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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1504.
Published online 2009 November 4. doi:  10.1107/S1600536809045322
PMCID: PMC2971817

Hexaaqua­manganese(II) tetra­aqua­bis(2-amino­pyrazine-κN 4)manganese(II) disulfate dihydrate

Abstract

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

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

An external file that holds a picture, illustration, etc.
Object name is e-65-m1504-scheme1.jpg

Experimental

Crystal data

  • [Mn(H2O)6][Mn(C4H5N3)2(H2O)4](SO4)2·2H2O
  • M r = 708.43
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1504-efi1.jpg
  • a = 6.6242 (3) Å
  • b = 8.4639 (4) Å
  • c = 13.2719 (8) Å
  • α = 75.654 (2)°
  • β = 78.364 (2)°
  • γ = 78.834 (2)°
  • V = 697.95 (6) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 1.14 mm−1
  • T = 293 K
  • 0.38 × 0.20 × 0.18 mm

Data collection

  • Rigaku R-AXIS RAPID IP diffractometer
  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995 [triangle]) T min = 0.670, T max = 0.821
  • 6866 measured reflections
  • 3159 independent reflections
  • 2874 reflections with I > 2σ(I)
  • R int = 0.025

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.129
  • S = 1.15
  • 3159 reflections
  • 231 parameters
  • 14 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.74 e Å−3
  • Δρmin = −0.40 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809045322/xu2658sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045322/xu2658Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Experimental

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

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.

Figures

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.

Crystal data

[Mn(H2O)6][Mn(C4H5N3)2(H2O)4](SO4)2·2H2OZ = 1
Mr = 708.43F(000) = 366
Triclinic, P1Dx = 1.685 Mg m3
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 mm1
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

Rigaku R-AXIS RAPID IP diffractometer3159 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

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 = 1.15w = 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 Å3
14 restraintsΔρmin = −0.40 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

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)

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, °)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2658).

References

  • 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, m1503. [PMC free article] [PubMed]
  • Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
  • Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF. In preparation.

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