Tetra­ethyl­ammonium (2,2′-bipyridine)tetra­cyanidocobaltate(III) sesquihydrate acetonitrile solvate

Lyubartseva, G.; Parkin, S.

doi:10.1107/S1600536810011311

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages m475-m476

doi:10.1107/S1600536810011311

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Tetraethylammonium (2,2′-bipyridine)tetracyanidocobaltate(III) sesquihydrate acetonitrile solvate

Ganna Lyubartseva ^a ^* and Sean Parkin ^b

^aDepartment of Chemistry and Physics, College of Science and Technology, Southern Arkansas University, Magnolia, AR 71753, USA, and ^bDepartment of Chemistry, University of Kentucky, Lexington, KY 40506, USA
^*Correspondence e-mail: GannaLyubartseva@saumag.edu

(Received 19 March 2010; accepted 25 March 2010; online 31 March 2010)

The title complex, (C₈H₂₀N)[Co(CN)₄(C₁₀H₈N₂)]·CH₃CN·1.5H₂O, consists of tetraethyl ammonium cations, mononuclear [Co^IIIbpy(CN)₄]⁻ anions and uncoordinated water and acetonitrile molecules. The Co^III atom is six-coordinated by two 2,2′-bipyridine (bpy) N atoms and four cyanide C atoms in a distorted octahedral geometry. The acute bite angle of the chelating bpy [82.28 (8)°] is the main factor accounting for this distortion. In addition, the tetraethylammonium cation is significantly disordered [occupancy ratio 0.611 (3):0.389 (3)]. The presence of water molecules, one of which is disordered over two positions about an inversion center, results in the formation of a network of O—H⋯N hydrogen bonds involving the cyanide N atoms.

Related literature

For the starting complex [Co(bpy)₃]Cl₂·2H₂O·CH₃CH₂OH, see: Szalda et al. (1983 ). For a similar building block with a tetraphenylphosphonium cation and chromium(III), and a nuclearity controlled cyanide-bridged bimetallic compound, see: Toma et al. (2004 ); with a potassium cation and tetraphenylarsonium cation and iron(III), and cyanide-bridged heterobimetallic complexes, see: Toma et al. (2007 ); with a tetraphenylphosphonium cation and iron(III) and ribbon-like ferromagnetic cyano-bridged chains, see: Lescoueezec et al. (2002 ). For potential applications of bimetallic clusters as catalysts, see: Darensbourg & Phelps (2004 ), as room temperature magnets, see: Mallah et al. (1993 ); Garde et al. (2002 ); Holmes & Girolami (1999 ) and as single-molecule magnets, see: Sokol et al. (2002 ). For attempts to make a similar building block with nickel(II), see: Lyubartseva & Parkin (2009 ).

Experimental

Crystal data

(C₈H₂₀N)[Co(CN)₄(C₁₀H₈N₂)]·C₂H₃N·1.5H₂O
M_r = 517.52
Monoclinic, P 2₁ /n
a = 10.1591 (1) Å
b = 23.4015 (3) Å
c = 11.3422 (2) Å
β = 97.3080 (5)°
V = 2674.57 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 90 K
0.30 × 0.27 × 0.25 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.709, T_max = 0.849
28623 measured reflections
4704 independent reflections
3689 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.108
S = 1.05
4704 reflections
378 parameters
60 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯N5ⁱ	0.83 (2)	2.10 (2)	2.925 (3)	176 (3)
O1W—H2W1⋯N4	0.82 (2)	2.08 (2)	2.899 (3)	174 (3)
O2W—H1W2⋯N3	0.84 (2)	1.83 (2)	2.665 (5)	172 (7)
O2W—H2W2⋯N3ⁱⁱ	0.84 (2)	1.92 (2)	2.740 (5)	165 (7)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y, -z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 and local procedures.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810011311/kp2254sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810011311/kp2254Isup2.hkl

checkCIF report

Comment top

Self-assembly of cyano-linked metal complexes draws considerable interest as a strategy for developing new bimetallic clusters. Typically one needs a stable cyanometallate anion as a ligand for fully or partially solvated metal ions. Hexacyanometallate anion [M(CN)₆]^3- is very useful but it often gives three dimensional Prussian Blue analogs. If the metal ions are partially blocked with a bidentate ligand it is possible to control the nuclearity of the bimetallic clusters which have potential application as catalysts, see Darensbourg et al. (2004); room temperature magnets, see Mallah et al. (1993), Garde et al. (2002) and Holmes & Girolami (1999); or single-molecule magnets, see Sokol et al. (2002). Here we report a new building block [(Co^IIIbpy(CN)₄]^-- which can be applied to make new bimetallic clusters.

The structure consists of tetraethyl ammonium cations, mononuclear [Co^IIIbpy(CN)₄]^- anions, uncoordinated water and acetonitrile molecules. The cobalt (III) atom is six-coordinate with two bpy-nitrogen atoms and four cyanide-carbon atoms in a distorted octahedral geometry (Fig.1). The acute bite angle of the chelating bpy [82.28 (8)°] is the main factor accounting for this distortion from the ideal geometry. The values of the Co^III-nitrogen bond lengths are shorter than bond lengths in the similar chromium (III) anionic complex reported by Toma et al. (2004). The cobalt—carbon—nitrogen angles for the terminally bound cyanide ligands are quasilinear [178.5 (2)–179.5 (3)°]. The values of the cyanide bonds vary in the range 1.147 (4)–1.159 (3) Å. The presence of terminally bound cyanide groups in the structure is consistent with the presence of cyanide stretching vibrations at 2133(m)cm^-1. Also, the tetraethyl ammonium cationic part is significantly disordered. Presence of water molecules, one of which is disordered over two positions about an inversion centre, results in the formation of a network of O—H···N hydrogen bonds involving nitrogen atoms of cyano ligands.

Related literature top

For the starting complex [Co(bpy)₃]Cl₂.2H₂0.CH₃CH₂OH, see: Szalda et al. (1983). For a similar building block with a tetraphenylphosphonium cation and chromium(III), and a nuclearity controlled cyanide-bridged bimetallic compound, see: Toma et al. (2004); with a potassium cation and tetraphenylarsonium cation and iron(III), and cyanide-bridged heterobimetallic complexes, see: Toma et al.(2007); with a tetraphenylphosphonium cation and iron(III) and ribbon-like ferromagnetic cyano-bridged chains, see: Lescoueezec et al. (2002). For potential applications of bimetallic clusters as catalysts, see: Darensbourg & Phelps (2004), as room temperature magnets, see: Mallah et al. (1993); Garde et al. (2002); Holmes & Girolami (1999) and as single-molecule magnets, see: Sokol et al. (2002). For attempts to make a similar building block with nickel(II), see: Lyubartseva & Parkin (2009).

Experimental top

2,2'-bipyridine and tetraethylammonium cyanide were purchased from Sigma-Aldrich and used as received. The starting complex [Co(bpy)₃]Cl₂.2H₂O.CH₃CH₂OH was synthesized according to the previously published procedure by Szalda et al.(1983). [Co(bpy)₃]Cl₂.2H₂0.CH₃CH₂OH (680 mg, 1 mmol) was dissolved in 20 ml 1:1 mixture of methanol and acetonitrile. Tetraethylammonium cyanide (468 mg, 3 mmol) was dissolved in 10 ml wet acetonitrile. The cyanide solution was added dropwise to metal solution with slow stirring. Once the addition was complete, the resulting solution was filtered and solvent was evaporated slowly. Yellow coloured, analytically pure monoclinic crystals were obtained after one week and found to be [tetraethylammonium][(2-(pyridin-2-yl)pyridine) tetracyanocobaltate (III)]. 2H₂O.CH₃CN (198 mg, 37.6% yield). Elemental analysis calculated for CoC₂₄H₃₅N₈O₂: C 54.75, H 6.70, N 21.28; found C 55.55, H 6.49, N 20.43. IR(cm^-1) 3496, 2997, 2133, 1578, 1557, 1453, 1412, 1313, 1250, 1185, 1083, 997, 791, 773,757,653, 620, 403.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures top

Fig. 1. View of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Tetraethylammonium (2,2'-bipyridine)tetracyanidocobaltate(III) sesquihydrate acetonitrile solvate top

Crystal data top

(C₈H₂₀N)[Co(CN)₄(C₁₀H₈N₂)]·C₂H₃N·1.5H₂O	F(000) = 1092
M_r = 517.52	D_x = 1.285 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6273 reflections
a = 10.1591 (1) Å	θ = 1.0–27.5°
b = 23.4015 (3) Å	µ = 0.68 mm⁻¹
c = 11.3422 (2) Å	T = 90 K
β = 97.3080 (5)°	Block, yellow
V = 2674.57 (6) Å³	0.30 × 0.27 × 0.25 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	4704 independent reflections
Radiation source: fine-focus sealed tube	3689 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 9.1 pixels mm^-1	θ_max = 25.0°, θ_min = 2.0°
ω scans at fixed χ = 55°	h = −12→12
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −27→27
T_min = 0.709, T_max = 0.849	l = −13→13
28623 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0481P)² + 2.6305P] where P = (F_o² + 2F_c²)/3
4704 reflections	(Δ/σ)_max = 0.001
378 parameters	Δρ_max = 0.69 e Å⁻³
60 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

(C₈H₂₀N)[Co(CN)₄(C₁₀H₈N₂)]·C₂H₃N·1.5H₂O	V = 2674.57 (6) Å³
M_r = 517.52	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1591 (1) Å	µ = 0.68 mm⁻¹
b = 23.4015 (3) Å	T = 90 K
c = 11.3422 (2) Å	0.30 × 0.27 × 0.25 mm
β = 97.3080 (5)°

Data collection top

Nonius KappaCCD diffractometer	4704 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	3689 reflections with I > 2σ(I)
T_min = 0.709, T_max = 0.849	R_int = 0.048
28623 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	60 restraints
wR(F²) = 0.108	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.69 e Å⁻³
4704 reflections	Δρ_min = −0.33 e Å⁻³
378 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 > 2σ(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	Occ. (<1)
Co1	0.66787 (3)	0.093308 (13)	0.27408 (3)	0.02317 (12)
N1	0.7419 (2)	0.05486 (8)	0.42108 (19)	0.0238 (5)
N2	0.5597 (2)	0.02349 (8)	0.25393 (18)	0.0240 (5)
C1	0.8401 (3)	0.07455 (11)	0.5019 (2)	0.0292 (6)
H1	0.8782	0.1108	0.4895	0.035*
C2	0.8872 (3)	0.04358 (12)	0.6025 (3)	0.0383 (7)
H2	0.9566	0.0584	0.6582	0.046*
C3	0.8320 (3)	−0.00906 (13)	0.6209 (3)	0.0431 (8)
H3	0.8626	−0.0308	0.6896	0.052*
C4	0.7314 (3)	−0.02991 (12)	0.5380 (2)	0.0350 (7)
H4	0.6926	−0.0661	0.5491	0.042*
C5	0.6881 (3)	0.00296 (10)	0.4384 (2)	0.0254 (6)
C6	0.5839 (3)	−0.01476 (10)	0.3436 (2)	0.0239 (6)
C7	0.5152 (3)	−0.06600 (11)	0.3423 (2)	0.0287 (6)
H7	0.5339	−0.0925	0.4057	0.034*
C8	0.4195 (3)	−0.07813 (11)	0.2483 (2)	0.0320 (6)
H8	0.3712	−0.1129	0.2463	0.038*
C9	0.3946 (3)	−0.03900 (11)	0.1567 (2)	0.0321 (6)
H9	0.3293	−0.0465	0.0909	0.039*
C10	0.4668 (3)	0.01138 (11)	0.1630 (2)	0.0293 (6)
H10	0.4497	0.0383	0.1002	0.035*
N3	0.8813 (3)	0.03848 (11)	0.1447 (3)	0.0600 (9)
C11	0.8014 (3)	0.05929 (11)	0.1935 (3)	0.0350 (7)
N4	0.8354 (2)	0.19977 (9)	0.3179 (2)	0.0337 (5)
C12	0.7721 (3)	0.15893 (11)	0.3010 (2)	0.0263 (6)
N5	0.5526 (3)	0.14664 (10)	0.0403 (2)	0.0375 (6)
C13	0.5958 (3)	0.12650 (11)	0.1303 (2)	0.0293 (6)
N6	0.4571 (2)	0.15090 (9)	0.4029 (2)	0.0281 (5)
C14	0.5359 (2)	0.12964 (10)	0.3530 (2)	0.0224 (5)
N1C	0.1397 (2)	0.17482 (9)	0.03158 (18)	0.0240 (5)
C1C	0.2239 (5)	0.16359 (19)	−0.0684 (4)	0.0317 (11)	0.611 (3)
H1C1	0.1910	0.1883	−0.1368	0.038*	0.611 (3)
H1C2	0.3164	0.1752	−0.0408	0.038*	0.611 (3)
C2C	0.225 (3)	0.1027 (8)	−0.1111 (16)	0.0409 (18)	0.611 (3)
H2C1	0.2810	0.0997	−0.1750	0.061*	0.611 (3)
H2C2	0.1343	0.0909	−0.1410	0.061*	0.611 (3)
H2C3	0.2602	0.0778	−0.0450	0.061*	0.611 (3)
C3C	0.0006 (4)	0.1547 (2)	0.0034 (4)	0.0306 (11)	0.611 (3)
H3C1	−0.0495	0.1659	0.0691	0.037*	0.611 (3)
H3C2	0.0007	0.1124	−0.0005	0.037*	0.611 (3)
C4C	−0.0712 (10)	0.1778 (4)	−0.1124 (10)	0.040 (2)	0.611 (3)
H4C1	−0.1620	0.1627	−0.1244	0.060*	0.611 (3)
H4C2	−0.0241	0.1658	−0.1785	0.060*	0.611 (3)
H4C3	−0.0739	0.2196	−0.1090	0.060*	0.611 (3)
C5C	0.2059 (4)	0.14187 (17)	0.1426 (4)	0.0271 (10)	0.611 (3)
H5C1	0.2023	0.1005	0.1246	0.033*	0.611 (3)
H5C2	0.3007	0.1530	0.1573	0.033*	0.611 (3)
C6C	0.1447 (19)	0.1518 (9)	0.2535 (7)	0.029 (2)	0.611 (3)
H6C1	0.1928	0.1297	0.3187	0.044*	0.611 (3)
H6C2	0.0517	0.1396	0.2412	0.044*	0.611 (3)
H6C3	0.1495	0.1925	0.2735	0.044*	0.611 (3)
C7C	0.1441 (5)	0.23881 (17)	0.0576 (4)	0.0310 (11)	0.611 (3)
H7C1	0.1056	0.2565	−0.0183	0.037*	0.611 (3)
H7C2	0.0770	0.2443	0.1127	0.037*	0.611 (3)
C8C	0.2393 (7)	0.2726 (3)	0.0975 (11)	0.049 (2)	0.611 (3)
H8C1	0.2046	0.3114	0.1036	0.074*	0.611 (3)
H8C2	0.3069	0.2725	0.0431	0.074*	0.611 (3)
H8C3	0.2789	0.2596	0.1762	0.074*	0.611 (3)
C1C'	0.1829 (7)	0.1151 (3)	0.0039 (6)	0.0313 (17)	0.389 (3)
H1C3	0.2515	0.1028	0.0687	0.038*	0.389 (3)
H1C4	0.1058	0.0893	0.0049	0.038*	0.389 (3)
C2C'	0.237 (4)	0.1069 (13)	−0.112 (3)	0.0409 (18)	0.389 (3)
H2C4	0.2643	0.0670	−0.1196	0.061*	0.389 (3)
H2C5	0.3141	0.1319	−0.1150	0.061*	0.389 (3)
H2C6	0.1685	0.1164	−0.1781	0.061*	0.389 (3)
C3C'	0.0367 (7)	0.1966 (3)	−0.0737 (6)	0.0302 (16)	0.389 (3)
H3C3	0.0068	0.2353	−0.0539	0.036*	0.389 (3)
H3C4	0.0820	0.2000	−0.1457	0.036*	0.389 (3)
C4C'	−0.0849 (16)	0.1587 (7)	−0.1027 (18)	0.040 (2)	0.389 (3)
H4C4	−0.1428	0.1749	−0.1701	0.060*	0.389 (3)
H4C5	−0.1333	0.1566	−0.0334	0.060*	0.389 (3)
H4C6	−0.0569	0.1203	−0.1232	0.060*	0.389 (3)
C5C'	0.0653 (6)	0.1730 (3)	0.1398 (5)	0.0225 (14)	0.389 (3)
H5C3	0.0202	0.2101	0.1467	0.027*	0.389 (3)
H5C4	−0.0039	0.1431	0.1273	0.027*	0.389 (3)
C6C'	0.152 (3)	0.1611 (15)	0.2544 (12)	0.029 (2)	0.389 (3)
H6C4	0.0982	0.1601	0.3199	0.044*	0.389 (3)
H6C5	0.2194	0.1913	0.2691	0.044*	0.389 (3)
H6C6	0.1967	0.1241	0.2491	0.044*	0.389 (3)
C7C'	0.2528 (6)	0.2158 (3)	0.0447 (6)	0.0274 (16)	0.389 (3)
H7C3	0.3307	0.1902	0.0616	0.033*	0.389 (3)
H7C4	0.2551	0.2291	−0.0378	0.033*	0.389 (3)
C8C'	0.2884 (13)	0.2594 (5)	0.1049 (17)	0.049 (2)	0.389 (3)
H8C4	0.3714	0.2741	0.0811	0.074*	0.389 (3)
H8C5	0.3021	0.2494	0.1895	0.074*	0.389 (3)
H8C6	0.2194	0.2888	0.0911	0.074*	0.389 (3)
N1S	0.0766 (3)	0.15711 (15)	0.6193 (3)	0.0686 (10)
C1S	0.1527 (3)	0.18783 (14)	0.5901 (3)	0.0407 (7)
C2S	0.2493 (3)	0.22731 (12)	0.5543 (3)	0.0404 (7)
H2S1	0.2060	0.2531	0.4933	0.061*
H2S2	0.3197	0.2060	0.5220	0.061*
H2S3	0.2879	0.2496	0.6233	0.061*
O1W	1.0262 (2)	0.29166 (9)	0.31420 (19)	0.0423 (5)
H1W1	1.034 (3)	0.3105 (13)	0.376 (2)	0.063*
H2W1	0.969 (3)	0.2672 (12)	0.318 (3)	0.063*
O2W	1.1073 (4)	−0.0035 (2)	0.0843 (4)	0.0494 (12)	0.50
H1W2	1.032 (4)	0.008 (3)	0.098 (6)	0.074*	0.50
H2W2	1.098 (7)	−0.010 (3)	0.011 (2)	0.074*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0327 (2)	0.01501 (19)	0.0242 (2)	−0.00140 (14)	0.01285 (15)	−0.00014 (14)
N1	0.0272 (11)	0.0178 (10)	0.0289 (12)	−0.0035 (9)	0.0129 (9)	−0.0010 (9)
N2	0.0318 (12)	0.0179 (10)	0.0246 (12)	−0.0017 (9)	0.0120 (9)	−0.0022 (9)
C1	0.0329 (15)	0.0223 (13)	0.0335 (15)	−0.0050 (11)	0.0084 (12)	0.0009 (12)
C2	0.0467 (17)	0.0315 (16)	0.0353 (17)	−0.0054 (13)	0.0001 (14)	0.0007 (13)
C3	0.059 (2)	0.0351 (17)	0.0338 (17)	−0.0089 (15)	0.0020 (15)	0.0095 (14)
C4	0.0479 (17)	0.0244 (14)	0.0336 (16)	−0.0089 (13)	0.0081 (13)	0.0046 (12)
C5	0.0329 (14)	0.0190 (13)	0.0265 (14)	−0.0009 (11)	0.0126 (11)	−0.0009 (11)
C6	0.0332 (14)	0.0179 (12)	0.0231 (13)	−0.0008 (11)	0.0133 (11)	−0.0028 (10)
C7	0.0417 (16)	0.0185 (13)	0.0289 (15)	−0.0041 (11)	0.0162 (12)	−0.0008 (11)
C8	0.0396 (16)	0.0212 (13)	0.0376 (16)	−0.0090 (12)	0.0149 (13)	−0.0090 (12)
C9	0.0389 (16)	0.0281 (14)	0.0302 (15)	−0.0043 (12)	0.0076 (12)	−0.0081 (12)
C10	0.0416 (16)	0.0222 (14)	0.0253 (14)	0.0005 (12)	0.0094 (12)	−0.0015 (11)
N3	0.086 (2)	0.0285 (14)	0.078 (2)	0.0051 (14)	0.0623 (19)	0.0012 (14)
C11	0.0521 (18)	0.0173 (14)	0.0405 (17)	−0.0043 (12)	0.0255 (14)	0.0019 (12)
N4	0.0389 (13)	0.0227 (12)	0.0425 (14)	−0.0040 (11)	0.0167 (11)	0.0010 (10)
C12	0.0306 (14)	0.0215 (14)	0.0297 (14)	0.0042 (12)	0.0153 (11)	0.0035 (11)
N5	0.0548 (16)	0.0277 (13)	0.0315 (14)	−0.0001 (11)	0.0113 (12)	0.0055 (11)
C13	0.0422 (16)	0.0190 (13)	0.0299 (16)	−0.0052 (12)	0.0166 (13)	−0.0024 (12)
N6	0.0300 (12)	0.0221 (11)	0.0337 (13)	−0.0004 (9)	0.0100 (10)	−0.0031 (10)
C14	0.0287 (14)	0.0161 (12)	0.0227 (13)	−0.0052 (10)	0.0048 (11)	0.0003 (10)
N1C	0.0295 (11)	0.0203 (11)	0.0236 (11)	−0.0016 (9)	0.0087 (9)	0.0000 (9)
C1C	0.041 (3)	0.035 (3)	0.022 (2)	−0.007 (2)	0.0130 (19)	−0.0034 (19)
C2C	0.048 (4)	0.038 (3)	0.0396 (18)	0.006 (3)	0.015 (2)	−0.0112 (17)
C3C	0.028 (2)	0.036 (3)	0.029 (2)	−0.0050 (19)	0.0056 (18)	−0.006 (2)
C4C	0.042 (3)	0.049 (7)	0.028 (2)	0.003 (4)	0.000 (2)	0.002 (4)
C5C	0.031 (2)	0.021 (2)	0.028 (2)	0.0054 (18)	0.0038 (18)	0.0008 (18)
C6C	0.038 (2)	0.021 (7)	0.0286 (15)	0.004 (3)	0.0031 (14)	0.0039 (17)
C7C	0.046 (3)	0.020 (2)	0.027 (2)	0.0013 (19)	0.007 (2)	0.0004 (18)
C8C	0.080 (6)	0.029 (4)	0.048 (3)	−0.016 (4)	0.043 (5)	−0.016 (3)
C1C'	0.037 (4)	0.015 (3)	0.044 (4)	0.002 (3)	0.015 (3)	−0.006 (3)
C2C'	0.048 (4)	0.038 (3)	0.0396 (18)	0.006 (3)	0.015 (2)	−0.0112 (17)
C3C'	0.039 (4)	0.029 (4)	0.022 (3)	0.002 (3)	0.003 (3)	−0.001 (3)
C4C'	0.042 (3)	0.049 (7)	0.028 (2)	0.003 (4)	0.000 (2)	0.002 (4)
C5C'	0.022 (3)	0.021 (3)	0.027 (3)	0.000 (3)	0.011 (3)	0.006 (3)
C6C'	0.038 (2)	0.021 (7)	0.0286 (15)	0.004 (3)	0.0031 (14)	0.0039 (17)
C7C'	0.031 (4)	0.021 (3)	0.033 (4)	−0.007 (3)	0.012 (3)	−0.003 (3)
C8C'	0.080 (6)	0.029 (4)	0.048 (3)	−0.016 (4)	0.043 (5)	−0.016 (3)
N1S	0.078 (2)	0.082 (2)	0.0462 (18)	−0.045 (2)	0.0083 (16)	−0.0021 (16)
C1S	0.0477 (18)	0.0448 (18)	0.0296 (16)	−0.0135 (15)	0.0054 (14)	−0.0090 (14)
C2S	0.0436 (17)	0.0330 (16)	0.0486 (19)	−0.0068 (13)	0.0212 (15)	−0.0123 (14)
O1W	0.0548 (14)	0.0344 (12)	0.0429 (13)	−0.0221 (10)	0.0265 (11)	−0.0162 (10)
O2W	0.033 (2)	0.078 (3)	0.035 (2)	0.018 (2)	−0.0045 (19)	−0.015 (2)

Geometric parameters (Å, º) top

Co1—C12	1.868 (3)	C4C—H4C1	0.9800
Co1—C13	1.869 (3)	C4C—H4C2	0.9800
Co1—C11	1.904 (3)	C4C—H4C3	0.9800
Co1—C14	1.904 (3)	C5C—C6C	1.490 (14)
Co1—N1	1.959 (2)	C5C—H5C1	0.9900
Co1—N2	1.966 (2)	C5C—H5C2	0.9900
N1—C1	1.347 (3)	C6C—H6C1	0.9800
N1—C5	1.356 (3)	C6C—H6C2	0.9800
N2—C10	1.337 (3)	C6C—H6C3	0.9800
N2—C6	1.354 (3)	C7C—C8C	1.286 (8)
C1—C2	1.385 (4)	C7C—H7C1	0.9900
C1—H1	0.9500	C7C—H7C2	0.9900
C2—C3	1.380 (4)	C8C—H8C1	0.9800
C2—H2	0.9500	C8C—H8C2	0.9800
C3—C4	1.386 (4)	C8C—H8C3	0.9800
C3—H3	0.9500	C1C'—C2C'	1.505 (19)
C4—C5	1.392 (4)	C1C'—H1C3	0.9900
C4—H4	0.9500	C1C'—H1C4	0.9900
C5—C6	1.469 (4)	C2C'—H2C4	0.9800
C6—C7	1.387 (3)	C2C'—H2C5	0.9800
C7—C8	1.379 (4)	C2C'—H2C6	0.9800
C7—H7	0.9500	C3C'—C4C'	1.522 (12)
C8—C9	1.383 (4)	C3C'—H3C3	0.9900
C8—H8	0.9500	C3C'—H3C4	0.9900
C9—C10	1.386 (4)	C4C'—H4C4	0.9800
C9—H9	0.9500	C4C'—H4C5	0.9800
C10—H10	0.9500	C4C'—H4C6	0.9800
N3—C11	1.147 (4)	C5C'—C6C'	1.504 (18)
N4—C12	1.155 (3)	C5C'—H5C3	0.9900
N5—C13	1.159 (3)	C5C'—H5C4	0.9900
N6—C14	1.151 (3)	C6C'—H6C4	0.9800
N1C—C3C	1.485 (4)	C6C'—H6C5	0.9800
N1C—C7C'	1.489 (6)	C6C'—H6C6	0.9800
N1C—C1C'	1.509 (6)	C7C'—C8C'	1.256 (11)
N1C—C5C'	1.521 (6)	C7C'—H7C3	0.9900
N1C—C7C	1.526 (4)	C7C'—H7C4	0.9900
N1C—C1C	1.528 (4)	C8C'—H8C4	0.9800
N1C—C5C	1.555 (4)	C8C'—H8C5	0.9800
N1C—C3C'	1.570 (7)	C8C'—H8C6	0.9800
C1C—C2C	1.506 (16)	N1S—C1S	1.136 (4)
C1C—H1C1	0.9900	C1S—C2S	1.443 (4)
C1C—H1C2	0.9900	C2S—H2S1	0.9800
C2C—H2C1	0.9800	C2S—H2S2	0.9800
C2C—H2C2	0.9800	C2S—H2S3	0.9800
C2C—H2C3	0.9800	O1W—H1W1	0.827 (18)
C3C—C4C	1.518 (9)	O1W—H2W1	0.821 (18)
C3C—H3C1	0.9900	O2W—H1W2	0.84 (2)
C3C—H3C2	0.9900	O2W—H2W2	0.84 (2)

C12—Co1—C13	87.23 (11)	H2C2—C2C—H2C3	109.5
C12—Co1—C11	89.91 (11)	N1C—C3C—C4C	114.4 (5)
C13—Co1—C11	88.80 (12)	N1C—C3C—H3C1	108.7
C12—Co1—C14	88.53 (10)	C4C—C3C—H3C1	108.7
C13—Co1—C14	90.20 (11)	N1C—C3C—H3C2	108.7
C11—Co1—C14	178.18 (10)	C4C—C3C—H3C2	108.7
C12—Co1—N1	95.18 (10)	H3C1—C3C—H3C2	107.6
C13—Co1—N1	177.20 (10)	C3C—C4C—H4C1	109.5
C11—Co1—N1	89.79 (11)	C3C—C4C—H4C2	109.5
C14—Co1—N1	91.28 (9)	H4C1—C4C—H4C2	109.5
C12—Co1—N2	177.28 (10)	C3C—C4C—H4C3	109.5
C13—Co1—N2	95.33 (10)	H4C1—C4C—H4C3	109.5
C11—Co1—N2	91.07 (10)	H4C2—C4C—H4C3	109.5
C14—Co1—N2	90.54 (9)	C6C—C5C—N1C	115.0 (7)
N1—Co1—N2	82.28 (8)	C6C—C5C—H5C1	108.5
C1—N1—C5	119.0 (2)	N1C—C5C—H5C1	108.5
C1—N1—Co1	126.39 (17)	C6C—C5C—H5C2	108.5
C5—N1—Co1	114.58 (17)	N1C—C5C—H5C2	108.5
C10—N2—C6	118.8 (2)	H5C1—C5C—H5C2	107.5
C10—N2—Co1	126.51 (17)	C5C—C6C—H6C1	109.5
C6—N2—Co1	114.64 (17)	C5C—C6C—H6C2	109.5
N1—C1—C2	122.0 (2)	H6C1—C6C—H6C2	109.5
N1—C1—H1	119.0	C5C—C6C—H6C3	109.5
C2—C1—H1	119.0	H6C1—C6C—H6C3	109.5
C3—C2—C1	119.1 (3)	H6C2—C6C—H6C3	109.5
C3—C2—H2	120.4	C8C—C7C—N1C	132.3 (5)
C1—C2—H2	120.4	C8C—C7C—H7C1	104.2
C2—C3—C4	119.4 (3)	N1C—C7C—H7C1	104.2
C2—C3—H3	120.3	C8C—C7C—H7C2	104.2
C4—C3—H3	120.3	N1C—C7C—H7C2	104.2
C3—C4—C5	119.1 (3)	H7C1—C7C—H7C2	105.5
C3—C4—H4	120.5	C7C—C8C—H8C1	109.5
C5—C4—H4	120.5	C7C—C8C—H8C2	109.5
N1—C5—C4	121.4 (2)	H8C1—C8C—H8C2	109.5
N1—C5—C6	114.4 (2)	C7C—C8C—H8C3	109.5
C4—C5—C6	124.2 (2)	H8C1—C8C—H8C3	109.5
N2—C6—C7	121.4 (2)	H8C2—C8C—H8C3	109.5
N2—C6—C5	114.1 (2)	C2C'—C1C'—N1C	116.7 (14)
C7—C6—C5	124.5 (2)	C2C'—C1C'—H1C3	108.1
C8—C7—C6	119.4 (2)	N1C—C1C'—H1C3	108.1
C8—C7—H7	120.3	C2C'—C1C'—H1C4	108.1
C6—C7—H7	120.3	N1C—C1C'—H1C4	108.1
C7—C8—C9	119.2 (2)	H1C3—C1C'—H1C4	107.3
C7—C8—H8	120.4	C1C'—C2C'—H2C4	109.5
C9—C8—H8	120.4	C1C'—C2C'—H2C5	109.5
C8—C9—C10	118.7 (3)	H2C4—C2C'—H2C5	109.5
C8—C9—H9	120.7	C1C'—C2C'—H2C6	109.5
C10—C9—H9	120.7	H2C4—C2C'—H2C6	109.5
N2—C10—C9	122.5 (2)	H2C5—C2C'—H2C6	109.5
N2—C10—H10	118.8	C4C'—C3C'—N1C	114.8 (8)
C9—C10—H10	118.8	C4C'—C3C'—H3C3	108.6
N3—C11—Co1	179.5 (3)	N1C—C3C'—H3C3	108.6
N4—C12—Co1	179.4 (2)	C4C'—C3C'—H3C4	108.6
N5—C13—Co1	179.0 (3)	N1C—C3C'—H3C4	108.6
N6—C14—Co1	178.5 (2)	H3C3—C3C'—H3C4	107.5
C3C—N1C—C7C'	157.9 (4)	C3C'—C4C'—H4C4	109.5
C3C—N1C—C1C'	87.4 (3)	C3C'—C4C'—H4C5	109.5
C7C'—N1C—C1C'	112.1 (4)	H4C4—C4C'—H4C5	109.5
C3C—N1C—C5C'	66.9 (3)	C3C'—C4C'—H4C6	109.5
C7C'—N1C—C5C'	113.2 (4)	H4C4—C4C'—H4C6	109.5
C1C'—N1C—C5C'	109.2 (4)	H4C5—C4C'—H4C6	109.5
C3C—N1C—C7C	110.9 (3)	C6C'—C5C'—N1C	113.9 (12)
C7C'—N1C—C7C	49.2 (3)	C6C'—C5C'—H5C3	108.8
C1C'—N1C—C7C	161.2 (4)	N1C—C5C'—H5C3	108.8
C5C'—N1C—C7C	82.9 (3)	C6C'—C5C'—H5C4	108.8
C3C—N1C—C1C	113.1 (3)	N1C—C5C'—H5C4	108.8
C7C'—N1C—C1C	71.8 (3)	H5C3—C5C'—H5C4	107.7
C1C'—N1C—C1C	58.8 (3)	C5C'—C6C'—H6C4	109.5
C5C'—N1C—C1C	167.6 (3)	C5C'—C6C'—H6C5	109.5
C7C—N1C—C1C	107.9 (3)	H6C4—C6C'—H6C5	109.5
C3C—N1C—C5C	108.6 (3)	C5C'—C6C'—H6C6	109.5
C7C'—N1C—C5C	89.4 (3)	H6C4—C6C'—H6C6	109.5
C1C'—N1C—C5C	66.5 (3)	H6C5—C6C'—H6C6	109.5
C5C'—N1C—C5C	62.7 (3)	C8C'—C7C'—N1C	138.0 (9)
C7C—N1C—C5C	109.4 (3)	C8C'—C7C'—H7C3	102.6
C1C—N1C—C5C	106.9 (3)	N1C—C7C'—H7C3	102.6
C3C—N1C—C3C'	54.2 (3)	C8C'—C7C'—H7C4	102.6
C7C'—N1C—C3C'	107.4 (4)	N1C—C7C'—H7C4	102.6
C1C'—N1C—C3C'	109.0 (4)	H7C3—C7C'—H7C4	105.0
C5C'—N1C—C3C'	105.7 (4)	C7C'—C8C'—H8C4	109.5
C7C—N1C—C3C'	80.1 (3)	C7C'—C8C'—H8C5	109.5
C1C—N1C—C3C'	82.7 (3)	H8C4—C8C'—H8C5	109.5
C5C—N1C—C3C'	162.8 (3)	C7C'—C8C'—H8C6	109.5
C2C—C1C—N1C	115.4 (8)	H8C4—C8C'—H8C6	109.5
C2C—C1C—H1C1	108.4	H8C5—C8C'—H8C6	109.5
N1C—C1C—H1C1	108.4	N1S—C1S—C2S	179.2 (4)
C2C—C1C—H1C2	108.4	C1S—C2S—H2S1	109.5
N1C—C1C—H1C2	108.4	C1S—C2S—H2S2	109.5
H1C1—C1C—H1C2	107.5	H2S1—C2S—H2S2	109.5
C1C—C2C—H2C1	109.5	C1S—C2S—H2S3	109.5
C1C—C2C—H2C2	109.5	H2S1—C2S—H2S3	109.5
H2C1—C2C—H2C2	109.5	H2S2—C2S—H2S3	109.5
C1C—C2C—H2C3	109.5	H1W1—O1W—H2W1	108 (3)
H2C1—C2C—H2C3	109.5	H1W2—O2W—H2W2	105 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···N5ⁱ	0.83 (2)	2.10 (2)	2.925 (3)	176 (3)
O1W—H2W1···N4	0.82 (2)	2.08 (2)	2.899 (3)	174 (3)
O2W—H1W2···N3	0.84 (2)	1.83 (2)	2.665 (5)	172 (7)
O2W—H2W2···N3ⁱⁱ	0.84 (2)	1.92 (2)	2.740 (5)	165 (7)

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

Experimental details

Crystal data
Chemical formula	(C₈H₂₀N)[Co(CN)₄(C₁₀H₈N₂)]·C₂H₃N·1.5H₂O
M_r	517.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	90
a, b, c (Å)	10.1591 (1), 23.4015 (3), 11.3422 (2)
β (°)	97.3080 (5)
V (Å³)	2674.57 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.30 × 0.27 × 0.25

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.709, 0.849
No. of measured, independent and observed [I > 2σ(I)] reflections	28623, 4704, 3689
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.108, 1.05
No. of reflections	4704
No. of parameters	378
No. of restraints	60
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.33

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and local procedures.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···N5ⁱ	0.827 (18)	2.099 (18)	2.925 (3)	176 (3)
O1W—H2W1···N4	0.821 (18)	2.081 (18)	2.899 (3)	174 (3)
O2W—H1W2···N3	0.84 (2)	1.83 (2)	2.665 (5)	172 (7)
O2W—H2W2···N3ⁱⁱ	0.84 (2)	1.92 (2)	2.740 (5)	165 (7)

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

Acknowledgements

GL gratefully acknowledges the College of Science and Technology, Southern Arkansas University, for financial support.

References

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Pages m475-m476

doi:10.1107/S1600536810011311

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Tetra­ethyl­ammonium (2,2′-bi­pyridine)tetra­cyanidocobaltate(III) sesquihydrate aceto­nitrile solvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Tetraethylammonium (2,2′-bipyridine)tetracyanidocobaltate(III) sesquihydrate acetonitrile solvate