Tris(2,2′-bipyridine)­cobalt(II) μ6-oxido-dodeca-μ2-oxido-hexa­oxidohexa­molydate(VI)

Liu, Y.; Zhang, X.; Xue, Z.; Sheng, J.

doi:10.1107/S1600536810020775

Tris(2,2′-bipyridine)cobalt(II) μ₆-oxido-dodeca-μ₂-oxido-hexaoxidohexamolydate(VI)

In the title compound, [Co(C₁₀H₈N₂)₃][Mo₆O₁₉], the Co²⁺ cation is surrounded in a distorted octahedral coordination by six N atoms from three 2,2′-bipyridine ligands. The distribution of Mo—O bond lengths in the Lindqvist isopolyanion is consistent with other structures containing the same unit. In the crystal, the cations and anions are linked by C—H

O interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810020775/hb5476sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810020775/hb5476Isup2.hkl Contains datablock I

checkCIF report

Key indicators

Single-crystal X-ray study
T = 296 K
Mean (C-C) = 0.010 Å
R factor = 0.032
wR factor = 0.092
Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level C
THETM01_ALERT_3_C  The value of sine(theta_max)/wavelength is less than 0.590
            Calculated sin(theta_max)/wavelength =    0.5830
PLAT023_ALERT_3_C Resolution (too) Low [sin(theta)/Lambda < 0.6]..      24.48 Deg.
PLAT342_ALERT_3_C Low Bond Precision on  C-C Bonds (x 1000) Ang ..         10
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.583         30

Alert level G
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.      10.18
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

There has been extensive interest in heteropolyoxometalates, owing to their fascinating properties and great potential applications in many fields such as, catalysis, material science, medicine, and magnetochemistry (Pope et al., 1991). The organic amines, such as 3-(2-pyridyl)pyrazole and pyrazine, are used to effectively modify heteropolyoxomolybdates under hydrothermal condictions (Zhang, Dou et al., 2009; Zhang, Wei, Sun et al., 2009). 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 complex [Co(C₁₀H₈N₂)₃]²⁺ cation, one typical Lindqvist isopolyanion [Mo₆O₁₉]^2- anion (Dahlstrom et al., 1982). The Co²⁺ cation is surrounded in a distorted octahedral coordination by six N atoms from three chelating 2,2'-bipyridine ligands. The Co—N bond lengths are in the range of 2.075 (5)—2.100 (5) Å, respectively, compared to reported one (Li & Xu, 2009).

The [Mo₆O₁₉]^2- polyoxoanion, possessing well known Lindquist structure, is formed by six MoO₆ octahedra connected with each other through edge-sharing oxygen atoms and thus exhibits approximate Oh symmetry. Three kinds of oxygen atoms exist in the cluster, that is, terminal Oa, double-bridging oxygen Ob, and central oxygen Oc. Therefore, Mo—O band lengths can be grouped into three sets: Mo—Oa 1.669 (5)—1.682 (5) Å; Mo—Ob 1.888 (4)—1.951 (5) Å; and Mo—Oc 2.299 (4)—2.318 (4) Å; these bond distances have a rule of Mo—Oa<Mo—Ob<Mo—Oc. Comparing Mo=O bond distances with that of Lindqvist isopolyanion salt (Dahlstrom, 1982), Mo=O distances have no obvious change.

Related literature top

For general background to polyoxometalates, see: Pope & Müller (1991). For polyoxometalates modified with amines, see: Zhang, Dou et al. (2009); Zhang, Wei, Sun et al. (2009). For another structure containing the (µ6-oxo)-dodecakis(µ2-oxo)-hexa-oxo-hexa-molydenum(VI) cluster, see: Dahlstrom et al. (1982). For Co—N bond lengths in a related structure, see: Li & Xu (2009).

Experimental top

A mixture of 2,2'-bipyridine (0.5 mmoL, 0.07 g), molybdenum(VI) oxide (1 mmol, 0.14 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. Upon cooling, red blocks of (I) were obtained. Anal. Calc. for C₃₀H₂₄CoMo₆N₆O₁₉: C, 25.58; H, 1.71; N, 5.97. Found: C, 22.38; H, 1.52; N, 5.78%.

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 molecular structure of (I) shoiwng displacement ellipsoids drawn at the 30% probability level; H atoms are given as spheres of arbitrary radius.

Tris(2,2'-bipyridine)cobalt(II) µ₆-oxido-dodeca-µ₂-oxido-hexaoxidohexamolydate(VI) top

Crystal data top

[Co(C₁₀H₈N₂)₃][Mo₆O₁₉]	F(000) = 2708
M_r = 1407.12	D_x = 2.376 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2413 reflections
a = 12.310 (2) Å	θ = 2.4–24.3°
b = 18.979 (4) Å	µ = 2.35 mm⁻¹
c = 17.150 (4) Å	T = 296 K
β = 100.895 (3)°	Block, red
V = 3934.4 (14) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	6500 independent reflections
Radiation source: fine-focus sealed tube	4649 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.041
ϕ and ω scans	θ_max = 24.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→13
T_min = 0.766, T_max = 0.834	k = −22→22
25652 measured reflections	l = −18→19

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.041P)² + 10.1791P] where P = (F_o² + 2F_c²)/3
6500 reflections	(Δ/σ)_max = 0.003
559 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Co(C₁₀H₈N₂)₃][Mo₆O₁₉]	V = 3934.4 (14) Å³
M_r = 1407.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.310 (2) Å	µ = 2.35 mm⁻¹
b = 18.979 (4) Å	T = 296 K
c = 17.150 (4) Å	0.12 × 0.10 × 0.08 mm
β = 100.895 (3)°

Data collection top

Bruker APEXII CCD diffractometer	6500 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4649 reflections with I > 2σ(I)
T_min = 0.766, T_max = 0.834	R_int = 0.041
25652 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.041P)² + 10.1791P] where P = (F_o² + 2F_c²)/3
6500 reflections	Δρ_max = 0.65 e Å⁻³
559 parameters	Δρ_min = −0.54 e Å⁻³

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	0.8841 (6)	0.1849 (4)	0.0079 (4)	0.0458 (17)
H1	0.8962	0.1371	0.0008	0.055*
C2	0.9125 (6)	0.2314 (4)	−0.0452 (4)	0.0523 (19)
H2	0.9438	0.2154	−0.0873	0.063*
C3	0.8947 (7)	0.3012 (4)	−0.0362 (4)	0.061 (2)
H3	0.9130	0.3336	−0.0723	0.073*
C4	0.8498 (6)	0.3235 (4)	0.0264 (4)	0.0526 (19)
H4	0.8378	0.3712	0.0338	0.063*
C5	0.8221 (5)	0.2735 (3)	0.0793 (4)	0.0395 (15)
C6	0.7754 (5)	0.2926 (3)	0.1498 (4)	0.0355 (14)
C7	0.7683 (6)	0.3610 (3)	0.1751 (4)	0.0478 (17)
H7	0.7896	0.3982	0.1461	0.057*
C8	0.7294 (6)	0.3736 (4)	0.2435 (4)	0.0554 (19)
H8	0.7250	0.4196	0.2615	0.066*
C9	0.6975 (5)	0.3189 (4)	0.2848 (4)	0.0472 (17)
H9	0.6711	0.3265	0.3315	0.057*
C10	0.7051 (5)	0.2527 (4)	0.2561 (4)	0.0425 (16)
H10	0.6830	0.2152	0.2843	0.051*
C11	0.5497 (5)	0.1943 (4)	0.0374 (4)	0.0478 (17)
H11	0.5492	0.2282	0.0765	0.057*
C12	0.4747 (6)	0.1997 (5)	−0.0318 (5)	0.063 (2)
H12	0.4248	0.2369	−0.0398	0.076*
C13	0.4737 (7)	0.1496 (5)	−0.0891 (5)	0.078 (3)
H13	0.4225	0.1521	−0.1364	0.094*
C14	0.5478 (6)	0.0964 (5)	−0.0764 (4)	0.065 (2)
H14	0.5484	0.0622	−0.1151	0.078*
C15	0.6226 (5)	0.0931 (4)	−0.0056 (4)	0.0427 (16)
C16	0.7059 (6)	0.0373 (3)	0.0130 (4)	0.0447 (16)
C17	0.7080 (7)	−0.0232 (4)	−0.0324 (5)	0.067 (2)
H17	0.6542	−0.0295	−0.0779	0.080*
C18	0.7867 (8)	−0.0727 (4)	−0.0117 (6)	0.079 (3)
H18	0.7881	−0.1130	−0.0423	0.095*
C19	0.8636 (7)	−0.0623 (4)	0.0551 (5)	0.063 (2)
H19	0.9189	−0.0955	0.0709	0.076*
C20	0.8592 (6)	−0.0022 (4)	0.0993 (4)	0.0542 (19)
H20	0.9124	0.0043	0.1450	0.065*
C21	1.0059 (5)	0.1421 (3)	0.2316 (4)	0.0452 (17)
H21	1.0236	0.1587	0.1845	0.054*
C22	1.0883 (6)	0.1384 (4)	0.2973 (4)	0.0529 (19)
H22	1.1604	0.1515	0.2949	0.063*
C23	0.9551 (5)	0.0950 (4)	0.3682 (4)	0.0472 (17)
H23	0.9360	0.0791	0.4151	0.057*
C24	0.8764 (5)	0.0987 (3)	0.2994 (3)	0.0329 (14)
C25	0.7600 (5)	0.0778 (3)	0.2945 (4)	0.0330 (14)
C26	0.7195 (6)	0.0507 (3)	0.3593 (4)	0.0454 (17)
H26	0.7657	0.0443	0.4083	0.054*
C27	0.6079 (6)	0.0339 (4)	0.3479 (4)	0.0519 (18)
H27	0.5784	0.0159	0.3898	0.062*
C28	0.5422 (6)	0.0433 (4)	0.2765 (4)	0.0511 (18)
H28	0.4675	0.0316	0.2686	0.061*
C29	0.5867 (5)	0.0701 (4)	0.2165 (4)	0.0451 (17)
H29	0.5410	0.0771	0.1673	0.054*
C30	1.0613 (6)	0.1148 (4)	0.3668 (5)	0.0531 (19)
H30	1.1151	0.1124	0.4128	0.064*
Co1	0.76522 (6)	0.13938 (4)	0.14146 (4)	0.02958 (19)
Mo1	0.62552 (4)	0.16746 (3)	0.70535 (3)	0.03880 (16)
Mo2	0.68058 (5)	0.03933 (3)	0.59227 (3)	0.03863 (15)
Mo3	0.93267 (4)	0.09804 (3)	0.60537 (3)	0.04001 (16)
Mo4	0.72000 (5)	0.20190 (3)	0.54351 (3)	0.04164 (16)
Mo5	0.87672 (5)	0.22739 (3)	0.71735 (4)	0.04679 (17)
Mo6	0.83628 (5)	0.06397 (3)	0.76648 (3)	0.04393 (17)
N1	0.8397 (4)	0.2045 (3)	0.0694 (3)	0.0371 (12)
N2	0.7428 (4)	0.2385 (3)	0.1891 (3)	0.0355 (12)
N3	0.6238 (4)	0.1425 (3)	0.0512 (3)	0.0421 (13)
N4	0.7816 (4)	0.0472 (3)	0.0790 (3)	0.0401 (13)
N5	0.6935 (4)	0.0870 (3)	0.2251 (3)	0.0395 (13)
N6	0.9018 (4)	0.1232 (3)	0.2313 (3)	0.0373 (12)
O1	0.6778 (4)	0.2537 (3)	0.4646 (3)	0.0632 (14)
O2	0.8518 (4)	0.1606 (2)	0.5229 (3)	0.0467 (11)
O3	0.6467 (3)	0.1147 (2)	0.5161 (2)	0.0424 (11)
O4	0.9808 (3)	0.1811 (2)	0.6620 (3)	0.0492 (12)
O5	0.8119 (4)	0.2659 (2)	0.6171 (3)	0.0518 (12)
O6	0.9511 (4)	0.2935 (3)	0.7643 (3)	0.0744 (17)
O7	0.6093 (3)	0.2189 (2)	0.6099 (3)	0.0447 (11)
O8	0.7392 (4)	0.2354 (2)	0.7496 (3)	0.0494 (12)
O9	0.5168 (4)	0.1929 (3)	0.7438 (3)	0.0539 (12)
O10	0.7046 (3)	0.1044 (2)	0.7871 (3)	0.0484 (12)
O11	0.9111 (4)	0.1509 (3)	0.7929 (3)	0.0518 (12)
O12	0.7786 (3)	0.13302 (19)	0.6550 (2)	0.0329 (9)
O13	0.5755 (3)	0.0853 (2)	0.6474 (3)	0.0419 (11)
O14	0.8815 (4)	0.0131 (3)	0.8463 (3)	0.0705 (16)
O15	0.7458 (4)	0.0007 (2)	0.6930 (3)	0.0485 (12)
O16	0.9500 (3)	0.0484 (2)	0.7010 (3)	0.0475 (12)
O17	0.6077 (4)	−0.0283 (2)	0.5469 (3)	0.0600 (14)
O18	0.8188 (3)	0.0303 (2)	0.5606 (2)	0.0438 (11)
O19	1.0407 (4)	0.0735 (3)	0.5655 (3)	0.0565 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.057 (4)	0.042 (4)	0.041 (4)	−0.006 (3)	0.017 (3)	−0.004 (3)
C2	0.064 (5)	0.061 (5)	0.034 (4)	−0.010 (4)	0.015 (4)	−0.004 (4)
C3	0.086 (6)	0.055 (5)	0.043 (4)	−0.018 (4)	0.015 (4)	0.010 (4)
C4	0.079 (5)	0.036 (4)	0.041 (4)	−0.006 (4)	0.006 (4)	0.006 (3)
C5	0.036 (4)	0.048 (4)	0.032 (4)	−0.004 (3)	0.001 (3)	0.002 (3)
C6	0.036 (4)	0.033 (4)	0.034 (4)	−0.003 (3)	−0.002 (3)	−0.001 (3)
C7	0.061 (5)	0.030 (4)	0.050 (4)	−0.001 (3)	0.006 (4)	−0.002 (3)
C8	0.064 (5)	0.042 (4)	0.057 (5)	0.009 (4)	0.003 (4)	−0.016 (4)
C9	0.049 (4)	0.049 (4)	0.043 (4)	0.009 (3)	0.008 (3)	−0.011 (4)
C10	0.043 (4)	0.055 (4)	0.029 (4)	0.011 (3)	0.005 (3)	0.005 (3)
C11	0.048 (4)	0.055 (4)	0.040 (4)	0.011 (4)	0.009 (3)	−0.003 (3)
C12	0.043 (4)	0.089 (6)	0.056 (5)	0.028 (4)	0.007 (4)	0.004 (5)
C13	0.045 (5)	0.128 (8)	0.056 (5)	0.025 (5)	−0.001 (4)	−0.008 (6)
C14	0.053 (5)	0.091 (6)	0.048 (5)	0.005 (5)	0.002 (4)	−0.022 (4)
C15	0.036 (4)	0.054 (4)	0.038 (4)	−0.008 (3)	0.006 (3)	−0.006 (3)
C16	0.055 (4)	0.035 (4)	0.048 (4)	−0.009 (3)	0.017 (4)	−0.003 (3)
C17	0.083 (6)	0.051 (5)	0.060 (5)	−0.005 (4)	0.000 (4)	−0.018 (4)
C18	0.115 (8)	0.039 (5)	0.087 (7)	0.003 (5)	0.029 (6)	−0.021 (5)
C19	0.076 (6)	0.040 (4)	0.080 (6)	0.011 (4)	0.030 (5)	0.004 (4)
C20	0.055 (5)	0.050 (5)	0.057 (5)	0.012 (4)	0.011 (4)	0.006 (4)
C21	0.046 (4)	0.041 (4)	0.050 (4)	−0.004 (3)	0.013 (3)	0.005 (3)
C22	0.038 (4)	0.048 (4)	0.068 (5)	−0.006 (3)	0.000 (4)	0.006 (4)
C23	0.047 (4)	0.051 (4)	0.040 (4)	0.007 (3)	0.000 (3)	0.004 (3)
C24	0.045 (4)	0.025 (3)	0.029 (3)	0.005 (3)	0.008 (3)	−0.001 (3)
C25	0.039 (4)	0.026 (3)	0.034 (4)	−0.001 (3)	0.008 (3)	−0.005 (3)
C26	0.056 (5)	0.045 (4)	0.036 (4)	−0.001 (3)	0.011 (3)	0.003 (3)
C27	0.058 (5)	0.054 (4)	0.049 (4)	−0.008 (4)	0.022 (4)	0.004 (4)
C28	0.043 (4)	0.057 (5)	0.055 (5)	−0.011 (3)	0.013 (4)	0.003 (4)
C29	0.039 (4)	0.057 (4)	0.037 (4)	−0.010 (3)	0.003 (3)	0.004 (3)
C30	0.042 (4)	0.046 (4)	0.065 (5)	0.002 (3)	−0.006 (4)	0.005 (4)
Co1	0.0301 (4)	0.0305 (4)	0.0280 (4)	−0.0009 (3)	0.0050 (3)	0.0012 (3)
Mo1	0.0331 (3)	0.0401 (3)	0.0451 (3)	0.0020 (2)	0.0123 (3)	−0.0020 (3)
Mo2	0.0368 (3)	0.0331 (3)	0.0451 (4)	−0.0059 (2)	0.0056 (3)	−0.0064 (3)
Mo3	0.0320 (3)	0.0490 (4)	0.0402 (3)	0.0000 (3)	0.0099 (3)	−0.0069 (3)
Mo4	0.0430 (3)	0.0396 (3)	0.0428 (3)	0.0011 (3)	0.0094 (3)	0.0095 (3)
Mo5	0.0413 (3)	0.0481 (4)	0.0522 (4)	−0.0139 (3)	0.0117 (3)	−0.0186 (3)
Mo6	0.0384 (3)	0.0556 (4)	0.0369 (3)	0.0076 (3)	0.0049 (3)	0.0077 (3)
N1	0.042 (3)	0.039 (3)	0.030 (3)	−0.003 (2)	0.007 (2)	−0.002 (2)
N2	0.036 (3)	0.041 (3)	0.028 (3)	0.001 (2)	0.001 (2)	0.001 (2)
N3	0.037 (3)	0.045 (3)	0.045 (3)	0.001 (3)	0.008 (3)	0.003 (3)
N4	0.040 (3)	0.038 (3)	0.042 (3)	−0.001 (2)	0.007 (3)	0.000 (3)
N5	0.042 (3)	0.037 (3)	0.039 (3)	−0.004 (2)	0.006 (3)	0.004 (2)
N6	0.035 (3)	0.036 (3)	0.040 (3)	−0.005 (2)	0.005 (2)	0.003 (2)
O1	0.063 (3)	0.067 (3)	0.060 (3)	0.004 (3)	0.014 (3)	0.027 (3)
O2	0.046 (3)	0.053 (3)	0.044 (3)	−0.002 (2)	0.015 (2)	0.002 (2)
O3	0.035 (2)	0.049 (3)	0.039 (3)	−0.003 (2)	−0.004 (2)	0.001 (2)
O4	0.036 (3)	0.062 (3)	0.049 (3)	−0.012 (2)	0.007 (2)	−0.014 (2)
O5	0.054 (3)	0.032 (2)	0.073 (3)	−0.008 (2)	0.019 (3)	0.003 (2)
O6	0.063 (3)	0.069 (4)	0.090 (4)	−0.023 (3)	0.012 (3)	−0.036 (3)
O7	0.041 (3)	0.040 (3)	0.054 (3)	0.005 (2)	0.011 (2)	0.004 (2)
O8	0.044 (3)	0.051 (3)	0.056 (3)	−0.001 (2)	0.015 (2)	−0.021 (2)
O9	0.039 (3)	0.066 (3)	0.061 (3)	0.006 (2)	0.018 (2)	0.000 (3)
O10	0.043 (3)	0.064 (3)	0.042 (3)	0.007 (2)	0.016 (2)	0.009 (2)
O11	0.040 (3)	0.070 (3)	0.043 (3)	−0.004 (2)	0.003 (2)	−0.012 (2)
O12	0.032 (2)	0.031 (2)	0.038 (2)	−0.0016 (18)	0.0104 (18)	−0.0038 (19)
O13	0.034 (2)	0.038 (2)	0.054 (3)	−0.0053 (19)	0.008 (2)	0.001 (2)
O14	0.056 (3)	0.096 (4)	0.057 (3)	0.017 (3)	0.006 (3)	0.026 (3)
O15	0.050 (3)	0.036 (2)	0.059 (3)	−0.001 (2)	0.008 (2)	0.010 (2)
O16	0.039 (3)	0.059 (3)	0.043 (3)	0.007 (2)	0.005 (2)	−0.001 (2)
O17	0.057 (3)	0.043 (3)	0.079 (4)	−0.010 (2)	0.008 (3)	−0.018 (3)
O18	0.044 (3)	0.044 (3)	0.043 (3)	0.004 (2)	0.008 (2)	−0.010 (2)
O19	0.041 (3)	0.080 (4)	0.050 (3)	0.006 (2)	0.014 (2)	−0.009 (3)

Geometric parameters (Å, º) top

C1—N1	1.330 (8)	C25—C26	1.398 (8)
C1—C2	1.361 (9)	C26—C27	1.387 (9)
C1—H1	0.9300	C26—H26	0.9300
C2—C3	1.358 (10)	C27—C28	1.346 (9)
C2—H2	0.9300	C27—H27	0.9300
C3—C4	1.364 (10)	C28—C29	1.354 (9)
C3—H3	0.9300	C28—H28	0.9300
C4—C5	1.400 (9)	C29—N5	1.334 (8)
C4—H4	0.9300	C29—H29	0.9300
C5—N1	1.343 (8)	C30—H30	0.9300
C5—C6	1.479 (8)	Co1—N5	2.075 (5)
C6—N2	1.331 (7)	Co1—N6	2.078 (5)
C6—C7	1.376 (8)	Co1—N1	2.079 (5)
C7—C8	1.367 (9)	Co1—N4	2.081 (5)
C7—H7	0.9300	Co1—N2	2.091 (5)
C8—C9	1.358 (10)	Co1—N3	2.100 (5)
C8—H8	0.9300	Mo1—O9	1.671 (4)
C9—C10	1.359 (9)	Mo1—O7	1.884 (4)
C9—H9	0.9300	Mo1—O13	1.888 (4)
C10—N2	1.345 (7)	Mo1—O8	1.948 (4)
C10—H10	0.9300	Mo1—O10	1.957 (4)
C11—N3	1.331 (8)	Mo1—O12	2.310 (4)
C11—C12	1.362 (9)	Mo2—O17	1.671 (4)
C11—H11	0.9300	Mo2—O18	1.888 (4)
C12—C13	1.366 (11)	Mo2—O15	1.909 (4)
C12—H12	0.9300	Mo2—O3	1.929 (4)
C13—C14	1.350 (11)	Mo2—O13	1.948 (4)
C13—H13	0.9300	Mo2—O12	2.299 (4)
C14—C15	1.379 (9)	Mo3—O19	1.673 (4)
C14—H14	0.9300	Mo3—O16	1.868 (4)
C15—N3	1.350 (8)	Mo3—O4	1.888 (4)
C15—C16	1.467 (9)	Mo3—O18	1.950 (4)
C16—N4	1.336 (8)	Mo3—O2	1.968 (4)
C16—C17	1.390 (9)	Mo3—O12	2.318 (4)
C17—C18	1.349 (11)	Mo4—O1	1.673 (5)
C17—H17	0.9300	Mo4—O2	1.894 (4)
C18—C19	1.354 (11)	Mo4—O3	1.900 (4)
C18—H18	0.9300	Mo4—O5	1.951 (5)
C19—C20	1.377 (10)	Mo4—O7	1.961 (4)
C19—H19	0.9300	Mo4—O12	2.316 (4)
C20—N4	1.336 (8)	Mo5—O6	1.669 (5)
C20—H20	0.9300	Mo5—O8	1.884 (4)
C21—N6	1.330 (8)	Mo5—O5	1.900 (5)
C21—C22	1.368 (9)	Mo5—O11	1.939 (5)
C21—H21	0.9300	Mo5—O4	1.943 (4)
C22—C30	1.373 (10)	Mo5—O12	2.307 (4)
C22—H22	0.9300	Mo6—O14	1.682 (5)
C23—C30	1.365 (9)	Mo6—O10	1.887 (4)
C23—C24	1.379 (8)	Mo6—O11	1.902 (5)
C23—H23	0.9300	Mo6—O15	1.934 (4)
C24—N6	1.347 (7)	Mo6—O16	1.976 (4)
C24—C25	1.474 (8)	Mo6—O12	2.316 (4)
C25—N5	1.323 (7)

N1—C1—C2	123.1 (7)	O17—Mo2—O18	103.3 (2)
N1—C1—H1	118.5	O17—Mo2—O15	102.9 (2)
C2—C1—H1	118.5	O18—Mo2—O15	88.73 (19)
C3—C2—C1	119.3 (7)	O17—Mo2—O3	103.1 (2)
C3—C2—H2	120.3	O18—Mo2—O3	87.96 (18)
C1—C2—H2	120.3	O15—Mo2—O3	153.89 (18)
C2—C3—C4	119.4 (7)	O17—Mo2—O13	102.9 (2)
C2—C3—H3	120.3	O18—Mo2—O13	153.82 (17)
C4—C3—H3	120.3	O15—Mo2—O13	86.36 (19)
C3—C4—C5	119.0 (7)	O3—Mo2—O13	85.28 (18)
C3—C4—H4	120.5	O17—Mo2—O12	179.2 (2)
C5—C4—H4	120.5	O18—Mo2—O12	77.50 (15)
N1—C5—C4	120.9 (6)	O15—Mo2—O12	77.28 (16)
N1—C5—C6	116.1 (5)	O3—Mo2—O12	76.72 (16)
C4—C5—C6	123.0 (6)	O13—Mo2—O12	76.34 (15)
N2—C6—C7	121.6 (6)	O19—Mo3—O16	104.5 (2)
N2—C6—C5	115.2 (5)	O19—Mo3—O4	104.3 (2)
C7—C6—C5	123.2 (6)	O16—Mo3—O4	89.9 (2)
C8—C7—C6	119.3 (7)	O19—Mo3—O18	102.9 (2)
C8—C7—H7	120.4	O16—Mo3—O18	88.10 (19)
C6—C7—H7	120.4	O4—Mo3—O18	152.37 (18)
C9—C8—C7	119.8 (6)	O19—Mo3—O2	102.0 (2)
C9—C8—H8	120.1	O16—Mo3—O2	153.38 (18)
C7—C8—H8	120.1	O4—Mo3—O2	86.13 (19)
C8—C9—C10	118.1 (6)	O18—Mo3—O2	83.50 (18)
C8—C9—H9	120.9	O19—Mo3—O12	177.44 (19)
C10—C9—H9	120.9	O16—Mo3—O12	77.75 (16)
N2—C10—C9	123.6 (6)	O4—Mo3—O12	76.77 (16)
N2—C10—H10	118.2	O18—Mo3—O12	75.87 (15)
C9—C10—H10	118.2	O2—Mo3—O12	75.71 (16)
N3—C11—C12	122.6 (7)	O1—Mo4—O2	103.8 (2)
N3—C11—H11	118.7	O1—Mo4—O3	104.5 (2)
C12—C11—H11	118.7	O2—Mo4—O3	88.71 (19)
C13—C12—C11	119.1 (7)	O1—Mo4—O5	102.2 (2)
C13—C12—H12	120.5	O2—Mo4—O5	88.06 (19)
C11—C12—H12	120.5	O3—Mo4—O5	153.15 (18)
C14—C13—C12	119.4 (7)	O1—Mo4—O7	103.3 (2)
C14—C13—H13	120.3	O2—Mo4—O7	152.92 (18)
C12—C13—H13	120.3	O3—Mo4—O7	86.39 (18)
C13—C14—C15	119.6 (7)	O5—Mo4—O7	84.46 (19)
C13—C14—H14	120.2	O1—Mo4—O12	178.4 (2)
C15—C14—H14	120.2	O2—Mo4—O12	77.12 (16)
N3—C15—C14	121.2 (7)	O3—Mo4—O12	76.83 (15)
N3—C15—C16	115.6 (6)	O5—Mo4—O12	76.46 (16)
C14—C15—C16	123.2 (6)	O7—Mo4—O12	75.83 (15)
N4—C16—C17	120.5 (7)	O6—Mo5—O8	103.8 (2)
N4—C16—C15	115.5 (6)	O6—Mo5—O5	104.2 (2)
C17—C16—C15	124.0 (7)	O8—Mo5—O5	89.3 (2)
C18—C17—C16	121.0 (8)	O6—Mo5—O11	102.1 (3)
C18—C17—H17	119.5	O8—Mo5—O11	87.6 (2)
C16—C17—H17	119.5	O5—Mo5—O11	153.44 (19)
C17—C18—C19	118.2 (8)	O6—Mo5—O4	102.9 (2)
C17—C18—H18	120.9	O8—Mo5—O4	153.17 (18)
C19—C18—H18	120.9	O5—Mo5—O4	86.3 (2)
C18—C19—C20	119.6 (8)	O11—Mo5—O4	84.69 (19)
C18—C19—H19	120.2	O6—Mo5—O12	177.9 (2)
C20—C19—H19	120.2	O8—Mo5—O12	77.15 (16)
N4—C20—C19	122.6 (7)	O5—Mo5—O12	77.63 (16)
N4—C20—H20	118.7	O11—Mo5—O12	75.97 (16)
C19—C20—H20	118.7	O4—Mo5—O12	76.05 (15)
N6—C21—C22	123.6 (6)	O14—Mo6—O10	104.1 (2)
N6—C21—H21	118.2	O14—Mo6—O11	103.5 (2)
C22—C21—H21	118.2	O10—Mo6—O11	89.9 (2)
C21—C22—C30	117.9 (7)	O14—Mo6—O15	103.6 (2)
C21—C22—H22	121.0	O10—Mo6—O15	88.0 (2)
C30—C22—H22	121.0	O11—Mo6—O15	152.55 (19)
C30—C23—C24	119.4 (7)	O14—Mo6—O16	102.5 (2)
C30—C23—H23	120.3	O10—Mo6—O16	153.36 (18)
C24—C23—H23	120.3	O11—Mo6—O16	84.39 (19)
N6—C24—C23	121.2 (6)	O15—Mo6—O16	85.39 (19)
N6—C24—C25	115.2 (5)	O14—Mo6—O12	178.3 (2)
C23—C24—C25	123.6 (6)	O10—Mo6—O12	77.53 (16)
N5—C25—C26	120.7 (6)	O11—Mo6—O12	76.43 (17)
N5—C25—C24	116.5 (5)	O15—Mo6—O12	76.39 (15)
C26—C25—C24	122.9 (6)	O16—Mo6—O12	75.83 (16)
C27—C26—C25	117.7 (6)	C1—N1—C5	118.3 (5)
C27—C26—H26	121.2	C1—N1—Co1	126.7 (4)
C25—C26—H26	121.2	C5—N1—Co1	113.9 (4)
C28—C27—C26	120.5 (6)	C6—N2—C10	117.6 (6)
C28—C27—H27	119.8	C6—N2—Co1	114.9 (4)
C26—C27—H27	119.8	C10—N2—Co1	127.3 (4)
C27—C28—C29	118.8 (7)	C11—N3—C15	118.0 (6)
C27—C28—H28	120.6	C11—N3—Co1	126.6 (5)
C29—C28—H28	120.6	C15—N3—Co1	114.0 (4)
N5—C29—C28	122.6 (6)	C20—N4—C16	118.1 (6)
N5—C29—H29	118.7	C20—N4—Co1	126.1 (5)
C28—C29—H29	118.7	C16—N4—Co1	115.7 (4)
C23—C30—C22	119.7 (7)	C25—N5—C29	119.8 (5)
C23—C30—H30	120.2	C25—N5—Co1	114.4 (4)
C22—C30—H30	120.2	C29—N5—Co1	125.3 (4)
N5—Co1—N6	78.9 (2)	C21—N6—C24	118.1 (6)
N5—Co1—N1	171.4 (2)	C21—N6—Co1	127.3 (4)
N6—Co1—N1	98.20 (19)	C24—N6—Co1	114.0 (4)
N5—Co1—N4	92.8 (2)	Mo4—O2—Mo3	116.7 (2)
N6—Co1—N4	96.5 (2)	Mo4—O3—Mo2	116.5 (2)
N1—Co1—N4	95.6 (2)	Mo3—O4—Mo5	117.2 (2)
N5—Co1—N2	93.2 (2)	Mo5—O5—Mo4	116.0 (2)
N6—Co1—N2	89.51 (19)	Mo1—O7—Mo4	116.6 (2)
N1—Co1—N2	78.62 (19)	Mo5—O8—Mo1	116.8 (2)
N4—Co1—N2	172.2 (2)	Mo6—O10—Mo1	116.3 (2)
N5—Co1—N3	97.0 (2)	Mo6—O11—Mo5	117.1 (2)
N6—Co1—N3	173.0 (2)	Mo2—O12—Mo5	179.7 (2)
N1—Co1—N3	86.7 (2)	Mo2—O12—Mo1	90.06 (13)
N4—Co1—N3	78.0 (2)	Mo5—O12—Mo1	89.99 (13)
N2—Co1—N3	96.3 (2)	Mo2—O12—Mo4	89.78 (14)
O9—Mo1—O7	103.4 (2)	Mo5—O12—Mo4	89.91 (13)
O9—Mo1—O13	103.9 (2)	Mo1—O12—Mo4	90.02 (13)
O7—Mo1—O13	90.01 (18)	Mo2—O12—Mo6	90.04 (13)
O9—Mo1—O8	103.0 (2)	Mo5—O12—Mo6	90.27 (14)
O7—Mo1—O8	86.9 (2)	Mo1—O12—Mo6	89.78 (13)
O13—Mo1—O8	152.92 (17)	Mo4—O12—Mo6	179.7 (2)
O9—Mo1—O10	102.8 (2)	Mo2—O12—Mo3	90.00 (13)
O7—Mo1—O10	153.66 (18)	Mo5—O12—Mo3	89.96 (13)
O13—Mo1—O10	86.59 (19)	Mo1—O12—Mo3	179.6 (2)
O8—Mo1—O10	84.4 (2)	Mo4—O12—Mo3	90.40 (13)
O9—Mo1—O12	178.6 (2)	Mo6—O12—Mo3	89.79 (13)
O7—Mo1—O12	77.40 (16)	Mo1—O13—Mo2	116.4 (2)
O13—Mo1—O12	77.16 (15)	Mo2—O15—Mo6	116.3 (2)
O8—Mo1—O12	75.91 (15)	Mo3—O16—Mo6	116.6 (2)
O10—Mo1—O12	76.38 (15)	Mo2—O18—Mo3	116.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O11ⁱ	0.93	2.36	3.166 (9)	145
C4—H4···O17ⁱⁱ	0.93	2.52	3.165 (9)	127
C11—H11···O4ⁱⁱⁱ	0.93	2.51	3.400 (8)	161
C12—H12···O2ⁱⁱⁱ	0.93	2.47	3.277 (10)	145
C20—H20···O14^iv	0.93	2.53	3.159 (9)	125
C22—H22···O8^v	0.93	2.54	3.230 (9)	132
C26—H26···O18	0.93	2.58	3.459 (8)	157

Symmetry codes: (i) x, y, z−1; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+2, −y, −z+1; (v) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₈N₂)₃][Mo₆O₁₉]
M_r	1407.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.310 (2), 18.979 (4), 17.150 (4)
β (°)	100.895 (3)
V (Å³)	3934.4 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.35
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	0.766, 0.834
No. of measured, independent and observed [I > 2σ(I)] reflections	25652, 6500, 4649
R_int	0.041
(sin θ/λ)_max (Å⁻¹)	0.583

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.092, 1.00
No. of reflections	6500
No. of parameters	559
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.041P)² + 10.1791P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.54

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

Selected bond lengths (Å) top

Co1—N5	2.075 (5)	Co1—N4	2.081 (5)
Co1—N6	2.078 (5)	Co1—N2	2.091 (5)
Co1—N1	2.079 (5)	Co1—N3	2.100 (5)