Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047174/hb2558sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047174/hb2558Isup2.hkl |
CCDC reference: 667104
A mixture of Co(SO4)·7H2O (1.12 g; 4 mmol), ethylenediamine (0.135 ml; 2 mmol) and H2SO4 (0.11 ml; 2 mmol) was loaded into a 23 ml Teflon-lined stainless autoclave. Deionized water (0.072 ml) was added to form a mixture with a molar composition CoSO4·7H2O:en:H2SO4:H2O of 2:1:1:1. After stirring the mixture, the container was closed, heated at 443 K for 5 days, and then cooled to room temperature at a cooling rate of 1 K min-1. The product was filtered, washed with deionized water, methanol and acetone and dried in air at room temperature to yield many pink blocks of (I).
The H atoms were located in difference maps and their positions and Uiso values were freely refined.
Solvothermal synthesis is increasingly used for the preparation of organically templated metal sulfates, and a number of one-, two- and three-dimensional structures have been reported in recent years (Rao et al., 2006). Examples containing transition metals include the one-dimensional structure of [Zn(SO4)(H2O)2(C10N2H8)] (Behera & Rao, 2005), the layered [H3N(CH2)6NH3][Fe1.5F(SO4)]·0.5H2O, which possesses an unusual Fe(II) Kagomé lattice (Rao et al., 2004) and the open-framework structure of [C4N2H12][Ni2F4(SO4)H2O], which contains 10-membered channels (Behera et al., 2004).
The title compound, which was prepared under solvothermal conditions, is a cobalt sulfate which contains isolated [Co(SO4)2(H2O)4]2- anions, separated by diprotonated [NH3(CH2)2NH3]2+ cations. The local coordination and the atom-labelling scheme are shown in Figure 1. The environment of the cobalt(II) ion consist of six oxygen atoms in a distorted octahedral coordination. Four O atoms are associated with H2O molecules, and the other two with monodentate SO42- anions. The Co—O distances in (I) (Table 1) are similar to those found in inorganic cobalt sulfates such as Co(SO4)·H2O (Oswald, 1965) or CoSO4·6H2O (Zalkin et al., 1962). While in the title compound the [Co(SO4)2(H2O)4]2- anions are isolated, similar [Co(SO4)2(H2O)4]2- units have been found in the three-dimensional structure of Co5(OH)6(SO4)(H2O)4 (Salah et al., 2006), where they act as linkages between brucite-like layers of cobalt-centered edge-sharing octahedra. In (I), the [Co(SO4)2(H2O)4]2- anions are interconnected through O—H···O hydrogen bonds from the hydrogen of the water molecules to the O atoms of SO42- groups of neighbouring anions. Additional N—H···O hydrogen bonds link the anions and cations, forming an infinite three-dimensional network (Table 2, Fig. 2). This compound is isostructural with the analogous iron (Held, 2003) and manganese (Chaabouni et al., 1996) materials.
The isostructural manganese(II)- and iron(II)-containing compounds were described by Chaabouni et al. (1996) and Held (2003), respectively. For background, see: Rao et al. (2006, 2004); Behera & Rao (2005); Behera et al. (2004). Related inorganic cobalt sulfates include Co(SO4)·H2O (Oswald, 1965), CoSO4·6H2O (Zalkin et al., 1962) and Co5(OH)6(SO4)(H2O)4 (Salah et al., 2006). For related literature, see: Prince (1982); Watkin (1994).
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Dowty, 2000); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).
(C2H10N2)[Co(SO4)2(H2O)4] | Z = 1 |
Mr = 385.24 | F(000) = 199 |
Triclinic, P1 | Dx = 2.005 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.8164 (2) Å | Cell parameters from 1929 reflections |
b = 7.0862 (3) Å | θ = 3.0–30.6° |
c = 7.2305 (3) Å | µ = 1.74 mm−1 |
α = 74.925 (2)° | T = 293 K |
β = 72.281 (2)° | Block, pink |
γ = 79.183 (2)° | 0.40 × 0.30 × 0.24 mm |
V = 318.99 (2) Å3 |
Bruker Nonius APEXII CCD area-detector diffractometer | 1698 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.016 |
ω/2θ scans | θmax = 30.6°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.499, Tmax = 0.659 | k = −10→10 |
8586 measured reflections | l = −10→10 |
1929 independent reflections |
Refinement on F | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.017 | All H-atom parameters refined |
wR(F2) = 0.019 | Method, part 1, Chebychev polynomial, (Watkin, 1994; Prince, 1982)
[weight] = 1.0/[A0*T0(x) + A1*T1(x) ··· + An-1]*Tn-1(x)]
where Ai are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)2]2 Ai are: 0.499 0.168 0.293 |
S = 1.06 | (Δ/σ)max = 0.001 |
1698 reflections | Δρmax = 0.33 e Å−3 |
124 parameters | Δρmin = −0.35 e Å−3 |
0 restraints |
(C2H10N2)[Co(SO4)2(H2O)4] | γ = 79.183 (2)° |
Mr = 385.24 | V = 318.99 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.8164 (2) Å | Mo Kα radiation |
b = 7.0862 (3) Å | µ = 1.74 mm−1 |
c = 7.2305 (3) Å | T = 293 K |
α = 74.925 (2)° | 0.40 × 0.30 × 0.24 mm |
β = 72.281 (2)° |
Bruker Nonius APEXII CCD area-detector diffractometer | 1929 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1698 reflections with I > 3σ(I) |
Tmin = 0.499, Tmax = 0.659 | Rint = 0.016 |
8586 measured reflections |
R[F2 > 2σ(F2)] = 0.017 | 0 restraints |
wR(F2) = 0.019 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.33 e Å−3 |
1698 reflections | Δρmin = −0.35 e Å−3 |
124 parameters |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.5000 | 0.5000 | 0.0000 | 0.0145 | |
O2 | 0.66383 (12) | 0.68463 (11) | 0.06949 (10) | 0.0232 | |
S3 | 0.69800 (3) | 0.72331 (3) | 0.24984 (3) | 0.0142 | |
O4 | 0.49557 (11) | 0.76164 (12) | 0.39107 (11) | 0.0265 | |
O5 | 0.80946 (12) | 0.89975 (10) | 0.18192 (11) | 0.0225 | |
O6 | 0.82269 (12) | 0.55493 (11) | 0.34286 (12) | 0.0263 | |
O7 | 0.24143 (12) | 0.56705 (12) | 0.23321 (12) | 0.0248 | |
C8 | 0.04829 (16) | 1.08330 (14) | 0.41936 (14) | 0.0213 | |
N9 | 0.17194 (14) | 1.00681 (13) | 0.24180 (12) | 0.0221 | |
O1 | 0.58219 (16) | 0.25962 (12) | 0.20735 (12) | 0.0324 | |
H81 | 0.142 (2) | 1.137 (2) | 0.466 (2) | 0.028 (4)* | |
H82 | −0.058 (3) | 1.192 (3) | 0.375 (3) | 0.045 (5)* | |
H1 | 0.650 (3) | 0.156 (3) | 0.192 (3) | 0.042 (5)* | |
H2 | 0.227 (3) | 1.103 (3) | 0.146 (3) | 0.033 (4)* | |
H4 | 0.119 (3) | 0.561 (3) | 0.246 (3) | 0.039 (4)* | |
H5 | 0.095 (3) | 0.953 (3) | 0.198 (3) | 0.036 (4)* | |
H6 | 0.248 (3) | 0.537 (3) | 0.346 (3) | 0.039 (4)* | |
H7 | 0.268 (3) | 0.918 (3) | 0.267 (3) | 0.040 (4)* | |
H8 | 0.555 (3) | 0.259 (3) | 0.326 (3) | 0.042 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.01667 (8) | 0.01479 (8) | 0.01339 (8) | −0.00381 (5) | −0.00494 (6) | −0.00292 (5) |
O2 | 0.0306 (4) | 0.0290 (4) | 0.0151 (3) | −0.0159 (3) | −0.0065 (3) | −0.0045 (2) |
S3 | 0.01444 (9) | 0.01676 (10) | 0.01245 (9) | −0.00355 (7) | −0.00478 (7) | −0.00235 (7) |
O4 | 0.0191 (3) | 0.0383 (4) | 0.0181 (3) | 0.0006 (3) | −0.0010 (2) | −0.0066 (3) |
O5 | 0.0269 (3) | 0.0199 (3) | 0.0248 (3) | −0.0093 (3) | −0.0100 (3) | −0.0037 (2) |
O6 | 0.0227 (3) | 0.0244 (3) | 0.0279 (4) | −0.0002 (3) | −0.0101 (3) | 0.0034 (3) |
O7 | 0.0178 (3) | 0.0379 (4) | 0.0199 (3) | −0.0042 (3) | −0.0038 (2) | −0.0090 (3) |
C8 | 0.0268 (4) | 0.0201 (4) | 0.0162 (4) | −0.0074 (3) | −0.0025 (3) | −0.0030 (3) |
N9 | 0.0233 (4) | 0.0257 (4) | 0.0153 (3) | −0.0052 (3) | −0.0029 (3) | −0.0022 (3) |
O1 | 0.0543 (5) | 0.0227 (4) | 0.0200 (4) | 0.0087 (3) | −0.0171 (3) | −0.0054 (3) |
Co1—O7i | 2.1140 (7) | O7—H6 | 0.80 (2) |
Co1—O2i | 2.1079 (6) | C8—C8ii | 1.5150 (18) |
Co1—O1i | 2.0707 (8) | C8—N9 | 1.4779 (13) |
Co1—O2 | 2.1079 (6) | C8—H81 | 0.972 (15) |
Co1—O7 | 2.1140 (7) | C8—H82 | 1.012 (19) |
Co1—O1 | 2.0707 (8) | N9—H2 | 0.883 (18) |
O2—S3 | 1.4915 (7) | N9—H5 | 0.873 (18) |
S3—O4 | 1.4719 (7) | N9—H7 | 0.850 (19) |
S3—O5 | 1.4804 (7) | O1—H1 | 0.81 (2) |
S3—O6 | 1.4656 (7) | O1—H8 | 0.82 (2) |
O7—H4 | 0.823 (19) | ||
O7i—Co1—O2i | 88.63 (3) | O4—S3—O6 | 110.21 (5) |
O7i—Co1—O1i | 86.51 (3) | O5—S3—O6 | 110.15 (4) |
O2i—Co1—O1i | 92.44 (3) | Co1—O7—H4 | 127.5 (13) |
O7i—Co1—O2 | 91.37 (3) | Co1—O7—H6 | 120.9 (13) |
O2i—Co1—O2 | 180.0 | H4—O7—H6 | 102.4 (18) |
O1i—Co1—O2 | 87.56 (3) | C8ii—C8—N9 | 109.46 (10) |
O7i—Co1—O7 | 180.0 | C8ii—C8—H81 | 109.5 (9) |
O2i—Co1—O7 | 91.37 (3) | N9—C8—H81 | 107.8 (9) |
O1i—Co1—O7 | 93.49 (4) | C8ii—C8—H82 | 113.1 (11) |
O2—Co1—O7 | 88.63 (3) | N9—C8—H82 | 106.8 (11) |
O7i—Co1—O1 | 93.49 (3) | H81—C8—H82 | 110.0 (14) |
O2i—Co1—O1 | 87.56 (3) | C8—N9—H2 | 110.3 (11) |
O1i—Co1—O1 | 180.0 | C8—N9—H5 | 111.0 (12) |
O2—Co1—O1 | 92.44 (3) | H2—N9—H5 | 108.5 (16) |
O7—Co1—O1 | 86.51 (3) | C8—N9—H7 | 111.9 (12) |
Co1—O2—S3 | 138.29 (4) | H2—N9—H7 | 109.1 (16) |
O2—S3—O4 | 109.01 (4) | H5—N9—H7 | 106.0 (16) |
O2—S3—O5 | 106.54 (4) | Co1—O1—H1 | 130.2 (13) |
O4—S3—O5 | 110.29 (5) | Co1—O1—H8 | 123.1 (13) |
O2—S3—O6 | 110.56 (5) | H1—O1—H8 | 106.6 (18) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z+1. |
D—H···A | D—H | H···A | D—H···A |
O1—H1···O5iii | 0.81 (2) | 1.94 (2) | 174.8 (19) |
O1—H8···O4iv | 0.82 (2) | 1.94 (2) | 175.5 (19) |
O7—H4···O6v | 0.823 (19) | 1.928 (19) | 165.1 (18) |
O7—H6···O6iv | 0.80 (2) | 2.10 (2) | 163.8 (18) |
N9—H2···O2vi | 0.883 (18) | 1.932 (18) | 177.3 (16) |
N9—H5···O5v | 0.873 (18) | 2.093 (18) | 153.0 (16) |
N9—H7···O4 | 0.850 (19) | 2.03 (2) | 160.7 (17) |
Symmetry codes: (iii) x, y−1, z; (iv) −x+1, −y+1, −z+1; (v) x−1, y, z; (vi) −x+1, −y+2, −z. |
Experimental details
Crystal data | |
Chemical formula | (C2H10N2)[Co(SO4)2(H2O)4] |
Mr | 385.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.8164 (2), 7.0862 (3), 7.2305 (3) |
α, β, γ (°) | 74.925 (2), 72.281 (2), 79.183 (2) |
V (Å3) | 318.99 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.74 |
Crystal size (mm) | 0.40 × 0.30 × 0.24 |
Data collection | |
Diffractometer | Bruker Nonius APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.499, 0.659 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 8586, 1929, 1698 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.715 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.017, 0.019, 1.06 |
No. of reflections | 1698 |
No. of parameters | 124 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.33, −0.35 |
Computer programs: APEX2 (Bruker, 2005), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), ATOMS (Dowty, 2000).
D—H···A | D—H | H···A | D—H···A |
O1—H1···O5i | 0.81 (2) | 1.94 (2) | 174.8 (19) |
O1—H8···O4ii | 0.82 (2) | 1.94 (2) | 175.5 (19) |
O7—H4···O6iii | 0.823 (19) | 1.928 (19) | 165.1 (18) |
O7—H6···O6ii | 0.80 (2) | 2.10 (2) | 163.8 (18) |
N9—H2···O2iv | 0.883 (18) | 1.932 (18) | 177.3 (16) |
N9—H5···O5iii | 0.873 (18) | 2.093 (18) | 153.0 (16) |
N9—H7···O4 | 0.850 (19) | 2.03 (2) | 160.7 (17) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+2, −z. |
Solvothermal synthesis is increasingly used for the preparation of organically templated metal sulfates, and a number of one-, two- and three-dimensional structures have been reported in recent years (Rao et al., 2006). Examples containing transition metals include the one-dimensional structure of [Zn(SO4)(H2O)2(C10N2H8)] (Behera & Rao, 2005), the layered [H3N(CH2)6NH3][Fe1.5F(SO4)]·0.5H2O, which possesses an unusual Fe(II) Kagomé lattice (Rao et al., 2004) and the open-framework structure of [C4N2H12][Ni2F4(SO4)H2O], which contains 10-membered channels (Behera et al., 2004).
The title compound, which was prepared under solvothermal conditions, is a cobalt sulfate which contains isolated [Co(SO4)2(H2O)4]2- anions, separated by diprotonated [NH3(CH2)2NH3]2+ cations. The local coordination and the atom-labelling scheme are shown in Figure 1. The environment of the cobalt(II) ion consist of six oxygen atoms in a distorted octahedral coordination. Four O atoms are associated with H2O molecules, and the other two with monodentate SO42- anions. The Co—O distances in (I) (Table 1) are similar to those found in inorganic cobalt sulfates such as Co(SO4)·H2O (Oswald, 1965) or CoSO4·6H2O (Zalkin et al., 1962). While in the title compound the [Co(SO4)2(H2O)4]2- anions are isolated, similar [Co(SO4)2(H2O)4]2- units have been found in the three-dimensional structure of Co5(OH)6(SO4)(H2O)4 (Salah et al., 2006), where they act as linkages between brucite-like layers of cobalt-centered edge-sharing octahedra. In (I), the [Co(SO4)2(H2O)4]2- anions are interconnected through O—H···O hydrogen bonds from the hydrogen of the water molecules to the O atoms of SO42- groups of neighbouring anions. Additional N—H···O hydrogen bonds link the anions and cations, forming an infinite three-dimensional network (Table 2, Fig. 2). This compound is isostructural with the analogous iron (Held, 2003) and manganese (Chaabouni et al., 1996) materials.