Tris(2,2'-bipyridine-κN,N')cobalt(III) octa-cyanido-tungstate(V).

In the title compound, [Co(C(10)H(8)N(2))(3)][W(CN)(8)], the Co atom (..2 site symmetry) is coordinated by six N atoms from three 2,2'-bipyridine ligands in an octa-hedral geometry; the Co-N bond distances range from 1.926 (2) to 1.939 (2) Å. The W (..2 site symmetry) metal center is coordinated by eight cyanide ligands, resulting in a dodeca-hedral conformation with W-C distances in the range 1.165 (3)-2.176 (3) Å. The cations and anions are linked into a three-demensional structure by weak C-H⋯N hydrogen bonds.

Related literature

For compounds with similar architectures, see: Przychodzeń et al. (2006 ▶); Withers et al. (2005 ▶); Mathonière et al. (2005 ▶). For related structures, see: Liu et al. (2008 ▶); Chang et al. (2002 ▶).

Experimental

Crystal data

[Co(C10H8N2)3][W(CN)8]

M = 919.48

Orthorhombic,

a = 11.465 (2) Å

b = 15.141 (3) Å

c = 20.007 (4) Å

V = 3473.0 (12) Å3

Z = 4

Mo Kα radiation

μ = 3.84 mm−1

T = 250 K

0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.841, T max = 1.000

12594 measured reflections

3554 independent reflections

3023 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.059

S = 1.10

3554 reflections

245 parameters

H-atom parameters constrained

Δρmax = 1.33 e Å−3

Δρmin = −0.41 e Å−3

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051654/pv2237sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809051654/pv2237Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co(C10H8N2)3][W(CN)8]	F(000) = 1803
Mr = 919.48	Dx = 1.758 Mg m−3
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 10230 reflections
a = 11.465 (2) Å	θ = 2.5–31.3°
b = 15.141 (3) Å	µ = 3.84 mm−1
c = 20.007 (4) Å	T = 250 K
V = 3473.0 (12) Å3	Prism, red
Z = 4	0.20 × 0.20 × 0.20 mm

Rigaku Mercury CCD diffractometer	3554 independent reflections
Radiation source: fine-focus sealed tube	3023 reflections with I > 2σ(I)
graphite	Rint = 0.018
Detector resolution: 28.5714 pixels mm-1	θmax = 26.4°, θmin = 2.5°
dtprofit.ref scans	h = −14→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −15→18
Tmin = 0.841, Tmax = 1.000	l = −25→15
12594 measured reflections

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059	H-atom parameters constrained
S = 1.10	w = 1/[σ2(Fo2) + (0.0237P)2 + 2.7418P] where P = (Fo2 + 2Fc2)/3
3554 reflections	(Δ/σ)max = 0.001
245 parameters	Δρmax = 1.33 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

Experimental. Yield: 62.1 mg in pure form, 42.1% based on Co. Analysis calculated for C38H24CoN14W: C 49.59, H 2.61, N 21.32%; found: C 50.31, H 2.88, N 21.44%. IR: ν, cm-1,2132 s.

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.

	x	y	z	Uiso*/Ueq
Co1	0.2500	0.2500	0.44279 (2)	0.02694 (12)
N1	0.0967 (2)	0.19603 (17)	0.44129 (11)	0.0332 (5)
N2	0.2836 (2)	0.16505 (16)	0.37377 (12)	0.0329 (5)
N3	0.2091 (2)	0.32944 (16)	0.51483 (12)	0.0328 (5)
C1	0.0030 (3)	0.2192 (2)	0.47655 (17)	0.0474 (8)
H1A	0.0068	0.2693	0.5033	0.057*
C2	−0.0986 (3)	0.1720 (3)	0.47478 (18)	0.0574 (10)
H2A	−0.1631	0.1906	0.4992	0.069*
C3	−0.1042 (3)	0.0979 (3)	0.43700 (18)	0.0606 (11)
H3A	−0.1725	0.0647	0.4358	0.073*
C4	−0.0087 (3)	0.0716 (2)	0.40038 (18)	0.0521 (9)
H4A	−0.0114	0.0204	0.3747	0.063*
C5	0.0911 (3)	0.1222 (2)	0.40228 (14)	0.0352 (7)
C6	0.1962 (2)	0.10663 (18)	0.36179 (14)	0.0321 (6)
C7	0.2071 (3)	0.0426 (2)	0.31379 (16)	0.0434 (8)
H7A	0.1467	0.0027	0.3064	0.052*
C8	0.3073 (3)	0.0376 (2)	0.27679 (17)	0.0479 (8)
H8A	0.3156	−0.0056	0.2440	0.058*
C9	0.3944 (3)	0.0961 (2)	0.28839 (17)	0.0499 (9)
H9A	0.4628	0.0935	0.2635	0.060*
C10	0.3813 (3)	0.1595 (2)	0.33709 (16)	0.0442 (8)
H10A	0.4415	0.1995	0.3448	0.053*
C12	0.1644 (3)	0.4112 (2)	0.50934 (16)	0.0399 (7)
H12A	0.1572	0.4364	0.4671	0.048*
C13	0.1381 (3)	0.4211 (2)	0.62628 (17)	0.0530 (9)
H13A	0.1120	0.4514	0.6639	0.064*
C14	0.1288 (3)	0.4588 (2)	0.56437 (16)	0.0455 (8)
H14A	0.0989	0.5155	0.5595	0.055*
C11	0.1858 (3)	0.3387 (2)	0.63277 (17)	0.0522 (9)
H11A	0.1927	0.3130	0.6748	0.063*
C15	0.2235 (3)	0.2939 (2)	0.57651 (15)	0.0369 (7)
W1	0.7500	0.2500	0.194217 (8)	0.02995 (7)
N4	0.9827 (3)	0.3555 (2)	0.13727 (15)	0.0565 (8)
N5	0.8322 (3)	0.3742 (2)	0.32171 (16)	0.0571 (8)
N6	0.5146 (3)	0.3489 (2)	0.25333 (15)	0.0590 (8)
N7	0.6578 (3)	0.3788 (2)	0.07078 (15)	0.0569 (8)
C16	0.9012 (3)	0.3203 (2)	0.15643 (15)	0.0398 (7)
C17	0.8039 (3)	0.3325 (2)	0.27706 (16)	0.0401 (7)
C18	0.5961 (3)	0.3157 (2)	0.23298 (15)	0.0397 (7)
C19	0.6896 (3)	0.3344 (2)	0.11329 (16)	0.0396 (7)

	U11	U22	U33	U12	U13	U23
Co1	0.0231 (3)	0.0306 (3)	0.0271 (3)	−0.0031 (2)	0.000	0.000
N1	0.0237 (12)	0.0422 (15)	0.0337 (13)	−0.0050 (11)	0.0019 (10)	0.0019 (11)
N2	0.0287 (12)	0.0375 (14)	0.0326 (13)	−0.0011 (10)	0.0032 (10)	−0.0005 (11)
N3	0.0290 (12)	0.0350 (13)	0.0343 (13)	−0.0030 (10)	0.0011 (10)	−0.0033 (11)
C1	0.0336 (16)	0.063 (2)	0.0456 (18)	−0.0053 (16)	0.0092 (15)	−0.0064 (17)
C2	0.0346 (18)	0.081 (3)	0.057 (2)	−0.0131 (18)	0.0170 (16)	−0.009 (2)
C3	0.0351 (19)	0.080 (3)	0.067 (2)	−0.0240 (19)	0.0093 (17)	−0.004 (2)
C4	0.0433 (19)	0.055 (2)	0.058 (2)	−0.0181 (17)	0.0029 (16)	−0.0068 (18)
C5	0.0304 (15)	0.0398 (17)	0.0356 (15)	−0.0044 (13)	−0.0006 (12)	0.0055 (14)
C6	0.0301 (15)	0.0328 (15)	0.0334 (15)	−0.0011 (12)	−0.0028 (12)	0.0044 (13)
C7	0.0379 (17)	0.0415 (19)	0.051 (2)	−0.0034 (15)	−0.0036 (14)	−0.0026 (15)
C8	0.052 (2)	0.0439 (19)	0.0476 (19)	0.0035 (16)	0.0046 (17)	−0.0108 (16)
C9	0.0405 (19)	0.061 (2)	0.0481 (19)	0.0016 (17)	0.0129 (16)	−0.0079 (17)
C10	0.0307 (16)	0.053 (2)	0.0486 (19)	−0.0076 (14)	0.0094 (14)	−0.0056 (16)
C12	0.0357 (16)	0.0383 (17)	0.0457 (18)	−0.0006 (14)	0.0011 (14)	0.0009 (15)
C13	0.065 (2)	0.048 (2)	0.047 (2)	−0.0058 (18)	0.0108 (17)	−0.0167 (17)
C14	0.0397 (18)	0.0386 (18)	0.058 (2)	−0.0019 (15)	0.0057 (15)	−0.0076 (16)
C11	0.070 (3)	0.050 (2)	0.0364 (18)	−0.0059 (19)	0.0034 (17)	−0.0029 (16)
C15	0.0372 (17)	0.0398 (17)	0.0336 (15)	−0.0084 (13)	0.0014 (13)	−0.0033 (14)
W1	0.02626 (9)	0.03213 (11)	0.03147 (10)	0.00157 (7)	0.000	0.000
N4	0.0450 (17)	0.065 (2)	0.0592 (19)	−0.0143 (15)	0.0015 (15)	0.0043 (16)
N5	0.0503 (19)	0.062 (2)	0.0592 (19)	−0.0056 (16)	−0.0012 (15)	−0.0185 (16)
N6	0.0415 (17)	0.082 (2)	0.0530 (18)	0.0177 (16)	0.0023 (14)	−0.0080 (16)
N7	0.0489 (18)	0.069 (2)	0.0526 (18)	0.0133 (16)	0.0029 (14)	0.0204 (16)
C16	0.0356 (17)	0.0418 (17)	0.0421 (18)	−0.0027 (14)	−0.0030 (14)	0.0017 (15)
C17	0.0314 (16)	0.0430 (18)	0.0459 (18)	−0.0010 (14)	0.0006 (14)	−0.0029 (16)
C18	0.0346 (17)	0.0471 (19)	0.0373 (16)	0.0043 (14)	−0.0005 (13)	−0.0007 (15)
C19	0.0312 (16)	0.0458 (18)	0.0419 (17)	0.0057 (14)	0.0043 (14)	0.0032 (15)

Co1—N2	1.926 (2)	C8—H8A	0.9300
Co1—N2i	1.926 (2)	C9—C10	1.376 (4)
Co1—N3i	1.935 (2)	C9—H9A	0.9300
Co1—N3	1.935 (2)	C10—H10A	0.9300
Co1—N1i	1.939 (2)	C12—C14	1.377 (4)
Co1—N1	1.939 (2)	C12—H12A	0.9300
N1—C1	1.332 (4)	C13—C14	1.368 (5)
N1—C5	1.364 (4)	C13—C11	1.368 (5)
N2—C10	1.342 (4)	C13—H13A	0.9300
N2—C6	1.358 (4)	C14—H14A	0.9300
N3—C12	1.345 (4)	C11—C15	1.384 (4)
N3—C15	1.357 (4)	C11—H11A	0.9300
C1—C2	1.367 (5)	C15—C15i	1.460 (6)
C1—H1A	0.9300	W1—C17	2.165 (3)
C2—C3	1.355 (5)	W1—C17ii	2.165 (3)
C2—H2A	0.9300	W1—C18ii	2.169 (3)
C3—C4	1.376 (5)	W1—C18	2.169 (3)
C3—H3A	0.9300	W1—C16	2.170 (3)
C4—C5	1.378 (4)	W1—C16ii	2.170 (3)
C4—H4A	0.9300	W1—C19ii	2.176 (3)
C5—C6	1.471 (4)	W1—C19	2.176 (3)
C6—C7	1.370 (4)	N4—C16	1.142 (4)
C7—C8	1.369 (5)	N5—C17	1.141 (4)
C7—H7A	0.9300	N6—C18	1.137 (4)
C8—C9	1.355 (5)	N7—C19	1.144 (4)
N2—Co1—N2i	88.39 (15)	N2—C10—C9	121.5 (3)
N2—Co1—N3i	94.04 (11)	N2—C10—H10A	119.3
N2i—Co1—N3i	176.06 (10)	C9—C10—H10A	119.3
N2—Co1—N3	176.06 (10)	N3—C12—C14	121.9 (3)
N2i—Co1—N3	94.04 (11)	N3—C12—H12A	119.0
N3i—Co1—N3	83.70 (15)	C14—C12—H12A	119.0
N2—Co1—N1i	95.11 (10)	C14—C13—C11	119.8 (3)
N2i—Co1—N1i	83.60 (10)	C14—C13—H13A	120.1
N3i—Co1—N1i	93.09 (10)	C11—C13—H13A	120.1
N3—Co1—N1i	88.24 (10)	C13—C14—C12	118.9 (3)
N2—Co1—N1	83.60 (10)	C13—C14—H14A	120.6
N2i—Co1—N1	95.11 (10)	C12—C14—H14A	120.6
N3i—Co1—N1	88.24 (10)	C13—C11—C15	119.7 (3)
N3—Co1—N1	93.09 (10)	C13—C11—H11A	120.2
N1i—Co1—N1	178.22 (13)	C15—C11—H11A	120.2
C1—N1—C5	118.7 (3)	N3—C15—C11	120.5 (3)
C1—N1—Co1	127.7 (2)	N3—C15—C15i	114.32 (17)
C5—N1—Co1	113.36 (19)	C11—C15—C15i	125.2 (2)
C10—N2—C6	118.6 (3)	C17—W1—C17ii	80.10 (17)
C10—N2—Co1	126.9 (2)	C17—W1—C18ii	76.03 (12)
C6—N2—Co1	114.46 (19)	C17ii—W1—C18ii	72.18 (12)
C12—N3—C15	119.1 (3)	C17—W1—C18	72.18 (12)
C12—N3—Co1	127.2 (2)	C17ii—W1—C18	76.03 (12)
C15—N3—Co1	113.7 (2)	C18ii—W1—C18	138.10 (16)
N1—C1—C2	122.4 (3)	C17—W1—C16	75.86 (12)
N1—C1—H1A	118.8	C17ii—W1—C16	141.03 (12)
C2—C1—H1A	118.8	C18ii—W1—C16	72.52 (12)
C3—C2—C1	119.2 (3)	C18—W1—C16	123.33 (12)
C3—C2—H2A	120.4	C17—W1—C16ii	141.03 (12)
C1—C2—H2A	120.4	C17ii—W1—C16ii	75.86 (12)
C2—C3—C4	119.9 (3)	C18ii—W1—C16ii	123.33 (12)
C2—C3—H3A	120.0	C18—W1—C16ii	72.52 (12)
C4—C3—H3A	120.0	C16—W1—C16ii	139.23 (16)
C3—C4—C5	119.0 (3)	C17—W1—C19ii	144.84 (12)
C3—C4—H4A	120.5	C17ii—W1—C19ii	108.76 (12)
C5—C4—H4A	120.5	C18ii—W1—C19ii	74.80 (11)
N1—C5—C4	120.7 (3)	C18—W1—C19ii	142.59 (11)
N1—C5—C6	114.1 (2)	C16—W1—C19ii	76.99 (12)
C4—C5—C6	125.1 (3)	C16ii—W1—C19ii	72.95 (11)
N2—C6—C7	121.1 (3)	C17—W1—C19	108.76 (12)
N2—C6—C5	113.7 (3)	C17ii—W1—C19	144.84 (12)
C7—C6—C5	125.1 (3)	C18ii—W1—C19	142.59 (11)
C8—C7—C6	119.6 (3)	C18—W1—C19	74.80 (11)
C8—C7—H7A	120.2	C16—W1—C19	72.95 (11)
C6—C7—H7A	120.2	C16ii—W1—C19	76.99 (12)
C9—C8—C7	119.3 (3)	C19ii—W1—C19	83.84 (16)
C9—C8—H8A	120.3	N4—C16—W1	178.2 (3)
C7—C8—H8A	120.3	N5—C17—W1	178.3 (3)
C8—C9—C10	119.8 (3)	N6—C18—W1	178.9 (3)
C8—C9—H9A	120.1	N7—C19—W1	179.9 (4)
C10—C9—H9A	120.1

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···N4iii	0.93	2.53	3.371 (4)	151
C10—H10A···N1iv	0.93	2.54	3.032 (4)	114
C12—H12A···N2iv	0.93	2.51	3.008 (4)	114
C1—H1A···N3	0.93	2.50	2.993 (4)	113

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯N4i	0.93	2.53	3.371 (4)	151
C10—H10A⋯N1ii	0.93	2.54	3.032 (4)	114
C12—H12A⋯N2ii	0.93	2.51	3.008 (4)	114
C1—H1A⋯N3	0.93	2.50	2.993 (4)	113

Symmetry codes: (i) ; (ii) .