Ethyl­enediammonium tetra­aqua­bis(sulfato)cobaltate(II)

In the title compound, [NH₃(CH₂)₂NH₃][Co(SO₄)₂(H₂O)₄], both the cation and anion are centrosymmetric. The Co^II ion adopts a slightly distorted CoO₆ octa­hedral geometry, arising from four water mol­ecules and two monodentate SO₄²⁻ anions. In addition to electrostatic inter­actions, the constituent species are linked through N—H...O and O—H...O hydrogen bonds, forming a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.001 Å
• R factor = 0.017
• wR factor = 0.019
• Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          2
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    -   O7      ..       6.77 su

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1         (2)       2.01

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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][Fe_1.5F(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 SO₄^2- 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 SO₄^2- 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.

Related literature

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).

S2. Experimental

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).

S3. Refinement

The H atoms were located in difference maps and their positions and U_iso values were freely refined.

Computing details

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).

Figures

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at 50% probability for non-H atoms. Primed atoms in the anion are generated by (1 - x, -y, -z); those in the cation by (-x, 2 - y, 1 - z).
	Fig. 2. View of (I) along the[100] direction, showing the SO4 tetrahedra (yellow), Co(H2O)4O2 octahedra (green), nitrogen (blue), carbon (light green) and hydrogen (white) atoms. (N—H···O) and (O—H···O) hydrogen bonds (red dashed lines) are shown.

Ethylenediammonium tetraaquabis(sulfato)cobaltate(II)

Crystal data

(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) Å^3

Data collection

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

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.017	All H-atom parameters refined
wR(F^2) = 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

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

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Co1—O7^i	2.1140 (7)	O7—H6	0.80 (2)
Co1—O2^i	2.1079 (6)	C8—C8^ii	1.5150 (18)
Co1—O1^i	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)
O7^i—Co1—O2^i	88.63 (3)	O4—S3—O6	110.21 (5)
O7^i—Co1—O1^i	86.51 (3)	O5—S3—O6	110.15 (4)
O2^i—Co1—O1^i	92.44 (3)	Co1—O7—H4	127.5 (13)
O7^i—Co1—O2	91.37 (3)	Co1—O7—H6	120.9 (13)
O2^i—Co1—O2	180.0	H4—O7—H6	102.4 (18)
O1^i—Co1—O2	87.56 (3)	C8^ii—C8—N9	109.46 (10)
O7^i—Co1—O7	180.0	C8^ii—C8—H81	109.5 (9)
O2^i—Co1—O7	91.37 (3)	N9—C8—H81	107.8 (9)
O1^i—Co1—O7	93.49 (4)	C8^ii—C8—H82	113.1 (11)
O2—Co1—O7	88.63 (3)	N9—C8—H82	106.8 (11)
O7^i—Co1—O1	93.49 (3)	H81—C8—H82	110.0 (14)
O2^i—Co1—O1	87.56 (3)	C8—N9—H2	110.3 (11)
O1^i—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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D—H···A
O1—H1···O5^iii	0.81 (2)	1.94 (2)	174.8 (19)
O1—H8···O4^iv	0.82 (2)	1.94 (2)	175.5 (19)
O7—H4···O6^v	0.823 (19)	1.928 (19)	165.1 (18)
O7—H6···O6^iv	0.80 (2)	2.10 (2)	163.8 (18)
N9—H2···O2^vi	0.883 (18)	1.932 (18)	177.3 (16)
N9—H5···O5^v	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.