Inter-calated brucite-type layered cobalt(II) hydroxy-sulfate.

In an attempt to synthesize new cobalt(II) sulfate framework structures using 1,4-diaza-bicyclo-[2.2.2]octane as a template, crystals of poly[0.35-[hexa-aqua-cobalt(II)] [tri-μ-hydroxido-μ-sulfato-dicobalt(II)]], {[Co(H(2)O)(6)](0.35)[Co(2)(OH)(3)(SO(4))]}(n), were obtained as a mixture with [Co(H(2)O)(6)]SO(4) crystals. The crystal structure can be described as being constructed from discrete brucite-type [Co(4)(OH)(6)(SO(4))(2)] layers, each of which is built up from edge-shared [Co(OH)(6)] and [Co(OH)(4)(OSO(3))(2)] octa-hedra, with partial inter-calation by [Co(H(2)O)(6)](2+) ions. The absence of ca 30% of the [Co(H(2)O)(6)](2+) cations indicates partial oxidation of cobalt(II) to cobalt(III) within the layer.

Related literature

The crystal structure of the title compound is closely related to that of Co5(OH)6(SO4)2(H2O)4 (Ben Salah et al., 2004 ▶, 2006 ▶), which is composed of brucite-type cobalt hydroxide layers. The fundamental difference lies in the way that adjacent layers are linked; being pillared by ⋯O3SO—Co(H2O)4—OSO3⋯ groups in Co5(OH)6(SO4)2(H2O)4 but partially inter­calated by [Co(H2O)6]2+ ions in the title compound. For the crystal structures of layered materials of this type, see: Poudret et al. (2008 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Co(H2O)6]0.35[Co2(OH)3(SO4)]

M = 323.41

Trigonal,

a = 6.3627 (19) Å

c = 12.180 (4) Å

V = 427.0 (2) Å3

Z = 2

Mo Kα radiation

μ = 4.80 mm−1

T = 150 K

0.21 × 0.13 × 0.03 mm

Data collection

Stoe IPDS2 diffractometer

Absorption correction: multi-scan (X-RED; Stoe & Cie, 2008 ▶) T min = 0.415, T max = 0.862

1663 measured reflections

497 independent reflections

325 reflections with I > 2σ(I)

R int = 0.097

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.132

S = 0.90

497 reflections

40 parameters

3 restraints

Only H-atom coordinates refined

Δρmax = 1.04 e Å−3

Δρmin = −1.05 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2008 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 1999 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902251X/lh2832sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902251X/lh2832Isup2.hkl

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

[Co(H2O)6]0.35[Co2(OH)3(SO4)]	Dx = 2.515 Mg m−3
Mr = 323.41	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3m1	Cell parameters from 1764 reflections
Hall symbol: -P 3 2"	θ = 1.7–29.3°
a = 6.3627 (19) Å	µ = 4.80 mm−1
c = 12.180 (4) Å	T = 150 K
V = 427.0 (2) Å3	Plate, pale pink
Z = 2	0.21 × 0.13 × 0.03 mm
F(000) = 318.9

Stoe IPDS2 diffractometer	497 independent reflections
Radiation source: fine-focus sealed tube	325 reflections with I > 2σ(I)
graphite	Rint = 0.097
Detector resolution: 6.67 pixels mm-1	θmax = 29.3°, θmin = 1.7°
ω scans	h = −7→8
Absorption correction: multi-scan (X-RED; Stoe & Cie, 2008)	k = −7→8
Tmin = 0.415, Tmax = 0.862	l = −14→16
1663 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048	Hydrogen site location: difference Fourier map
wR(F2) = 0.132	Only H-atom coordinates refined
S = 0.90	w = 1/[σ2(Fo2) + (0.0839P)2] where P = (Fo2 + 2Fc2)/3
497 reflections	(Δ/σ)max < 0.001
40 parameters	Δρmax = 1.04 e Å−3
3 restraints	Δρmin = −1.05 e Å−3

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	Occ. (<1)
Co2	0.5000	0.0000	0.5000	0.0170 (3)
Co1	0.0000	0.0000	0.5000	0.0163 (5)
S1	0.6667	0.3333	0.2679 (2)	0.0214 (6)
O1	0.1717 (3)	−0.1717 (3)	0.4215 (3)	0.0164 (9)
O2	0.6667	0.3333	0.3913 (6)	0.0188 (15)
O3	0.5403 (5)	0.0807 (9)	0.2298 (4)	0.0292 (11)
Co3	0.0000	0.0000	0.0000	0.0250 (11)	0.700 (11)
O4	0.1574 (8)	0.3148 (16)	0.0920 (7)	0.039 (2)	0.700 (11)
H1	0.188 (9)	−0.188 (9)	0.355 (3)	0.059*
H4	0.073 (9)	0.353 (18)	0.128 (5)	0.059*	0.700 (11)

	U11	U22	U33	U12	U13	U23
Co2	0.0146 (5)	0.0156 (6)	0.0211 (6)	0.0078 (3)	0.0001 (2)	0.0002 (4)
Co1	0.0144 (6)	0.0144 (6)	0.0202 (9)	0.0072 (3)	0.000	0.000
S1	0.0220 (9)	0.0220 (9)	0.0203 (12)	0.0110 (4)	0.000	0.000
O1	0.0177 (16)	0.0177 (16)	0.0167 (18)	0.0111 (17)	−0.0002 (8)	0.0002 (8)
O2	0.017 (2)	0.017 (2)	0.023 (4)	0.0083 (11)	0.000	0.000
O3	0.034 (2)	0.023 (2)	0.027 (2)	0.0116 (12)	−0.0034 (10)	−0.0069 (19)
Co3	0.0256 (13)	0.0256 (13)	0.0238 (17)	0.0128 (7)	0.000	0.000
O4	0.034 (3)	0.043 (5)	0.044 (4)	0.022 (2)	−0.0080 (18)	−0.016 (4)

Co2—O1	2.047 (3)	S1—O3ix	1.467 (5)
Co2—O1i	2.047 (3)	S1—O2	1.502 (7)
Co2—O1ii	2.047 (3)	O1—Co2x	2.047 (3)
Co2—O1iii	2.047 (3)	O1—H1	0.83 (3)
Co2—O2	2.264 (4)	O2—Co2viii	2.264 (4)
Co2—O2i	2.264 (4)	O2—Co2ix	2.264 (4)
Co1—O1iv	2.121 (4)	Co3—O4xi	2.065 (8)
Co1—O1iii	2.121 (4)	Co3—O4	2.065 (8)
Co1—O1v	2.121 (4)	Co3—O4iv	2.065 (8)
Co1—O1vi	2.121 (4)	Co3—O4vi	2.065 (8)
Co1—O1	2.121 (4)	Co3—O4xii	2.065 (8)
Co1—O1vii	2.121 (4)	Co3—O4xiii	2.065 (8)
S1—O3	1.467 (5)	O4—H4	0.82 (3)
S1—O3viii	1.467 (5)
O1—Co2—O1i	180.000 (1)	O3viii—S1—O3ix	110.49 (19)
O1—Co2—O1ii	97.8 (2)	O3—S1—O2	108.4 (2)
O1i—Co2—O1ii	82.2 (2)	O3viii—S1—O2	108.4 (2)
O1—Co2—O1iii	82.2 (2)	O3ix—S1—O2	108.4 (2)
O1i—Co2—O1iii	97.8 (2)	Co2—O1—Co2x	102.00 (17)
O1ii—Co2—O1iii	180.0 (2)	Co2—O1—Co1	99.51 (14)
O1—Co2—O2	95.83 (13)	Co2x—O1—Co1	99.51 (14)
O1i—Co2—O2	84.17 (13)	Co2—O1—H1	112 (4)
O1ii—Co2—O2	95.83 (13)	Co2x—O1—H1	112 (4)
O1iii—Co2—O2	84.17 (13)	Co1—O1—H1	129 (7)
O1—Co2—O2i	84.17 (13)	S1—O2—Co2viii	125.79 (14)
O1i—Co2—O2i	95.83 (13)	S1—O2—Co2	125.79 (14)
O1ii—Co2—O2i	84.17 (13)	Co2viii—O2—Co2	89.3 (2)
O1iii—Co2—O2i	95.83 (13)	S1—O2—Co2ix	125.79 (14)
O2—Co2—O2i	180.0	Co2viii—O2—Co2ix	89.3 (2)
O1iv—Co1—O1iii	180.0 (2)	Co2—O2—Co2ix	89.3 (2)
O1iv—Co1—O1v	78.77 (13)	O4xi—Co3—O4	180.0 (4)
O1iii—Co1—O1v	101.23 (13)	O4xi—Co3—O4iv	86.7 (4)
O1iv—Co1—O1vi	101.23 (13)	O4—Co3—O4iv	93.3 (4)
O1iii—Co1—O1vi	78.77 (13)	O4xi—Co3—O4vi	86.7 (4)
O1v—Co1—O1vi	180.00 (15)	O4—Co3—O4vi	93.3 (4)
O1iv—Co1—O1	101.23 (13)	O4iv—Co3—O4vi	93.3 (4)
O1iii—Co1—O1	78.77 (13)	O4xi—Co3—O4xii	93.3 (4)
O1v—Co1—O1	78.77 (13)	O4—Co3—O4xii	86.7 (4)
O1vi—Co1—O1	101.23 (13)	O4iv—Co3—O4xii	86.7 (4)
O1iv—Co1—O1vii	78.77 (13)	O4vi—Co3—O4xii	180.0 (4)
O1iii—Co1—O1vii	101.23 (13)	O4xi—Co3—O4xiii	93.3 (4)
O1v—Co1—O1vii	101.23 (13)	O4—Co3—O4xiii	86.7 (4)
O1vi—Co1—O1vii	78.77 (13)	O4iv—Co3—O4xiii	180.0 (4)
O1—Co1—O1vii	180.0 (2)	O4vi—Co3—O4xiii	86.7 (4)
O3—S1—O3viii	110.49 (19)	O4xii—Co3—O4xiii	93.3 (4)
O3—S1—O3ix	110.49 (19)	Co3—O4—H4	120 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3x	0.83 (3)	2.54 (5)	3.125 (6)	129 (4)
O1—H1···O3	0.83 (3)	2.54 (5)	3.125 (6)	129 (4)
O4—H4···O3vi	0.82 (3)	1.90 (9)	2.712 (1)	170 (7)