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

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2000). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Muthu, S., Ni, Z. & Vittal, J. J. (2005). Inorg. Chim. Acta, 358, 595–605 Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wen, Y.-H., Cheng, J.-K., Zhang, J., Li, Z.-J. & Yao, Y.-G. (2004). Acta Cryst. C60, m618–m619. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Xu, Q.-F., Zhou, Q.-X., Lu, J.-M., Xia, X.-W., Wang, L.-H. & Zhang, Y. (2007). Polyhedron, 26, 4849–4859 Web of Science CSD CrossRef CAS Google Scholar
Zhang, J., Cheng, J.-K., Qin, Y.-Y., Li, Z.-J. & Yao, Y.-G. (2008). Inorg. Chem. Commun. 11, 164–166 Web of Science CSD CrossRef CAS Google Scholar

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Volume 66| Part 5| May 2010| Page m487

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