[μ-4-Benzoyl-1-(1-oxido-2-naphthyl­carbon­yl)thio­semicarbazidato(4−)]bis­[pyridine­copper(II)]

Zhang, W.; Gao, J.-P.; Shi, X.-F.; Li, D.-C.

doi:10.1107/S1600536809040951

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1363

https://doi.org/10.1107/S1600536809040951

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[μ-4-Benzoyl-1-(1-oxido-2-naphthylcarbonyl)thiosemicarbazidato(4−)]bis[pyridinecopper(II)]

Wen Zhang,^a Jin-Ping Gao,^a Xue-Feng Shi ^a and Da-Cheng Li ^a ^*

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: lidacheng@lcu.edu.cn

(Received 12 September 2009; accepted 7 October 2009; online 17 October 2009)

In the title dinuclear complex, [Cu₂(C₁₉H₁₁N₃O₃S)(C₅H₅N)₂], the two Cu^II centers have different coordination environments, viz. N₂OS and N₂O₂, each exhibiting a distorted square-planar geometry. π–π interactions between the aromatic rings of neighbouring complexes [centroid–centroid distance = 3.856 (5) Å] link pairs of molecules into centrosymmetric dimers, which are further packed into stacks along the b axis with relatively short Cu⋯Cu separations of 3.482 (1) Å. Weak intermolecular C—H⋯N hydrogen bonds help to consolidate the crystal packing.

Related literature

For details of the synthesis, see: Chen et al. (2007 ). For pharmacological properties of complexes of acylthiosemicarbazides, see: Wei et al. (1995 ).

Experimental

Crystal data

[Cu₂(C₁₉H₁₁N₃O₃S)(C₅H₅N)₂]
M_r = 646.65
Monoclinic, P 2₁ /n
a = 12.7621 (14) Å
b = 9.2609 (11) Å
c = 21.683 (2) Å
β = 92.168 (2)°
V = 2560.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.79 mm⁻¹
T = 298 K
0.48 × 0.42 × 0.21 mm

Data collection

Bruker SMART 1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.481, T_max = 0.706
12450 measured reflections
4504 independent reflections
2532 reflections with I > 2σ(I)
R_int = 0.064

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.161
S = 1.00
4504 reflections
361 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C23—H23⋯N3ⁱ	0.93	2.53	3.451 (8)	173
Symmetry code: (i) -x+1, -y+1, -z+2.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809040951/cv2616sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809040951/cv2616Isup2.hkl

checkCIF report

Comment top

Acylthiosemicarbazides possess strong coordination ability, and their complexes exhibit various biological activities (Wei et al., 1995). Herewith we present the crystal structure of the title compound (I) - new dinuclear complex of naphthalenecarbothiosemicarbazide.

In (I) (Fig. 1), two Cu centers have different coordination environments - N₂OS and N₂O₂, respectively, exhibiting distorted square-planar geometry each. The Cu1 atom is coordinated with one phenolate oxygen, one nitrogen atom of pyridine, one sulfur atom and one hydrazide nitrogen atom, forming five-membered and six-membered chelating rings. The Cu2 atom is coordinated with two carbonyl oxygen atoms, one nitrogen atom of pyridine and one hydrazide nitrogen atom, forming five-membered and six-membered chelating rings too. π–π interactions between the aromatic rings of neighbouring complexes [centroid-to centroid distance = 3.856 (5) Å] link two molecules into centrosymmetric dimers, which are further packed into stacks along b axis with relatively short Cu···Cu separation of 3.482 (1) Å. Weak intermolecular C—H···N hydrogen bonds (Table 1) help to consolidate the crystal packing.

Related literature top

For details of the synthesis, see: Chen et al. (2007). For pharmacological properties of complexes of acylthiosemicarbazides, see: Wei et al. (1995).

Experimental top

1.406 g (10 mmol) of benzoyl chloride was added dropwise to a stirred solution of acetonitrile (50 ml) containing 0.981 g (10 mmol) of potassium thiocyanate. Stirring was continued for 1 h, and the solution was slowly warmed to ambient temperature. Then 1.68 g (10 mmol) of 1-hydroxy-2-naphthalenecarbohydrazide was added to the mixture, with stirring being continued for 5 h. After staying for overnight at refrigerator, the resulting yellow precipitate was filtered and rinsed with diethyl ether, then dried in vacuo, 87% yield. m.p. 225–227 C. The solution of CuNO₃(0.04 g, 0.2 mmol) in pyridine(10 ml) was added to the mixture of N-benzoyl-1-hydroxy-2-naphthalenecarbothiosemicarbazide (0.073 g, 0.2 mmol)and sodium methylate(0.0324 g,0.6 mmol)in DMSO(10 ml). A green solution was obtained after refluxing for 3 h. After filtrated,dimethyl ether was slowly diffused into the filtrate, then crystals suitable for X-ray diffraction were obtained after two weeks (m.p. >400 K) (Chen et al. 2007) Elemental analysis calculated for Cu₂C₂₉H₂₁N₅O₃S₁: C, 53.64; H, 3.29; N, 9.43. Found (%): C, 53.86; H, 3.27; N, 10.83.

Structure description top

For details of the synthesis, see: Chen et al. (2007). For pharmacological properties of complexes of acylthiosemicarbazides, see: Wei et al. (1995).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. H atoms have been omitted for clarity.

[µ-4-Benzoyl-1-(1-oxido-2- naphthylcarbonyl)thiosemicarbazidato(4-)]bis[pyridinecopper(II)] top

Crystal data top

[Cu₂(C₁₉H₁₁N₃O₃S)(C₅H₅N)₂]	F(000) = 1312
M_r = 646.65	D_x = 1.677 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.7621 (14) Å	Cell parameters from 2465 reflections
b = 9.2609 (11) Å	θ = 2.4–22.0°
c = 21.683 (2) Å	µ = 1.79 mm⁻¹
β = 92.168 (2)°	T = 298 K
V = 2560.9 (5) Å³	Block, green
Z = 4	0.48 × 0.42 × 0.21 mm

Data collection top

Bruker SMART 1000 diffractometer	4504 independent reflections
Radiation source: fine-focus sealed tube	2532 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.064
φ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.481, T_max = 0.706	k = −9→11
12450 measured reflections	l = −22→25

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0835P)²], where P = (F_o² + 2F_c²)/3
4504 reflections	(Δ/σ)_max = 0.001
361 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu₂(C₁₉H₁₁N₃O₃S)(C₅H₅N)₂]	V = 2560.9 (5) Å³
M_r = 646.65	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.7621 (14) Å	µ = 1.79 mm⁻¹
b = 9.2609 (11) Å	T = 298 K
c = 21.683 (2) Å	0.48 × 0.42 × 0.21 mm
β = 92.168 (2)°

Data collection top

Bruker SMART 1000 diffractometer	4504 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2532 reflections with I > 2σ(I)
T_min = 0.481, T_max = 0.706	R_int = 0.064
12450 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.00	Δρ_max = 0.48 e Å⁻³
4504 reflections	Δρ_min = −0.42 e Å⁻³
361 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.28704 (5)	0.20605 (8)	1.04261 (3)	0.0436 (3)
Cu2	−0.01899 (6)	0.36338 (9)	0.94557 (3)	0.0496 (3)
S1	0.33285 (12)	0.34418 (19)	0.96271 (7)	0.0508 (5)
N1	0.1252 (4)	0.3405 (5)	0.9676 (2)	0.0431 (12)
N2	0.1458 (4)	0.2438 (5)	1.0159 (2)	0.0416 (12)
N3	0.1971 (4)	0.4823 (5)	0.8891 (2)	0.0418 (12)
N4	0.4361 (4)	0.1750 (5)	1.0747 (2)	0.0432 (12)
N5	−0.1717 (4)	0.3765 (6)	0.9268 (2)	0.0469 (13)
O1	0.0142 (3)	0.4972 (5)	0.88313 (19)	0.0540 (12)
O2	−0.0331 (3)	0.2309 (5)	1.0121 (2)	0.0585 (12)
O3	0.2433 (3)	0.0804 (5)	1.10597 (19)	0.0526 (11)
C1	0.2062 (5)	0.3912 (6)	0.9385 (3)	0.0415 (15)
C2	0.1062 (5)	0.5270 (7)	0.8657 (3)	0.0446 (15)
C3	0.1091 (5)	0.6286 (6)	0.8125 (3)	0.0407 (14)
C4	0.0197 (5)	0.6999 (8)	0.7931 (3)	0.0595 (19)
H4	−0.0429	0.6815	0.8122	0.071*
C5	0.0213 (6)	0.7982 (8)	0.7456 (3)	0.067 (2)
H5	−0.0396	0.8474	0.7337	0.080*
C6	0.1120 (5)	0.8241 (7)	0.7158 (3)	0.0542 (18)
H6	0.1135	0.8910	0.6839	0.065*
C7	0.2003 (5)	0.7498 (8)	0.7339 (3)	0.0561 (18)
H7	0.2620	0.7652	0.7134	0.067*
C8	0.1998 (5)	0.6532 (7)	0.7815 (3)	0.0527 (17)
H8	0.2609	0.6038	0.7931	0.063*
C9	0.0565 (5)	0.1886 (7)	1.0356 (3)	0.0488 (16)
C10	0.1489 (5)	0.0355 (7)	1.1163 (3)	0.0459 (16)
C11	0.0576 (5)	0.0804 (7)	1.0840 (3)	0.0466 (16)
C12	−0.0399 (5)	0.0174 (8)	1.0983 (3)	0.066 (2)
H12	−0.0999	0.0467	1.0760	0.079*
C13	−0.0496 (6)	−0.0831 (9)	1.1429 (3)	0.070 (2)
H13	−0.1151	−0.1215	1.1507	0.084*
C14	0.0390 (5)	−0.1290 (7)	1.1771 (3)	0.0552 (18)
C15	0.1381 (5)	−0.0719 (7)	1.1649 (3)	0.0460 (16)
C16	0.2265 (5)	−0.1219 (7)	1.1990 (3)	0.0511 (17)
H16	0.2925	−0.0856	1.1908	0.061*
C17	0.2165 (6)	−0.2236 (8)	1.2443 (3)	0.0607 (19)
H17	0.2755	−0.2570	1.2665	0.073*
C18	0.1178 (6)	−0.2766 (8)	1.2570 (3)	0.064 (2)
H18	0.1110	−0.3431	1.2888	0.077*
C19	0.0320 (6)	−0.2337 (8)	1.2244 (3)	0.0615 (19)
H19	−0.0328	−0.2733	1.2329	0.074*
C20	0.4648 (6)	0.0479 (8)	1.0975 (3)	0.0620 (19)
H20	0.4152	−0.0257	1.0978	0.074*
C21	0.5641 (6)	0.0195 (9)	1.1207 (4)	0.075 (2)
H21	0.5816	−0.0723	1.1351	0.090*
C22	0.6363 (6)	0.1260 (9)	1.1223 (3)	0.071 (2)
H22	0.7040	0.1089	1.1380	0.085*
C23	0.6084 (5)	0.2589 (8)	1.1005 (3)	0.0593 (19)
H23	0.6562	0.3347	1.1019	0.071*
C24	0.5086 (5)	0.2789 (7)	1.0765 (3)	0.0497 (16)
H24	0.4905	0.3693	1.0606	0.060*
C25	−0.2383 (5)	0.2922 (8)	0.9581 (3)	0.0553 (18)
H25	−0.2114	0.2330	0.9896	0.066*
C26	−0.3436 (5)	0.2916 (8)	0.9450 (3)	0.060 (2)
H26	−0.3874	0.2313	0.9667	0.072*
C27	−0.3842 (5)	0.3799 (9)	0.8998 (3)	0.063 (2)
H27	−0.4559	0.3805	0.8904	0.075*
C28	−0.3189 (5)	0.4669 (9)	0.8687 (3)	0.065 (2)
H28	−0.3447	0.5290	0.8380	0.078*
C29	−0.2128 (5)	0.4602 (8)	0.8839 (3)	0.0571 (18)
H29	−0.1679	0.5190	0.8623	0.069*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0386 (4)	0.0450 (5)	0.0473 (5)	−0.0080 (4)	0.0043 (3)	0.0035 (4)
Cu2	0.0350 (4)	0.0602 (6)	0.0536 (5)	−0.0116 (4)	0.0012 (4)	0.0081 (4)
S1	0.0370 (9)	0.0626 (12)	0.0528 (10)	−0.0031 (8)	0.0045 (7)	0.0147 (8)
N1	0.038 (3)	0.044 (3)	0.047 (3)	−0.012 (2)	−0.001 (2)	0.008 (2)
N2	0.039 (3)	0.051 (3)	0.035 (3)	−0.010 (2)	0.000 (2)	0.011 (2)
N3	0.036 (3)	0.046 (3)	0.043 (3)	−0.005 (2)	0.000 (2)	0.009 (2)
N4	0.043 (3)	0.036 (3)	0.050 (3)	−0.003 (2)	0.002 (2)	0.005 (2)
N5	0.038 (3)	0.056 (4)	0.046 (3)	−0.006 (3)	−0.004 (3)	−0.005 (3)
O1	0.033 (2)	0.065 (3)	0.063 (3)	−0.012 (2)	−0.001 (2)	0.015 (2)
O2	0.042 (3)	0.075 (3)	0.059 (3)	−0.012 (2)	0.001 (2)	0.017 (2)
O3	0.038 (2)	0.061 (3)	0.059 (3)	−0.009 (2)	0.003 (2)	0.014 (2)
C1	0.043 (4)	0.038 (4)	0.043 (4)	−0.004 (3)	0.000 (3)	−0.005 (3)
C2	0.039 (4)	0.048 (4)	0.047 (4)	−0.009 (3)	0.001 (3)	−0.004 (3)
C3	0.038 (3)	0.042 (4)	0.041 (3)	−0.006 (3)	−0.005 (3)	0.004 (3)
C4	0.041 (4)	0.080 (5)	0.058 (4)	−0.003 (4)	0.006 (3)	0.011 (4)
C5	0.050 (4)	0.082 (6)	0.069 (5)	0.011 (4)	−0.003 (4)	0.019 (4)
C6	0.060 (5)	0.055 (5)	0.048 (4)	−0.010 (4)	−0.002 (3)	0.011 (3)
C7	0.044 (4)	0.068 (5)	0.056 (4)	−0.001 (4)	0.007 (3)	0.009 (4)
C8	0.046 (4)	0.059 (5)	0.053 (4)	0.001 (3)	−0.001 (3)	0.006 (3)
C9	0.042 (4)	0.060 (5)	0.045 (4)	−0.012 (3)	0.006 (3)	−0.003 (3)
C10	0.044 (4)	0.052 (4)	0.042 (4)	−0.013 (3)	0.003 (3)	−0.005 (3)
C11	0.044 (4)	0.053 (4)	0.043 (4)	−0.015 (3)	0.009 (3)	0.005 (3)
C12	0.044 (4)	0.087 (6)	0.067 (5)	−0.021 (4)	0.003 (3)	0.024 (4)
C13	0.052 (5)	0.091 (6)	0.069 (5)	−0.032 (4)	0.015 (4)	0.020 (4)
C14	0.054 (4)	0.053 (5)	0.059 (4)	−0.016 (4)	0.008 (4)	0.010 (3)
C15	0.060 (4)	0.042 (4)	0.037 (4)	−0.007 (3)	0.013 (3)	−0.003 (3)
C16	0.048 (4)	0.056 (5)	0.050 (4)	−0.005 (3)	0.008 (3)	0.005 (3)
C17	0.070 (5)	0.058 (5)	0.054 (4)	0.012 (4)	0.006 (4)	0.002 (4)
C18	0.079 (6)	0.057 (5)	0.057 (5)	0.000 (4)	0.026 (4)	0.012 (4)
C19	0.060 (5)	0.061 (5)	0.065 (5)	−0.016 (4)	0.011 (4)	0.008 (4)
C20	0.061 (5)	0.049 (5)	0.075 (5)	−0.008 (4)	−0.001 (4)	0.008 (4)
C21	0.067 (5)	0.050 (5)	0.107 (6)	0.010 (4)	−0.005 (5)	0.021 (4)
C22	0.047 (4)	0.079 (6)	0.087 (6)	0.007 (4)	−0.005 (4)	0.006 (5)
C23	0.048 (4)	0.061 (5)	0.068 (5)	−0.016 (4)	−0.005 (4)	0.006 (4)
C24	0.045 (4)	0.046 (4)	0.059 (4)	−0.003 (3)	0.011 (3)	0.011 (3)
C25	0.045 (4)	0.072 (5)	0.050 (4)	−0.013 (4)	0.011 (3)	−0.003 (4)
C26	0.048 (4)	0.081 (6)	0.053 (4)	−0.022 (4)	0.016 (3)	−0.011 (4)
C27	0.039 (4)	0.088 (6)	0.062 (5)	−0.014 (4)	0.006 (4)	−0.022 (4)
C28	0.036 (4)	0.093 (6)	0.067 (5)	−0.010 (4)	−0.005 (4)	−0.009 (4)
C29	0.039 (4)	0.073 (5)	0.060 (4)	−0.010 (4)	0.005 (3)	−0.002 (4)

Geometric parameters (Å, º) top

Cu1—O3	1.900 (4)	C10—C15	1.460 (8)
Cu1—N2	1.905 (5)	C11—C12	1.420 (8)
Cu1—N4	2.022 (5)	C12—C13	1.350 (9)
Cu1—S1	2.2487 (17)	C12—H12	0.9300
Cu2—O1	1.895 (4)	C13—C14	1.395 (9)
Cu2—N1	1.896 (5)	C13—H13	0.9300
Cu2—O2	1.908 (4)	C14—C15	1.405 (8)
Cu2—N5	1.980 (5)	C14—C19	1.415 (9)
S1—C1	1.736 (6)	C15—C16	1.404 (8)
N1—C1	1.317 (7)	C16—C17	1.370 (9)
N1—N2	1.395 (6)	C16—H16	0.9300
N2—C9	1.333 (7)	C17—C18	1.390 (9)
N3—C2	1.314 (7)	C17—H17	0.9300
N3—C1	1.366 (7)	C18—C19	1.341 (9)
N4—C20	1.322 (8)	C18—H18	0.9300
N4—C24	1.335 (7)	C19—H19	0.9300
N5—C29	1.305 (8)	C20—C21	1.372 (9)
N5—C25	1.355 (8)	C20—H20	0.9300
O1—C2	1.278 (7)	C21—C22	1.349 (10)
O2—C9	1.295 (7)	C21—H21	0.9300
O3—C10	1.302 (7)	C22—C23	1.361 (10)
C2—C3	1.490 (8)	C22—H22	0.9300
C3—C4	1.372 (8)	C23—C24	1.371 (8)
C3—C8	1.379 (8)	C23—H23	0.9300
C4—C5	1.375 (9)	C24—H24	0.9300
C4—H4	0.9300	C25—C26	1.363 (9)
C5—C6	1.368 (9)	C25—H25	0.9300
C5—H5	0.9300	C26—C27	1.364 (10)
C6—C7	1.365 (8)	C26—H26	0.9300
C6—H6	0.9300	C27—C28	1.356 (9)
C7—C8	1.367 (9)	C27—H27	0.9300
C7—H7	0.9300	C28—C29	1.384 (8)
C8—H8	0.9300	C28—H28	0.9300
C9—C11	1.451 (8)	C29—H29	0.9300
C10—C11	1.400 (8)

O3—Cu1—N2	91.84 (18)	C11—C10—C15	117.6 (5)
O3—Cu1—N4	87.81 (18)	C10—C11—C12	119.3 (6)
N2—Cu1—N4	176.7 (2)	C10—C11—C9	123.5 (5)
O3—Cu1—S1	175.88 (14)	C12—C11—C9	117.2 (6)
N2—Cu1—S1	86.09 (14)	C13—C12—C11	122.9 (6)
N4—Cu1—S1	94.46 (14)	C13—C12—H12	118.5
O1—Cu2—N1	90.70 (19)	C11—C12—H12	118.5
O1—Cu2—O2	172.29 (18)	C12—C13—C14	119.8 (6)
N1—Cu2—O2	81.73 (19)	C12—C13—H13	120.1
O1—Cu2—N5	93.3 (2)	C14—C13—H13	120.1
N1—Cu2—N5	176.0 (2)	C13—C14—C15	120.1 (6)
O2—Cu2—N5	94.3 (2)	C13—C14—C19	121.5 (6)
C1—S1—Cu1	96.3 (2)	C15—C14—C19	118.4 (6)
C1—N1—N2	117.4 (5)	C16—C15—C14	119.2 (6)
C1—N1—Cu2	127.7 (4)	C16—C15—C10	120.6 (6)
N2—N1—Cu2	114.4 (3)	C14—C15—C10	120.2 (6)
C9—N2—N1	110.4 (5)	C17—C16—C15	120.6 (6)
C9—N2—Cu1	129.9 (4)	C17—C16—H16	119.7
N1—N2—Cu1	119.7 (3)	C15—C16—H16	119.7
C2—N3—C1	123.0 (5)	C16—C17—C18	119.6 (7)
C20—N4—C24	116.7 (6)	C16—C17—H17	120.2
C20—N4—Cu1	119.9 (4)	C18—C17—H17	120.2
C24—N4—Cu1	123.3 (4)	C19—C18—C17	121.2 (7)
C29—N5—C25	117.2 (6)	C19—C18—H18	119.4
C29—N5—Cu2	123.2 (4)	C17—C18—H18	119.4
C25—N5—Cu2	119.5 (5)	C18—C19—C14	120.9 (7)
C2—O1—Cu2	125.8 (4)	C18—C19—H19	119.6
C9—O2—Cu2	112.6 (4)	C14—C19—H19	119.6
C10—O3—Cu1	128.3 (4)	N4—C20—C21	123.1 (7)
N1—C1—N3	123.4 (5)	N4—C20—H20	118.4
N1—C1—S1	120.3 (5)	C21—C20—H20	118.4
N3—C1—S1	116.3 (4)	C22—C21—C20	119.4 (7)
O1—C2—N3	128.8 (6)	C22—C21—H21	120.3
O1—C2—C3	114.5 (5)	C20—C21—H21	120.3
N3—C2—C3	116.7 (5)	C21—C22—C23	118.8 (7)
C4—C3—C8	118.3 (6)	C21—C22—H22	120.6
C4—C3—C2	119.8 (6)	C23—C22—H22	120.6
C8—C3—C2	121.8 (6)	C22—C23—C24	118.8 (7)
C3—C4—C5	120.9 (6)	C22—C23—H23	120.6
C3—C4—H4	119.6	C24—C23—H23	120.6
C5—C4—H4	119.6	N4—C24—C23	123.1 (6)
C6—C5—C4	120.5 (7)	N4—C24—H24	118.4
C6—C5—H5	119.8	C23—C24—H24	118.4
C4—C5—H5	119.8	N5—C25—C26	122.0 (7)
C7—C6—C5	118.7 (6)	N5—C25—H25	119.0
C7—C6—H6	120.7	C26—C25—H25	119.0
C5—C6—H6	120.7	C25—C26—C27	119.5 (7)
C6—C7—C8	121.4 (6)	C25—C26—H26	120.2
C6—C7—H7	119.3	C27—C26—H26	120.2
C8—C7—H7	119.3	C28—C27—C26	119.3 (7)
C7—C8—C3	120.3 (6)	C28—C27—H27	120.3
C7—C8—H8	119.9	C26—C27—H27	120.3
C3—C8—H8	119.9	C27—C28—C29	117.9 (7)
O2—C9—N2	120.7 (6)	C27—C28—H28	121.0
O2—C9—C11	118.5 (5)	C29—C28—H28	121.0
N2—C9—C11	120.8 (6)	N5—C29—C28	124.0 (7)
O3—C10—C11	125.2 (6)	N5—C29—H29	118.0
O3—C10—C15	117.1 (6)	C28—C29—H29	118.0

O3—Cu1—S1—C1	63.1 (19)	C3—C4—C5—C6	1.7 (11)
N2—Cu1—S1—C1	3.2 (2)	C4—C5—C6—C7	0.4 (11)
N4—Cu1—S1—C1	−173.5 (2)	C5—C6—C7—C8	−1.3 (11)
O1—Cu2—N1—C1	−8.4 (5)	C6—C7—C8—C3	0.0 (11)
O2—Cu2—N1—C1	173.0 (6)	C4—C3—C8—C7	2.0 (10)
N5—Cu2—N1—C1	167 (3)	C2—C3—C8—C7	−178.4 (6)
O1—Cu2—N1—N2	−179.8 (4)	Cu2—O2—C9—N2	4.1 (8)
O2—Cu2—N1—N2	1.6 (4)	Cu2—O2—C9—C11	−176.1 (5)
N5—Cu2—N1—N2	−5 (3)	N1—N2—C9—O2	−2.8 (8)
C1—N1—N2—C9	−172.4 (5)	Cu1—N2—C9—O2	178.5 (4)
Cu2—N1—N2—C9	0.0 (6)	N1—N2—C9—C11	177.5 (5)
C1—N1—N2—Cu1	6.5 (7)	Cu1—N2—C9—C11	−1.2 (9)
Cu2—N1—N2—Cu1	178.9 (2)	Cu1—O3—C10—C11	−4.5 (9)
O3—Cu1—N2—C9	−3.5 (6)	Cu1—O3—C10—C15	174.4 (4)
N4—Cu1—N2—C9	−87 (3)	O3—C10—C11—C12	177.1 (6)
S1—Cu1—N2—C9	172.9 (6)	C15—C10—C11—C12	−1.9 (9)
O3—Cu1—N2—N1	177.9 (4)	O3—C10—C11—C9	−2.4 (11)
N4—Cu1—N2—N1	94 (3)	C15—C10—C11—C9	178.6 (6)
S1—Cu1—N2—N1	−5.7 (4)	O2—C9—C11—C10	−174.5 (6)
O3—Cu1—N4—C20	34.8 (5)	N2—C9—C11—C10	5.3 (10)
N2—Cu1—N4—C20	119 (3)	O2—C9—C11—C12	6.0 (9)
S1—Cu1—N4—C20	−141.7 (5)	N2—C9—C11—C12	−174.2 (6)
O3—Cu1—N4—C24	−142.7 (5)	C10—C11—C12—C13	1.3 (12)
N2—Cu1—N4—C24	−59 (3)	C9—C11—C12—C13	−179.2 (7)
S1—Cu1—N4—C24	40.7 (5)	C11—C12—C13—C14	0.0 (12)
O1—Cu2—N5—C29	−0.9 (5)	C12—C13—C14—C15	−0.6 (12)
N1—Cu2—N5—C29	−176 (3)	C12—C13—C14—C19	179.8 (7)
O2—Cu2—N5—C29	177.8 (5)	C13—C14—C15—C16	−178.6 (7)
O1—Cu2—N5—C25	177.0 (5)	C19—C14—C15—C16	1.0 (10)
N1—Cu2—N5—C25	2 (3)	C13—C14—C15—C10	−0.1 (10)
O2—Cu2—N5—C25	−4.3 (5)	C19—C14—C15—C10	179.6 (6)
N1—Cu2—O1—C2	7.9 (5)	O3—C10—C15—C16	0.9 (9)
O2—Cu2—O1—C2	18.4 (18)	C11—C10—C15—C16	179.9 (6)
N5—Cu2—O1—C2	−171.8 (5)	O3—C10—C15—C14	−177.7 (6)
O1—Cu2—O2—C9	−13.7 (18)	C11—C10—C15—C14	1.3 (9)
N1—Cu2—O2—C9	−3.0 (4)	C14—C15—C16—C17	−0.9 (10)
N5—Cu2—O2—C9	176.6 (4)	C10—C15—C16—C17	−179.5 (6)
N2—Cu1—O3—C10	6.4 (5)	C15—C16—C17—C18	−0.7 (10)
N4—Cu1—O3—C10	−176.9 (5)	C16—C17—C18—C19	2.3 (11)
S1—Cu1—O3—C10	−53 (2)	C17—C18—C19—C14	−2.2 (11)
N2—N1—C1—N3	177.5 (5)	C13—C14—C19—C18	−179.8 (7)
Cu2—N1—C1—N3	6.3 (9)	C15—C14—C19—C18	0.5 (11)
N2—N1—C1—S1	−3.0 (8)	C24—N4—C20—C21	−1.6 (10)
Cu2—N1—C1—S1	−174.2 (3)	Cu1—N4—C20—C21	−179.3 (6)
C2—N3—C1—N1	−0.4 (9)	N4—C20—C21—C22	1.9 (12)
C2—N3—C1—S1	180.0 (5)	C20—C21—C22—C23	−0.3 (12)
Cu1—S1—C1—N1	−1.1 (5)	C21—C22—C23—C24	−1.4 (11)
Cu1—S1—C1—N3	178.5 (4)	C20—N4—C24—C23	−0.2 (9)
Cu2—O1—C2—N3	−5.5 (10)	Cu1—N4—C24—C23	177.4 (5)
Cu2—O1—C2—C3	175.8 (4)	C22—C23—C24—N4	1.7 (10)
C1—N3—C2—O1	0.1 (10)	C29—N5—C25—C26	1.4 (10)
C1—N3—C2—C3	178.8 (5)	Cu2—N5—C25—C26	−176.7 (5)
O1—C2—C3—C4	10.6 (9)	N5—C25—C26—C27	−1.2 (11)
N3—C2—C3—C4	−168.2 (6)	C25—C26—C27—C28	0.0 (11)
O1—C2—C3—C8	−168.9 (6)	C26—C27—C28—C29	0.9 (11)
N3—C2—C3—C8	12.2 (9)	C25—N5—C29—C28	−0.4 (10)
C8—C3—C4—C5	−2.9 (10)	Cu2—N5—C29—C28	177.6 (5)
C2—C3—C4—C5	177.5 (6)	C27—C28—C29—N5	−0.7 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···N3ⁱ	0.93	2.53	3.451 (8)	173

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₉H₁₁N₃O₃S)(C₅H₅N)₂]
M_r	646.65
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	12.7621 (14), 9.2609 (11), 21.683 (2)
β (°)	92.168 (2)
V (Å³)	2560.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.79
Crystal size (mm)	0.48 × 0.42 × 0.21

Data collection
Diffractometer	Bruker SMART 1000
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.481, 0.706
No. of measured, independent and observed [I > 2σ(I)] reflections	12450, 4504, 2532
R_int	0.064
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.161, 1.00
No. of reflections	4504
No. of parameters	361
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.42

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23···N3ⁱ	0.93	2.53	3.451 (8)	172.7

Symmetry code: (i) −x+1, −y+1, −z+2.

Acknowledgements

We acknowledge the National Natural Science Foundation of China for financial support (grant No. 20671048).

References

Chen, Y.-T., Dou, J.-M., Li, D.-C., Wang, D.-Q. & Zhu, Y.-H. (2007). Acta Cryst. E63, m2503–m2504. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Wei, T. B., Chen, J. C., Yang, S. Y. & Wang, X. C. (1995). Chem. Res. Appl. 7, 194–198. CAS Google Scholar

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

[μ-4-Benzoyl-1-(1-oxido-2-naphthyl­carbon­yl)thio­semicarbazidato(4−)]bis­­[pyridine­copper(II)]

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

[μ-4-Benzoyl-1-(1-oxido-2-naphthylcarbonyl)thiosemicarbazidato(4−)]bis[pyridinecopper(II)]