Bis[bis­(1,10-phenanthroline-κ2N,N′)copper(I)] μ6-oxido-dodeca­kis-μ2-oxido-hexa­oxidohexa­tungsten(VI)

Li, Z.-F.; Zhang, B.-S.; Wu, C.-S.

doi:10.1107/S1600536809020170

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Pages m741-m742

doi:10.1107/S1600536809020170

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Bis[bis(1,10-phenanthroline-κ²N,N′)copper(I)] μ₆-oxido-dodecakis-μ₂-oxido-hexaoxidohexatungsten(VI)

Zhen-Fang Li,^a Bi-Song Zhang ^a ^* and Chang-Sheng Wu ^a

^aCollege of Materials Science and Chemical Engineering, Jinhua College of Profession and Technology, Jinhua, Zhejiang 321017, People's Republic of China
^*Correspondence e-mail: zbs_jy@163.com

(Received 2 May 2009; accepted 27 May 2009; online 6 June 2009)

The title compound, [Cu(C₁₂H₈N₂)₂]₂[W₆O₁₉], consists of two [Cu(phen)₂]⁺ cations (phen = 1,10-phenanthroline) and one typical [W₆O₁₉]²⁻ isopolyanion. The Cu^I atom is coordinated by four N atoms from two bidentate chelating phen ligands in a distorted tetrahedral geometry. The hexatungstate anion, lying on an inversion center and possessing the well known Lindqvist structure, is formed by six edge-sharing WO₆ octahedra, thus exhibiting an approximate O_h symmetry. Three kinds of O atoms exist in the hexatungstate, viz. terminal O_a, bridging O_b and central O_c atoms. Besides the electrostatic effects between the anions and cations, weak C—H⋯O hydrogen bonds exist between the phen ligands and O_a or O_b atoms. The mean interplanar distances of 3.485 (1) and 3.344 (1) Å indicate π–π stacking interactions between neighboring phen ligands. These weak hydrogen bonds and π–π stacking interactions lead to a two-dimensional network.

Related literature

For general background to hexatungstate compounds, see: Khan et al. (1998 ); Meng et al. (2006 ); Zhang et al. (2004 ). For related structures, see: Li & Zhang (2008 ); Zhang (2008 ).

Experimental

Crystal data

[Cu(C₁₂H₈N₂)₂]₂[W₆O₁₉]
M_r = 2255.00
Triclinic, $[P \overline 1]$
a = 10.364 (2) Å
b = 11.772 (2) Å
c = 11.899 (2) Å
α = 108.603 (3)°
β = 102.151 (3)°
γ = 100.694 (3)°
V = 1294.0 (4) Å³
Z = 1
Mo Kα radiation
μ = 14.17 mm⁻¹
T = 290 K
0.19 × 0.16 × 0.07 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.09, T_max = 0.39
7111 measured reflections
4932 independent reflections
3737 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.157
S = 1.00
4932 reflections
376 parameters
H-atom parameters constrained
Δρ_max = 2.72 e Å⁻³
Δρ_min = −4.78 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.027 (14)
Cu1—N2	2.013 (11)
Cu1—N3	2.050 (12)
Cu1—N4	2.007 (11)
W1—O4	1.678 (10)
W1—O3ⁱ	1.904 (10)
W1—O1	1.926 (8)
W1—O9	1.929 (9)
W1—O8ⁱ	1.931 (8)
W1—O10	2.3139 (6)
W2—O2	1.672 (9)
W2—O3	1.904 (11)
W2—O6	1.915 (9)
W2—O1	1.923 (8)
W2—O5ⁱ	1.941 (9)
W2—O10	2.3314 (6)
W3—O7	1.691 (11)
W3—O5	1.899 (10)
W3—O9	1.907 (9)
W3—O6	1.912 (9)
W3—O8	1.921 (9)
W3—O10	2.3392 (6)
Symmetry code: (i) -x+2, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O3ⁱⁱ	0.93	2.53	3.36 (2)	149
C17—H17⋯O4ⁱⁱⁱ	0.93	2.52	3.45 (2)	178
C15—H15⋯O9ⁱⁱⁱ	0.93	2.49	3.43 (1)	178
Symmetry codes: (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+1, -z+2.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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: 10.1107/S1600536809020170/hy2197sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809020170/hy2197Isup2.hkl

checkCIF report

Comment top

Organic–inorganic hybrid compounds comprise hexatungstate and organic components (Khan et al., 1998; Meng et al., 2006; Zhang et al., 2004). In this context, we have studied and reported the crystal structures of dodecahydroxydodecatungsten henicosahydrate (Li & Zhang, 2008) and hexakis(3-hydroxo)tetra(2-hydroxo)octadeca(2-oxo)tetradecaoxodisodium(I) dodecatungsten dodecahydrate (Zhang, 2008). In this paper, we report the synthesis and structure of the title complex, [Cu(phen)₂]₂[W₆O₁₉].

The analysis of crystal structure shows that the title organic–inorganic hybrid compound consists of one hexatungstate cluster anion (W₆O₁₉)^2- and two monovalent coordination cations [Cu(phen)₂]⁺ (Fig. 1). In the [Cu(phen)₂]⁺ cation, the Cu^I atom is coordinated by four N atoms from two bidentate chelating phen ligands in a distorted tetrahedral geometry (Table 1). The dihedral angle of the two phen ligands is 104.9 (2)°, and the bond distances of Cu—N are in the range of 2.007 (11)—2.050 (12) Å. The hexatungstate (W₆O₁₉)^2- anion, lying on an inversion center and possessing the well-known lindqvist structure, is formed by six edge-sharing WO₆ octahedra, thus exhibiting an approximate O_h symmetry. Three kinds of O atoms exist in the hexatungstate, the ending O_a (O2, O4, O7), the bridging O_b (O1, O3, O5, O6, O8, O9) and the central O_c (O10) atoms. The bond lengths of W—O are obviously different, d(W—O_a) = 1.672 (9)—1.691 (11)Å, d(W—O_b) = 1.904 (10)—1.941 (9)Å, and d(W—O_c) = 2.3139 (6)—2.3392 (6)Å. As we can see, the lengths of W—O_c are the longest and the W—O_a shortest. Besides the electrostatic effects between the anions and cations, the weak C—H···O hydrogen bonds exist between the phen ligands and O_a or O_b atoms (Fig.1, Fig.2, Fig.3 and Table 2). The mean interplanar distances of 3.485 (1) and 3.344 (1)Å indicate π–π stacking interactions between the neighboring phen ligands. These weak hydrogen bonds and π–π stacking interactions lead to a two-dimensional network.

Related literature top

For general background to hexatungstate compounds, see: Khan et al. (1998); Meng et al. (2006); Zhang et al. (2004). For related structures, see: Li & Zhang (2008); Zhang (2008).

Experimental top

A mixture of CuCO₃ (0.124 g, 1.00 mmol), phen.H₂O (0.050 g, 0.50 mmol), 2-chlorobenzoic acid (0.043 g, 0.25 mmol) and freshly prepared (NH₄)₂(WO₂S₂) (0.086 g, 0.27 mmol) in a ratio of 4:2:1:1 was added to CH₃OH/H₂O (1:2, v/v) mixed solution. After stirring for 2 h, the brown suspension obtained was sealed in a 50 ml Teflon-lined stainless steel vessel (degree of filling: 40%), heated to 393 K for 7 d and then naturally cooled to room temperature. The red crystals were collected, then washed with distilled water and dried in air.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The π–π stacking interactions (dashed double arrows), with the mean interplanar distance of 3.485 (1) Å, and C—H···O hydrogen bonds (dashed lines) in the title compound.
	Fig. 3. The π–π stacking interactions (dashed double arrows), with the mean interplanar distance of 3.344 (1) Å, and C—H···O hydrogen bonds (dashed lines) in the title compound.

Bis[bis(1,10-phenanthroline-κ²N,N')copper(I)] µ₆-oxido-dodecakis-µ₂-oxido-hexaoxidohexatungsten(VI) top

Crystal data top

[Cu(C₁₂H₈N₂)₂]₂[W₆O₁₉]	Z = 1
M_r = 2255.00	F(000) = 1030
Triclinic, P1	D_x = 2.894 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.364 (2) Å	Cell parameters from 226 reflections
b = 11.772 (2) Å	θ = 1.9–26.0°
c = 11.899 (2) Å	µ = 14.17 mm⁻¹
α = 108.603 (3)°	T = 290 K
β = 102.151 (3)°	Block, red
γ = 100.694 (3)°	0.19 × 0.16 × 0.07 mm
V = 1294.0 (4) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	4932 independent reflections
Radiation source: fine-focus sealed tube	3737 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.09, T_max = 0.39	k = −14→14
7111 measured reflections	l = −7→14

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1032P)²] where P = (F_o² + 2F_c²)/3
4932 reflections	(Δ/σ)_max = 0.001
376 parameters	Δρ_max = 2.72 e Å⁻³
0 restraints	Δρ_min = −4.78 e Å⁻³

Crystal data top

[Cu(C₁₂H₈N₂)₂]₂[W₆O₁₉]	γ = 100.694 (3)°
M_r = 2255.00	V = 1294.0 (4) Å³
Triclinic, P1	Z = 1
a = 10.364 (2) Å	Mo Kα radiation
b = 11.772 (2) Å	µ = 14.17 mm⁻¹
c = 11.899 (2) Å	T = 290 K
α = 108.603 (3)°	0.19 × 0.16 × 0.07 mm
β = 102.151 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	4932 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3737 reflections with I > 2σ(I)
T_min = 0.09, T_max = 0.39	R_int = 0.035
7111 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.00	Δρ_max = 2.72 e Å⁻³
4932 reflections	Δρ_min = −4.78 e Å⁻³
376 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.3440 (2)	0.17655 (17)	0.7772 (2)	0.0595 (5)
W1	0.99864 (5)	0.40295 (4)	0.64114 (5)	0.03513 (18)
W2	0.79637 (5)	0.54681 (4)	0.52487 (5)	0.03706 (19)
W3	1.12578 (5)	0.68912 (4)	0.66080 (5)	0.03581 (18)
O1	0.8370 (8)	0.4620 (8)	0.6363 (8)	0.0341 (19)
O2	0.6510 (10)	0.5825 (9)	0.5417 (12)	0.059 (3)
O3	0.8394 (10)	0.6130 (8)	0.4065 (11)	0.050 (3)
O4	0.9960 (11)	0.3340 (9)	0.7445 (10)	0.051 (3)
O5	1.2619 (9)	0.6145 (8)	0.6099 (10)	0.045 (2)
O6	0.9382 (9)	0.6879 (8)	0.6456 (9)	0.041 (2)
O7	1.2177 (11)	0.8247 (9)	0.7782 (11)	0.061 (3)
O8	1.1010 (8)	0.7305 (7)	0.5155 (8)	0.035 (2)
O9	1.0969 (9)	0.5744 (8)	0.7415 (9)	0.039 (2)
O10	1.0000	0.5000	0.5000	0.031 (3)
N1	0.2642 (13)	0.0765 (10)	0.5929 (13)	0.048 (3)
N2	0.4498 (12)	0.0484 (10)	0.7689 (11)	0.044 (3)
N3	0.2306 (12)	0.2179 (10)	0.8990 (12)	0.047 (3)
N4	0.3947 (12)	0.3613 (10)	0.8196 (10)	0.042 (3)
C1	0.178 (2)	0.0906 (14)	0.504 (2)	0.068 (5)
H1	0.1385	0.1560	0.5268	0.082*
C2	0.142 (2)	0.0199 (17)	0.385 (2)	0.080 (6)
H2	0.0773	0.0344	0.3278	0.096*
C3	0.2024 (16)	−0.0766 (14)	0.3453 (16)	0.056 (4)
H3	0.1787	−0.1268	0.2618	0.068*
C4	0.2968 (15)	−0.0962 (12)	0.4310 (14)	0.044 (3)
C5	0.3614 (17)	−0.1966 (13)	0.4029 (16)	0.054 (4)
H5	0.3440	−0.2488	0.3208	0.065*
C6	0.4458 (16)	−0.2159 (13)	0.4929 (15)	0.050 (4)
H6	0.4824	−0.2835	0.4724	0.060*
C7	0.4805 (13)	−0.1353 (11)	0.6187 (14)	0.039 (3)
C8	0.5707 (16)	−0.1458 (14)	0.7184 (18)	0.058 (4)
H8	0.6135	−0.2095	0.7022	0.069*
C9	0.5981 (17)	−0.0672 (16)	0.8371 (18)	0.062 (4)
H9	0.6565	−0.0772	0.9021	0.075*
C10	0.5340 (17)	0.0312 (14)	0.8582 (16)	0.055 (4)
H10	0.5523	0.0865	0.9391	0.066*
C11	0.4206 (14)	−0.0325 (12)	0.6521 (14)	0.043 (3)
C12	0.3243 (13)	−0.0200 (11)	0.5541 (15)	0.044 (4)
C13	0.1527 (18)	0.1470 (15)	0.9380 (15)	0.057 (4)
H13	0.1458	0.0622	0.9088	0.069*
C14	0.082 (2)	0.189 (2)	1.017 (2)	0.081 (6)
H14	0.0293	0.1342	1.0418	0.097*
C15	0.0890 (16)	0.3146 (17)	1.0626 (15)	0.059 (4)
H15	0.0407	0.3452	1.1178	0.071*
C16	0.1710 (13)	0.3947 (13)	1.0228 (14)	0.044 (3)
C17	0.1811 (16)	0.5272 (16)	1.0604 (14)	0.058 (4)
H17	0.1343	0.5636	1.1145	0.069*
C18	0.2586 (16)	0.5961 (14)	1.0160 (15)	0.058 (4)
H18	0.2639	0.6805	1.0404	0.069*
C19	0.3338 (14)	0.5465 (12)	0.9329 (15)	0.046 (4)
C20	0.4137 (14)	0.6171 (12)	0.8855 (14)	0.048 (4)
H20	0.4201	0.7015	0.9061	0.058*
C21	0.4822 (15)	0.5605 (13)	0.8086 (14)	0.048 (3)
H21	0.5372	0.6056	0.7762	0.057*
C22	0.4684 (16)	0.4334 (14)	0.7791 (13)	0.047 (3)
H22	0.5159	0.3967	0.7259	0.056*
C23	0.3262 (14)	0.4188 (12)	0.8966 (14)	0.040 (3)
C24	0.2409 (14)	0.3435 (12)	0.9414 (13)	0.040 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0742 (13)	0.0385 (9)	0.0669 (13)	0.0301 (9)	0.0312 (11)	0.0058 (10)
W1	0.0357 (3)	0.0281 (3)	0.0464 (4)	0.0106 (2)	0.0163 (2)	0.0163 (3)
W2	0.0287 (3)	0.0320 (3)	0.0566 (4)	0.0150 (2)	0.0205 (3)	0.0157 (3)
W3	0.0350 (3)	0.0243 (3)	0.0448 (3)	0.0056 (2)	0.0146 (2)	0.0081 (2)
O1	0.035 (4)	0.039 (5)	0.043 (5)	0.012 (4)	0.024 (4)	0.025 (4)
O2	0.042 (6)	0.050 (6)	0.094 (9)	0.026 (5)	0.032 (6)	0.023 (6)
O3	0.045 (5)	0.032 (5)	0.076 (7)	0.013 (4)	0.019 (5)	0.020 (5)
O4	0.057 (6)	0.039 (5)	0.063 (7)	0.013 (4)	0.033 (5)	0.018 (5)
O5	0.032 (5)	0.033 (4)	0.064 (7)	0.004 (4)	0.009 (4)	0.015 (5)
O6	0.038 (5)	0.031 (4)	0.055 (6)	0.013 (4)	0.026 (4)	0.009 (4)
O7	0.061 (6)	0.037 (5)	0.077 (8)	0.003 (5)	0.030 (6)	0.009 (6)
O8	0.036 (5)	0.027 (4)	0.039 (5)	0.004 (3)	0.008 (4)	0.010 (4)
O9	0.042 (5)	0.030 (4)	0.045 (5)	0.007 (4)	0.018 (4)	0.013 (4)
O10	0.016 (5)	0.024 (5)	0.052 (8)	0.010 (4)	0.011 (5)	0.010 (6)
N1	0.050 (7)	0.034 (6)	0.067 (9)	0.025 (5)	0.022 (7)	0.014 (6)
N2	0.051 (7)	0.037 (6)	0.046 (7)	0.023 (5)	0.022 (6)	0.006 (6)
N3	0.048 (7)	0.037 (6)	0.058 (8)	0.017 (5)	0.019 (6)	0.013 (6)
N4	0.051 (7)	0.032 (5)	0.035 (6)	0.019 (5)	0.005 (5)	0.003 (5)
C1	0.073 (12)	0.034 (8)	0.090 (15)	0.007 (8)	0.036 (11)	0.008 (10)
C2	0.066 (11)	0.065 (12)	0.110 (18)	0.018 (9)	−0.004 (11)	0.051 (14)
C3	0.066 (10)	0.037 (8)	0.059 (10)	0.003 (7)	0.022 (9)	0.012 (8)
C4	0.053 (8)	0.027 (6)	0.050 (9)	0.000 (6)	0.025 (7)	0.014 (7)
C5	0.074 (11)	0.034 (7)	0.062 (10)	0.010 (7)	0.048 (9)	0.010 (8)
C6	0.063 (9)	0.037 (7)	0.068 (11)	0.028 (7)	0.046 (9)	0.017 (8)
C7	0.039 (7)	0.022 (6)	0.063 (9)	0.009 (5)	0.030 (7)	0.013 (6)
C8	0.052 (9)	0.048 (8)	0.090 (14)	0.031 (7)	0.035 (9)	0.027 (10)
C9	0.062 (10)	0.064 (10)	0.072 (12)	0.024 (8)	0.017 (9)	0.037 (10)
C10	0.071 (11)	0.045 (8)	0.053 (10)	0.023 (7)	0.026 (9)	0.011 (8)
C11	0.047 (8)	0.029 (6)	0.062 (9)	0.012 (5)	0.033 (7)	0.018 (7)
C12	0.039 (7)	0.025 (6)	0.080 (11)	0.015 (5)	0.036 (7)	0.019 (7)
C13	0.075 (11)	0.043 (8)	0.047 (9)	0.018 (8)	0.012 (8)	0.010 (8)
C14	0.085 (14)	0.088 (14)	0.109 (17)	0.035 (11)	0.059 (13)	0.061 (14)
C15	0.055 (9)	0.088 (12)	0.050 (10)	0.035 (9)	0.032 (8)	0.025 (10)
C16	0.035 (7)	0.046 (8)	0.046 (8)	0.021 (6)	0.011 (6)	0.007 (7)
C17	0.055 (9)	0.068 (10)	0.043 (9)	0.031 (8)	0.024 (8)	−0.005 (8)
C18	0.058 (9)	0.041 (8)	0.059 (10)	0.027 (7)	0.012 (8)	−0.004 (8)
C19	0.042 (7)	0.031 (7)	0.057 (10)	0.018 (6)	0.012 (7)	0.002 (7)
C20	0.052 (8)	0.029 (7)	0.053 (9)	0.008 (6)	0.001 (7)	0.012 (7)
C21	0.058 (9)	0.040 (7)	0.047 (9)	0.022 (7)	0.016 (7)	0.013 (7)
C22	0.064 (9)	0.053 (9)	0.031 (8)	0.031 (7)	0.016 (7)	0.016 (7)
C23	0.041 (7)	0.038 (7)	0.046 (8)	0.023 (6)	0.014 (6)	0.013 (7)
C24	0.050 (8)	0.034 (6)	0.035 (7)	0.022 (6)	0.008 (6)	0.008 (6)

Geometric parameters (Å, º) top

Cu1—N1	2.027 (14)	C3—H3	0.9300
Cu1—N2	2.013 (11)	C4—C12	1.39 (2)
Cu1—N3	2.050 (12)	C4—C5	1.45 (2)
Cu1—N4	2.007 (11)	C5—C6	1.34 (2)
W1—O4	1.678 (10)	C5—H5	0.9300
W1—O3ⁱ	1.904 (10)	C6—C7	1.42 (2)
W1—O1	1.926 (8)	C6—H6	0.9300
W1—O9	1.929 (9)	C7—C8	1.40 (2)
W1—O8ⁱ	1.931 (8)	C7—C11	1.444 (18)
W1—O10	2.3139 (6)	C8—C9	1.35 (2)
W2—O2	1.672 (9)	C8—H8	0.9300
W2—O3	1.904 (11)	C9—C10	1.42 (2)
W2—O6	1.915 (9)	C9—H9	0.9300
W2—O1	1.923 (8)	C10—H10	0.9300
W2—O5ⁱ	1.941 (9)	C11—C12	1.43 (2)
W2—O10	2.3314 (6)	C13—C14	1.34 (2)
W3—O7	1.691 (11)	C13—H13	0.9300
W3—O5	1.899 (10)	C14—C15	1.38 (3)
W3—O9	1.907 (9)	C14—H14	0.9300
W3—O6	1.912 (9)	C15—C16	1.41 (2)
W3—O8	1.921 (9)	C15—H15	0.9300
W3—O10	2.3392 (6)	C16—C24	1.383 (19)
N1—C1	1.31 (2)	C16—C17	1.46 (2)
N1—C12	1.393 (15)	C17—C18	1.34 (2)
N2—C10	1.321 (19)	C17—H17	0.9300
N2—C11	1.342 (18)	C18—C19	1.43 (2)
N3—C13	1.310 (19)	C18—H18	0.9300
N3—C24	1.377 (17)	C19—C20	1.39 (2)
N4—C22	1.308 (18)	C19—C23	1.407 (18)
N4—C23	1.363 (17)	C20—C21	1.36 (2)
C1—C2	1.33 (3)	C20—H20	0.9300
C1—H1	0.9300	C21—C22	1.39 (2)
C2—C3	1.40 (3)	C21—H21	0.9300
C2—H2	0.9300	C22—H22	0.9300
C3—C4	1.37 (2)	C23—C24	1.436 (19)

N4—Cu1—N2	134.8 (5)	C13—N3—C24	118.4 (13)
N4—Cu1—N1	113.4 (5)	C13—N3—Cu1	131.6 (10)
N2—Cu1—N1	83.1 (5)	C24—N3—Cu1	110.1 (10)
N4—Cu1—N3	83.3 (5)	C22—N4—C23	115.1 (11)
N2—Cu1—N3	122.9 (5)	C22—N4—Cu1	132.8 (10)
N1—Cu1—N3	124.7 (5)	C23—N4—Cu1	111.7 (9)
O4—W1—O3ⁱ	105.4 (5)	N1—C1—C2	125.8 (17)
O4—W1—O1	102.4 (4)	N1—C1—H1	117.1
O3ⁱ—W1—O1	152.1 (4)	C2—C1—H1	117.1
O4—W1—O9	103.8 (5)	C1—C2—C3	119.4 (18)
O3ⁱ—W1—O9	87.0 (4)	C1—C2—H2	120.3
O1—W1—O9	84.9 (4)	C3—C2—H2	120.3
O4—W1—O8ⁱ	103.6 (4)	C4—C3—C2	119.1 (16)
O3ⁱ—W1—O8ⁱ	86.7 (4)	C4—C3—H3	120.5
O1—W1—O8ⁱ	88.4 (4)	C2—C3—H3	120.5
O9—W1—O8ⁱ	152.6 (4)	C3—C4—C12	117.3 (14)
O4—W1—O10	179.0 (4)	C3—C4—C5	124.4 (14)
O3ⁱ—W1—O10	75.4 (3)	C12—C4—C5	118.2 (14)
O1—W1—O10	76.7 (2)	C6—C5—C4	121.2 (14)
O9—W1—O10	75.8 (3)	C6—C5—H5	119.4
O8ⁱ—W1—O10	76.8 (2)	C4—C5—H5	119.4
O2—W2—O3	104.0 (5)	C5—C6—C7	121.4 (13)
O2—W2—O6	104.2 (5)	C5—C6—H6	119.3
O3—W2—O6	85.8 (4)	C7—C6—H6	119.3
O2—W2—O1	104.6 (5)	C8—C7—C6	125.5 (13)
O3—W2—O1	151.4 (4)	C8—C7—C11	114.8 (13)
O6—W2—O1	86.5 (4)	C6—C7—C11	119.8 (14)
O2—W2—O5ⁱ	105.0 (5)	C9—C8—C7	122.9 (14)
O3—W2—O5ⁱ	85.8 (4)	C9—C8—H8	118.6
O6—W2—O5ⁱ	150.8 (4)	C7—C8—H8	118.6
O1—W2—O5ⁱ	87.6 (4)	C8—C9—C10	117.1 (16)
O2—W2—O10	178.9 (4)	C8—C9—H9	121.4
O3—W2—O10	75.0 (3)	C10—C9—H9	121.4
O6—W2—O10	75.4 (3)	N2—C10—C9	123.5 (15)
O1—W2—O10	76.4 (2)	N2—C10—H10	118.3
O5ⁱ—W2—O10	75.4 (3)	C9—C10—H10	118.3
O7—W3—O5	103.7 (5)	N2—C11—C12	119.9 (12)
O7—W3—O9	103.7 (5)	N2—C11—C7	123.1 (14)
O5—W3—O9	87.3 (4)	C12—C11—C7	117.0 (13)
O7—W3—O6	105.1 (5)	C4—C12—N1	123.4 (15)
O5—W3—O6	151.2 (4)	C4—C12—C11	122.2 (12)
O9—W3—O6	86.1 (4)	N1—C12—C11	114.4 (13)
O7—W3—O8	104.4 (5)	N3—C13—C14	124.0 (16)
O5—W3—O8	87.2 (4)	N3—C13—H13	118.0
O9—W3—O8	151.9 (4)	C14—C13—H13	118.0
O6—W3—O8	85.6 (4)	C13—C14—C15	120.0 (17)
O7—W3—O10	179.2 (4)	C13—C14—H14	120.0
O5—W3—O10	75.9 (3)	C15—C14—H14	120.0
O9—W3—O10	75.6 (3)	C14—C15—C16	118.1 (15)
O6—W3—O10	75.3 (3)	C14—C15—H15	120.9
O8—W3—O10	76.3 (2)	C16—C15—H15	120.9
W2—O1—W1	117.0 (4)	C24—C16—C15	118.1 (13)
W2—O3—W1ⁱ	119.4 (5)	C24—C16—C17	119.0 (14)
W3—O5—W2ⁱ	118.7 (4)	C15—C16—C17	122.9 (14)
W3—O6—W2	119.3 (4)	C18—C17—C16	119.1 (13)
W3—O8—W1ⁱ	117.0 (4)	C18—C17—H17	120.5
W3—O9—W1	118.4 (5)	C16—C17—H17	120.5
W1—O10—W1ⁱ	180.000 (1)	C17—C18—C19	123.5 (13)
W1—O10—W2	89.885 (19)	C17—C18—H18	118.3
W1ⁱ—O10—W2	90.115 (19)	C19—C18—H18	118.3
W1—O10—W2ⁱ	90.115 (19)	C20—C19—C23	118.0 (14)
W1ⁱ—O10—W2ⁱ	89.885 (19)	C20—C19—C18	123.8 (13)
W2—O10—W2ⁱ	180.00 (3)	C23—C19—C18	118.2 (14)
W1—O10—W3	90.18 (2)	C21—C20—C19	118.8 (12)
W1ⁱ—O10—W3	89.82 (2)	C21—C20—H20	120.6
W2—O10—W3	89.97 (2)	C19—C20—H20	120.6
W2ⁱ—O10—W3	90.03 (2)	C20—C21—C22	118.7 (14)
W1—O10—W3ⁱ	89.82 (2)	C20—C21—H21	120.7
W1ⁱ—O10—W3ⁱ	90.18 (2)	C22—C21—H21	120.7
W2—O10—W3ⁱ	90.03 (2)	N4—C22—C21	125.8 (14)
W2ⁱ—O10—W3ⁱ	89.97 (2)	N4—C22—H22	117.1
W3—O10—W3ⁱ	180.00 (2)	C21—C22—H22	117.1
C1—N1—C12	115.1 (14)	N4—C23—C19	123.7 (13)
C1—N1—Cu1	133.2 (10)	N4—C23—C24	117.5 (11)
C12—N1—Cu1	111.5 (10)	C19—C23—C24	118.8 (13)
C10—N2—C11	118.6 (12)	N3—C24—C16	121.4 (13)
C10—N2—Cu1	130.3 (10)	N3—C24—C23	117.2 (12)
C11—N2—Cu1	111.0 (10)	C16—C24—C23	121.4 (12)

O6—W2—O1—W1	−77.3 (5)	O3—W2—O6—W3	−76.6 (6)
O5ⁱ—W2—O1—W1	74.1 (5)	O1—W2—O6—W3	75.8 (5)
O3ⁱ—W1—O1—W2	4.5 (11)	O5ⁱ—W2—O6—W3	−3.0 (12)
O9—W1—O1—W2	78.0 (5)	O10—W2—O6—W3	−1.0 (4)
O8ⁱ—W1—O1—W2	−75.4 (5)	O7—W3—O8—W1ⁱ	179.1 (5)
O6—W2—O3—W1ⁱ	75.4 (6)	O5—W3—O8—W1ⁱ	75.6 (5)
O5ⁱ—W2—O3—W1ⁱ	−76.6 (6)	O9—W3—O8—W1ⁱ	−3.3 (11)
O9—W3—O5—W2ⁱ	76.2 (6)	O6—W3—O8—W1ⁱ	−76.5 (5)
O6—W3—O5—W2ⁱ	−0.6 (12)	O7—W3—O9—W1	−178.3 (5)
O8—W3—O5—W2ⁱ	−76.3 (6)	O5—W3—O9—W1	−74.9 (5)
O7—W3—O6—W2	−178.3 (6)	O6—W3—O9—W1	77.1 (5)
O9—W3—O6—W2	−75.1 (6)	O4—W1—O9—W3	179.6 (5)
O8—W3—O6—W2	78.1 (5)	O3ⁱ—W1—O9—W3	74.5 (6)
O2—W2—O6—W3	180.0 (6)	O1—W1—O9—W3	−78.9 (5)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱⁱ	0.93	2.53	3.36 (2)	149
C17—H17···O4ⁱⁱⁱ	0.93	2.52	3.45 (2)	178
C15—H15···O9ⁱⁱⁱ	0.93	2.49	3.43 (1)	178

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₈N₂)₂]₂[W₆O₁₉]
M_r	2255.00
Crystal system, space group	Triclinic, P1
Temperature (K)	290
a, b, c (Å)	10.364 (2), 11.772 (2), 11.899 (2)
α, β, γ (°)	108.603 (3), 102.151 (3), 100.694 (3)
V (Å³)	1294.0 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	14.17
Crystal size (mm)	0.19 × 0.16 × 0.07

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.09, 0.39
No. of measured, independent and observed [I > 2σ(I)] reflections	7111, 4932, 3737
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.157, 1.00
No. of reflections	4932
No. of parameters	376
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.72, −4.78

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	2.027 (14)	W2—O3	1.904 (11)
Cu1—N2	2.013 (11)	W2—O6	1.915 (9)
Cu1—N3	2.050 (12)	W2—O1	1.923 (8)
Cu1—N4	2.007 (11)	W2—O5ⁱ	1.941 (9)
W1—O4	1.678 (10)	W2—O10	2.3314 (6)
W1—O3ⁱ	1.904 (10)	W3—O7	1.691 (11)
W1—O1	1.926 (8)	W3—O5	1.899 (10)
W1—O9	1.929 (9)	W3—O9	1.907 (9)
W1—O8ⁱ	1.931 (8)	W3—O6	1.912 (9)
W1—O10	2.3139 (6)	W3—O8	1.921 (9)
W2—O2	1.672 (9)	W3—O10	2.3392 (6)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O3ⁱⁱ	0.93	2.53	3.36 (2)	149
C17—H17···O4ⁱⁱⁱ	0.93	2.52	3.45 (2)	178
C15—H15···O9ⁱⁱⁱ	0.93	2.49	3.43 (1)	178

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

Acknowledgements

The authors gratefully acknowledge financial support from the Jinhun Municipal Science and Technology (grant No. 2003-01-179).

References

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