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Acta Cryst. (2009). E65, m1503    [ doi:10.1107/S1600536809045310 ]

Hexaaquacobalt(II) tetraaquabis(2-aminopyrazine-[kappa]N4)cobalt(II) disulfate dihydrate

W. Kang, L.-H. Huo, S. Gao and S. W. Ng

Abstract top

The reaction of cobalt(II) sulfate and 2-aminopyrazine affords the title salt, [Co(H2O)6][Co(C4H5N3)2(H2O)4](SO4)2·2H2O. The metal atoms in the tetraaqua-coordinated and hexaaqua-coordinated complex cations lie on centers of inversion in slightly distorted octahedral geometries. The cations, anions and solvent water molecules are linked by O-H...O, O-H...N and N-H...O hydrogen bonds into a three-dimensional network.

Related literature top

The reaction of cobalt(II) chloride and 3-aminopyrazine yields tetrakis(3-aminopyrazine)dichloridocobalt(II); see: Csöregh et al. (2000); Kang et al. (2009).

Experimental top

To an aqueous solution of 3-aminopyrazine (0.19 g, 2 mmol) was added cobalt(II) sulfate heptahydrate (0.56 g, 2 mmol). Red crystals of the salt separated from the solution after a few days. CH&N elemental analysis. Calc. for C8H34N6O20S2Co2: C 13.41, H 4.78, N 11.73%; found: C 13.39, H 4.72, N 11.76%.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The amino and water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of N–H = O–H = 0.85±0.01 Å; their temperature factors were refined.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [Co(H2O)6] [Co(H2O)4(C4H5N3)2] 2[SO4].2H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Hexaaquacobalt(II) tetraaquabis(2-aminopyrazine-κN4)cobalt(II) disulfate dihydrate top
Crystal data top
[Co(H2O)6][Co(C4H5N3)2(H2O)4](SO4)2·2H2OZ = 1
Mr = 716.40F(000) = 370
Triclinic, P1Dx = 1.750 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.5722 (3) ÅCell parameters from 6326 reflections
b = 8.3264 (4) Åθ = 3.2–27.5°
c = 13.2337 (7) ŵ = 1.47 mm−1
α = 75.732 (2)°T = 293 K
β = 78.571 (1)°Prism, red
γ = 78.795 (1)°0.30 × 0.20 × 0.20 mm
V = 679.81 (6) Å3
Data collection top
Rigaku RAXIS-RAPID IP
diffractometer		3071 independent reflections
Radiation source: fine-focus sealed tube2762 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.4°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −7→8
Tmin = 0.668, Tmax = 0.758k = −10→10
6692 measured reflectionsl = −17→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.085H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0511P)2 + 0.1887P]
where P = (Fo2 + 2Fc2)/3
3071 reflections(Δ/σ)max = 0.001
231 parametersΔρmax = 0.47 e Å−3
14 restraintsΔρmin = −0.33 e Å−3
Crystal data top
[Co(H2O)6][Co(C4H5N3)2(H2O)4](SO4)2·2H2Oγ = 78.795 (1)°
Mr = 716.40V = 679.81 (6) Å3
Triclinic, P1Z = 1
a = 6.5722 (3) ÅMo Kα radiation
b = 8.3264 (4) ŵ = 1.47 mm−1
c = 13.2337 (7) ÅT = 293 K
α = 75.732 (2)°0.30 × 0.20 × 0.20 mm
β = 78.571 (1)°
Data collection top
Rigaku RAXIS-RAPID IP
diffractometer		3071 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2762 reflections with I > 2σ(I)
Tmin = 0.668, Tmax = 0.758Rint = 0.027
6692 measured reflectionsθmax = 27.4°
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.085Δρmax = 0.47 e Å−3
S = 1.05Δρmin = −0.33 e Å−3
3071 reflectionsAbsolute structure: ?
231 parametersFlack parameter: ?
14 restraintsRogers parameter: ?
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Co11.00001.00000.50000.02058 (10)
Co20.00000.50001.00000.02713 (11)
S10.48109 (7)0.88842 (5)0.80066 (3)0.02386 (12)
O10.4133 (2)0.98162 (18)0.70001 (10)0.0309 (3)
O20.5369 (3)0.70948 (18)0.79992 (14)0.0439 (4)
O30.6685 (2)0.95119 (18)0.81446 (11)0.0317 (3)
O40.3094 (2)0.9161 (2)0.88747 (12)0.0410 (4)
O1W0.7178 (2)0.91396 (17)0.53377 (11)0.0295 (3)
O2W1.0213 (2)0.96509 (18)0.66021 (11)0.0305 (3)
O3W0.2836 (2)0.4730 (2)0.90039 (14)0.0435 (4)
O4W−0.1433 (3)0.4747 (2)0.87641 (13)0.0399 (4)
O5W0.0399 (2)0.23895 (19)1.05544 (14)0.0421 (4)
O6W0.6169 (3)0.2195 (2)0.91230 (13)0.0397 (3)
N10.8413 (2)1.25974 (19)0.49825 (13)0.0257 (3)
N20.7121 (3)1.6016 (2)0.49242 (14)0.0302 (3)
N30.7876 (3)1.6554 (2)0.30956 (16)0.0423 (4)
C10.8491 (3)1.3722 (2)0.40789 (15)0.0289 (4)
H10.90121.33610.34520.035*
C20.7812 (3)1.5450 (2)0.40335 (16)0.0283 (4)
C30.7021 (3)1.4852 (3)0.58309 (16)0.0317 (4)
H30.65161.52070.64610.038*
C40.7624 (3)1.3170 (2)0.58746 (15)0.0306 (4)
H40.74891.24150.65230.037*
H1W10.615 (3)0.941 (3)0.5778 (16)0.039 (7)*
H1W20.708 (4)0.822 (2)0.521 (2)0.043 (7)*
H2W10.924 (3)0.961 (3)0.7118 (14)0.038 (7)*
H2W21.136 (3)0.983 (4)0.671 (2)0.058 (9)*
H3W10.348 (5)0.556 (3)0.872 (3)0.072 (10)*
H3W20.376 (3)0.387 (2)0.906 (2)0.050 (8)*
H4W1−0.199 (5)0.387 (3)0.886 (3)0.068 (10)*
H4W2−0.234 (3)0.558 (2)0.856 (2)0.043 (7)*
H5W10.135 (3)0.176 (3)1.0881 (19)0.046 (8)*
H5W2−0.062 (4)0.185 (4)1.076 (2)0.066 (9)*
H6W10.637 (6)0.145 (4)0.876 (3)0.094 (13)*
H6W20.625 (5)0.164 (4)0.9747 (12)0.065 (10)*
H3N10.830 (5)1.618 (4)0.2538 (15)0.062 (9)*
H3N20.751 (5)1.7602 (15)0.307 (3)0.064 (9)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.02009 (17)0.01865 (17)0.02239 (18)−0.00235 (12)−0.00307 (13)−0.00400 (12)
Co20.02194 (19)0.02479 (19)0.0323 (2)−0.00440 (14)−0.00566 (14)0.00002 (14)
S10.0220 (2)0.0245 (2)0.0240 (2)−0.00519 (17)−0.00492 (16)−0.00072 (16)
O10.0285 (7)0.0353 (7)0.0270 (7)−0.0006 (6)−0.0095 (5)−0.0022 (5)
O20.0429 (9)0.0237 (7)0.0623 (10)−0.0039 (6)−0.0138 (8)−0.0005 (7)
O30.0241 (6)0.0394 (8)0.0336 (7)−0.0094 (6)−0.0057 (5)−0.0074 (6)
O40.0292 (7)0.0610 (10)0.0311 (7)−0.0127 (7)0.0028 (6)−0.0080 (7)
O1W0.0249 (7)0.0264 (7)0.0383 (8)−0.0067 (5)0.0030 (6)−0.0134 (6)
O2W0.0266 (7)0.0413 (8)0.0242 (7)−0.0062 (6)−0.0044 (5)−0.0069 (6)
O3W0.0280 (8)0.0322 (8)0.0594 (10)−0.0041 (6)0.0049 (7)0.0007 (7)
O4W0.0383 (8)0.0344 (8)0.0493 (9)−0.0060 (7)−0.0199 (7)−0.0029 (7)
O5W0.0314 (8)0.0290 (8)0.0618 (10)−0.0075 (6)−0.0170 (7)0.0077 (7)
O6W0.0501 (9)0.0321 (8)0.0387 (9)−0.0050 (7)−0.0107 (7)−0.0089 (7)
N10.0231 (7)0.0206 (7)0.0326 (8)−0.0019 (6)−0.0050 (6)−0.0053 (6)
N20.0271 (8)0.0234 (8)0.0425 (9)−0.0026 (6)−0.0079 (7)−0.0104 (7)
N30.0564 (12)0.0247 (9)0.0399 (11)0.0015 (8)−0.0053 (9)−0.0040 (8)
C10.0305 (9)0.0241 (9)0.0318 (10)−0.0029 (7)−0.0039 (8)−0.0072 (7)
C20.0244 (9)0.0224 (9)0.0378 (10)−0.0034 (7)−0.0059 (7)−0.0052 (7)
C30.0290 (9)0.0318 (10)0.0361 (10)0.0005 (8)−0.0061 (8)−0.0138 (8)
C40.0305 (10)0.0296 (10)0.0294 (9)−0.0018 (8)−0.0040 (8)−0.0052 (7)
Geometric parameters (Å, °) top
Co1—O1W2.0451 (13)O3W—H3W10.846 (10)
Co1—O1Wi2.0451 (13)O3W—H3W20.846 (10)
Co1—O2Wi2.0970 (13)O4W—H4W10.847 (10)
Co1—O2W2.0970 (13)O4W—H4W20.850 (10)
Co1—N1i2.2076 (15)O5W—H5W10.849 (10)
Co1—N12.2076 (15)O5W—H5W20.840 (10)
Co2—O3W2.0670 (16)O6W—H6W10.849 (10)
Co2—O3Wii2.0670 (16)O6W—H6W20.847 (10)
Co2—O5W2.0977 (15)N1—C11.324 (2)
Co2—O5Wii2.0977 (15)N1—C41.352 (3)
Co2—O4W2.1128 (16)N2—C21.340 (3)
Co2—O4Wii2.1128 (16)N2—C31.343 (3)
S1—O21.4656 (16)N3—C21.349 (3)
S1—O41.4703 (15)N3—H3N10.849 (10)
S1—O11.4717 (13)N3—H3N20.852 (10)
S1—O31.4866 (14)C1—C21.411 (3)
O1W—H1W10.836 (10)C1—H10.9300
O1W—H1W20.846 (10)C3—C41.370 (3)
O2W—H2W10.838 (10)C3—H30.9300
O2W—H2W20.843 (10)C4—H40.9300
O1W—Co1—O1Wi180.0Co1—O1W—H1W1126.4 (17)
O1W—Co1—O2Wi87.43 (6)Co1—O1W—H1W2120.7 (18)
O1Wi—Co1—O2Wi92.57 (6)H1W1—O1W—H1W2110 (2)
O1W—Co1—O2W92.57 (6)Co1—O2W—H2W1128.2 (18)
O1Wi—Co1—O2W87.43 (6)Co1—O2W—H2W2114 (2)
O2Wi—Co1—O2W180.000 (1)H2W1—O2W—H2W2116 (3)
O1W—Co1—N1i88.71 (6)Co2—O3W—H3W1121 (2)
O1Wi—Co1—N1i91.29 (6)Co2—O3W—H3W2125.2 (19)
O2Wi—Co1—N1i90.16 (6)H3W1—O3W—H3W2107 (3)
O2W—Co1—N1i89.84 (6)Co2—O4W—H4W1117 (2)
O1W—Co1—N191.29 (6)Co2—O4W—H4W2114.2 (18)
O1Wi—Co1—N188.71 (6)H4W1—O4W—H4W2107 (3)
O2Wi—Co1—N189.84 (6)Co2—O5W—H5W1128.5 (19)
O2W—Co1—N190.16 (6)Co2—O5W—H5W2122 (2)
N1i—Co1—N1180.000 (1)H5W1—O5W—H5W2103 (3)
O3W—Co2—O3Wii180.0H6W1—O6W—H6W2104 (3)
O3W—Co2—O5W88.95 (7)C1—N1—C4117.08 (16)
O3Wii—Co2—O5W91.05 (7)C1—N1—Co1119.42 (13)
O3W—Co2—O5Wii91.05 (7)C4—N1—Co1122.75 (13)
O3Wii—Co2—O5Wii88.95 (7)C2—N2—C3116.49 (17)
O5W—Co2—O5Wii180.0C2—N3—H3N1118 (2)
O3W—Co2—O4W87.20 (7)C2—N3—H3N2121 (2)
O3Wii—Co2—O4W92.80 (7)H3N1—N3—H3N2121 (3)
O5W—Co2—O4W89.82 (7)N1—C1—C2122.25 (18)
O5Wii—Co2—O4W90.18 (7)N1—C1—H1118.9
O3W—Co2—O4Wii92.80 (7)C2—C1—H1118.9
O3Wii—Co2—O4Wii87.20 (7)N2—C2—N3119.21 (18)
O5W—Co2—O4Wii90.18 (7)N2—C2—C1120.28 (18)
O5Wii—Co2—O4Wii89.82 (7)N3—C2—C1120.50 (19)
O4W—Co2—O4Wii180.0N2—C3—C4123.26 (19)
O2—S1—O4110.72 (10)N2—C3—H3118.4
O2—S1—O1109.81 (9)C4—C3—H3118.4
O4—S1—O1108.83 (9)N1—C4—C3120.53 (18)
O2—S1—O3108.89 (9)N1—C4—H4119.7
O4—S1—O3109.26 (9)C3—C4—H4119.7
O1—S1—O3109.31 (8)
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O10.84 (1)1.93 (1)2.755 (2)168 (3)
O1w—H1w2···N2iii0.85 (1)1.95 (1)2.795 (2)175 (3)
O2w—H2w1···O30.84 (1)1.94 (1)2.769 (2)170 (2)
O2w—H2w2···O1iv0.84 (1)1.93 (1)2.765 (2)170 (3)
O3w—H3w1···O20.85 (1)1.91 (1)2.743 (2)169 (3)
O3w—H3w2···O6w0.85 (1)1.89 (1)2.730 (2)170 (3)
O4w—H4w1···O6wv0.85 (1)1.95 (1)2.781 (2)168 (3)
O4w—H4w2···O2v0.85 (1)1.91 (1)2.745 (2)167 (2)
O5w—H5w1···O3vi0.85 (1)1.98 (1)2.816 (2)170 (3)
O5w—H5w2···O4ii0.84 (1)1.90 (1)2.737 (2)174 (3)
O6w—H6w1···O3iii0.85 (1)1.94 (1)2.782 (2)171 (4)
O6w—H6w2···O4vi0.85 (1)1.89 (1)2.711 (2)164 (3)
N3—H3n2···O1vii0.85 (1)2.20 (1)3.036 (2)168 (3)
Symmetry codes: (iii) x, y−1, z; (iv) x+1, y, z; (v) x−1, y, z; (vi) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+2; (vii) −x+1, −y+3, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1w—H1w1···O10.84 (1)1.93 (1)2.755 (2)168 (3)
O1w—H1w2···N2i0.85 (1)1.95 (1)2.795 (2)175 (3)
O2w—H2w1···O30.84 (1)1.94 (1)2.769 (2)170 (2)
O2w—H2w2···O1ii0.84 (1)1.93 (1)2.765 (2)170 (3)
O3w—H3w1···O20.85 (1)1.91 (1)2.743 (2)169 (3)
O3w—H3w2···O6w0.85 (1)1.89 (1)2.730 (2)170 (3)
O4w—H4w1···O6wiii0.85 (1)1.95 (1)2.781 (2)168 (3)
O4w—H4w2···O2iii0.85 (1)1.91 (1)2.745 (2)167 (2)
O5w—H5w1···O3iv0.85 (1)1.98 (1)2.816 (2)170 (3)
O5w—H5w2···O4v0.84 (1)1.90 (1)2.737 (2)174 (3)
O6w—H6w1···O3i0.85 (1)1.94 (1)2.782 (2)171 (4)
O6w—H6w2···O4iv0.85 (1)1.89 (1)2.711 (2)164 (3)
N3—H3n2···O1vi0.85 (1)2.20 (1)3.036 (2)168 (3)
Symmetry codes: (i) x, y−1, z; (ii) x+1, y, z; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+2; (v) −x, −y+1, −z+2; (vi) −x+1, −y+3, −z+1.
Acknowledgements top

We thank the Natural Science Foundation of Heilongjiang Province (No. B200501), Heilongjiang University, China, and the University of Malaya for supporting this study.

references
References top

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Westrip, S. P. (2009). publCIF. In preparation.