(μ-Oxalato-κ4O1,O2:O1′,O2′)bis­[bis­(2,2′-bipyridine-κ2N,N′)cobalt(II)] μ6-oxido-dodeca-μ2-oxido-hexa­oxido-hexa­tungstate(VI)

Shi, C.; Fan, L.; Wei, P.; Li, B.; Zhang, X.

doi:10.1107/S1600536810023007

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages m822-m823

doi:10.1107/S1600536810023007

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(μ-Oxalato-κ⁴O¹,O²:O^1′,O^2′)bis[bis(2,2′-bipyridine-κ²N,N′)cobalt(II)] μ₆-oxido-dodeca-μ₂-oxido-hexaoxido-hexatungstate(VI)

Congwen Shi,^a Liming Fan,^a,^b Peihai Wei,^a Bin Li ^b and Xiutang Zhang ^a,^b ^*

^aAdvanced Material Institute of Research, Department of Chemistry, Qilu Normal University, Jinan 250013, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, 252059, People's Republic of China
^*Correspondence e-mail: xiutangzhang@yahoo.com.cn

(Received 27 May 2010; accepted 15 June 2010; online 18 June 2010)

The asymmetric unit of the title compound, [Co₂(C₂O₄)(C₁₀H₈N₂)₄][W₆O₁₉], consists of one half of the complex [Co₂(C₂O₄)(C₁₀H₈N₂)₄]²⁺ cation and one half of the Lindqvist-type [W₆O₁₉]²⁻ isopolyanion. Both constituents are completed by crystallographic inversion symmetry. In the dimeric cation, the Co^II atom is surrounded in a distorted octahedral coordination by four N atoms from two chelating 2,2′-bipyridine ligands and by two O atoms from the chelating oxalate anion. The Lindqvist-type anion exhibits the characteristic W—O bond-length distribution, with the shortest bonds being the W—O_terminal bonds and the longest being those to the central O atom.

Related literature

For general background to polyoxidometalates, see: Pope & Müller (1991 ). For polyoxidometalates modified with amines, see: Zhang, Dou et al. (2009 ); Zhang, Wei et al. (2009 ); Zhang et al. (2010 ). For another structure comprising a Lindqvist-type isopolyanion, see: Meng et al. (2006 ). For a related structure, see: Li & Xu (2009 ).

Experimental

Crystal data

[Co₂(C₂O₄)(C₁₀H₈N₂)₄][W₆O₁₉]
M_r = 2237.72
Triclinic, $[P \overline 1]$
a = 9.4876 (15) Å
b = 9.8548 (15) Å
c = 14.174 (2) Å
α = 90.769 (2)°
β = 91.576 (2)°
γ = 91.113 (2)°
V = 1324.3 (4) Å³
Z = 1
Mo Kα radiation
μ = 13.67 mm⁻¹
T = 293 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.291, T_max = 0.408
9331 measured reflections
4613 independent reflections
3755 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.076
S = 1.00
4613 reflections
368 parameters
H-atom parameters constrained
Δρ_max = 2.41 e Å⁻³
Δρ_min = −1.10 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.104 (6)
Co1—N1	2.101 (7)
Co1—N4	2.105 (6)
Co1—N2	2.114 (6)
Co1—N3	2.119 (7)
Co1—O2	2.134 (6)
O3—W2	1.690 (6)
O4—W2	1.919 (6)
O4—W3	1.926 (6)
O5—W3	1.904 (5)
O5—W2ⁱ	1.935 (5)
O6—W3	1.698 (6)
O7—W3	1.915 (6)
O7—W1	1.931 (6)
O8—W3ⁱ	2.3185 (4)
O8—W3	2.3185 (4)
O8—W1	2.3240 (4)
O8—W1ⁱ	2.3240 (4)
O8—W2ⁱ	2.3252 (5)
O8—W2	2.3252 (5)
O9—W2	1.912 (6)
O9—W1	1.915 (5)
O10—W1	1.914 (6)
O10—W3ⁱ	1.914 (6)
O11—W1	1.696 (6)
O12—W1	1.922 (5)
O12—W2ⁱ	1.920 (6)
Symmetry code: (i) -x+1, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; 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 global, I. DOI: 10.1107/S1600536810023007/wm2358sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810023007/wm2358Isup2.hkl

checkCIF report

Comment top

There has been extensive interest in polyoxidometalates, owing to their fascinating properties and great potential applications in many fields such in catalysis, material science, medicine and magnetochemistry (Pope & Müller, 1991). Organic amines, such as 3-(2-pyridyl)pyrazole and pyrazine, are used to effectively modify polyoxidomolybdates or heteropolyoxidomolybdates under hydrothermal condictions (Zhang, Dou et al., 2009; Zhang, Wei et al., 2009; Zhang et al., 2010). Here, we describe the synthesis and structural characterization of the title compound.

As shown in Figure 1, the title compound consists of two subunits, viz. of a binuclear complex [Co₂(C₂O₄)(C₁₀H₈N₂)₄]²⁺ cation, and one Lindqvist-type [W₆O₁₉]^2- isopolyanion. Both constituents exhibit 1 symmetry. The Co²⁺ cation is surrounded in a distorted octahedral coordination by four N atoms from two chelating 2,2'-bipyridine ligands and two O atoms from a chelating oxalate anion. The Co—N and Co—O bond lengths are in the range of 2.101 (7)—2.119 (7) and 2.104 (6)—2.134 (6) Å, respectively, and are in good agreement with the bond lenghts observed for catena-poly[[(2,2'-bipyridine-κN,N')cobalt(II)]-µ-oxalato- κ⁴O¹,O²:O^1',O^2'] (Li & Xu, 2009).

The [W₆O₁₉]^2- polyoxidoanion, possessing the well known Lindquist structure, is formed by six WO₆ octahedra connected with each other through edge-sharing oxygen atoms. This anion approaches an approximate O_h symmetry, but actually has 1 symmetry. Three different kinds of oxygen atoms exist in the cluster, viz. terminal Oa, double-bridging Ob, and central Oc oxygen atoms. Therefore, W—O bond lengths can be grouped into three sets: W—Oa: 1.690 (6)—1.698 (6) Å; W—Ob: 1.904 (5)—1.935 (5) Å; W—Oc: 2.3185 (4)—2.3252 (5) Å; these bond lengths strictly follow the rule W—Oa < W—Ob < W—Oc, which is in agreement with the Lindqvist-type polyoxidotungstate reported by Meng et al. (2006).

Related literature top

For general background to polyoxidometalates, see: Pope & Müller (1991). For polyoxidometalates modified with amines, see: Zhang, Dou et al. (2009); Zhang, Wei et al. (2009); Zhang et al. (2010). For another structure comprising a Lindqvist-type isopolyanion, see: Meng et al. (2006). For a related structure, see: Li & Xu (2009).

Experimental top

2,2'-bipyridine (0.5 mmoL 0.07 g) and p-carboxyphenylboronic acid were purchased from Jinan Henghua Science & Technology Co. Ltd. A mixture of 2,2'-bipyridine (0.5 mmol 0.07 g), tungstic acid (0.4 mmoL, 0.10 g), oxalic aicd (10 mmol, 0.09), p-carboxyphenylboronic acid (0.3 mmol, 0.05 g), and cobalt(II) sulfate heptahydrate (0.2 mmol, 0.05 g) in 14 ml distilled water was sealed in a 25 ml Teflon-lined stainless steel autoclave and was kept at 433 K for three days. Red crystals suitable for the X-ray experiment were obtained. Anal. Calc. for C₄₂H₃₂Co₂N₈O₂₃W₆: C, 22.53; H, 1.43; N, 5.01. Found: C, 22.26; H, 1.33; N, 4.85%.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 cation and anion of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius.

(µ-Oxalato-κ⁴O¹,O²:O^1',O^2')bis[bis(2,2'- bipyridine-κ²N,N')cobalt(II)] µ₆-oxido-dodeca-µ₂-oxido-hexaoxido-hexatungstate(VI) top

Crystal data top

[Co₂(C₂O₄)(C₁₀H₈N₂)₄][W₆O₁₉]	Z = 1
M_r = 2237.72	F(000) = 1022
Triclinic, P1	D_x = 2.806 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4876 (15) Å	Cell parameters from 3530 reflections
b = 9.8548 (15) Å	θ = 2.5–27.3°
c = 14.174 (2) Å	µ = 13.67 mm⁻¹
α = 90.769 (2)°	T = 293 K
β = 91.576 (2)°	Block, red
γ = 91.113 (2)°	0.12 × 0.10 × 0.08 mm
V = 1324.3 (4) Å³

Data collection top

Bruker APEXII CCD diffractometer	4613 independent reflections
Radiation source: fine-focus sealed tube	3755 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.291, T_max = 0.408	k = −11→11
9331 measured reflections	l = −16→16

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.076	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0375P)² + 1.9139P] where P = (F_o² + 2F_c²)/3
4613 reflections	(Δ/σ)_max = 0.001
368 parameters	Δρ_max = 2.41 e Å⁻³
0 restraints	Δρ_min = −1.10 e Å⁻³

Crystal data top

[Co₂(C₂O₄)(C₁₀H₈N₂)₄][W₆O₁₉]	γ = 91.113 (2)°
M_r = 2237.72	V = 1324.3 (4) Å³
Triclinic, P1	Z = 1
a = 9.4876 (15) Å	Mo Kα radiation
b = 9.8548 (15) Å	µ = 13.67 mm⁻¹
c = 14.174 (2) Å	T = 293 K
α = 90.769 (2)°	0.12 × 0.10 × 0.08 mm
β = 91.576 (2)°

Data collection top

Bruker APEXII CCD diffractometer	4613 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3755 reflections with I > 2σ(I)
T_min = 0.291, T_max = 0.408	R_int = 0.027
9331 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.076	H-atom parameters constrained
S = 1.00	Δρ_max = 2.41 e Å⁻³
4613 reflections	Δρ_min = −1.10 e Å⁻³
368 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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	0.5864 (9)	0.5558 (9)	0.7481 (6)	0.039 (2)
H1	0.6557	0.5423	0.7040	0.046*
C2	0.4503 (10)	0.5210 (10)	0.7228 (7)	0.050 (3)
H2	0.4275	0.4831	0.6638	0.060*
C3	0.3498 (10)	0.5440 (10)	0.7869 (7)	0.050 (3)
H3	0.2562	0.5220	0.7714	0.060*
C4	0.3841 (9)	0.5996 (10)	0.8753 (6)	0.045 (2)
H4	0.3150	0.6150	0.9192	0.054*
C5	0.5239 (8)	0.6314 (8)	0.8957 (5)	0.0262 (18)
C6	0.5713 (9)	0.6925 (8)	0.9874 (5)	0.031 (2)
C7	0.4828 (10)	0.7231 (11)	1.0590 (7)	0.050 (3)
H7	0.3869	0.7028	1.0521	0.061*
C8	0.5343 (12)	0.7834 (12)	1.1405 (7)	0.062 (3)
H8	0.4747	0.8067	1.1889	0.074*
C9	0.6775 (12)	0.8085 (12)	1.1486 (7)	0.064 (3)
H9	0.7157	0.8488	1.2035	0.077*
C10	0.7625 (11)	0.7754 (10)	1.0781 (6)	0.046 (2)
H10	0.8589	0.7931	1.0851	0.055*
C11	0.8337 (10)	0.9655 (10)	0.8619 (7)	0.046 (2)
H11	0.7816	0.9641	0.9166	0.055*
C12	0.8660 (11)	1.0894 (10)	0.8234 (7)	0.052 (3)
H12	0.8396	1.1705	0.8515	0.062*
C13	0.9399 (12)	1.0868 (11)	0.7404 (8)	0.062 (3)
H13	0.9621	1.1676	0.7105	0.074*
C14	0.9796 (10)	0.9684 (10)	0.7032 (7)	0.047 (2)
H14	1.0299	0.9669	0.6478	0.057*
C15	0.9459 (8)	0.8496 (9)	0.7469 (6)	0.0306 (19)
C16	0.9845 (8)	0.7135 (9)	0.7095 (6)	0.0294 (19)
C17	1.0644 (9)	0.6960 (10)	0.6295 (6)	0.040 (2)
H17	1.1000	0.7709	0.5981	0.048*
C18	1.0897 (9)	0.5675 (10)	0.5977 (6)	0.043 (2)
H18	1.1428	0.5541	0.5443	0.052*
C19	1.0363 (9)	0.4584 (10)	0.6452 (6)	0.043 (2)
H19	1.0522	0.3703	0.6243	0.051*
C20	0.9589 (9)	0.4815 (9)	0.7240 (6)	0.035 (2)
H20	0.9230	0.4076	0.7564	0.042*
C21	1.0517 (8)	0.5600 (8)	1.0069 (5)	0.0255 (18)
Co1	0.83213 (11)	0.65380 (11)	0.88211 (7)	0.0263 (3)
N1	0.6258 (7)	0.6078 (7)	0.8323 (4)	0.0302 (16)
N2	0.7116 (7)	0.7170 (7)	0.9974 (5)	0.0328 (17)
N3	0.8729 (7)	0.8481 (7)	0.8254 (5)	0.0325 (16)
N4	0.9334 (7)	0.6070 (7)	0.7558 (4)	0.0269 (15)
O1	1.0227 (6)	0.6668 (6)	0.9616 (4)	0.0350 (14)
O2	0.8466 (5)	0.4532 (6)	0.9359 (4)	0.0318 (13)
O3	0.4860 (7)	0.8809 (7)	0.7694 (4)	0.0521 (18)
O4	0.3221 (6)	1.0289 (6)	0.6381 (4)	0.0362 (14)
O5	0.3335 (6)	1.1440 (6)	0.3892 (4)	0.0369 (15)
O6	0.1293 (7)	1.1836 (7)	0.5300 (5)	0.0540 (18)
O7	0.2326 (6)	0.9278 (6)	0.4737 (4)	0.0383 (15)
O8	0.5000	1.0000	0.5000	0.0219 (16)
O9	0.3985 (6)	0.7844 (6)	0.5844 (4)	0.0342 (14)
O10	0.5765 (6)	0.7561 (6)	0.4464 (4)	0.0373 (14)
O11	0.2952 (7)	0.6576 (7)	0.4139 (5)	0.0528 (18)
O12	0.4107 (6)	0.8997 (6)	0.3357 (4)	0.0338 (14)
W1	0.38156 (4)	0.80202 (4)	0.45023 (2)	0.03214 (12)
W2	0.49167 (4)	0.92799 (4)	0.65534 (2)	0.03134 (12)
W3	0.28645 (4)	1.10717 (4)	0.51619 (2)	0.03216 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.039 (5)	0.051 (6)	0.025 (4)	0.002 (5)	−0.004 (4)	−0.011 (4)
C2	0.047 (6)	0.057 (7)	0.044 (6)	0.004 (5)	−0.018 (5)	−0.008 (5)
C3	0.028 (5)	0.061 (7)	0.058 (6)	−0.010 (5)	−0.014 (5)	0.004 (5)
C4	0.031 (5)	0.063 (7)	0.041 (5)	−0.004 (5)	0.000 (4)	−0.002 (5)
C5	0.024 (4)	0.028 (5)	0.027 (4)	0.000 (4)	−0.003 (3)	0.001 (3)
C6	0.032 (5)	0.031 (5)	0.030 (4)	0.001 (4)	0.012 (4)	0.001 (4)
C7	0.038 (6)	0.064 (7)	0.049 (6)	−0.004 (5)	0.011 (5)	−0.014 (5)
C8	0.057 (7)	0.074 (8)	0.055 (7)	−0.002 (6)	0.027 (5)	−0.027 (6)
C9	0.072 (8)	0.083 (9)	0.036 (6)	−0.003 (7)	0.003 (5)	−0.030 (5)
C10	0.052 (6)	0.051 (6)	0.036 (5)	−0.007 (5)	0.003 (4)	−0.014 (5)
C11	0.044 (6)	0.039 (6)	0.056 (6)	0.007 (5)	0.010 (5)	−0.002 (5)
C12	0.064 (7)	0.023 (5)	0.067 (7)	0.006 (5)	−0.001 (6)	−0.008 (5)
C13	0.066 (8)	0.044 (7)	0.074 (8)	−0.007 (6)	−0.002 (6)	0.013 (6)
C14	0.053 (6)	0.042 (6)	0.047 (6)	−0.007 (5)	0.006 (5)	0.001 (5)
C15	0.021 (4)	0.038 (5)	0.033 (4)	−0.002 (4)	−0.006 (3)	0.001 (4)
C16	0.016 (4)	0.038 (5)	0.034 (4)	−0.009 (4)	−0.009 (3)	0.002 (4)
C17	0.039 (5)	0.049 (6)	0.031 (5)	−0.001 (5)	0.011 (4)	0.009 (4)
C18	0.036 (5)	0.056 (7)	0.038 (5)	0.002 (5)	0.009 (4)	−0.005 (5)
C19	0.047 (6)	0.044 (6)	0.037 (5)	0.004 (5)	0.003 (4)	−0.015 (4)
C20	0.034 (5)	0.028 (5)	0.042 (5)	0.000 (4)	0.002 (4)	−0.002 (4)
C21	0.016 (4)	0.029 (5)	0.032 (4)	−0.004 (3)	0.005 (3)	−0.005 (4)
Co1	0.0243 (6)	0.0289 (6)	0.0258 (6)	0.0001 (5)	0.0035 (4)	−0.0003 (5)
N1	0.026 (4)	0.034 (4)	0.031 (4)	0.001 (3)	0.005 (3)	−0.001 (3)
N2	0.034 (4)	0.031 (4)	0.033 (4)	−0.003 (3)	0.006 (3)	−0.011 (3)
N3	0.034 (4)	0.027 (4)	0.037 (4)	0.001 (3)	0.004 (3)	0.004 (3)
N4	0.026 (4)	0.028 (4)	0.027 (3)	−0.001 (3)	0.003 (3)	−0.002 (3)
O1	0.030 (3)	0.037 (4)	0.038 (3)	−0.002 (3)	−0.003 (3)	0.007 (3)
O2	0.023 (3)	0.036 (4)	0.035 (3)	−0.004 (3)	−0.005 (2)	0.004 (3)
O3	0.065 (5)	0.059 (5)	0.033 (3)	0.007 (4)	0.004 (3)	0.003 (3)
O4	0.032 (3)	0.048 (4)	0.029 (3)	0.001 (3)	0.014 (2)	−0.008 (3)
O5	0.037 (3)	0.041 (4)	0.032 (3)	0.009 (3)	0.000 (3)	0.000 (3)
O6	0.039 (4)	0.068 (5)	0.055 (4)	0.010 (4)	0.002 (3)	−0.014 (4)
O7	0.028 (3)	0.053 (4)	0.034 (3)	0.002 (3)	0.002 (3)	−0.008 (3)
O8	0.021 (4)	0.024 (4)	0.021 (4)	0.004 (3)	0.006 (3)	−0.003 (3)
O9	0.035 (3)	0.033 (4)	0.035 (3)	−0.004 (3)	0.008 (3)	0.000 (3)
O10	0.047 (4)	0.027 (3)	0.039 (3)	0.007 (3)	0.006 (3)	−0.006 (3)
O11	0.054 (4)	0.042 (4)	0.061 (4)	−0.016 (3)	0.009 (3)	−0.013 (3)
O12	0.033 (3)	0.046 (4)	0.022 (3)	0.002 (3)	0.003 (2)	−0.008 (3)
W1	0.0353 (2)	0.0295 (2)	0.0313 (2)	−0.00686 (16)	0.00560 (15)	−0.00922 (15)
W2	0.0381 (2)	0.0338 (2)	0.02229 (18)	0.00114 (16)	0.00478 (14)	−0.00123 (14)
W3	0.0274 (2)	0.0368 (2)	0.0325 (2)	0.00719 (16)	0.00465 (14)	−0.00600 (15)

Geometric parameters (Å, º) top

C1—N1	1.333 (10)	C19—C20	1.373 (11)
C1—C2	1.366 (13)	C19—H19	0.9300
C1—H1	0.9300	C20—N4	1.340 (10)
C2—C3	1.355 (13)	C20—H20	0.9300
C2—H2	0.9300	C21—O2ⁱ	1.254 (9)
C3—C4	1.388 (13)	C21—O1	1.271 (9)
C3—H3	0.9300	C21—C21ⁱ	1.528 (15)
C4—C5	1.379 (11)	Co1—O1	2.104 (6)
C4—H4	0.9300	Co1—N1	2.101 (7)
C5—N1	1.360 (9)	Co1—N4	2.105 (6)
C5—C6	1.479 (11)	Co1—N2	2.114 (6)
C6—N2	1.351 (10)	Co1—N3	2.119 (7)
C6—C7	1.370 (11)	Co1—O2	2.134 (6)
C7—C8	1.366 (13)	O2—C21ⁱ	1.254 (9)
C7—H7	0.9300	O3—W2	1.690 (6)
C8—C9	1.378 (15)	O4—W2	1.919 (6)
C8—H8	0.9300	O4—W3	1.926 (6)
C9—C10	1.343 (12)	O5—W3	1.904 (5)
C9—H9	0.9300	O5—W2ⁱⁱ	1.935 (5)
C10—N2	1.346 (10)	O6—W3	1.698 (6)
C10—H10	0.9300	O7—W3	1.915 (6)
C11—N3	1.325 (11)	O7—W1	1.931 (6)
C11—C12	1.377 (13)	O8—W3ⁱⁱ	2.3185 (4)
C11—H11	0.9300	O8—W3	2.3185 (4)
C12—C13	1.386 (14)	O8—W1	2.3240 (4)
C12—H12	0.9300	O8—W1ⁱⁱ	2.3240 (4)
C13—C14	1.339 (14)	O8—W2ⁱⁱ	2.3252 (5)
C13—H13	0.9300	O8—W2	2.3252 (5)
C14—C15	1.368 (12)	O9—W2	1.912 (6)
C14—H14	0.9300	O9—W1	1.915 (5)
C15—N3	1.327 (10)	O10—W1	1.914 (6)
C15—C16	1.491 (11)	O10—W3ⁱⁱ	1.914 (6)
C16—N4	1.336 (10)	O11—W1	1.696 (6)
C16—C17	1.391 (11)	O12—W1	1.922 (5)
C17—C18	1.367 (12)	O12—W2ⁱⁱ	1.920 (6)
C17—H17	0.9300	W2—O12ⁱⁱ	1.920 (6)
C18—C19	1.372 (12)	W2—O5ⁱⁱ	1.935 (5)
C18—H18	0.9300	W3—O10ⁱⁱ	1.914 (6)

N1—C1—C2	124.0 (8)	C1—N1—Co1	127.4 (5)
N1—C1—H1	118.0	C5—N1—Co1	114.6 (5)
C2—C1—H1	118.0	C10—N2—C6	118.9 (7)
C3—C2—C1	117.5 (9)	C10—N2—Co1	126.0 (6)
C3—C2—H2	121.3	C6—N2—Co1	115.1 (5)
C1—C2—H2	121.3	C11—N3—C15	118.4 (8)
C2—C3—C4	121.2 (9)	C11—N3—Co1	125.9 (6)
C2—C3—H3	119.4	C15—N3—Co1	115.7 (6)
C4—C3—H3	119.4	C20—N4—C16	119.2 (7)
C3—C4—C5	117.8 (8)	C20—N4—Co1	125.2 (6)
C3—C4—H4	121.1	C16—N4—Co1	115.4 (5)
C5—C4—H4	121.1	C21—O1—Co1	114.2 (5)
N1—C5—C4	121.5 (7)	C21ⁱ—O2—Co1	113.0 (5)
N1—C5—C6	116.4 (7)	W2—O4—W3	117.6 (2)
C4—C5—C6	122.1 (7)	W3—O5—W2ⁱⁱ	117.3 (3)
N2—C6—C7	120.6 (8)	W3—O7—W1	117.5 (3)
N2—C6—C5	115.4 (6)	W3ⁱⁱ—O8—W3	180.0
C7—C6—C5	124.0 (8)	W3ⁱⁱ—O8—W1	89.833 (16)
C8—C7—C6	120.4 (9)	W3—O8—W1	90.167 (16)
C8—C7—H7	119.8	W3ⁱⁱ—O8—W1ⁱⁱ	90.167 (16)
C6—C7—H7	119.8	W3—O8—W1ⁱⁱ	89.833 (16)
C7—C8—C9	117.8 (9)	W1—O8—W1ⁱⁱ	180.0
C7—C8—H8	121.1	W3ⁱⁱ—O8—W2ⁱⁱ	90.173 (13)
C9—C8—H8	121.1	W3—O8—W2ⁱⁱ	89.827 (13)
C10—C9—C8	120.7 (10)	W1—O8—W2ⁱⁱ	90.203 (14)
C10—C9—H9	119.7	W1ⁱⁱ—O8—W2ⁱⁱ	89.797 (14)
C8—C9—H9	119.7	W3ⁱⁱ—O8—W2	89.827 (13)
N2—C10—C9	121.6 (10)	W3—O8—W2	90.173 (13)
N2—C10—H10	119.2	W1—O8—W2	89.797 (14)
C9—C10—H10	119.2	W1ⁱⁱ—O8—W2	90.203 (14)
N3—C11—C12	123.5 (9)	W2ⁱⁱ—O8—W2	180.0
N3—C11—H11	118.2	W2—O9—W1	118.1 (3)
C12—C11—H11	118.2	W1—O10—W3ⁱⁱ	117.8 (3)
C13—C12—C11	116.4 (9)	W1—O12—W2ⁱⁱ	118.0 (3)
C13—C12—H12	121.8	O11—W1—O10	103.9 (3)
C11—C12—H12	121.8	O11—W1—O9	104.0 (3)
C14—C13—C12	120.2 (10)	O10—W1—O9	86.9 (2)
C14—C13—H13	119.9	O11—W1—O12	104.1 (3)
C12—C13—H13	119.9	O10—W1—O12	86.8 (2)
C13—C14—C15	119.8 (9)	O9—W1—O12	151.9 (2)
C13—C14—H14	120.1	O11—W1—O7	104.1 (3)
C15—C14—H14	120.1	O10—W1—O7	152.1 (2)
N3—C15—C14	121.6 (8)	O9—W1—O7	86.5 (2)
N3—C15—C16	115.2 (7)	O12—W1—O7	86.3 (2)
C14—C15—C16	123.2 (8)	O11—W1—O8	180.0 (3)
N4—C16—C17	121.1 (8)	O10—W1—O8	76.11 (17)
N4—C16—C15	115.8 (7)	O9—W1—O8	76.06 (17)
C17—C16—C15	123.0 (8)	O12—W1—O8	75.87 (17)
C18—C17—C16	119.2 (8)	O7—W1—O8	75.96 (18)
C18—C17—H17	120.4	O3—W2—O9	105.6 (3)
C16—C17—H17	120.4	O3—W2—O4	103.1 (3)
C17—C18—C19	119.5 (8)	O9—W2—O4	87.0 (2)
C17—C18—H18	120.2	O3—W2—O12ⁱⁱ	102.5 (3)
C19—C18—H18	120.2	O9—W2—O12ⁱⁱ	152.0 (2)
C18—C19—C20	118.9 (8)	O4—W2—O12ⁱⁱ	86.6 (2)
C18—C19—H19	120.6	O3—W2—O5ⁱⁱ	104.7 (3)
C20—C19—H19	120.6	O9—W2—O5ⁱⁱ	86.7 (2)
N4—C20—C19	122.1 (8)	O4—W2—O5ⁱⁱ	152.2 (2)
N4—C20—H20	118.9	O12ⁱⁱ—W2—O5ⁱⁱ	86.3 (2)
C19—C20—H20	118.9	O3—W2—O8	178.2 (2)
O2ⁱ—C21—O1	125.8 (7)	O9—W2—O8	76.08 (16)
O2ⁱ—C21—C21ⁱ	117.7 (9)	O4—W2—O8	76.11 (15)
O1—C21—C21ⁱ	116.4 (9)	O12ⁱⁱ—W2—O8	75.88 (15)
O1—Co1—N1	164.8 (2)	O5ⁱⁱ—W2—O8	76.08 (16)
O1—Co1—N4	93.3 (2)	O6—W3—O5	104.3 (3)
N1—Co1—N4	96.6 (2)	O6—W3—O7	103.2 (3)
O1—Co1—N2	92.9 (2)	O5—W3—O7	87.2 (2)
N1—Co1—N2	78.4 (3)	O6—W3—O10ⁱⁱ	104.2 (3)
N4—Co1—N2	172.1 (3)	O5—W3—O10ⁱⁱ	87.1 (2)
O1—Co1—N3	90.4 (2)	O7—W3—O10ⁱⁱ	152.6 (2)
N1—Co1—N3	103.0 (3)	O6—W3—O4	102.7 (3)
N4—Co1—N3	77.4 (3)	O5—W3—O4	153.0 (2)
N2—Co1—N3	97.7 (3)	O7—W3—O4	86.6 (2)
O1—Co1—O2	78.3 (2)	O10ⁱⁱ—W3—O4	86.3 (2)
N1—Co1—O2	89.4 (2)	O6—W3—O8	178.8 (2)
N4—Co1—O2	94.3 (2)	O5—W3—O8	76.81 (16)
N2—Co1—O2	91.7 (2)	O7—W3—O8	76.38 (16)
N3—Co1—O2	165.6 (2)	O10ⁱⁱ—W3—O8	76.26 (16)
C1—N1—C5	118.0 (7)	O4—W3—O8	76.16 (15)

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

Experimental details

Crystal data
Chemical formula	[Co₂(C₂O₄)(C₁₀H₈N₂)₄][W₆O₁₉]
M_r	2237.72
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.4876 (15), 9.8548 (15), 14.174 (2)
α, β, γ (°)	90.769 (2), 91.576 (2), 91.113 (2)
V (Å³)	1324.3 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	13.67
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.291, 0.408
No. of measured, independent and observed [I > 2σ(I)] reflections	9331, 4613, 3755
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.076, 1.00
No. of reflections	4613
No. of parameters	368
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.41, −1.10

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O1	2.104 (6)	O8—W3ⁱ	2.3185 (4)
Co1—N1	2.101 (7)	O8—W3	2.3185 (4)
Co1—N4	2.105 (6)	O8—W1	2.3240 (4)
Co1—N2	2.114 (6)	O8—W1ⁱ	2.3240 (4)
Co1—N3	2.119 (7)	O8—W2ⁱ	2.3252 (5)
Co1—O2	2.134 (6)	O8—W2	2.3252 (5)
O3—W2	1.690 (6)	O9—W2	1.912 (6)
O4—W2	1.919 (6)	O9—W1	1.915 (5)
O4—W3	1.926 (6)	O10—W1	1.914 (6)
O5—W3	1.904 (5)	O10—W3ⁱ	1.914 (6)
O5—W2ⁱ	1.935 (5)	O11—W1	1.696 (6)
O6—W3	1.698 (6)	O12—W1	1.922 (5)
O7—W3	1.915 (6)	O12—W2ⁱ	1.920 (6)
O7—W1	1.931 (6)

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

Financial support from the 973 Key Program of the MOST (2006CB932905 and 2007CB81532), the National Natural Science Foundation of China (20873160), the Chinese Academy of Sciences (KJCX2-YW—M02), Shandong Provincial Education Department and Shandong Institute of Education is gratefully acknowledged.

References

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