Crystal structure of bis-(di-methyl-ammonium) hexa-aqua-cobalt(II) bis-(sulfate) dihydrate.

The title salt, (C2H8N)2[Co(H2O)6)](SO4)2·2H2O, is isotypic with (C2H8N)2[Ni(H2O)6)](SO4)2·2H2O. The Co-O bond lengths in the [Co(H2O)6](2+) complex cation show very similar distances as in the related Tutton salt (NH4)2[Co(H2O)6)](SO4)2 [average 2.093 (17) Å], but are significantly longer than in the isotypic Ni(II) compound (Δd ≃ 0.04 Å). The cobalt cation reaches an overall bond-valence sum of 1.97 valence units. The S-O distances are nearly equal, ranging from 1.454 (4) to 1.470 (3) Å [mean 1.465 (12) Å]; however, the O-S-O angles vary clearly from 108.1 (2) to 110.2 (2)° [average bond angle 109.5 (9)°]. The non-coordinating water mol-ecules and di-methyl-ammonium cations connect the sulfate tetrahedra and the [Co(H2O)6](2+) octa-hedron via O-H⋯O and N-H⋯O hydrogen bonds of weak up to medium strength into a three-dimensional framework whereby the complex metal cations and sulfate anions are arranged in sheets parallel to (001).

Related literature

For the synthesis and coordination geometry of the isotypic structure (C2H8N)2[Ni(H2O)6)](SO4)2·2H2O, see: Held (2014 ▸). For the related Tutton salt (NH4)2[Co(H2O)6)](SO4)2, see: Grimes et al. (1963 ▸). For the bond-valence-sum method, see: Brown & Altermatt (1985 ▸).

Experimental

Crystal data

(C2H8N)2[Co(H2O)6](SO4)2·2H2O

M = 487.37

Orthorhombic,

a = 8.975 (5) Å

b = 13.268 (5) Å

c = 16.528 (5) Å

V = 1968.2 (15) Å3

Z = 4

Mo Kα radiation

μ = 1.16 mm−1

T = 295 K

0.30 × 0.27 × 0.24 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▸) T min = 0.903, T max = 1.000

3383 measured reflections

1733 independent reflections

936 reflections with I > 2σ(I)

R int = 0.077

3 standard reflections every 100 reflections intensity decay: 1.5%

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.111

S = 0.98

1733 reflections

148 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.37 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1989 ▸); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ▸); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ATOMS (Dowty, 2011 ▸); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015003400/fk2085sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015003400/fk2085Isup2.hkl

Click here for additional data file.

x y z . DOI: 10.1107/S2056989015003400/fk2085fig1.tif

The mol­ecular entities in the structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) −x, −y + 1, −z − 1.]

Click here for additional data file.

. DOI: 10.1107/S2056989015003400/fk2085fig2.tif

(100)-projection of the crystal structure of the title compound. Colour scheme: S (yellow), Co (red), O (blue), N (orange), C (grey), H (colourless), H⋯O bonds up to 1.8 Å are given as red dashed lines, and from 1.85 to 2.7 Å as light-blue dashed lines.

CCDC reference: 1050102

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C2H8N)2[Co(H2O)6](SO4)2·2H2O	F(000) = 1028
Mr = 487.37	Dx = 1.645 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 8.975 (5) Å	θ = 12.0–20.8°
b = 13.268 (5) Å	µ = 1.16 mm−1
c = 16.528 (5) Å	T = 295 K
V = 1968.2 (15) Å3	Parallelepiped, light blue
Z = 4	0.30 × 0.27 × 0.24 mm

Enraf–Nonius CAD-4 diffractometer	936 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.077
Graphite monochromator	θmax = 25.0°, θmin = 2.5°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = 0→15
Tmin = 0.903, Tmax = 1.000	l = −19→19
3383 measured reflections	3 standard reflections every 100 reflections
1733 independent reflections	intensity decay: 1.5%

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.111	w = 1/[σ2(Fo2) + (0.0529P)2] where P = (Fo2 + 2Fc2)/3
S = 0.98	(Δ/σ)max < 0.001
1733 reflections	Δρmax = 0.41 e Å−3
148 parameters	Δρmin = −0.37 e Å−3
2 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (6)

Experimental. A suitable single-crystal was carefully selected under a polarizing microscope and mounted in a glass capillary.

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
Co	0.0000	0.5000	0.5000	0.0278 (3)
S1	0.44510 (13)	0.65726 (9)	0.59555 (8)	0.0319 (3)
O1	0.3702 (4)	0.6999 (2)	0.5243 (2)	0.0466 (10)
O2	0.3355 (4)	0.6107 (3)	0.6497 (2)	0.0419 (9)
O3	0.5255 (5)	0.7366 (3)	0.6378 (2)	0.0634 (12)
O4	0.5493 (5)	0.5793 (3)	0.5696 (3)	0.0791 (15)
O5	−0.0505 (5)	0.4446 (3)	0.3854 (2)	0.0422 (10)
H51	−0.136 (7)	0.422 (4)	0.380 (3)	0.040 (18)*
H52	0.010 (8)	0.403 (5)	0.365 (5)	0.11 (3)*
O6	0.1413 (5)	0.6068 (3)	0.4439 (3)	0.0391 (10)
H61	0.103 (8)	0.653 (5)	0.415 (4)	0.09 (3)*
H62	0.198 (6)	0.620 (4)	0.470 (3)	0.03 (2)*
O7	0.1808 (5)	0.4036 (3)	0.5066 (3)	0.0444 (10)
H71	0.251 (7)	0.412 (4)	0.484 (3)	0.037 (19)*
H72	0.172 (5)	0.350 (3)	0.512 (3)	0.021 (16)*
O8	0.1675 (5)	0.3224 (4)	0.3135 (3)	0.0558 (13)
H81	0.245 (7)	0.326 (5)	0.322 (4)	0.06 (2)*
H82	0.174 (8)	0.348 (5)	0.268 (4)	0.09 (3)*
N3	0.0327 (6)	0.1120 (3)	0.3563 (3)	0.0567 (14)
H3A	0.1016	0.1541	0.3769	0.068*
H3B	0.0187	0.0622	0.3925	0.068*
C1	0.0909 (10)	0.0689 (5)	0.2833 (4)	0.094 (3)
H1A	0.1825	0.0344	0.2950	0.141*
H1B	0.1092	0.1214	0.2446	0.141*
H1C	0.0201	0.0219	0.2615	0.141*
C2	−0.1060 (7)	0.1669 (5)	0.3473 (4)	0.074 (2)
H2A	−0.1450	0.1833	0.3998	0.111*
H2B	−0.1767	0.1260	0.3187	0.111*
H2C	−0.0883	0.2279	0.3175	0.111*

	U11	U22	U33	U12	U13	U23
Co	0.0269 (5)	0.0257 (4)	0.0309 (4)	0.0003 (5)	−0.0026 (5)	−0.0010 (5)
S1	0.0249 (6)	0.0340 (6)	0.0368 (7)	−0.0010 (6)	−0.0005 (6)	0.0065 (6)
O1	0.055 (2)	0.042 (2)	0.044 (2)	−0.0080 (19)	−0.0180 (18)	0.0107 (17)
O2	0.0289 (19)	0.052 (2)	0.045 (2)	−0.0104 (17)	0.0059 (17)	0.0093 (18)
O3	0.084 (3)	0.060 (2)	0.047 (2)	−0.034 (3)	−0.023 (2)	0.0151 (19)
O4	0.063 (3)	0.067 (3)	0.108 (4)	0.026 (2)	0.042 (3)	0.032 (3)
O5	0.034 (2)	0.053 (2)	0.040 (2)	−0.004 (2)	−0.002 (2)	−0.0102 (19)
O6	0.035 (2)	0.039 (2)	0.043 (2)	−0.004 (2)	−0.007 (2)	0.007 (2)
O7	0.035 (2)	0.036 (3)	0.062 (3)	0.007 (2)	0.012 (2)	0.010 (2)
O8	0.035 (3)	0.093 (4)	0.039 (3)	−0.004 (3)	−0.001 (2)	−0.009 (3)
N3	0.069 (4)	0.047 (3)	0.054 (3)	0.005 (3)	−0.018 (3)	−0.004 (2)
C1	0.135 (8)	0.056 (4)	0.090 (6)	0.016 (5)	0.054 (5)	0.009 (4)
C2	0.057 (4)	0.084 (5)	0.080 (5)	0.005 (4)	0.007 (4)	0.016 (4)

Co—O7i	2.069 (4)	O7—H71	0.74 (6)
Co—O7	2.069 (4)	O7—H72	0.72 (4)
Co—O5i	2.081 (4)	O8—H81	0.71 (6)
Co—O5	2.081 (4)	O8—H82	0.83 (6)
Co—O6	2.116 (4)	N3—C1	1.434 (7)
Co—O6i	2.116 (4)	N3—C2	1.450 (7)
S1—O3	1.454 (4)	N3—H3A	0.9000
S1—O4	1.459 (4)	N3—H3B	0.9000
S1—O2	1.467 (3)	C1—H1A	0.9600
S1—O1	1.470 (3)	C1—H1B	0.9600
O5—H51	0.82 (6)	C1—H1C	0.9600
O5—H52	0.84 (7)	C2—H2A	0.9600
O6—H61	0.85 (7)	C2—H2B	0.9600
O6—H62	0.69 (5)	C2—H2C	0.9600
O7i—Co—O7	180.0 (3)	Co—O6—H62	109 (4)
O7i—Co—O5i	90.04 (18)	H61—O6—H62	119 (6)
O7—Co—O5i	89.96 (18)	Co—O7—H71	123 (4)
O7i—Co—O5	89.96 (18)	Co—O7—H72	122 (4)
O7—Co—O5	90.04 (18)	H71—O7—H72	109 (6)
O5i—Co—O5	180.000 (1)	H81—O8—H82	95 (7)
O7i—Co—O6	91.87 (19)	C1—N3—C2	115.3 (5)
O7—Co—O6	88.13 (19)	C1—N3—H3A	108.5
O5i—Co—O6	91.80 (18)	C2—N3—H3A	108.5
O5—Co—O6	88.20 (18)	C1—N3—H3B	108.5
O7i—Co—O6i	88.13 (19)	C2—N3—H3B	108.5
O7—Co—O6i	91.87 (19)	H3A—N3—H3B	107.5
O5i—Co—O6i	88.20 (18)	N3—C1—H1A	109.5
O5—Co—O6i	91.80 (18)	N3—C1—H1B	109.5
O6—Co—O6i	180.0	H1A—C1—H1B	109.5
O3—S1—O4	109.6 (3)	N3—C1—H1C	109.5
O3—S1—O2	110.1 (2)	H1A—C1—H1C	109.5
O4—S1—O2	108.1 (2)	H1B—C1—H1C	109.5
O3—S1—O1	109.5 (2)	N3—C2—H2A	109.5
O4—S1—O1	109.3 (3)	N3—C2—H2B	109.5
O2—S1—O1	110.2 (2)	H2A—C2—H2B	109.5
Co—O5—H51	116 (4)	N3—C2—H2C	109.5
Co—O5—H52	117 (5)	H2A—C2—H2C	109.5
H51—O5—H52	108 (6)	H2B—C2—H2C	109.5
Co—O6—H61	119 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H51···O2i	0.82 (6)	1.91 (6)	2.724 (6)	169 (5)
O5—H52···O8	0.84 (7)	1.97 (8)	2.806 (7)	171 (7)
O6—H61···O3ii	0.85 (7)	1.85 (7)	2.687 (6)	173 (6)
O6—H62···O1	0.69 (5)	2.08 (5)	2.740 (6)	161 (6)
O7—H71···O4iii	0.74 (6)	2.01 (6)	2.740 (6)	173 (6)
O7—H72···O1iv	0.72 (4)	2.04 (4)	2.756 (6)	176 (5)
O8—H81···O3iii	0.71 (6)	2.32 (6)	2.975 (7)	154 (7)
O8—H82···O2v	0.83 (6)	2.02 (6)	2.849 (6)	169 (7)
N3—H3A···O6iv	0.90	2.63	3.265 (6)	128
N3—H3B···O4vi	0.90	2.00	2.823 (6)	152

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O5H51O2i	0.82(6)	1.91(6)	2.724(6)	169(5)
O5H52O8	0.84(7)	1.97(8)	2.806(7)	171(7)
O6H61O3ii	0.85(7)	1.85(7)	2.687(6)	173(6)
O6H62O1	0.69(5)	2.08(5)	2.740(6)	161(6)
O7H71O4iii	0.74(6)	2.01(6)	2.740(6)	173(6)
O7H72O1iv	0.72(4)	2.04(4)	2.756(6)	176(5)
O8H81O3iii	0.71(6)	2.32(6)	2.975(7)	154(7)
O8H82O2v	0.83(6)	2.02(6)	2.849(6)	169(7)
N3H3AO6iv	0.90	2.63	3.265(6)	128
N3H3BO4vi	0.90	2.00	2.823(6)	152

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .