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Acta Cryst. (2009). E65, m1504    [ doi:10.1107/S1600536809045322 ]

Hexaaquamanganese(II) tetraaquabis(2-aminopyrazine-[kappa]N4)manganese(II) disulfate dihydrate

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

Abstract top

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

Related literature top

For the isostructural cobalt(II) analog, see: Kang et al. (2009).

Experimental top

To an aqueous solution of 3-aminopyrazine (0.19 g, 2 mmol) was added manganese(II) sulfate tetrahydrate (0.45 g, 2 mmol). Colorless crystals of the salt separated from the solution after a few days. CH&N elemental analysis. Calc. for C8H34N6O20S2Mn2: C 13.56, H 4.84, N 11.86%; found: C 13.52, H 4.80, N 11.85%.

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 [Mn(H2O)6] [Mn(H2O)4(C4H5N3)2] 2[SO4].2H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
Hexaaquamanganese(II) tetraaquabis(2-aminopyrazine-κN4)manganese(II) disulfate dihydrate top
Crystal data top
[Mn(H2O)6][Mn(C4H5N3)2(H2O)4](SO4)2·2H2OZ = 1
Mr = 708.43F(000) = 366
Triclinic, P1Dx = 1.685 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.6242 (3) ÅCell parameters from 6492 reflections
b = 8.4639 (4) Åθ = 3.2–27.5°
c = 13.2719 (8) ŵ = 1.14 mm−1
α = 75.654 (2)°T = 293 K
β = 78.364 (2)°Prism, colorless
γ = 78.834 (2)°0.38 × 0.20 × 0.18 mm
V = 697.95 (6) Å3
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		3159 independent reflections
Radiation source: fine-focus sealed tube2874 reflections with I > 2σ(I)
graphiteRint = 0.025
ω scansθmax = 27.5°, θmin = 3.2°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −8→8
Tmin = 0.670, Tmax = 0.821k = −10→10
6866 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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129H atoms treated by a mixture of independent and constrained refinement
S = 1.15 w = 1/[σ2(Fo2) + (0.0556P)2 + 1.1503P]
where P = (Fo2 + 2Fc2)/3
3159 reflections(Δ/σ)max = 0.001
231 parametersΔρmax = 0.74 e Å−3
14 restraintsΔρmin = −0.40 e Å−3
Crystal data top
[Mn(H2O)6][Mn(C4H5N3)2(H2O)4](SO4)2·2H2Oγ = 78.834 (2)°
Mr = 708.43V = 697.95 (6) Å3
Triclinic, P1Z = 1
a = 6.6242 (3) ÅMo Kα radiation
b = 8.4639 (4) ŵ = 1.14 mm−1
c = 13.2719 (8) ÅT = 293 K
α = 75.654 (2)°0.38 × 0.20 × 0.18 mm
β = 78.364 (2)°
Data collection top
Rigaku R-AXIS RAPID IP
diffractometer		3159 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2874 reflections with I > 2σ(I)
Tmin = 0.670, Tmax = 0.821Rint = 0.025
6866 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.041H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.129Δρmax = 0.74 e Å−3
S = 1.15Δρmin = −0.40 e Å−3
3159 reflectionsAbsolute structure: ?
231 parametersFlack parameter: ?
14 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn11.00001.00000.50000.02349 (17)
Mn20.00000.50001.00000.02867 (18)
S10.47994 (10)0.88750 (9)0.80279 (5)0.02457 (18)
O10.4091 (3)0.9828 (3)0.70435 (17)0.0322 (5)
O20.5386 (4)0.7129 (3)0.7978 (2)0.0444 (6)
O30.6644 (3)0.9501 (3)0.81657 (17)0.0318 (5)
O40.3121 (4)0.9084 (4)0.89137 (19)0.0441 (6)
O1W0.7084 (4)0.9110 (3)0.53580 (19)0.0335 (5)
O2W1.0209 (4)0.9617 (3)0.66525 (17)0.0345 (5)
O3W0.2937 (4)0.4732 (3)0.8939 (2)0.0471 (7)
O4W−0.1480 (4)0.4748 (3)0.8707 (2)0.0429 (6)
O5W0.0400 (4)0.2353 (3)1.0577 (2)0.0456 (6)
O6W0.6189 (4)0.2200 (3)0.9081 (2)0.0399 (6)
N10.8363 (4)1.2689 (3)0.4980 (2)0.0301 (5)
N20.7098 (4)1.6040 (3)0.4930 (2)0.0344 (6)
N30.7810 (6)1.6587 (4)0.3104 (3)0.0482 (8)
C10.8414 (5)1.3800 (4)0.4078 (3)0.0334 (7)
H10.88991.34470.34500.040*
C20.7760 (5)1.5496 (4)0.4039 (3)0.0325 (6)
C30.7019 (5)1.4892 (4)0.5836 (3)0.0376 (7)
H30.65321.52370.64660.045*
C40.7623 (5)1.3238 (4)0.5874 (3)0.0348 (7)
H40.75221.24910.65210.042*
H1W10.614 (5)0.948 (5)0.581 (3)0.048 (12)*
H1W20.715 (7)0.817 (3)0.521 (4)0.053 (13)*
H2W10.919 (4)0.972 (5)0.714 (2)0.028 (9)*
H2W21.135 (4)0.967 (5)0.683 (3)0.044 (11)*
H3W10.357 (7)0.556 (4)0.866 (4)0.066 (15)*
H3W20.391 (5)0.392 (3)0.901 (3)0.039 (11)*
H4W1−0.195 (8)0.386 (4)0.876 (4)0.073 (17)*
H4W2−0.247 (5)0.554 (4)0.859 (4)0.063 (15)*
H5W10.126 (6)0.160 (4)1.089 (3)0.059 (14)*
H5W2−0.072 (5)0.194 (7)1.074 (5)0.081 (18)*
H6W10.624 (9)0.148 (5)0.873 (4)0.079 (18)*
H6W20.641 (9)0.170 (6)0.9698 (19)0.072 (17)*
H3N10.831 (7)1.629 (6)0.252 (2)0.062 (15)*
H3N20.738 (8)1.7613 (19)0.308 (4)0.060 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0217 (3)0.0225 (3)0.0255 (3)−0.0022 (2)−0.0054 (2)−0.0034 (2)
Mn20.0218 (3)0.0271 (3)0.0341 (3)−0.0032 (2)−0.0067 (2)0.0002 (2)
S10.0209 (3)0.0257 (3)0.0260 (3)−0.0046 (3)−0.0066 (2)−0.0004 (3)
O10.0289 (11)0.0353 (12)0.0302 (11)−0.0007 (9)−0.0115 (9)−0.0009 (9)
O20.0423 (14)0.0252 (11)0.0645 (17)−0.0035 (10)−0.0175 (12)−0.0014 (11)
O30.0224 (10)0.0385 (12)0.0356 (11)−0.0062 (9)−0.0079 (8)−0.0062 (9)
O40.0313 (12)0.0672 (17)0.0317 (12)−0.0132 (12)0.0012 (10)−0.0078 (11)
O1W0.0277 (11)0.0325 (12)0.0423 (13)−0.0092 (9)0.0038 (9)−0.0157 (10)
O2W0.0258 (11)0.0521 (14)0.0264 (10)−0.0058 (10)−0.0080 (9)−0.0068 (10)
O3W0.0281 (12)0.0356 (14)0.0671 (18)−0.0064 (11)0.0055 (12)−0.0012 (12)
O4W0.0395 (14)0.0380 (14)0.0542 (15)−0.0039 (11)−0.0212 (12)−0.0059 (12)
O5W0.0318 (13)0.0320 (12)0.0679 (17)−0.0074 (10)−0.0194 (12)0.0096 (12)
O6W0.0477 (14)0.0317 (12)0.0413 (14)−0.0016 (11)−0.0131 (11)−0.0086 (10)
N10.0269 (12)0.0226 (12)0.0390 (14)−0.0011 (10)−0.0063 (10)−0.0044 (10)
N20.0293 (13)0.0255 (12)0.0498 (16)−0.0013 (10)−0.0095 (12)−0.0109 (11)
N30.063 (2)0.0285 (15)0.0451 (18)0.0031 (15)−0.0061 (16)−0.0039 (13)
C10.0347 (16)0.0256 (15)0.0380 (16)0.0001 (12)−0.0061 (13)−0.0069 (12)
C20.0289 (15)0.0238 (14)0.0435 (17)−0.0014 (12)−0.0071 (13)−0.0060 (12)
C30.0337 (16)0.0391 (18)0.0425 (18)0.0019 (14)−0.0073 (14)−0.0182 (14)
C40.0318 (16)0.0335 (16)0.0352 (16)0.0037 (13)−0.0075 (13)−0.0051 (13)
Geometric parameters (Å, °) top
Mn1—O1W2.131 (2)O3W—H3W10.849 (10)
Mn1—O1Wi2.131 (2)O3W—H3W20.849 (10)
Mn1—O2Wi2.165 (2)O4W—H4W10.848 (10)
Mn1—O2W2.165 (2)O4W—H4W20.850 (10)
Mn1—N12.320 (2)O5W—H5W10.849 (10)
Mn1—N1i2.320 (2)O5W—H5W20.850 (10)
Mn2—O3W2.168 (3)O6W—H6W10.850 (10)
Mn2—O3Wii2.168 (3)O6W—H6W20.850 (10)
Mn2—O4W2.212 (3)N1—C11.325 (4)
Mn2—O4Wii2.212 (3)N1—C41.347 (4)
Mn2—O5Wii2.163 (2)N2—C21.337 (4)
Mn2—O5W2.163 (2)N2—C31.344 (5)
S1—O41.466 (2)N3—C21.350 (5)
S1—O21.468 (3)N3—H3N10.855 (10)
S1—O11.468 (2)N3—H3N20.854 (10)
S1—O31.482 (2)C1—C21.408 (4)
O1W—H1W10.844 (10)C1—H10.9300
O1W—H1W20.851 (10)C3—C41.371 (5)
O2W—H2W10.846 (10)C3—H30.9300
O2W—H2W20.852 (10)C4—H40.9300
O1W—Mn1—O1Wi180.000 (1)Mn1—O1W—H1W1118 (3)
O1W—Mn1—O2Wi87.90 (9)Mn1—O1W—H1W2114 (3)
O1Wi—Mn1—O2Wi92.10 (9)H1W1—O1W—H1W2123 (4)
O1W—Mn1—O2W92.10 (9)Mn1—O2W—H2W1125 (3)
O1Wi—Mn1—O2W87.90 (9)Mn1—O2W—H2W2120 (3)
O2Wi—Mn1—O2W180.000 (1)H2W1—O2W—H2W2112 (4)
O1W—Mn1—N191.71 (9)Mn2—O3W—H3W1120 (4)
O1Wi—Mn1—N188.29 (9)Mn2—O3W—H3W2126 (3)
O2Wi—Mn1—N189.32 (10)H3W1—O3W—H3W2104 (4)
O2W—Mn1—N190.68 (10)Mn2—O4W—H4W1119 (4)
O1W—Mn1—N1i88.29 (9)Mn2—O4W—H4W2110 (3)
O1Wi—Mn1—N1i91.71 (9)H4W1—O4W—H4W2107 (5)
O2Wi—Mn1—N1i90.68 (10)Mn2—O5W—H5W1139 (3)
O2W—Mn1—N1i89.32 (10)Mn2—O5W—H5W2115 (4)
N1—Mn1—N1i180.000 (1)H5W1—O5W—H5W2103 (5)
O5Wii—Mn2—O5W180.000 (1)H6W1—O6W—H6W2108 (5)
O5Wii—Mn2—O3W90.64 (10)C1—N1—C4117.4 (3)
O5W—Mn2—O3W89.36 (10)C1—N1—Mn1119.9 (2)
O5Wii—Mn2—O3Wii89.36 (10)C4—N1—Mn1121.9 (2)
O5W—Mn2—O3Wii90.64 (10)C2—N2—C3116.8 (3)
O3W—Mn2—O3Wii180.000 (1)C2—N3—H3N1122 (3)
O5Wii—Mn2—O4W89.84 (10)C2—N3—H3N2121 (3)
O5W—Mn2—O4W90.16 (10)H3N1—N3—H3N2117 (5)
O3W—Mn2—O4W86.45 (11)N1—C1—C2122.2 (3)
O3Wii—Mn2—O4W93.55 (11)N1—C1—H1118.9
O5Wii—Mn2—O4Wii90.16 (10)C2—C1—H1118.9
O5W—Mn2—O4Wii89.84 (10)N2—C2—N3119.4 (3)
O3W—Mn2—O4Wii93.55 (11)N2—C2—C1120.2 (3)
O3Wii—Mn2—O4Wii86.45 (11)N3—C2—C1120.4 (3)
O4W—Mn2—O4Wii180.000 (1)N2—C3—C4123.1 (3)
O4—S1—O2110.85 (17)N2—C3—H3118.4
O4—S1—O1109.03 (14)C4—C3—H3118.4
O2—S1—O1109.60 (15)N1—C4—C3120.3 (3)
O4—S1—O3109.10 (14)N1—C4—H4119.9
O2—S1—O3109.02 (14)C3—C4—H4119.9
O1—S1—O3109.22 (13)
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)1.95 (2)2.779 (3)167 (4)
O1w—H1w2···N2iii0.85 (1)1.94 (1)2.792 (3)176 (5)
O2w—H2w1···O30.85 (1)1.95 (1)2.775 (3)166 (4)
O2w—H2w2···O1iv0.85 (1)1.92 (1)2.770 (3)172 (4)
O3w—H3w1···O20.85 (1)1.90 (1)2.744 (4)170 (5)
O3w—H3w2···O6w0.85 (1)1.88 (1)2.728 (4)175 (4)
O4w—H4w1···O6wv0.85 (1)1.96 (2)2.780 (4)162 (5)
O4w—H4w2···O2v0.85 (1)1.92 (2)2.744 (4)164 (5)
O5w—H5w1···O3vi0.84 (1)2.00 (2)2.813 (3)159 (5)
O5w—H5w2···O4ii0.85 (1)1.88 (1)2.726 (4)177 (6)
O6w—H6w1···O3iii0.85 (1)1.95 (2)2.783 (3)167 (6)
O6w—H6w2···O4vi0.85 (1)1.87 (1)2.709 (4)172 (6)
N3—H3n2···O1vii0.85 (1)2.18 (1)3.026 (4)172 (5)
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)1.95 (2)2.779 (3)167 (4)
O1w—H1w2···N2i0.85 (1)1.94 (1)2.792 (3)176 (5)
O2w—H2w1···O30.85 (1)1.95 (1)2.775 (3)166 (4)
O2w—H2w2···O1ii0.85 (1)1.92 (1)2.770 (3)172 (4)
O3w—H3w1···O20.85 (1)1.90 (1)2.744 (4)170 (5)
O3w—H3w2···O6w0.85 (1)1.88 (1)2.728 (4)175 (4)
O4w—H4w1···O6wiii0.85 (1)1.96 (2)2.780 (4)162 (5)
O4w—H4w2···O2iii0.85 (1)1.92 (2)2.744 (4)164 (5)
O5w—H5w1···O3iv0.84 (1)2.00 (2)2.813 (3)159 (5)
O5w—H5w2···O4v0.85 (1)1.88 (1)2.726 (4)177 (6)
O6w—H6w1···O3i0.85 (1)1.95 (2)2.783 (3)167 (6)
O6w—H6w2···O4iv0.85 (1)1.87 (1)2.709 (4)172 (6)
N3—H3n2···O1vi0.85 (1)2.18 (1)3.026 (4)172 (5)
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

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.

Kang, W., Huo, L.-H., Gao, S. & Ng, S. W. (2009). Acta Cryst. E65, (xu2657).

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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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