Tris(2,2'-bipyridine-κN,N')cobalt(III) tris-(oxalato-κO,O)ferrate(III) mono-hydrate.

The title compound, [Co(C(10)H(8)N(2))(3)][Fe(C(2)O(4))(3)]·H(2)O, con-sists of two discrete tris-(chelate) metal ions (Co(III)N(6) and Fe(III)O(6) chromophores) and a water mol-ecule. The structure is highly symmetrical; the Co(III) and Fe(III) ions occupy positions with site symmetry 3.2. The coordination polyhedra of the metal atoms have a nearly octa-hedral geometry with noticeable trigonal distortions. The Co-N and Fe-O bond lengths are equal by symmetry, viz. 1.981 (2) and 1.998 (4) Å, respectively. The cations and anions are arranged alternately along their threefold rotation axes parallel to [001], forming chains that are packed in a hexa-gonal manner. The water mol-ecules occupy voids between the chains. The crystal under investigation was an inversion twin.

Related literature

For general background to direct synthesis, see: Makhankova (2011 ▶). For bond-valance sum calculation, see: Brown & Altermatt (1985 ▶) (http://www.iucr.org/resources/data/datasets/bond-valence-parameters). For related structures, see: Chygorin et al. (2010 ▶); Coronado et al. (2000 ▶); Devi et al. (2003 ▶); Jun & Zhang (2010 ▶); Yanagi et al. (1981 ▶); Zhang et al. (2009 ▶). For measuring of trigonal distortion angles, see: Muetterties & Guggenberger (1974 ▶).

Experimental

Crystal data

[Co(C10H8N2)3][Fe(C2O4)3]·H2O

M = 865.42

Hexagonal,

a = 13.056 (2) Å

c = 12.480 (3) Å

V = 1842.3 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.92 mm−1

T = 293 K

0.60 × 0.40 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur/Sapphire3 diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T min = 0.608, T max = 0.838

17786 measured reflections

1807 independent reflections

1393 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.155

S = 1.04

1807 reflections

90 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.83 e Å−3

Absolute structure: Flack (1983 ▶), 699 Friedel pairs

Flack parameter: 0.57 (3)

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL and PLATON (Spek, 2009 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812003224/br2188sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003224/br2188Isup2.hkl

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

[Co(C10H8N2)3][Fe(C2O4)3]·H2O	Dx = 1.560 Mg m−3
Mr = 865.42	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P622	Cell parameters from 1555 reflections
Hall symbol: P 6 2	θ = 3.1–32.0°
a = 13.056 (2) Å	µ = 0.92 mm−1
c = 12.480 (3) Å	T = 293 K
V = 1842.3 (7) Å3	Block, violet
Z = 2	0.60 × 0.40 × 0.20 mm
F(000) = 882

Oxford Diffraction Xcalibur/Sapphire3 diffractometer	1807 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1393 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
Detector resolution: 16.1827 pixels mm-1	θmax = 30.0°, θmin = 3.1°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009)	k = −18→17
Tmin = 0.608, Tmax = 0.838	l = −17→17
17786 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063	H-atom parameters constrained
wR(F2) = 0.155	w = 1/[σ2(Fo2) + (0.0909P)2] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
1807 reflections	Δρmax = 0.36 e Å−3
90 parameters	Δρmin = −0.83 e Å−3
0 restraints	Absolute structure: Flack (1983), 699 Friedel pairs
40 constraints	Flack parameter: 0.57 (3)
Primary atom site location: structure-invariant direct methods

Experimental. CrysAlis RED, Oxford Diffraction Ltd., 2009. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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)
Co1	0.3333	0.6667	0.5000	0.0271 (3)
Fe1	0.6667	0.3333	0.0000	0.0908 (6)
N1	0.4659 (2)	0.6789 (2)	0.41309 (19)	0.0281 (5)
C1	0.5760 (2)	0.7591 (2)	0.4502 (2)	0.0276 (6)
O1	0.6801 (4)	0.4676 (4)	0.0877 (3)	0.1027 (14)
O2	0.7734 (6)	0.6631 (5)	0.0909 (4)	0.1201 (18)
C2	0.6771 (3)	0.7820 (3)	0.3950 (3)	0.0408 (8)
H2	0.7512	0.8352	0.4226	0.049*
C3	0.6678 (3)	0.7257 (3)	0.2986 (3)	0.0459 (8)
H3	0.7352	0.7418	0.2600	0.055*
C4	0.5576 (3)	0.6457 (3)	0.2611 (3)	0.0412 (8)
H4	0.5490	0.6067	0.1965	0.049*
C5	0.4604 (3)	0.6239 (3)	0.3201 (3)	0.0376 (7)
H5	0.3863	0.5680	0.2946	0.045*
C6	0.7526 (6)	0.5702 (7)	0.0527 (4)	0.0870 (17)
O1W	1.0000	1.0000	0.4677 (4)	0.0314 (14)
H1W	0.9438	1.0000	0.5000	0.047*	0.667

	U11	U22	U33	U12	U13	U23
Co1	0.0289 (3)	0.0289 (3)	0.0235 (5)	0.01447 (16)	0.000	0.000
Fe1	0.1181 (10)	0.1181 (10)	0.0361 (8)	0.0591 (5)	0.000	0.000
N1	0.0325 (13)	0.0270 (12)	0.0280 (12)	0.0171 (11)	−0.0004 (10)	−0.0020 (10)
C1	0.0258 (12)	0.0267 (13)	0.0329 (16)	0.0149 (10)	0.0018 (12)	0.0013 (11)
O1	0.115 (3)	0.129 (4)	0.0414 (19)	0.045 (3)	0.028 (2)	0.003 (2)
O2	0.189 (5)	0.152 (4)	0.076 (3)	0.127 (4)	0.030 (3)	0.002 (3)
C2	0.0328 (16)	0.0451 (18)	0.0421 (19)	0.0176 (15)	0.0077 (15)	0.0008 (15)
C3	0.0467 (18)	0.060 (2)	0.043 (2)	0.0359 (18)	0.0151 (17)	0.0067 (16)
C4	0.0469 (18)	0.045 (2)	0.0368 (18)	0.0272 (16)	0.0051 (14)	−0.0044 (15)
C5	0.0422 (17)	0.0409 (17)	0.0317 (17)	0.0223 (14)	0.0002 (13)	−0.0082 (13)
C6	0.121 (5)	0.125 (5)	0.038 (3)	0.079 (4)	0.016 (3)	0.001 (3)
O1W	0.0168 (10)	0.0168 (10)	0.060 (4)	0.0084 (5)	0.000	0.000

Co1—N1i	1.981 (2)	C1—C2	1.383 (4)
Co1—N1ii	1.981 (2)	C1—C1iii	1.454 (6)
Co1—N1iii	1.981 (2)	O1—C6	1.270 (7)
Co1—N1iv	1.981 (2)	O2—C6	1.201 (7)
Co1—N1	1.981 (2)	C2—C3	1.384 (5)
Co1—N1v	1.981 (2)	C2—H2	0.9300
Fe1—O1vi	1.998 (4)	C3—C4	1.370 (5)
Fe1—O1vii	1.998 (4)	C3—H3	0.9300
Fe1—O1viii	1.998 (4)	C4—C5	1.368 (4)
Fe1—O1ix	1.998 (4)	C4—H4	0.9300
Fe1—O1x	1.998 (4)	C5—H5	0.9300
Fe1—O1	1.998 (4)	C6—C6viii	1.566 (9)
N1—C5	1.348 (4)	O1W—O1Wxi	0.807 (9)
N1—C1	1.368 (4)	O1W—H1W	0.8376
N1i—Co1—N1ii	81.59 (13)	O1viii—Fe1—O1	81.1 (2)
N1i—Co1—N1iii	93.20 (13)	O1ix—Fe1—O1	92.87 (17)
N1ii—Co1—N1iii	92.88 (9)	O1x—Fe1—O1	93.8 (3)
N1i—Co1—N1iv	92.88 (9)	C5—N1—C1	117.1 (3)
N1ii—Co1—N1iv	93.20 (13)	C5—N1—Co1	128.1 (2)
N1iii—Co1—N1iv	171.98 (13)	C1—N1—Co1	114.69 (19)
N1i—Co1—N1	92.88 (9)	N1—C1—C2	121.4 (3)
N1ii—Co1—N1	171.98 (13)	N1—C1—C1iii	114.47 (16)
N1iii—Co1—N1	81.59 (13)	C2—C1—C1iii	124.1 (2)
N1iv—Co1—N1	92.88 (9)	C6—O1—Fe1	115.4 (3)
N1i—Co1—N1v	171.98 (13)	C1—C2—C3	119.8 (3)
N1ii—Co1—N1v	92.88 (9)	C1—C2—H2	120.1
N1iii—Co1—N1v	92.88 (9)	C3—C2—H2	120.1
N1iv—Co1—N1v	81.59 (13)	C4—C3—C2	118.8 (3)
N1—Co1—N1v	93.20 (13)	C4—C3—H3	120.6
O1vi—Fe1—O1vii	81.1 (2)	C2—C3—H3	120.6
O1vi—Fe1—O1viii	93.8 (3)	C5—C4—C3	119.1 (3)
O1vii—Fe1—O1viii	92.87 (17)	C5—C4—H4	120.5
O1vi—Fe1—O1ix	92.87 (17)	C3—C4—H4	120.5
O1vii—Fe1—O1ix	93.8 (3)	N1—C5—C4	123.7 (3)
O1viii—Fe1—O1ix	171.3 (2)	N1—C5—H5	118.1
O1vi—Fe1—O1x	171.3 (2)	C4—C5—H5	118.1
O1vii—Fe1—O1x	92.87 (17)	O2—C6—O1	127.0 (5)
O1viii—Fe1—O1x	92.87 (17)	O2—C6—C6viii	119.0 (4)
O1ix—Fe1—O1x	81.1 (2)	O1—C6—C6viii	114.0 (3)
O1vi—Fe1—O1	92.87 (17)	O1Wxi—O1W—H1W	61.2
O1vii—Fe1—O1	171.3 (2)
N1i—Co1—N1—C5	−83.9 (2)	O1viii—Fe1—O1—C6	0.1 (3)
N1iii—Co1—N1—C5	−176.7 (3)	O1ix—Fe1—O1—C6	−173.5 (4)
N1iv—Co1—N1—C5	9.1 (3)	O1x—Fe1—O1—C6	−92.2 (4)
N1v—Co1—N1—C5	90.9 (3)	N1—C1—C2—C3	1.8 (5)
N1i—Co1—N1—C1	91.8 (2)	C1iii—C1—C2—C3	−177.6 (3)
N1iii—Co1—N1—C1	−1.05 (14)	C1—C2—C3—C4	−1.5 (5)
N1iv—Co1—N1—C1	−175.22 (19)	C2—C3—C4—C5	−0.1 (5)
N1v—Co1—N1—C1	−93.5 (2)	C1—N1—C5—C4	−1.3 (5)
C5—N1—C1—C2	−0.4 (4)	Co1—N1—C5—C4	174.3 (2)
Co1—N1—C1—C2	−176.6 (2)	C3—C4—C5—N1	1.6 (5)
C5—N1—C1—C1iii	179.0 (3)	Fe1—O1—C6—O2	178.4 (5)
Co1—N1—C1—C1iii	2.9 (4)	Fe1—O1—C6—C6viii	−0.2 (8)
O1vi—Fe1—O1—C6	93.5 (5)