Poly[bis(2,2′-bipyridine-κ2N,N′)heptadeca-μ-oxido-tetraoxidodicopper(II)divanadate(IV)hexavanadate(V)]

Yu, H.; Kong, L.

doi:10.1107/S1600536809052118

metal-organic compounds

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Volume 66| Part 1| January 2010| Page m32

doi:10.1107/S1600536809052118

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Poly[bis(2,2′-bipyridine-κ²N,N′)heptadeca-μ-oxido-tetraoxidodicopper(II)divanadate(IV)hexavanadate(V)]

Hai-hui Yu ^a and Li Kong ^b ^*

^aCollege of Chemical Engineering, North East Dianli University, Jilin 132012, People's Republic of China, and ^bJilin Institute of Chemical Technology, Jilin 132012, People's Republic of China
^*Correspondence e-mail: yhhhhyhhy@163.com

(Received 20 November 2009; accepted 3 December 2009; online 9 December 2009)

In the title complex, [Cu₂V₈O₂₁(2,2′-bpy)₂]_n (bpy = bipyridine, C₁₀H₈N₂), the asymmetric unit contains four independent V atoms briged by 11 O atoms, one of which lies on an inversion center, and a [Cu(2,2′-bpy)]²⁺ unit. Three V atoms in the polyoxoanion exhibit distorted tetrahedral coordination geometries while the fourth V atom adopts a trigonal-bipyramidal geometry. The Cu atom adopts a square-pyramidal geometry being coordinated by two nitrogen donors of a 2,2′-bpy ligand, and three bridging O atoms which are linked with V atoms. The V₈ polyoxoanion is connected to [Cu(2,2′-bpy)]²⁺ cations, resulting in a two-dimensional layer structure extending parallel to (010). C—H⋯O hydrogen bonding consolidates the structure.

Related literature

For hybrid organic-inorganic vanadium oxides, see: Zapf et al. (1997 ); Liu et al. (2001 , 2002 ); Yuan et al. (2002 ). For the organic substituents, see: Girginova et al. (2005 ); Paz & Klinowski (2003 ); Shi et al. (2005 ).

Experimental

Crystal data

[Cu₂V₈O₂₁(C₁₀H₈N₂)₂]
M_r = 591.48
Triclinic, $[P \overline 1]$
a = 8.0721 (16) Å
b = 9.764 (2) Å
c = 11.607 (2) Å
α = 85.58 (3)°
β = 72.79 (3)°
γ = 72.28 (3)°
V = 832.4 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.48 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.16 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.504, T_max = 0.573
7138 measured reflections
3261 independent reflections
2916 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.056
S = 1.06
3261 reflections
282 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯O4	0.94 (3)	2.53 (3)	3.068 (4)	117 (2)
C2—H2⋯O6ⁱ	0.91 (3)	2.57 (3)	3.132 (4)	121 (2)
C4—H4⋯O10ⁱⁱ	0.89 (3)	2.53 (3)	3.330 (4)	150 (3)
C7—H5⋯O9ⁱⁱ	0.91 (3)	2.59 (3)	3.306 (4)	136 (3)
C9—H7⋯O6ⁱⁱⁱ	0.89 (3)	2.36 (3)	3.216 (4)	160 (3)
C10—H8⋯O3	0.96 (3)	2.36 (3)	2.937 (4)	118 (2)
Symmetry codes: (i) -x, -y+2, -z+2; (ii) x+1, y-1, z; (iii) -x+1, -y+2, -z+1.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Burnett & Johnson, 1996 ); software used to prepare material for publication: SHELXTL97.

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536809052118/pv2241sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052118/pv2241Isup2.hkl

checkCIF report

Comment top

The introduction of hydrothermal technique and the use of organic groups which were performed not only as template agents, but also as ligands directly coordinated to the inorganic units, have led to the production of various organic-inorganic hybrid vanadium oxides with discrete clusters, one-dimensional, two-dimensional and three-dimensional structures (Zapf et al., 1997; Liu et al., 2001; Liu et al., 2002; Yuan et al.,2002). Typically, the organic substituents have been presented as charge-compensating cations and structural filling agents. Examples of such compounds include the one-dimensional and the two-dimensional phases (Paz et al., 2003; Girginova et al., 2005, Shi et al., 2005). Following interest in the hydrothermal approach to the synthesis of this family of hybrid compounds, we have synthesized a novel organic-inorganic hybrid vanadium oxide complexed with [Cu(2,2'-bpy)]²⁺ cation (bpy = bipyridine), [{Cu(2,2'-bpy)}₂V₈O₂₁], (I). In this article, the crystal structure of the title compound is presented.

The crystals of the title compound (Fig. 1) consist of an unusual two-dimensional layer-like structure grafted with [Cu(2,2'-bpy)]²⁺ complex. The asymmetric unit of (I) contsians four crystallographically independent V atoms briged by 11 oxygen atoms, one of which (O5) lies on an inversion center and a [Cu(2,2'-bpy)]²⁺ complex. The atoms V1, V3 and V4 exhibit distorted tetrahedral coordination geometry coordinated with four bridging oxygen atoms. V1 and V4 share oxygen atoms with one {CuN₂O₃} square pyramid unit, one {VO₅} square pyramid unit and two {VO₄} tetrahedra, while V3 shares oxygen atoms with one {CuN₂O₃} square pyramid unit, two {VO₅} square pyramids and one {VO₄} tetrahedron. The atom V2 shows a trigonal bipyramidal coordination geometry with O9 and O11 atoms in axial and O6, O8 and O10 atoms at equatorial positions. With the exception of O6, the remaining four oxygen atoms are linked with two symmetry related V3 atoms and another two are linked with V1 and V4. The Cu atom adopts a square pyramidal geometry being coordinated by two nitrogen donors of a 2,2'-bpy ligand, and three bridging oxygen atoms which are linked with V1, V3, and V4, respectively. As shown in Fig. 2, two {VO₄} tetrahedra shared a corner to give rise to a V₂O₇ moiety, which further produce a {V₈O₂₁}_n layer. Interestingly, each {CuN₂O₃} square pyramid attaches to three {VO₄} tetrahedra of the vanadate layer via corner-sharing interaction. Therefore, the {[Cu(2,2'-bpy)]₂V₈O₂₁}_n layer consists of 4-, 5- and 6- membered rings. The adjacent layers are stably packed together and exhibit an interesting three-dimensional supramolecular architecture.

Related literature top

For hybrid organic-inorganic vanadium oxides, see: Zapf et al. (1997); Liu et al. (2001, 2002); Yuan et al. (2002). For the organic substituents, see: Girginova et al. (2005); Paz & Klinowski (2003); Shi et al. (2005).

Experimental top

The title compound was hydrothermally synthesized under autogenous pressure. A mixture of V₂O₅(0.66 g,3.6 mmol), As₂O₃(0.48 g,2.4 mmol), CuSO₄.5H₂O(0.75 g, 3 mmol), 2,2'-bipy (0.18 g, 1.2 mmol), 4,4'-bipy (0.24 g, 1.2 mmol) and 18 ml water was stirred for 120 min in air; it was adjusted to pH = 6.5 with 2M KOH, and was heated in a 25-ml stainless steel reactor with a Teflon-liner at 453 K for 3 days, and then cooled to room temperature. The resulting product consisting of brown block crystals was isolated by filtration, washed with distilled water, and dried at ambient temperature (51% yield based on V).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: RAPID-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP drawing of the title compound with thermal ellipsoids at 50% probability. [symmetry codes: (i) 1 - x, 2 - y,1 - z; (ii) - x, 2 - y, 1 - z; (iii) -1 + x, y, z; (iv) - x, 2 - y, 2 - z.]
	Fig. 2. A polyhedral representation of two-dimensional layer-like structure of the title compound. All of the hydrogen atoms are omitted forclarity. [symmetry codes: (i) 1 - x, 2 - y, 1 - z; (ii) - x, 2 - y, 1 - z; (iii) -1 + x, y, z; (iv) - x, 2 - y, 2 - z; (v) 1 + x, y, z.]

Poly[bis(2,2'-bipyridine- κ²N,N')heptadeca-µ-oxido- tetraoxidodicopper(II)divanadate(IV)hexavanadate(V)] top

Crystal data top

[Cu₂V₈O₂₁(C₁₀H₈N₂)₂]	Z = 2
M_r = 591.48	F(000) = 574
Triclinic, P1	D_x = 2.360 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.0721 (16) Å	Cell parameters from 3536 reflections
b = 9.764 (2) Å	θ = 2.8–26.1°
c = 11.607 (2) Å	µ = 3.48 mm⁻¹
α = 85.58 (3)°	T = 293 K
β = 72.79 (3)°	Block, brown
γ = 72.28 (3)°	0.20 × 0.18 × 0.16 mm
V = 832.4 (3) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	3261 independent reflections
Radiation source: fine-focus sealed tube	2916 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 10 pixels mm^-1	θ_max = 26.1°, θ_min = 2.2°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
T_min = 0.504, T_max = 0.573	l = −14→14
7138 measured reflections

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0235P)² + 0.7292P] where P = (F_o² + 2F_c²)/3
3261 reflections	(Δ/σ)_max = 0.001
282 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

[Cu₂V₈O₂₁(C₁₀H₈N₂)₂]	γ = 72.28 (3)°
M_r = 591.48	V = 832.4 (3) Å³
Triclinic, P1	Z = 2
a = 8.0721 (16) Å	Mo Kα radiation
b = 9.764 (2) Å	µ = 3.48 mm⁻¹
c = 11.607 (2) Å	T = 293 K
α = 85.58 (3)°	0.20 × 0.18 × 0.16 mm
β = 72.79 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3261 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2916 reflections with I > 2σ(I)
T_min = 0.504, T_max = 0.573	R_int = 0.018
7138 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	0 restraints
wR(F²) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.39 e Å⁻³
3261 reflections	Δρ_min = −0.37 e Å⁻³
282 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.2395 (4)	0.5437 (3)	0.9302 (3)	0.0289 (7)
C2	0.2805 (5)	0.4323 (3)	1.0073 (3)	0.0320 (7)
C3	0.4432 (5)	0.3260 (3)	0.9710 (3)	0.0317 (7)
C4	0.5612 (4)	0.3335 (3)	0.8579 (3)	0.0274 (6)
C5	0.5109 (4)	0.4469 (3)	0.7846 (2)	0.0198 (6)
C6	0.6235 (4)	0.4644 (3)	0.6616 (2)	0.0201 (6)
C7	0.7827 (4)	0.3634 (3)	0.6024 (3)	0.0284 (7)
C8	0.8728 (4)	0.3894 (3)	0.4858 (3)	0.0322 (7)
C9	0.8050 (4)	0.5152 (3)	0.4314 (3)	0.0306 (7)
C10	0.6460 (4)	0.6144 (3)	0.4955 (3)	0.0265 (6)
Cu1	0.31722 (4)	0.71169 (3)	0.70685 (3)	0.01922 (9)
H1	0.128 (4)	0.617 (3)	0.952 (3)	0.029 (8)*
H2	0.200 (4)	0.430 (3)	1.081 (3)	0.029 (8)*
H3	0.472 (4)	0.254 (4)	1.021 (3)	0.033 (9)*
H4	0.668 (4)	0.267 (3)	0.832 (3)	0.029 (8)*
H5	0.823 (4)	0.284 (4)	0.644 (3)	0.036 (9)*
H6	0.987 (4)	0.315 (3)	0.445 (3)	0.029 (8)*
H7	0.865 (4)	0.532 (3)	0.356 (3)	0.027 (8)*
H8	0.591 (4)	0.703 (3)	0.461 (3)	0.026 (8)*
N1	0.3521 (3)	0.5516 (2)	0.8213 (2)	0.0210 (5)
N2	0.5557 (3)	0.5887 (2)	0.6079 (2)	0.0205 (5)
O1	0.4258 (3)	0.8537 (2)	0.79009 (18)	0.0333 (5)
O2	0.3334 (3)	1.0721 (2)	0.41281 (17)	0.0276 (4)
O3	0.3006 (3)	0.8439 (2)	0.57234 (18)	0.0270 (4)
O4	0.0648 (3)	0.8000 (2)	0.79171 (18)	0.0296 (5)
O5	0.0000	1.0000	0.5000	0.0330 (7)
O6	0.0361 (3)	1.3383 (2)	0.81792 (17)	0.0274 (5)
O7	−0.3076 (3)	0.9544 (2)	0.82587 (18)	0.0308 (5)
O8	0.3910 (2)	1.1332 (2)	0.75539 (17)	0.0262 (4)
O9	0.1379 (3)	1.1176 (2)	0.65337 (16)	0.0244 (4)
O10	−0.0633 (3)	1.0792 (2)	0.87494 (17)	0.0247 (4)
O11	−0.1608 (3)	0.8630 (2)	1.02173 (17)	0.0284 (5)
V1	0.54061 (6)	0.96749 (5)	0.74290 (4)	0.01637 (11)
V2	0.12848 (6)	1.16967 (5)	0.81859 (4)	0.01575 (10)
V3	−0.11097 (6)	0.92167 (5)	0.87896 (4)	0.01417 (10)
V4	0.19437 (6)	1.00633 (5)	0.53774 (4)	0.01430 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0296 (16)	0.0257 (16)	0.0275 (16)	−0.0045 (14)	−0.0062 (13)	0.0000 (13)
C2	0.0417 (19)	0.0330 (17)	0.0197 (16)	−0.0140 (15)	−0.0046 (14)	0.0047 (13)
C3	0.0436 (19)	0.0250 (16)	0.0297 (17)	−0.0111 (14)	−0.0167 (15)	0.0108 (13)
C4	0.0263 (16)	0.0228 (15)	0.0316 (17)	−0.0029 (13)	−0.0113 (13)	0.0033 (12)
C5	0.0228 (14)	0.0174 (13)	0.0222 (14)	−0.0052 (11)	−0.0113 (11)	−0.0006 (11)
C6	0.0199 (14)	0.0171 (13)	0.0243 (14)	−0.0036 (11)	−0.0095 (11)	−0.0003 (11)
C7	0.0241 (15)	0.0252 (16)	0.0335 (17)	−0.0007 (13)	−0.0115 (13)	0.0008 (13)
C8	0.0220 (15)	0.0311 (17)	0.0360 (18)	−0.0008 (13)	−0.0030 (14)	−0.0057 (14)
C9	0.0281 (16)	0.0340 (17)	0.0266 (17)	−0.0104 (14)	−0.0017 (13)	−0.0011 (13)
C10	0.0281 (16)	0.0274 (16)	0.0238 (15)	−0.0085 (13)	−0.0079 (13)	0.0045 (12)
Cu1	0.01834 (17)	0.01617 (17)	0.02058 (18)	−0.00094 (13)	−0.00635 (13)	0.00129 (13)
N1	0.0232 (12)	0.0174 (11)	0.0210 (12)	−0.0046 (9)	−0.0061 (10)	0.0021 (9)
N2	0.0209 (12)	0.0172 (11)	0.0233 (12)	−0.0040 (9)	−0.0080 (10)	0.0016 (9)
O1	0.0460 (13)	0.0461 (13)	0.0204 (10)	−0.0322 (11)	−0.0096 (10)	0.0041 (9)
O2	0.0322 (11)	0.0334 (11)	0.0166 (10)	−0.0143 (9)	−0.0020 (8)	0.0021 (8)
O3	0.0280 (11)	0.0242 (10)	0.0260 (11)	−0.0007 (9)	−0.0119 (9)	0.0042 (8)
O4	0.0204 (10)	0.0293 (11)	0.0314 (12)	0.0006 (9)	−0.0038 (9)	−0.0022 (9)
O5	0.0244 (15)	0.0468 (19)	0.0342 (17)	−0.0099 (14)	−0.0179 (13)	−0.0021 (14)
O6	0.0340 (11)	0.0217 (10)	0.0213 (10)	−0.0047 (9)	−0.0038 (9)	0.0000 (8)
O7	0.0211 (10)	0.0457 (13)	0.0304 (12)	−0.0080 (9)	−0.0159 (9)	−0.0024 (10)
O8	0.0198 (10)	0.0335 (11)	0.0233 (10)	−0.0052 (9)	−0.0064 (8)	0.0014 (9)
O9	0.0282 (11)	0.0295 (11)	0.0163 (10)	−0.0069 (9)	−0.0084 (8)	−0.0033 (8)
O10	0.0246 (10)	0.0259 (10)	0.0267 (11)	−0.0124 (9)	−0.0075 (8)	0.0029 (8)
O11	0.0348 (12)	0.0411 (12)	0.0181 (10)	−0.0201 (10)	−0.0132 (9)	0.0078 (9)
V1	0.0148 (2)	0.0247 (2)	0.0129 (2)	−0.00865 (19)	−0.00619 (17)	0.00187 (17)
V2	0.0192 (2)	0.0173 (2)	0.0117 (2)	−0.00599 (18)	−0.00523 (17)	0.00065 (17)
V3	0.0121 (2)	0.0199 (2)	0.0120 (2)	−0.00499 (17)	−0.00582 (16)	0.00196 (17)
V4	0.0136 (2)	0.0184 (2)	0.0109 (2)	−0.00274 (17)	−0.00571 (17)	0.00037 (16)

Geometric parameters (Å, º) top

C1—N1	1.333 (4)	Cu1—N2	1.991 (2)
C1—C2	1.378 (4)	Cu1—O1	2.252 (2)
C1—H1	0.94 (3)	O1—V1	1.621 (2)
C2—C3	1.375 (5)	O2—V4	1.763 (2)
C2—H2	0.91 (3)	O2—V1ⁱ	1.797 (2)
C3—C4	1.387 (4)	O3—V4	1.6398 (19)
C3—H3	0.90 (3)	O4—V3	1.661 (2)
C4—C5	1.379 (4)	O5—V4ⁱⁱ	1.7684 (6)
C4—H4	0.89 (3)	O5—V4	1.7684 (6)
C5—N1	1.348 (3)	O6—V2	1.588 (2)
C5—C6	1.477 (4)	O7—V1ⁱⁱⁱ	1.7405 (19)
C6—N2	1.357 (3)	O7—V3	1.8003 (19)
C6—C7	1.381 (4)	O8—V1	1.686 (2)
C7—C8	1.379 (4)	O8—V2	1.953 (2)
C7—H5	0.91 (3)	O9—V4	1.6586 (19)
C8—C9	1.372 (4)	O9—V2	1.9957 (19)
C8—H6	0.99 (3)	O10—V3	1.6894 (19)
C9—C10	1.389 (4)	O10—V2	1.936 (2)
C9—H7	0.89 (3)	O11—V3	1.6840 (19)
C10—N2	1.340 (4)	O11—V2^iv	1.9363 (19)
C10—H8	0.96 (3)	V1—O7^v	1.7405 (19)
Cu1—O4	1.934 (2)	V1—O2ⁱ	1.797 (2)
Cu1—O3	1.957 (2)	V2—O11^iv	1.9363 (19)
Cu1—N1	1.980 (2)

N1—C1—C2	122.2 (3)	C5—N1—Cu1	114.58 (18)
N1—C1—H1	116.7 (19)	C10—N2—C6	119.3 (2)
C2—C1—H1	121.0 (19)	C10—N2—Cu1	126.54 (19)
C3—C2—C1	118.9 (3)	C6—N2—Cu1	114.11 (18)
C3—C2—H2	121 (2)	V1—O1—Cu1	136.75 (11)
C1—C2—H2	120 (2)	V4—O2—V1ⁱ	142.02 (12)
C2—C3—C4	119.2 (3)	V4—O3—Cu1	143.18 (12)
C2—C3—H3	119 (2)	V3—O4—Cu1	156.12 (13)
C4—C3—H3	121 (2)	V4ⁱⁱ—O5—V4	180.0
C5—C4—C3	118.9 (3)	V1ⁱⁱⁱ—O7—V3	166.30 (13)
C5—C4—H4	120 (2)	V1—O8—V2	123.33 (11)
C3—C4—H4	121 (2)	V4—O9—V2	154.58 (12)
N1—C5—C4	121.5 (3)	V3—O10—V2	143.70 (12)
N1—C5—C6	114.8 (2)	V3—O11—V2^iv	153.85 (12)
C4—C5—C6	123.7 (3)	O1—V1—O8	107.63 (11)
N2—C6—C7	121.4 (3)	O1—V1—O7^v	110.71 (11)
N2—C6—C5	114.4 (2)	O8—V1—O7^v	111.38 (10)
C7—C6—C5	124.2 (3)	O1—V1—O2ⁱ	108.79 (10)
C8—C7—C6	119.0 (3)	O8—V1—O2ⁱ	109.54 (10)
C8—C7—H5	124 (2)	O7^v—V1—O2ⁱ	108.75 (10)
C6—C7—H5	117 (2)	O6—V2—O11^iv	103.25 (10)
C9—C8—C7	119.8 (3)	O6—V2—O10	107.76 (10)
C9—C8—H6	122.7 (18)	O11^iv—V2—O10	86.50 (9)
C7—C8—H6	117.5 (18)	O6—V2—O8	107.90 (10)
C8—C9—C10	119.0 (3)	O11^iv—V2—O8	87.79 (9)
C8—C9—H7	119 (2)	O10—V2—O8	144.26 (9)
C10—C9—H7	122 (2)	O6—V2—O9	99.91 (10)
N2—C10—C9	121.5 (3)	O11^iv—V2—O9	156.82 (9)
N2—C10—H8	116.0 (18)	O10—V2—O9	85.62 (9)
C9—C10—H8	122.4 (18)	O8—V2—O9	85.96 (9)
O4—Cu1—O3	91.37 (9)	O4—V3—O11	110.09 (11)
O4—Cu1—N1	94.77 (10)	O4—V3—O10	110.01 (10)
O3—Cu1—N1	170.15 (9)	O11—V3—O10	110.08 (10)
O4—Cu1—N2	167.12 (9)	O4—V3—O7	110.49 (10)
O3—Cu1—N2	90.36 (9)	O11—V3—O7	108.55 (10)
N1—Cu1—N2	81.96 (10)	O10—V3—O7	107.58 (10)
O4—Cu1—O1	95.62 (9)	O3—V4—O9	109.67 (10)
O3—Cu1—O1	90.80 (8)	O3—V4—O2	111.30 (10)
N1—Cu1—O1	96.24 (9)	O9—V4—O2	107.76 (10)
N2—Cu1—O1	97.12 (9)	O3—V4—O5	108.67 (8)
C1—N1—C5	119.1 (2)	O9—V4—O5	111.12 (7)
C1—N1—Cu1	126.2 (2)	O2—V4—O5	108.34 (7)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4	0.94 (3)	2.53 (3)	3.068 (4)	117 (2)
C2—H2···O6^iv	0.91 (3)	2.57 (3)	3.132 (4)	121 (2)
C4—H4···O10^vi	0.89 (3)	2.53 (3)	3.330 (4)	150 (3)
C7—H5···O9^vi	0.91 (3)	2.59 (3)	3.306 (4)	136 (3)
C9—H7···O6ⁱ	0.89 (3)	2.36 (3)	3.216 (4)	160 (3)
C10—H8···O3	0.96 (3)	2.36 (3)	2.937 (4)	118 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu₂V₈O₂₁(C₁₀H₈N₂)₂]
M_r	591.48
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.0721 (16), 9.764 (2), 11.607 (2)
α, β, γ (°)	85.58 (3), 72.79 (3), 72.28 (3)
V (Å³)	832.4 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.48
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.504, 0.573
No. of measured, independent and observed [I > 2σ(I)] reflections	7138, 3261, 2916
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.619

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.056, 1.06
No. of reflections	3261
No. of parameters	282
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.37

Computer programs: RAPID-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL (Sheldrick, 2008), ORTEP-3 (Burnett & Johnson, 1996), SHELXTL97 (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O4	0.94 (3)	2.53 (3)	3.068 (4)	117 (2)
C2—H2···O6ⁱ	0.91 (3)	2.57 (3)	3.132 (4)	121 (2)
C4—H4···O10ⁱⁱ	0.89 (3)	2.53 (3)	3.330 (4)	150 (3)
C7—H5···O9ⁱⁱ	0.91 (3)	2.59 (3)	3.306 (4)	136 (3)
C9—H7···O6ⁱⁱⁱ	0.89 (3)	2.36 (3)	3.216 (4)	160 (3)
C10—H8···O3	0.96 (3)	2.36 (3)	2.937 (4)	118 (2)

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

References

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