Poly[bis­(2,2′-bipyridine-κ²N,N′)deca-μ-oxido-dioxidodicopper(II)tetra­vanadium(V)]

The title compound, [Cu₂V₄O₁₂(C₁₀H₈N₂)₂]_n, shows a two-dimensional copper–vanadate layer composed of eight-membered rings, each containing four corner-sharing VO₄ tetra­hedra; these are linked through six penta­coordinated Cu^II atoms with the 2,2′-bipyridine ligands attached and pointing above and below the plane of the layer. The Cu atom is coordinated by two N donors from the 2,2′-bipyridine ligand and three O atoms from three adjacent VO₄ units to form a distorted tetragonal pyramid. These layers are further connected by π–π inter­actions between inter­leaving bipyridine ligands of adjacent layers [centroid–centroid distances = 3.63 (1) and 3.68 (1) Å] into a three-dimensional supra­molecular structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• R factor = 0.034
• wR factor = 0.084
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found


No errors found in this datablock

---

S1. Comment

Considerable efforts have been devoted to the hydrothermal synthesis of solid-state inorganic–organic hybrid vanadate(V) species based on discrete clusters, infinite chain and layer structures, such as [Zn(phen)₃][V₂O₆].10H₂O and [Cu(bipy)V₂O₆] (Yi et al., 2007), [Cu(bipy)][V₂O₆] and [Cu(bipy)₂][V₂O₆] (DeBord et al., 1996), [Mn(phen)₂]₂[V₄O₁₂].0.5H₂O (Lu et al., 2002), and [Co(phen)₂]₂[V₄O₁₂].H₂O (Kucsera et al., 2002), because of their diverse topologies and fascinating physical properties. We report here the crystal structure of a new complex, {[Cu(bipy)]₂V₄O₁₂}_n (bipy = 2,2'-bipyridine).

The asymmetric unit of the title compound consists of one Cu^II atom, one bipy molecule and a half of V₄O₁₂ unit (Fig. 1). The V₄O₁₂ units are linked through six square-pyramidal Cu^II atoms to six adjacent V₄O₁₂ rings (Fig. 2). Two of VO₄ units in the V₄O₁₂ unit each connect with one square-pyramidal Cu unit, while the other two VO₄ units each exhibit corner-sharing interactions with two Cu units. Each Cu unit links three V₄O₁₂ units through corner-sharing interactions. In this way, a two-dimensional layer is formed (Fig. 2). The Cu^II atom is coordinated by two pyridine N atoms and three tetravanadate O atoms (Fig. 1 and Table 1). The relative orientation of the bipy ligand with respect to the copper–vanadate layer is depicted by a dihedral angel of 84.6 (6)°. Furthermore, these bipy ligands interact with each other through π–π interactions between adjacent layers with centroid–centroid distances of 3.63 (1) and 3.68 (1) Å.

Related literature

For related literature, see: DeBord et al. (1996); Kucsera et al. (2002); Lu et al. (2002); Yi et al. (2007).

S2. Experimental

The title compound was prepared hydrothermally from a mixture of V₂O₅ (0.73 g, 4.0 mmol), 2,2'-bipyridine dihydrate (0.38 g, 2.0 mmol), CuCl₂.2H₂O (0.34 g, 2.0 mmol) and water (18 ml) (molar ratio 2:1:1:500), adjusting pH to ca 6.1 with 4 M KOH, in a 25 ml Teflon-lined stainless steel reactor heated to 443 K for 7 d. After cooling to room temperature, green crystals were collected.

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The asymmetric unit of the title compound, extended to show the V4O12 unit. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) x, y - 1, z; (iii) 2 - x, 1 - y, 1 - z.]
	Fig. 2. A view of the copper–vanadate layer with C and H atoms of the bipy ligands omitted for clarity.

poly[bis(2,2'-bipyridine-κ²N,N')deca-µ-oxido- dioxidodicopper(II)tetravanadium(V)],

Crystal data

[Cu2V4O12(C10H8N2)2]	Z = 2
Mr = 417.60	F(000) = 410
Triclinic, P1	Dx = 2.137 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1019 (4) Å	Cell parameters from 3811 reflections
b = 8.3122 (5) Å	θ = 2.1–28.3°
c = 10.3501 (4) Å	µ = 3.06 mm^−1
α = 72.332 (3)°	T = 298 K
β = 84.562 (3)°	Block, green
γ = 77.878 (3)°	0.33 × 0.31 × 0.25 mm
V = 648.98 (6) Å^3

Data collection

Bruker SMART APEX CCD diffractometer	3114 independent reflections
Radiation source: fine-focus sealed tube	2553 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ϕ and ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −10→9
Tmin = 0.379, Tmax = 0.469	k = −10→7
4603 measured reflections	l = −13→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 0.99	w = 1/[σ^2(Fo^2) + (0.0438P)^2] where P = (Fo^2 + 2Fc^2)/3
3114 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.75 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.59216 (4)	0.14236 (4)	0.28662 (3)	0.01368 (10)
V1	0.87679 (6)	0.39002 (6)	0.34998 (5)	0.01604 (12)
V2	0.73879 (6)	0.72867 (6)	0.47736 (5)	0.01495 (12)
O1	0.7741 (3)	0.2421 (3)	0.3367 (2)	0.0249 (5)
O2	0.9198 (3)	0.5062 (3)	0.1993 (2)	0.0359 (6)
O3	0.7425 (3)	0.5317 (3)	0.4394 (2)	0.0259 (5)
O4	0.5705 (3)	0.7685 (3)	0.5748 (2)	0.0270 (5)
O5	0.9278 (3)	0.7084 (3)	0.5595 (2)	0.0285 (5)
O6	0.7286 (3)	0.8942 (3)	0.3363 (2)	0.0247 (5)
N1	0.5900 (3)	0.2590 (3)	0.0777 (2)	0.0191 (5)
N2	0.3794 (3)	0.0700 (3)	0.2320 (2)	0.0202 (5)
C1	0.7065 (4)	0.3461 (4)	0.0041 (3)	0.0242 (6)
H1	0.7903	0.3671	0.0489	0.029*
C2	0.7057 (4)	0.4056 (4)	−0.1364 (3)	0.0300 (7)
H2	0.7869	0.4667	−0.1848	0.036*
C3	0.5828 (4)	0.3731 (4)	−0.2037 (3)	0.0270 (7)
H3	0.5811	0.4107	−0.2980	0.032*
C4	0.4620 (4)	0.2835 (4)	−0.1289 (3)	0.0232 (6)
H4	0.3787	0.2594	−0.1722	0.028*
C5	0.4675 (4)	0.2303 (4)	0.0120 (3)	0.0192 (6)
C6	0.3397 (4)	0.1390 (4)	0.1003 (3)	0.0187 (6)
C7	0.1878 (4)	0.1270 (4)	0.0534 (3)	0.0288 (7)
H7	0.1610	0.1775	−0.0372	0.035*
C8	0.0781 (4)	0.0386 (4)	0.1448 (4)	0.0309 (7)
H8	−0.0237	0.0290	0.1160	0.037*
C9	0.1209 (4)	−0.0351 (4)	0.2786 (3)	0.0274 (7)
H9	0.0492	−0.0962	0.3409	0.033*
C10	0.2718 (4)	−0.0166 (4)	0.3187 (3)	0.0247 (6)
H10	0.3001	−0.0660	0.4091	0.030*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01353 (17)	0.01631 (18)	0.01260 (17)	−0.00306 (12)	−0.00204 (12)	−0.00563 (13)
V1	0.0140 (2)	0.0172 (2)	0.0183 (2)	−0.00322 (18)	−0.00335 (18)	−0.00613 (19)
V2	0.0127 (2)	0.0155 (2)	0.0177 (2)	−0.00107 (17)	−0.00215 (18)	−0.00696 (18)
O1	0.0202 (11)	0.0282 (12)	0.0335 (12)	−0.0079 (9)	−0.0034 (9)	−0.0167 (10)
O2	0.0332 (14)	0.0428 (14)	0.0249 (12)	−0.0122 (11)	−0.0004 (10)	0.0031 (11)
O3	0.0243 (12)	0.0225 (11)	0.0346 (13)	−0.0036 (9)	0.0016 (10)	−0.0154 (10)
O4	0.0201 (11)	0.0366 (13)	0.0301 (12)	−0.0050 (9)	0.0047 (9)	−0.0201 (10)
O5	0.0228 (12)	0.0308 (12)	0.0346 (13)	−0.0013 (9)	−0.0112 (10)	−0.0128 (10)
O6	0.0245 (11)	0.0204 (11)	0.0266 (11)	−0.0018 (9)	−0.0051 (9)	−0.0034 (9)
N1	0.0195 (12)	0.0206 (12)	0.0179 (12)	−0.0040 (10)	−0.0029 (10)	−0.0059 (10)
N2	0.0225 (13)	0.0233 (13)	0.0178 (12)	−0.0065 (10)	−0.0011 (10)	−0.0088 (10)
C1	0.0211 (15)	0.0252 (16)	0.0269 (16)	−0.0057 (12)	−0.0012 (12)	−0.0077 (13)
C2	0.0264 (17)	0.0326 (18)	0.0299 (17)	−0.0117 (14)	0.0065 (14)	−0.0058 (14)
C3	0.0328 (18)	0.0269 (16)	0.0177 (15)	−0.0036 (13)	−0.0008 (13)	−0.0027 (12)
C4	0.0261 (16)	0.0256 (16)	0.0199 (15)	−0.0037 (12)	−0.0050 (12)	−0.0090 (12)
C5	0.0181 (14)	0.0190 (14)	0.0211 (14)	−0.0013 (11)	−0.0044 (11)	−0.0072 (11)
C6	0.0188 (14)	0.0207 (14)	0.0188 (14)	−0.0048 (11)	−0.0023 (11)	−0.0078 (11)
C7	0.0270 (17)	0.0350 (18)	0.0252 (16)	−0.0084 (14)	−0.0101 (13)	−0.0056 (14)
C8	0.0204 (16)	0.0381 (19)	0.0376 (19)	−0.0095 (14)	−0.0062 (14)	−0.0118 (15)
C9	0.0242 (16)	0.0299 (17)	0.0318 (18)	−0.0129 (13)	0.0058 (13)	−0.0110 (14)
C10	0.0263 (17)	0.0295 (17)	0.0192 (14)	−0.0094 (13)	0.0023 (12)	−0.0065 (12)

Geometric parameters (Å, º)

Cu1—O1	2.012 (2)	N2—C6	1.350 (4)
Cu1—O4^i	2.054 (2)	C1—C2	1.387 (4)
Cu1—O6^ii	2.061 (2)	C1—H1	0.9300
Cu1—N1	2.084 (2)	C2—C3	1.381 (5)
Cu1—N2	2.117 (2)	C2—H2	0.9300
V1—O2	1.615 (2)	C3—C4	1.388 (5)
V1—O1	1.667 (2)	C3—H3	0.9300
V1—O5^iii	1.824 (2)	C4—C5	1.392 (4)
V1—O3	1.833 (2)	C4—H4	0.9300
V2—O4	1.655 (2)	C5—C6	1.488 (4)
V2—O6	1.670 (2)	C6—C7	1.397 (4)
V2—O5	1.774 (2)	C7—C8	1.384 (5)
V2—O3	1.790 (2)	C7—H7	0.9300
O4—Cu1^i	2.054 (2)	C8—C9	1.379 (5)
O5—V1^iii	1.824 (2)	C8—H8	0.9300
O6—Cu1^iv	2.061 (2)	C9—C10	1.379 (4)
N1—C1	1.346 (4)	C9—H9	0.9300
N1—C5	1.352 (4)	C10—H10	0.9300
N2—C10	1.344 (4)
O1—Cu1—O4^i	89.62 (9)	C6—N2—Cu1	114.9 (2)
O1—Cu1—O6^ii	94.53 (9)	N1—C1—C2	122.1 (3)
O4^i—Cu1—O6^ii	121.32 (9)	N1—C1—H1	118.9
O1—Cu1—N1	100.17 (9)	C2—C1—H1	118.9
O4^i—Cu1—N1	124.55 (9)	C3—C2—C1	119.2 (3)
O6^ii—Cu1—N1	112.18 (9)	C3—C2—H2	120.4
O1—Cu1—N2	172.29 (9)	C1—C2—H2	120.4
O4^i—Cu1—N2	85.25 (9)	C2—C3—C4	119.1 (3)
O6^ii—Cu1—N2	93.05 (9)	C2—C3—H3	120.4
N1—Cu1—N2	78.18 (10)	C4—C3—H3	120.4
O2—V1—O1	108.65 (12)	C3—C4—C5	118.9 (3)
O2—V1—O5^iii	109.43 (12)	C3—C4—H4	120.6
O1—V1—O5^iii	111.53 (11)	C5—C4—H4	120.6
O2—V1—O3	107.98 (12)	N1—C5—C4	121.9 (3)
O1—V1—O3	110.08 (11)	N1—C5—C6	115.6 (3)
O5^iii—V1—O3	109.09 (10)	C4—C5—C6	122.5 (3)
O4—V2—O6	107.88 (11)	N2—C6—C7	121.6 (3)
O4—V2—O5	111.20 (11)	N2—C6—C5	114.8 (2)
O6—V2—O5	108.55 (11)	C7—C6—C5	123.6 (3)
O4—V2—O3	109.63 (11)	C8—C7—C6	118.6 (3)
O6—V2—O3	111.29 (11)	C8—C7—H7	120.7
O5—V2—O3	108.30 (10)	C6—C7—H7	120.7
V1—O1—Cu1	159.01 (14)	C9—C8—C7	119.6 (3)
V2—O3—V1	139.64 (14)	C9—C8—H8	120.2
V2—O4—Cu1^i	162.64 (14)	C7—C8—H8	120.2
V2—O5—V1^iii	160.20 (14)	C8—C9—C10	118.9 (3)
V2—O6—Cu1^iv	133.16 (13)	C8—C9—H9	120.6
C1—N1—C5	118.7 (3)	C10—C9—H9	120.6
C1—N1—Cu1	125.5 (2)	N2—C10—C9	122.5 (3)
C5—N1—Cu1	115.6 (2)	N2—C10—H10	118.7
C10—N2—C6	118.8 (3)	C9—C10—H10	118.7
C10—N2—Cu1	125.7 (2)
O2—V1—O1—Cu1	−60.3 (4)	N1—Cu1—N2—C10	−175.0 (3)
O5^iii—V1—O1—Cu1	179.0 (4)	O4^i—Cu1—N2—C6	122.4 (2)
O3—V1—O1—Cu1	57.8 (4)	O6^ii—Cu1—N2—C6	−116.4 (2)
O4^i—Cu1—O1—V1	−68.8 (4)	N1—Cu1—N2—C6	−4.4 (2)
O6^ii—Cu1—O1—V1	169.8 (4)	C5—N1—C1—C2	−0.6 (5)
N1—Cu1—O1—V1	56.3 (4)	Cu1—N1—C1—C2	173.5 (2)
O4—V2—O3—V1	−176.89 (19)	N1—C1—C2—C3	−0.8 (5)
O6—V2—O3—V1	63.8 (2)	C1—C2—C3—C4	0.8 (5)
O5—V2—O3—V1	−55.4 (2)	C2—C3—C4—C5	0.5 (5)
O2—V1—O3—V2	−51.5 (2)	C1—N1—C5—C4	2.0 (4)
O1—V1—O3—V2	−169.94 (19)	Cu1—N1—C5—C4	−172.6 (2)
O5^iii—V1—O3—V2	67.4 (2)	C1—N1—C5—C6	−177.8 (3)
O6—V2—O4—Cu1^i	−84.8 (5)	Cu1—N1—C5—C6	7.5 (3)
O5—V2—O4—Cu1^i	34.1 (5)	C3—C4—C5—N1	−2.0 (4)
O3—V2—O4—Cu1^i	153.8 (4)	C3—C4—C5—C6	177.9 (3)
O4—V2—O5—V1^iii	104.6 (4)	C10—N2—C6—C7	2.1 (4)
O6—V2—O5—V1^iii	−136.9 (4)	Cu1—N2—C6—C7	−169.2 (2)
O3—V2—O5—V1^iii	−15.9 (5)	C10—N2—C6—C5	−179.3 (3)
O4—V2—O6—Cu1^iv	17.23 (19)	Cu1—N2—C6—C5	9.5 (3)
O5—V2—O6—Cu1^iv	−103.38 (17)	N1—C5—C6—N2	−11.3 (4)
O3—V2—O6—Cu1^iv	137.53 (15)	C4—C5—C6—N2	168.8 (3)
O1—Cu1—N1—C1	11.4 (3)	N1—C5—C6—C7	167.3 (3)
O4^i—Cu1—N1—C1	108.1 (2)	C4—C5—C6—C7	−12.5 (5)
O6^ii—Cu1—N1—C1	−87.8 (3)	N2—C6—C7—C8	−1.5 (5)
N2—Cu1—N1—C1	−176.2 (3)	C5—C6—C7—C8	180.0 (3)
O1—Cu1—N1—C5	−174.30 (19)	C6—C7—C8—C9	0.0 (5)
O4^i—Cu1—N1—C5	−77.7 (2)	C7—C8—C9—C10	0.9 (5)
O6^ii—Cu1—N1—C5	86.5 (2)	C6—N2—C10—C9	−1.2 (5)
N2—Cu1—N1—C5	−1.97 (19)	Cu1—N2—C10—C9	169.1 (2)
O4^i—Cu1—N2—C10	−48.2 (3)	C8—C9—C10—N2	−0.3 (5)
O6^ii—Cu1—N2—C10	73.0 (3)

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