Tris[hexa-amminecobalt(III)] bis-[tri-oxalato-cobaltate(II)] chloride dodeca-hydrate.

The title compound, [Co(III)(NH₃)₆]₃[Co(II)(C₂O₄)₃]₂Cl·12H₂O, was synthesized under hydro-thermal conditions. The asymmetric unit comprises two [Co(NH₃)₆]³⁺ cations, one located on a threefold axis and the other on a site of symmetry -3, a [Co(C₂O₄)₃]⁴⁺ anion, located on a threefold axis, one sixth of a chloride anion [disordered over two sites, one threefold (site occupancy = 0.5) and the other -3 (site occupancy (0.25)] and two water molecules. Both Co(III) centers are six-coordinated by NH₃ mol-ecules, forming [Co(NH₃)₆]³⁺ octa-hedra, with Co-N distances in the range 1.958 (2)-1.977 (3) Å. The title structure gives the first example of the [Co(C₂O₄)₃]⁴⁻ anion, with the distorted octa-hedral environment of Co(II) center formed by six O atoms from three oxalate residues. The Co-O bond lengths are 2.0817 (18) to 2.0979 (18) Å. Multiple N-H⋯O, N-H⋯Cl and O-H⋯O hydrogen bonds link the cations, anions and water mol-ecules into a three-dimensional network.

Related literature

For metal phosphates and germanates templated by metal complexes, see: Wang et al. (2003 ▶, 2006 ▶); Pan et al. (2005 ▶, 2008 ▶). For our continued research inter­est, see: Pan et al. (2010 ▶, 2011 ▶). For a compound containing the [CoIII(NH3)6]3+ cation, see: Wu et al. (2012 ▶).

Experimental

Crystal data

[Co(NH3)6][Co(C2O4)3]Cl·12H2O

M = 1381.02

Trigonal,

a = 12.2138 (4) Å

c = 9.9090 (8) Å

V = 1280.15 (12) Å3

Z = 1

Mo Kα radiation

μ = 1.75 mm−1

T = 296 K

0.30 × 0.15 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.737, T max = 0.769

7736 measured reflections

1923 independent reflections

1514 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.108

S = 1.16

1923 reflections

115 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.61 e Å−3

Δρmin = −1.09 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812026414/yk2060sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026414/yk2060Isup2.hkl

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

[Co(NH3)6][Co(C2O4)3]Cl·12H2O	Dx = 1.791 Mg m−3
Mr = 1381.02	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 7736 reflections
Hall symbol: -P 3	θ = 2.1–27.2°
a = 12.2138 (4) Å	µ = 1.75 mm−1
c = 9.9090 (8) Å	T = 296 K
V = 1280.15 (12) Å3	Rod, orange
Z = 1	0.30 × 0.15 × 0.15 mm
F(000) = 716

Bruker APEXII CCD area-detector diffractometer	1923 independent reflections
Radiation source: fine-focus sealed tube	1514 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 5.00 pixels mm-1	θmax = 27.2°, θmin = 2.1°
φ and ω scans	h = −8→15
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −15→14
Tmin = 0.737, Tmax = 0.769	l = −12→12
7736 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.108	H-atom parameters constrained
S = 1.16	w = 1/[σ2(Fo2) + (0.0482P)2 + 0.6892P] where P = (Fo2 + 2Fc2)/3
1923 reflections	(Δ/σ)max = 0.011
115 parameters	Δρmax = 0.61 e Å−3
1 restraint	Δρmin = −1.09 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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)
Co1	0.6667	0.3333	0.14192 (6)	0.02287 (18)
Co2	0.6667	0.3333	0.64732 (5)	0.02393 (18)
Co3	0.0000	0.0000	0.0000	0.0646 (5)
Cl1	0.0000	0.0000	0.5000	0.085 (5)	0.498 (19)
Cl1'	0.0000	0.0000	0.3949 (17)	0.118 (4)	0.251 (9)
O1	0.3041 (2)	0.0971 (2)	0.2657 (2)	0.0530 (6)
O2	0.6796 (2)	0.65788 (19)	0.0164 (2)	0.0454 (6)
O3	0.64285 (18)	0.45991 (18)	0.02214 (18)	0.0311 (4)
O4	0.50524 (17)	0.24996 (18)	0.26488 (18)	0.0291 (4)
N1	−0.1492 (2)	−0.0618 (3)	0.1172 (4)	0.0725 (11)
H1A	−0.1436	−0.1075	0.1840	0.087*
H1B	−0.2187	−0.1096	0.0692	0.087*
H1C	−0.1528	0.0037	0.1514	0.087*
N2	0.6170 (2)	0.4327 (2)	0.5344 (2)	0.0328 (5)
H2B	0.6232	0.4999	0.5808	0.039*
H2A	0.5333	0.3879	0.5132	0.039*
H2	0.6626	0.4599	0.4568	0.039*
N3	0.5188 (2)	0.2924 (2)	0.7604 (2)	0.0307 (5)
H3B	0.4436	0.2449	0.7175	0.037*
H3A	0.5208	0.3659	0.7815	0.037*
H3	0.5185	0.2514	0.8372	0.037*
C1	0.4097 (3)	0.1551 (3)	0.2134 (3)	0.0310 (6)
C2	0.6835 (2)	0.5688 (2)	0.0718 (3)	0.0288 (6)
O1W	0.3354 (2)	0.2406 (3)	0.5187 (3)	0.0747 (9)
H1WA	0.2644	0.2152	0.5612	0.090*
H1W	0.3234	0.1853	0.4567	0.090*
O2W	0.5721 (2)	0.5645 (2)	0.7595 (2)	0.0523 (6)
H2WA	0.5434	0.6113	0.7265	0.063*
H2W	0.5970	0.5901	0.8416	0.063*

	U11	U22	U33	U12	U13	U23
Co1	0.0244 (2)	0.0244 (2)	0.0198 (3)	0.01220 (11)	0.000	0.000
Co2	0.0275 (2)	0.0275 (2)	0.0167 (3)	0.01377 (12)	0.000	0.000
Co3	0.0176 (3)	0.0176 (3)	0.1585 (15)	0.00881 (16)	0.000	0.000
Cl1	0.062 (2)	0.062 (2)	0.131 (13)	0.0310 (12)	0.000	0.000
Cl1'	0.148 (7)	0.148 (7)	0.060 (8)	0.074 (4)	0.000	0.000
O1	0.0294 (11)	0.0621 (15)	0.0463 (13)	0.0069 (10)	0.0097 (10)	−0.0024 (11)
O2	0.0507 (13)	0.0307 (11)	0.0548 (14)	0.0203 (10)	−0.0105 (11)	0.0070 (9)
O3	0.0394 (11)	0.0309 (10)	0.0263 (10)	0.0201 (9)	−0.0026 (8)	0.0002 (8)
O4	0.0269 (9)	0.0335 (10)	0.0246 (9)	0.0133 (8)	0.0009 (7)	−0.0008 (7)
N1	0.0262 (14)	0.0270 (14)	0.164 (4)	0.0127 (12)	0.0017 (18)	0.0026 (18)
N2	0.0411 (13)	0.0394 (13)	0.0220 (11)	0.0232 (11)	0.0011 (10)	0.0031 (9)
N3	0.0322 (12)	0.0354 (12)	0.0251 (11)	0.0172 (10)	0.0016 (9)	0.0010 (9)
C1	0.0286 (14)	0.0331 (14)	0.0308 (15)	0.0150 (12)	0.0000 (11)	0.0026 (11)
C2	0.0260 (13)	0.0287 (13)	0.0307 (14)	0.0129 (11)	0.0032 (11)	0.0031 (11)
O1W	0.0478 (15)	0.107 (2)	0.0662 (18)	0.0367 (16)	−0.0013 (13)	−0.0213 (17)
O2W	0.0805 (18)	0.0623 (15)	0.0407 (13)	0.0555 (15)	−0.0056 (12)	−0.0047 (11)

Co1—O3i	2.0817 (18)	Cl1'—Cl1'viii	2.08 (3)
Co1—O3ii	2.0817 (18)	O1—C1	1.233 (3)
Co1—O3	2.0817 (18)	O2—C2	1.240 (3)
Co1—O4ii	2.0979 (18)	O3—C2	1.264 (3)
Co1—O4i	2.0979 (18)	O4—C1	1.270 (3)
Co1—O4	2.0979 (18)	N1—H1A	0.8900
Co2—N2i	1.957 (2)	N1—H1B	0.8900
Co2—N2ii	1.957 (2)	N1—H1C	0.8900
Co2—N2	1.957 (2)	N2—H2B	0.9101
Co2—N3ii	1.966 (2)	N2—H2A	0.9100
Co2—N3i	1.966 (2)	N2—H2	0.9100
Co2—N3	1.966 (2)	N3—H3B	0.9100
Co3—N1iii	1.965 (3)	N3—H3A	0.9099
Co3—N1iv	1.965 (3)	N3—H3	0.9100
Co3—N1v	1.965 (3)	C1—C2ii	1.553 (4)
Co3—N1	1.965 (3)	C2—C1i	1.553 (4)
Co3—N1vi	1.965 (3)	O1W—H1WA	0.8700
Co3—N1vii	1.965 (3)	O1W—H1W	0.8700
Cl1—Cl1'viii	1.041 (17)	O2W—H2WA	0.8699
Cl1—Cl1'	1.041 (17)	O2W—H2W	0.8700
O3i—Co1—O3ii	90.71 (7)	N1iv—Co3—N1vi	91.36 (15)
O3i—Co1—O3	90.71 (7)	N1v—Co3—N1vi	180.0 (2)
O3ii—Co1—O3	90.71 (7)	N1—Co3—N1vi	88.64 (15)
O3i—Co1—O4ii	78.45 (7)	N1iii—Co3—N1vii	91.36 (15)
O3ii—Co1—O4ii	104.20 (7)	N1iv—Co3—N1vii	88.64 (15)
O3—Co1—O4ii	161.53 (7)	N1v—Co3—N1vii	88.64 (15)
O3i—Co1—O4i	104.20 (7)	N1—Co3—N1vii	180.0 (2)
O3ii—Co1—O4i	161.53 (7)	N1vi—Co3—N1vii	91.36 (15)
O3—Co1—O4i	78.45 (7)	Cl1'viii—Cl1—Cl1'	180.000 (2)
O4ii—Co1—O4i	89.66 (7)	C2—O3—Co1	115.64 (17)
O3i—Co1—O4	161.53 (7)	C1—O4—Co1	114.93 (16)
O3ii—Co1—O4	78.45 (7)	Co3—N1—H1A	109.5
O3—Co1—O4	104.20 (7)	Co3—N1—H1B	109.5
O4ii—Co1—O4	89.66 (7)	H1A—N1—H1B	109.5
O4i—Co1—O4	89.66 (7)	Co3—N1—H1C	109.5
N2i—Co2—N2ii	90.56 (10)	H1A—N1—H1C	109.5
N2i—Co2—N2	90.56 (10)	H1B—N1—H1C	109.5
N2ii—Co2—N2	90.56 (10)	Co2—N2—H2B	111.0
N2i—Co2—N3ii	91.47 (10)	Co2—N2—H2A	111.2
N2ii—Co2—N3ii	87.31 (10)	H2B—N2—H2A	102.8
N2—Co2—N3ii	177.07 (9)	Co2—N2—H2	112.7
N2i—Co2—N3i	87.31 (10)	H2B—N2—H2	109.7
N2ii—Co2—N3i	177.07 (9)	H2A—N2—H2	108.8
N2—Co2—N3i	91.47 (10)	Co2—N3—H3B	113.7
N3ii—Co2—N3i	90.74 (9)	Co2—N3—H3A	108.2
N2i—Co2—N3	177.07 (9)	H3B—N3—H3A	104.8
N2ii—Co2—N3	91.47 (10)	Co2—N3—H3	111.6
N2—Co2—N3	87.31 (10)	H3B—N3—H3	108.4
N3ii—Co2—N3	90.74 (9)	H3A—N3—H3	109.9
N3i—Co2—N3	90.74 (9)	O1—C1—O4	125.1 (3)
N1iii—Co3—N1iv	180.0 (2)	O1—C1—C2ii	119.5 (2)
N1iii—Co3—N1v	91.36 (15)	O4—C1—C2ii	115.4 (2)
N1iv—Co3—N1v	88.64 (15)	O2—C2—O3	125.7 (3)
N1iii—Co3—N1	88.64 (15)	O2—C2—C1i	118.7 (2)
N1iv—Co3—N1	91.36 (15)	O3—C2—C1i	115.5 (2)
N1v—Co3—N1	91.36 (15)	H1WA—O1W—H1W	108.3
N1iii—Co3—N1vi	88.64 (15)	H2WA—O2W—H2W	107.4

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1′	0.89	2.62	3.176 (15)	121
N1—H1A···O1iii	0.89	2.27	3.055 (4)	147
N1—H1B···O2ix	0.89	2.40	2.950 (4)	120
N1—H1B···O2x	0.89	2.52	3.151 (4)	128
N2—H2···O4i	0.91	2.09	2.993 (3)	171
N2—H2A···O1W	0.91	2.18	3.047 (4)	160
N2—H2B···O2W	0.91	2.15	2.958 (3)	147
N3—H3···O3xi	0.91	2.09	2.988 (3)	172
N3—H3A···O2W	0.91	2.19	3.051 (3)	157
N3—H3B···O1W	0.91	2.36	3.120 (4)	141
O1W—H1W···O1	0.87	2.13	2.971 (4)	162
O1W—H1WA···O1xii	0.87	2.32	2.973 (4)	132
O2W—H2W···O2xiii	0.87	1.97	2.830 (3)	171
O2W—H2WA···O4xiv	0.87	2.06	2.868 (3)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1′	0.89	2.62	3.176 (15)	121
N1—H1A⋯O1i	0.89	2.27	3.055 (4)	147
N1—H1B⋯O2ii	0.89	2.40	2.950 (4)	120
N1—H1B⋯O2iii	0.89	2.52	3.151 (4)	128
N2—H2⋯O4iv	0.91	2.09	2.993 (3)	171
N2—H2A⋯O1W	0.91	2.18	3.047 (4)	160
N2—H2B⋯O2W	0.91	2.15	2.958 (3)	147
N3—H3⋯O3v	0.91	2.09	2.988 (3)	172
N3—H3A⋯O2W	0.91	2.19	3.051 (3)	157
N3—H3B⋯O1W	0.91	2.36	3.120 (4)	141
O1W—H1W⋯O1	0.87	2.13	2.971 (4)	162
O1W—H1WA⋯O1vi	0.87	2.32	2.973 (4)	132
O2W—H2W⋯O2vii	0.87	1.97	2.830 (3)	171
O2W—H2WA⋯O4viii	0.87	2.06	2.868 (3)	154

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