Hexaamminecobalt(III) hexa­cyanido­manganate(III)

The asymmetric unit of the title compound, [Co(NH₃)₆][Mn(CN)₆], contains one Co and one Mn atom, both lying on threefold inversion axes, and one NH₃ and one CN group. The octa­hedral environments around Co^II and Mn^II are generated by symmetry and show very slight deviations from ideal geometry. A three-dimensional network is created by N—H...N hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](N-C) = 0.003 Å
• R factor = 0.025
• wR factor = 0.071
• Data-to-parameter ratio = 19.6

checkCIF/PLATON results

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Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn1    --  C2      ..      11.58 su

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   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

Our interest is in the use of cyanometalates as molecular building blocks for potentially constructing clusters and networks with adjustable magnetic properties [Przychodzen et al., (2006), Withers et al., (2005)].

The title compound crystallizes in the trigonal R-3 space group with Z = 3. The main part of the asymmetric unit contains one Co and one Mn atom, both lying on threefold rotational axes.

The octahedral environments around Co^II and Mn^II are generated by symmetry and shows very slight deviation from ideal geometry as illustrated by the C—Mn—C angles of 180.00 (7), 89.80 (7) and 90.20 (7) and N—Co—N angles of 180.00 (7), 89.47 (6) and 90.53 (6) ° respectively.

A three dimensional network is created by hydrogen bonds of the type N—H—N.

Related literature

For related structures, see: Buschmann et al. (1999). For the construction of clusters and networks with adjustable magnetic properties, see: Przychodzen et al. (2006); Withers et al. (2005)].

S2. Experimental

Equimolar amounts of K₃[Mn(CN)₆] and [Co(NH₃)₆]Cl₃ were dissolved in water, added together and allowed to stand. Orange crystals separated out after a few days.

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Figures

Fig. 1. An ellipsoid plot of the title compound (50% probability displacement ellipsoids).

Hexaamminecobalt(III) hexacyanidomanganate(III)

Crystal data

[Co(NH3)6][Mn(CN)6]	Dx = 1.653 Mg m^−3
Mr = 372.19	Mo Kα radiation, λ = 0.71069 Å
Trigonal, R3	Cell parameters from 1532 reflections
Hall symbol: -R 3	θ = 2.9–28.3°
a = 10.963 (5) Å	µ = 1.96 mm^−1
c = 10.779 (5) Å	T = 100 K
V = 1121.9 (9) Å^3	Cuboid, orange
Z = 3	0.35 × 0.26 × 0.25 mm
F(000) = 570

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	497 reflections with I > 2σ(I)
ϕ and ω scans	Rint = 0.038
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θmax = 28.3°, θmin = 2.9°
Tmin = 0.546, Tmax = 0.614	h = −12→14
3602 measured reflections	k = −14→9
628 independent reflections	l = −10→14

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.025	w = 1/[σ^2(Fo^2) + (0.0379P)^2 + 3.8029P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.071	(Δ/σ)max < 0.001
S = 0.93	Δρmax = 0.29 e Å^−3
628 reflections	Δρmin = −0.43 e Å^−3
32 parameters

Special details

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.

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

	x	y	z	Uiso*/Ueq
Co1	0	0	0	0.00732 (17)
Mn1	0.3333	0.6667	0.1667	0.00607 (17)
N1	−0.02748 (15)	0.13048 (15)	−0.10659 (13)	0.0107 (3)
H1A	0.0238	0.2179	−0.0777	0.016*
H1B	−0.1181	0.1061	−0.1065	0.016*
H1C	−0.0006	0.1264	−0.1837	0.016*
C2	0.31385 (18)	0.80238 (18)	0.06080 (16)	0.0119 (3)
N2	0.30018 (17)	0.87891 (17)	−0.00283 (15)	0.0184 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0076 (2)	0.0076 (2)	0.0067 (3)	0.00381 (10)	0	0
Mn1	0.0064 (2)	0.0064 (2)	0.0055 (3)	0.00318 (10)	0	0
N1	0.0117 (7)	0.0099 (7)	0.0111 (7)	0.0058 (6)	0.0007 (5)	0.0010 (5)
C2	0.0108 (8)	0.0144 (8)	0.0115 (8)	0.0070 (7)	0.0001 (6)	−0.0026 (6)
N2	0.0200 (8)	0.0248 (9)	0.0159 (7)	0.0152 (7)	0.0014 (6)	0.0013 (6)

Geometric parameters (Å, º)

Co1—N1^i	1.9718 (16)	Mn1—C2^vii	1.9696 (19)
Co1—N1^ii	1.9718 (16)	Mn1—C2^viii	1.9696 (19)
Co1—N1^iii	1.9718 (15)	Mn1—C2^ix	1.9696 (19)
Co1—N1^iv	1.9718 (15)	Mn1—C2^x	1.9696 (19)
Co1—N1	1.9718 (15)	N1—H1A	0.89
Co1—N1^v	1.9718 (15)	N1—H1B	0.89
Mn1—C2^vi	1.9696 (19)	N1—H1C	0.89
Mn1—C2	1.9696 (19)	C2—N2	1.150 (2)
N1^i—Co1—N1^ii	180.00 (7)	C2—Mn1—C2^viii	89.80 (7)
N1^i—Co1—N1^iii	89.47 (6)	C2^vii—Mn1—C2^viii	89.80 (7)
N1^ii—Co1—N1^iii	90.53 (6)	C2^vi—Mn1—C2^ix	89.80 (7)
N1^i—Co1—N1^iv	89.47 (6)	C2—Mn1—C2^ix	90.20 (7)
N1^ii—Co1—N1^iv	90.53 (6)	C2^vii—Mn1—C2^ix	180
N1^iii—Co1—N1^iv	89.47 (6)	C2^viii—Mn1—C2^ix	90.20 (7)
N1^i—Co1—N1	90.53 (6)	C2^vi—Mn1—C2^x	89.80 (7)
N1^ii—Co1—N1	89.47 (6)	C2—Mn1—C2^x	90.20 (7)
N1^iii—Co1—N1	180.00 (10)	C2^vii—Mn1—C2^x	90.20 (7)
N1^iv—Co1—N1	90.53 (6)	C2^viii—Mn1—C2^x	180.00 (7)
N1^i—Co1—N1^v	90.53 (6)	C2^ix—Mn1—C2^x	89.80 (7)
N1^ii—Co1—N1^v	89.47 (6)	Co1—N1—H1A	109.5
N1^iii—Co1—N1^v	90.53 (6)	Co1—N1—H1B	109.5
N1^iv—Co1—N1^v	180.00 (10)	H1A—N1—H1B	109.5
N1—Co1—N1^v	89.47 (6)	Co1—N1—H1C	109.5
C2^vi—Mn1—C2	180	H1A—N1—H1C	109.5
C2^vi—Mn1—C2^vii	90.20 (7)	H1B—N1—H1C	109.5
C2—Mn1—C2^vii	89.80 (7)	N2—C2—Mn1	178.31 (17)
C2^vi—Mn1—C2^viii	90.20 (7)

Symmetry codes: (i) y, −x+y, −z; (ii) −y, x−y, z; (iii) −x, −y, −z; (iv) x−y, x, −z; (v) −x+y, −x, z; (vi) −x+2/3, −y+4/3, −z+1/3; (vii) −y+1, x−y+1, z; (viii) −x+y, −x+1, z; (ix) y−1/3, −x+y+1/3, −z+1/3; (x) x−y+2/3, x+1/3, −z+1/3.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2^vii	0.89	2.09	2.979 (2)	173

Symmetry code: (vii) −y+1, x−y+1, z.