Hexaamminecobalt(III) hexa­cyanido­manganate(III)

Visser, H.G.; Purcell, W.

doi:10.1107/S1600536808032881

inorganic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page i76

doi:10.1107/S1600536808032881

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Hexaamminecobalt(III) hexacyanidomanganate(III)

Hendrik G. Visser ^a ^* and Walter Purcell ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa
^*Correspondence e-mail: visserhg.sci@ufs.ac.za

(Received 10 September 2008; accepted 10 October 2008; online 18 October 2008)

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.

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 ).

Experimental

Crystal data

[Co(NH₃)₆][Mn(CN)₆]
M_r = 372.19
Trigonal, $[R \overline 3]$
a = 10.963 (5) Å
c = 10.779 (5) Å
V = 1121.9 (9) Å³
Z = 3
Mo Kα radiation
μ = 1.96 mm⁻¹
T = 100 (2) K
0.35 × 0.26 × 0.25 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.546, T_max = 0.614
3602 measured reflections
628 independent reflections
497 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.071
S = 0.93
628 reflections
32 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2ⁱ	0.89	2.09	2.979 (2)	173
Symmetry code: (i) -y+1, x-y+1, z.

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 and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808032881/pk2122sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032881/pk2122Isup2.hkl

checkCIF report

Comment top

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 top

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)].

Experimental top

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 top

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 top

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

Hexaamminecobalt(III) hexacyanidomanganate(III) top

Crystal data top

[Co(NH₃)₆][Mn(CN)₆]	D_x = 1.653 Mg m⁻³
M_r = 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) Å³	Cuboid, orange
Z = 3	0.35 × 0.26 × 0.25 mm
F(000) = 570

Data collection top

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

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.025	w = 1/[σ²(F_o²) + (0.0379P)² + 3.8029P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.071	(Δ/σ)_max < 0.001
S = 0.93	Δρ_max = 0.29 e Å⁻³
628 reflections	Δρ_min = −0.43 e Å⁻³
32 parameters

Crystal data top

[Co(NH₃)₆][Mn(CN)₆]	Z = 3
M_r = 372.19	Mo Kα radiation
Trigonal, R3	µ = 1.96 mm⁻¹
a = 10.963 (5) Å	T = 100 K
c = 10.779 (5) Å	0.35 × 0.26 × 0.25 mm
V = 1121.9 (9) Å³

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	628 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	497 reflections with I > 2σ(I)
T_min = 0.546, T_max = 0.614	R_int = 0.038
3602 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 0.93	Δρ_max = 0.29 e Å⁻³
628 reflections	Δρ_min = −0.43 e Å⁻³
32 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
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) top

Co1—N1ⁱ	1.9718 (16)	Mn1—C2^vii	1.9696 (19)
Co1—N1ⁱⁱ	1.9718 (16)	Mn1—C2^viii	1.9696 (19)
Co1—N1ⁱⁱⁱ	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)

N1ⁱ—Co1—N1ⁱⁱ	180.00 (7)	C2—Mn1—C2^viii	89.80 (7)
N1ⁱ—Co1—N1ⁱⁱⁱ	89.47 (6)	C2^vii—Mn1—C2^viii	89.80 (7)
N1ⁱⁱ—Co1—N1ⁱⁱⁱ	90.53 (6)	C2^vi—Mn1—C2^ix	89.80 (7)
N1ⁱ—Co1—N1^iv	89.47 (6)	C2—Mn1—C2^ix	90.20 (7)
N1ⁱⁱ—Co1—N1^iv	90.53 (6)	C2^vii—Mn1—C2^ix	180
N1ⁱⁱⁱ—Co1—N1^iv	89.47 (6)	C2^viii—Mn1—C2^ix	90.20 (7)
N1ⁱ—Co1—N1	90.53 (6)	C2^vi—Mn1—C2^x	89.80 (7)
N1ⁱⁱ—Co1—N1	89.47 (6)	C2—Mn1—C2^x	90.20 (7)
N1ⁱⁱⁱ—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)
N1ⁱ—Co1—N1^v	90.53 (6)	C2^ix—Mn1—C2^x	89.80 (7)
N1ⁱⁱ—Co1—N1^v	89.47 (6)	Co1—N1—H1A	109.5
N1ⁱⁱⁱ—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) top

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.

Experimental details

Crystal data
Chemical formula	[Co(NH₃)₆][Mn(CN)₆]
M_r	372.19
Crystal system, space group	Trigonal, R3
Temperature (K)	100
a, c (Å)	10.963 (5), 10.779 (5)
V (Å³)	1121.9 (9)
Z	3
Radiation type	Mo Kα
µ (mm⁻¹)	1.96
Crystal size (mm)	0.35 × 0.26 × 0.25

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.546, 0.614
No. of measured, independent and observed [I > 2σ(I)] reflections	3602, 628, 497
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.071, 0.93
No. of reflections	628
No. of parameters	32
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.43

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2ⁱ	0.89	2.09	2.979 (2)	172.9

Symmetry code: (i) −y+1, x−y+1, z.

Acknowledgements

The University of the Free State is gratefully acknowledged for financial support. Dr A. J. Muller and Mr Leo Kirsten are acknowledged for help with the data collection.

References

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