catena-Poly[[bis­(nitrato-κ2O,O′)copper(II)]-μ-2,2′-(ethane-1,2-diyldithio)di-1,3,4-thia­diazole-κ2N4:N4′]

Huang, H.-M.; Ju, F.-Y.; Wang, J.-G.; Qin, J.-H.

doi:10.1107/S1600536808041202

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m80-m81

doi:10.1107/S1600536808041202

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catena-Poly[[bis(nitrato-κ²O,O′)copper(II)]-μ-2,2′-(ethane-1,2-diyldithio)di-1,3,4-thiadiazole-κ²N⁴:N^4′]

Hua-Ming Huang,^a Feng-Yang Ju,^a Jian-Ge Wang ^a and Jian-Hua Qin ^a ^*

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China
^*Correspondence e-mail: jh_q128105@126.com

(Received 20 November 2008; accepted 6 December 2008; online 17 December 2008)

In the title compound, [Cu(NO₃)₂(C₆H₆N₄S₄)]_n, the Cu^II atom, occupying a crystallographic inversion centre, is six-coordinated by two N atoms of two 2,2′-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands in trans positions, and four O atoms from two symmetry-related opposite nitrate anions, which are asymmetrically bonded, resulting in a strong distorted octahedral geometry of the central atom. The ethane group is equally disordered over two sites via another inversion centre. The bridging bidentate 2,2′-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands link the Cu^II centres into a one-dimensional chain. The chains are interconnected via intermolecular S⋯O interactions [3.044 (4) and 3.084 (5) Å] and weak C—H⋯O hydrogen bonds, generating a three-dimensional supramolecular structure.

Related literature

For related catena-poly Cu(II) complexes, see, for example: Wang et al. (2008 ). For elongated Cu—O bonds see, for example: Lee & Barboiu (2004 ); Youngme et al. (2007 ). For C—H⋯O hydrogen bonds, see: Bhogala et al. (2005 ).

Experimental

Crystal data

[Cu(NO₃)₂(C₆H₆N₄S₄)]
M_r = 449.95
Triclinic, $[P \overline 1]$
a = 5.2143 (8) Å
b = 7.0214 (10) Å
c = 10.6476 (16) Å
α = 105.144 (2)°
β = 100.000 (2)°
γ = 93.958 (2)°
V = 367.88 (9) Å³
Z = 1
Mo Kα radiation
μ = 2.09 mm⁻¹
T = 296 (2) K
0.48 × 0.29 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.432, T_max = 0.924
1983 measured reflections
1336 independent reflections
1273 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.173
S = 1.05
1336 reflections
110 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.86 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Cu1—O1	2.588 (4)
Cu1—O3	1.971 (3)
Cu1—N2	2.007 (4)

O1—Cu1—O3	54.74 (14)
N2—Cu1—O3	89.02 (15)
O1—Cu1—O3ⁱ	125.26 (14)
Symmetry code: (i) -x, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O1ⁱⁱ	0.93	2.49	3.083 (6)	122
Symmetry code: (ii) x+1, y, z.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELX97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041202/si2137sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041202/si2137Isup2.hkl

checkCIF report

Comment top

As shown in Fig. 1, the copper atom is coordinated by four O atoms from two chelating nitrate anions and two N atoms from two C_i symmetry-related 2,2'-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands. The geometry around the Cu(II) atom appears to be strong distorted octahedral, which is shown with the angle O1—Cu1—O3 = 54.74 (14) °. The nitrate anions are asymmetrically bonded, with Cu1—O3 = 1.971 (3) Å and Cu1—O1 = 2.588 (4) Å (Table 1). Two examples of asymmetrically bonded carboxylate groups show the wide range of short and long Cu(II)–O distances: 1.989 (2) Å and 2.339 (3) Å (Youngme et al., 2007); 1.962 (3) Å and 2.706 Å were reported by Lee & Barboiu (2004).

The ethane group was disordered and the C3 atom was refined on split positions with occupancy (50:50). The 2,2'-[1,2-ethanediylbis(thio)]bis[1,3,4-thiadiazole] ligands adopt a N, N-bidentate bridging mode in trans configuration and bridge the copper atoms into one-dimensional infinite chains, with the bridged Cu-Cu distance of 11.2455 (12) Å (Fig. 2). The chains interact with neigboring molecules via intermolecular S···O interactions (the shortest distances found: O2···S1 = 3.084 (5) Å and O2···S2 = 3.044 (4) Å, with symmetry codes (1 - x, -1 - y, -z) and (1 - x, 1 - y, 1 - z), respectively, and weak intermolecular C—H···O hydrogen bonds (Bhogala et al. (2005), (Table 2). These chains are linked by the S···O interactions into two-dimensional layers (Fig. 3), which are further connected by weak intermolecular C—H···O hydrogen bonds to generate a a three-dimensional supramolecular structure (Fig. 4).

Related literature top

For related catena-poly Cu(II) complexes, see, for example: Wang et al. (2008). For elongated Cu—O bonds see, for example: Lee & Barboiu (2004); Youngme et al. (2007). For C—H···O hydrogen bonds, see: Bhogala et al. (2005);

Experimental top

The reaction of 2,2'-[1,2-ethanediyl-bis(thio)]bis(1,3,4- thiadiazole) (0.2 mmol) with Cu(NO₃)₂ (0.2 mmol) in MeOH(10 ml) for a few minutes afforded a light blue solid, which was filtered, washed with acetone, and dried on air. The single crystals suitable for X-ray analysis were obtained by slow diffusion of Et₂O into the acetonitrile solution of the solid.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELX97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the local coordination of the Cu(II) cation in the title compound. Displacement ellipsoids are drawn at the 30% probability level. The disordered ethane group was omitted for clarity. Symmetry codes: (A) (-x, -y, -z); (B) (1 - x, 1 - y, 1 - z); (C) (-1 + x, -1 + y, -1 + z).
	Fig. 2. A view of the polymeric chain in the title compound.
	Fig. 3. A view of the two-dimensional network, indicating the S···O interactions by dashed lines.
	Fig. 4. A view of the compound packing down the b axis.

catena-Poly[[bis(nitrato-κ²O,O')copper(II)]-µ- 2,2'-(ethane-1,2-diyldithio)di-1,3,4-thiadiazole-κ²N⁴:N^4'] top

Crystal data top

[Cu(NO₃)₂(C₆H₆N₄S₄)]	Z = 1
M_r = 449.95	F(000) = 225
Triclinic, P1	D_x = 2.031 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.2143 (8) Å	Cell parameters from 1855 reflections
b = 7.0214 (10) Å	θ = 3.0–29.2°
c = 10.6476 (16) Å	µ = 2.09 mm⁻¹
α = 105.144 (2)°	T = 296 K
β = 100.000 (2)°	Plate, colorless
γ = 93.958 (2)°	0.48 × 0.29 × 0.04 mm
V = 367.88 (9) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1336 independent reflections
Radiation source: fine-focus sealed tube	1273 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
phi and ω scans	θ_max = 25.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −6→3
T_min = 0.432, T_max = 0.924	k = −8→8
1983 measured reflections	l = −11→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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.173	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1363P)² + 0.4692P] where P = (F_o² + 2F_c²)/3
1336 reflections	(Δ/σ)_max < 0.001
110 parameters	Δρ_max = 1.86 e Å⁻³
1 restraint	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Cu(NO₃)₂(C₆H₆N₄S₄)]	γ = 93.958 (2)°
M_r = 449.95	V = 367.88 (9) Å³
Triclinic, P1	Z = 1
a = 5.2143 (8) Å	Mo Kα radiation
b = 7.0214 (10) Å	µ = 2.09 mm⁻¹
c = 10.6476 (16) Å	T = 296 K
α = 105.144 (2)°	0.48 × 0.29 × 0.04 mm
β = 100.000 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1336 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1273 reflections with I > 2σ(I)
T_min = 0.432, T_max = 0.924	R_int = 0.020
1983 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	1 restraint
wR(F²) = 0.173	H-atom parameters constrained
S = 1.05	Δρ_max = 1.86 e Å⁻³
1336 reflections	Δρ_min = −0.50 e Å⁻³
110 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C3	0.6301 (17)	0.4878 (11)	0.4823 (9)	0.0366 (14)	0.499 (9)
H3A	0.7602	0.5921	0.5422	0.044*	0.499 (9)
H3B	0.6243	0.4972	0.3926	0.044*	0.499 (9)
C3'	0.4746 (17)	0.4163 (12)	0.5298 (9)	0.0366 (14)	0.501 (9)
H3B'	0.2988	0.3485	0.4917	0.044*	0.501 (9)
H3A'	0.4890	0.4680	0.6249	0.044*	0.501 (9)
Cu1	0.0000	0.0000	0.0000	0.0312 (3)
S1	0.6997 (3)	−0.12017 (17)	0.26648 (12)	0.0406 (4)
S2	0.7207 (3)	0.23982 (18)	0.49437 (12)	0.0455 (4)
O1	−0.2024 (8)	−0.3668 (6)	−0.0576 (4)	0.0546 (10)
O2	−0.0393 (10)	−0.5352 (6)	−0.2188 (4)	0.0650 (12)
O3	0.1101 (7)	−0.2255 (5)	−0.1244 (3)	0.0417 (8)
N1	−0.0491 (8)	−0.3829 (5)	−0.1353 (4)	0.0385 (9)
N2	0.3011 (8)	−0.0167 (6)	0.1409 (4)	0.0345 (8)
N3	0.3672 (7)	0.1312 (5)	0.2605 (4)	0.0370 (9)
C1	0.4554 (9)	−0.1563 (6)	0.1321 (4)	0.0355 (10)
H1A	0.4330	−0.2663	0.0583	0.043*
C2	0.5716 (9)	0.0958 (6)	0.3353 (4)	0.0347 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C3	0.036 (4)	0.032 (3)	0.038 (3)	0.005 (2)	0.007 (3)	0.004 (3)
C3'	0.036 (4)	0.032 (3)	0.038 (3)	0.005 (2)	0.007 (3)	0.004 (3)
Cu1	0.0330 (5)	0.0269 (5)	0.0289 (5)	0.0069 (3)	0.0028 (3)	0.0009 (3)
S1	0.0423 (7)	0.0364 (7)	0.0419 (7)	0.0170 (5)	0.0040 (5)	0.0086 (5)
S2	0.0479 (8)	0.0415 (7)	0.0367 (7)	0.0153 (5)	−0.0092 (5)	0.0016 (5)
O1	0.062 (2)	0.049 (2)	0.059 (2)	0.0151 (17)	0.020 (2)	0.0183 (17)
O2	0.088 (3)	0.0380 (19)	0.053 (2)	0.024 (2)	−0.002 (2)	−0.0102 (17)
O3	0.0405 (18)	0.0406 (17)	0.0388 (17)	0.0109 (14)	0.0058 (14)	0.0017 (14)
N1	0.049 (2)	0.0291 (17)	0.0304 (18)	0.0149 (16)	−0.0031 (17)	0.0004 (14)
N2	0.0384 (19)	0.0289 (17)	0.0321 (19)	0.0068 (15)	0.0039 (15)	0.0025 (14)
N3	0.039 (2)	0.0306 (19)	0.035 (2)	0.0102 (17)	−0.0015 (17)	0.0016 (16)
C1	0.039 (2)	0.032 (2)	0.033 (2)	0.0098 (18)	0.0062 (18)	0.0034 (17)
C2	0.037 (2)	0.0291 (19)	0.035 (2)	0.0078 (18)	0.0048 (19)	0.0054 (17)

Geometric parameters (Å, º) top

C3—C3ⁱ	1.479 (17)	Cu1—N2ⁱⁱ	2.007 (4)
C3—S2	1.866 (7)	S1—C1	1.693 (5)
C3—H3A	0.9700	S1—C2	1.735 (4)
C3—H3B	0.9700	S2—C2	1.743 (4)
C3'—C3'ⁱ	1.504 (17)	O1—N1	1.237 (6)
C3'—S2	1.863 (7)	O2—N1	1.209 (5)
C3'—H3B'	0.9700	O3—N1	1.303 (5)
C3'—H3A'	0.9700	N2—C1	1.305 (6)
Cu1—O1	2.588 (4)	N2—N3	1.389 (5)
Cu1—O3ⁱⁱ	1.971 (3)	N3—C2	1.295 (6)
Cu1—O3	1.971 (3)	C1—H1A	0.9300
Cu1—N2	2.007 (4)

C3ⁱ—C3—S2	108.9 (7)	C2—S2—C3'	100.6 (3)
C3ⁱ—C3—H3A	109.9	C2—S2—C3	99.5 (3)
S2—C3—H3A	109.9	N1—O3—Cu1	107.4 (2)
C3ⁱ—C3—H3B	109.9	O2—N1—O1	123.7 (5)
S2—C3—H3B	109.9	O2—N1—O3	119.2 (4)
H3A—C3—H3B	108.3	O1—N1—O3	117.1 (4)
C3'ⁱ—C3'—S2	108.5 (7)	O1—Cu1—O3	54.74 (14)
C3'ⁱ—C3'—H3B'	110.0	N2—Cu1—O3	89.02 (15)
S2—C3'—H3B'	110.0	O1—Cu1—O3ⁱⁱ	125.26 (14)
C3'ⁱ—C3'—H3A'	110.0	C1—N2—N3	113.3 (4)
S2—C3'—H3A'	110.0	C1—N2—Cu1	126.2 (3)
H3B'—C3'—H3A'	108.4	N3—N2—Cu1	120.5 (3)
O3ⁱⁱ—Cu1—O3	180.0	C2—N3—N2	110.7 (4)
O3ⁱⁱ—Cu1—N2	90.98 (15)	N2—C1—S1	114.2 (3)
O3—Cu1—N2	89.02 (15)	N2—C1—H1A	122.9
O3ⁱⁱ—Cu1—N2ⁱⁱ	89.02 (15)	S1—C1—H1A	122.9
O3—Cu1—N2ⁱⁱ	90.98 (15)	N3—C2—S1	114.8 (3)
N2—Cu1—N2ⁱⁱ	180.0	N3—C2—S2	126.5 (3)
C1—S1—C2	87.1 (2)	S1—C2—S2	118.7 (3)

C3'ⁱ—C3'—S2—C2	−83.9 (9)	Cu1—N2—N3—C2	−177.8 (3)
C3'ⁱ—C3'—S2—C3	7.8 (7)	N3—N2—C1—S1	−1.2 (5)
C3ⁱ—C3—S2—C2	87.1 (9)	Cu1—N2—C1—S1	177.3 (2)
C3ⁱ—C3—S2—C3'	−7.9 (7)	C2—S1—C1—N2	0.9 (4)
N2—Cu1—O3—N1	103.2 (3)	N2—N3—C2—S1	−0.1 (5)
N2ⁱⁱ—Cu1—O3—N1	−76.8 (3)	N2—N3—C2—S2	−179.2 (3)
Cu1—O3—N1—O2	171.2 (4)	C1—S1—C2—N3	−0.4 (4)
Cu1—O3—N1—O1	−9.2 (4)	C1—S1—C2—S2	178.7 (3)
O3ⁱⁱ—Cu1—N2—C1	171.9 (4)	C3'—S2—C2—N3	9.6 (5)
O3—Cu1—N2—C1	−8.1 (4)	C3—S2—C2—N3	−27.8 (5)
O3ⁱⁱ—Cu1—N2—N3	−9.7 (3)	C3'—S2—C2—S1	−169.5 (4)
O3—Cu1—N2—N3	170.3 (3)	C3—S2—C2—S1	153.1 (3)
C1—N2—N3—C2	0.8 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱⁱⁱ	0.93	2.49	3.083 (6)	122

Symmetry code: (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₆H₆N₄S₄)]
M_r	449.95
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	5.2143 (8), 7.0214 (10), 10.6476 (16)
α, β, γ (°)	105.144 (2), 100.000 (2), 93.958 (2)
V (Å³)	367.88 (9)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.09
Crystal size (mm)	0.48 × 0.29 × 0.04

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.432, 0.924
No. of measured, independent and observed [I > 2σ(I)] reflections	1983, 1336, 1273
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.173, 1.05
No. of reflections	1336
No. of parameters	110
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.86, −0.50

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELX97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Cu1—O1	2.588 (4)	Cu1—N2	2.007 (4)
Cu1—O3	1.971 (3)

O1—Cu1—O3	54.74 (14)	O1—Cu1—O3ⁱ	125.26 (14)
N2—Cu1—O3	89.02 (15)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O1ⁱⁱ	0.93	2.49	3.083 (6)	122.00

Symmetry code: (ii) x+1, y, z.

Acknowledgements

The authors thank Luo Yang Normal University for supporting this work.

References

Bhogala, B. R., Basavoju, S. & Nangia, A. (2005). Cryst. Growth Des. 5, 1683–1686. Web of Science CSD CrossRef CAS Google Scholar
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Lee, A. & Barboiu, M. (2004). Acta Cryst. C60, m156–m158. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Wang, J. G., Qin, J. H., Hu, P. Z. & Zhao, B. T. (2008). Z. Kristallogr. New Cryst. Struct. 223, 225–227. CAS Google Scholar
Youngme, S., Chotkhun, T. & Chaichit, N. (2007). Acta Cryst. C63, m59–m61. Web of Science CSD CrossRef IUCr Journals Google Scholar

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