Bis[(cyanido-κC)bis(1,10-phenanthroline-κ2N,N′)copper(II)] pentakis­(cyanido-κC)nitro­soferrate(II) dimethyl­formamide monosolvate

Kozachuk, O.V.; Kokozay, V.N.; Vassilyeva, O.Y.; Skelton, B.W.

doi:10.1107/S1600536812036264

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Pages m1218-m1219

doi:10.1107/S1600536812036264

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Bis[(cyanido-κC)bis(1,10-phenanthroline-κ²N,N′)copper(II)] pentakis(cyanido-κC)nitrosoferrate(II) dimethylformamide monosolvate

Olesia V. Kozachuk,^a,^b Vladimir N. Kokozay,^a Olga Yu. Vassilyeva ^a ^* and Brian W. Skelton ^c

^aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska str. 64, Kyiv 01601, Ukraine, ^bDepartment of Inorganic Chemistry II, Ruhr University Bochum, Universitätsstrasse 150, 44780, Bochum, Germany, and ^cCentre for Microscopy, Characterisation and Analysis, University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia
^*Correspondence e-mail: vassilyeva@univ.kiev.ua

(Received 27 July 2012; accepted 20 August 2012; online 25 August 2012)

The title compound, [Cu(CN)(C₁₂H₈N₂)₂]₂[Fe(CN)₅(NO)]·C₃H₇NO, is formed of discrete [Cu(phen)₂CN]⁺ cations (phen is 1,10-phenanthroline), nitroprusside [Fe(CN)₅(NO)]²⁻ anions and dimethylformamide (DMF) molecules of crystallization. The metal atom has a distorted trigonal–bipyramidal coordination environment, defined by four N atoms of two phen molecules and a C atom of the cyanide group (in the equatorial position). The [Fe(CN)₅(NO)]²⁻ anion was found to be disordered about (but not on) a crystallographic twofold rotation axis. Geometries were restrained to ideal values. The dimethylformamide solvent molecule was found to be disordered about a crystallographic inversion centre.

Related literature

For direct synthesis using sodium nitroprusside, see: Vreshch et al. (2009a ,b ). For structures containing [Cu(phen)₂CN]]⁺ cations, see: Dunaj-Jurčo et al. (1993 ); Potočňák et al. (1996a ,b ). For a review of structures containing nitroprusside anions, see: Soria et al. (2002 ).

Experimental

Crystal data

[Cu(CN)(C₁₂H₈N₂)₂]₂[Fe(CN)₅(NO)]·C₃H₇NO
M_r = 1188.99
Monoclinic, P 2/c
a = 11.9235 (16) Å
b = 10.7836 (16) Å
c = 19.805 (3) Å
β = 97.252 (3)°
V = 2526.1 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.18 mm⁻¹
T = 150 K
0.26 × 0.21 × 0.07 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.86, T_max = 1
26129 measured reflections
5844 independent reflections
3739 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.135
S = 1.04
5844 reflections
430 parameters
44 restraints
H-atom parameters constrained
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—C25	1.964 (4)
Cu1—N3	2.011 (3)
Cu1—N1	2.024 (3)
Cu1—N4	2.090 (3)
Cu1—N2	2.164 (3)
Fe1—N9	1.630 (6)
Fe1—C27	1.933 (7)
Fe1—C26′	1.934 (8)
Fe1—C27′	1.937 (7)
Fe1—C26	1.938 (7)
Fe1—C28	1.959 (6)

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEPII (Johnson, 1976 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812036264/hg5236sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812036264/hg5236Isup2.hkl

checkCIF report

Comment top

Recently, we have shown that sodium nitroprusside could be used as a source of metalloligand or could supply the second metal upon its destruction in direct synthesis of heterometallic Cu/Fe complexes (Vreshch et al., 2009a,b). Within this study we prepared a new cation-anion Cu/Fe complex based on the self-assembly of nitroprusside anion and Cu cation containing a bidentate amine.The title compound was isolated from the solution obtained by reacting copper powder and sodium nitroprusside with (NH₄)₂C₂O₄ and 1,10-phenanthroline in DMF. Obviously, the nitroprusside partially decomposed to supply a cyanide group to the cation while sodium oxalate did not participate. To the best of our knowledge the title compound has not been structurally characterized.

The title compound, [Cu(C₁₂H₈N₂)₂CN]₂[Fe(CN)₅(NO)].DMF, is formed of discrete [Cu(phen)₂CN]⁺ cations (phen is 1,10-phenanthroline), nitroprusside [Fe(CN)₅(NO)]^2- anions and DMF molecules of crystallization. The [Cu(phen)₂CN]⁺ cation has no crystallographically imposed symmetry (Fig. 1). The metal atom has a distorted trigonal-bipyramidal geometry, coordinating four nitrogen atoms of two phen molecules and a carbon atom of the cyanide group. One nitrogen from each phen ligand coordinates to the copper centre in an equatorial position, with Cu–N distances of 2.090 (3) and 2.164 (3) Å, while the other nitrogen atoms occur at axial positions, with Cu–N distances of 2.011 (3) and 2.024 (3) Å. The cyanide group occupies the remaining equatorial position with the Cu–C bond of 1.964 (4) Å. A similar coordination geometry was observed in other complexes containing [Cu(phen)₂CN]]⁺ cations (Dunaj-Jurčo et al., 1993; Potočňák et al., 1996a,b).

The [Fe(CN)₅(NO)]^2- anion was found to be disordered about (but not on) the crystallographic 2-fold axis. Geometries were restrained to ideal values (Soria et al., 2002): a usual distorted octahedral pagoda-like conformation of the nitroprusside anion, with Fe–C bond distances in the range 1.933 (7)–1.959 (6) Å and a Fe–N bond distance of 1.630 (6) Å. There was no indication from the refinement of any disorder between the nitrosyl and cyanide groups.

The structure is completed by dimethylformamide solvent molecules that were found to be disordered about the crystallographic inversion centre.

Related literature top

For direct synthesis using sodium nitroprusside, see: Vreshch et al. (2009a,b). For structures containing [Cu(phen)₂CN]]⁺ cations, see: Dunaj-Jurčo et al. (1993); Potočňák et al. (1996a,b). For a review of structures containing nitroprusside anions, see: Soria et al. (2002).

Experimental top

Copper powder (0.08 g, 1.25 mmol), (NH₄)₂C₂O₄.H₂O (0.18 g, 1.25 mmol), Na₂[Fe(CN)₅(NO)].2H₂O (0.37 g, 1.25 mmol), phen.H₂O (0.75 g, 3.77 mmol), and 20 ml DMF were heated to 323–333 K and magnetically stirred until total dissolution of the copper was observed (50 min). The resulting blue solution was filtered and allowed to stand at room temperature. Blue-green plate-like microcrystals of the title compound were formed after one day. They were collected by filter-suction, washed with dry PrⁱOH and finally dried in vacuo (yield: 20%).

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of the cation with the numbering scheme (the non-hydrogen atoms ellipsoids are shown at the 50% probability level).
	Fig. 2. Unit-cell contents of (I). Only one set of each of the disordered atoms is shown for clarity.

Bis[(Cyanido-κC)bis(1,10-phenanthroline-κ²N,N') copper(II)] pentakis(cyanido-κC)nitrosoferrate(II) dimethylformamide monosolvate top

Crystal data top

[Cu(CN)(C₁₂H₈N₂)₂]₂[Fe(CN)₅(NO)]·C₃H₇NO	F(000) = 1212
M_r = 1188.99	D_x = 1.563 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2yc	Cell parameters from 4070 reflections
a = 11.9235 (16) Å	θ = 2.5–27.6°
b = 10.7836 (16) Å	µ = 1.18 mm⁻¹
c = 19.805 (3) Å	T = 150 K
β = 97.252 (3)°	Plate, green
V = 2526.1 (6) Å³	0.26 × 0.21 × 0.07 mm
Z = 2

Data collection top

Siemens SMART CCD diffractometer	3739 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ω scans	θ_max = 27.6°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→15
T_min = 0.86, T_max = 1	k = −14→14
26129 measured reflections	l = −25→25
5844 independent reflections

Refinement top

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0315P)² + 6.0554P] where P = (F_o² + 2F_c²)/3
5844 reflections	(Δ/σ)_max = 0.034
430 parameters	Δρ_max = 0.56 e Å⁻³
44 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Cu(CN)(C₁₂H₈N₂)₂]₂[Fe(CN)₅(NO)]·C₃H₇NO	V = 2526.1 (6) Å³
M_r = 1188.99	Z = 2
Monoclinic, P2/c	Mo Kα radiation
a = 11.9235 (16) Å	µ = 1.18 mm⁻¹
b = 10.7836 (16) Å	T = 150 K
c = 19.805 (3) Å	0.26 × 0.21 × 0.07 mm
β = 97.252 (3)°

Data collection top

Siemens SMART CCD diffractometer	5844 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3739 reflections with I > 2σ(I)
T_min = 0.86, T_max = 1	R_int = 0.066
26129 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	44 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.04	Δρ_max = 0.56 e Å⁻³
5844 reflections	Δρ_min = −0.59 e Å⁻³
430 parameters

Special details top

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 > 2σ(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.

The Fe(CN)₅(NO) anion was found to be disordered about (but not on) the crystallographic 2-fold axis. Geometries were restrained to ideal values. There was no indication from the refinement of any disorder between the nitrosyl and cyanide groups. The dimethylformamide solvent molecule was found to be disordered about the crystallographic inversion centre.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.24634 (4)	0.51817 (4)	0.41187 (2)	0.02860 (12)
Fe1	0.48386 (19)	1.06768 (8)	0.25085 (16)	0.0258 (5)	0.5
O1	0.4694 (8)	1.3257 (5)	0.2553 (5)	0.064 (4)	0.5
O2	0.0132 (6)	0.0540 (6)	0.3713 (3)	0.0567 (18)	0.5
N1	0.2124 (3)	0.6513 (3)	0.34018 (13)	0.0286 (7)
N10	0.0187 (9)	0.0109 (9)	0.4835 (4)	0.046 (3)	0.5
N2	0.1909 (3)	0.4049 (3)	0.32377 (14)	0.0314 (7)
N3	0.2866 (3)	0.3710 (3)	0.47243 (14)	0.0281 (7)
N4	0.4172 (2)	0.5023 (3)	0.39952 (13)	0.0258 (6)
N5	0.0827 (3)	0.6436 (3)	0.50242 (15)	0.0407 (8)
N6	0.3618 (10)	1.0421 (12)	0.3797 (5)	0.034 (3)	0.5
N7	0.2577 (7)	1.0334 (7)	0.1589 (4)	0.0325 (15)	0.5
N6'	0.6170 (11)	1.0517 (13)	0.1269 (6)	0.038 (3)	0.5
N7'	0.7084 (7)	1.0498 (7)	0.3477 (4)	0.0325 (15)	0.5
N8	0.5	0.7807 (4)	0.25	0.0437 (13)
N9	0.4757 (8)	1.2186 (5)	0.2510 (7)	0.039 (3)	0.5
C1	0.1684 (3)	0.6090 (3)	0.27799 (16)	0.0276 (8)
C2	0.1320 (3)	0.6898 (4)	0.22391 (17)	0.0321 (9)
C3	0.1418 (3)	0.8171 (4)	0.23649 (19)	0.0399 (10)
H3	0.1176	0.8747	0.2014	0.048*
C4	0.1865 (4)	0.8588 (4)	0.29959 (19)	0.0406 (10)
H4	0.1939	0.9451	0.3086	0.049*
C5	0.2207 (3)	0.7723 (4)	0.35009 (18)	0.0358 (9)
H5	0.2515	0.8016	0.3938	0.043*
C6	0.0857 (3)	0.6375 (4)	0.16002 (17)	0.0355 (9)
H6	0.0587	0.6914	0.1236	0.043*
C7	0.1600 (3)	0.4779 (4)	0.26856 (16)	0.0279 (8)
C8	0.1175 (3)	0.4299 (4)	0.20479 (17)	0.0334 (9)
C9	0.1135 (3)	0.3004 (4)	0.19781 (19)	0.0414 (10)
H9	0.0873	0.2637	0.1551	0.05*
C10	0.1477 (4)	0.2278 (4)	0.2532 (2)	0.0462 (11)
H10	0.1458	0.14	0.2493	0.055*
C11	0.1856 (4)	0.2834 (4)	0.3154 (2)	0.0404 (10)
H11	0.2085	0.2317	0.3535	0.048*
C12	0.0793 (3)	0.5150 (4)	0.15008 (17)	0.0366 (9)
H12	0.0494	0.4834	0.1067	0.044*
C13	0.3944 (3)	0.3303 (3)	0.47224 (15)	0.0251 (8)
C14	0.4385 (3)	0.2252 (3)	0.50800 (16)	0.0283 (8)
C15	0.3657 (4)	0.1628 (3)	0.54723 (17)	0.0353 (9)
H15	0.3916	0.0922	0.5734	0.042*
C16	0.2570 (3)	0.2047 (4)	0.54740 (18)	0.0360 (9)
H16	0.2071	0.1625	0.5733	0.043*
C17	0.2198 (3)	0.3097 (3)	0.50953 (17)	0.0323 (8)
H17	0.1445	0.3378	0.5104	0.039*
C18	0.5514 (3)	0.1872 (3)	0.50234 (17)	0.0329 (9)
H18	0.5813	0.1155	0.5261	0.039*
C19	0.4645 (3)	0.3996 (3)	0.43208 (15)	0.0248 (7)
C20	0.5760 (3)	0.3616 (3)	0.42840 (16)	0.0280 (8)
C21	0.6399 (3)	0.4355 (4)	0.38890 (17)	0.0329 (9)
H21	0.7161	0.414	0.3848	0.039*
C22	0.5925 (3)	0.5385 (4)	0.35627 (17)	0.0344 (9)
H22	0.6354	0.5886	0.3295	0.041*
C23	0.4811 (3)	0.5690 (3)	0.36269 (16)	0.0290 (8)
H23	0.4491	0.6405	0.3398	0.035*
C24	0.6164 (3)	0.2517 (3)	0.46361 (17)	0.0327 (9)
H24	0.6907	0.2233	0.4597	0.039*
C25	0.1439 (3)	0.5939 (4)	0.47038 (17)	0.0321 (9)
C26	0.4078 (9)	1.0528 (11)	0.3314 (4)	0.024 (2)	0.5
C27	0.3411 (6)	1.0476 (9)	0.1938 (4)	0.021 (2)	0.5
C28	0.5	0.8869 (5)	0.25	0.0358 (13)
C26'	0.5654 (10)	1.0548 (15)	0.1727 (5)	0.036 (3)	0.5
C27'	0.6237 (6)	1.0557 (10)	0.3120 (4)	0.025 (2)	0.5
C29	0.1247 (8)	−0.0542 (8)	0.4854 (5)	0.052 (3)	0.5
H29A	0.1101	−0.141	0.4725	0.078*	0.5
H29B	0.1655	−0.0504	0.5315	0.078*	0.5
H29C	0.1704	−0.0155	0.4534	0.078*	0.5
C30	−0.0397 (12)	0.0140 (12)	0.5423 (6)	0.057 (4)	0.5
H30A	−0.0972	0.0794	0.5369	0.086*	0.5
H30B	0.0143	0.031	0.5828	0.086*	0.5
H30C	−0.0762	−0.0663	0.5475	0.086*	0.5
C31	−0.0278 (8)	0.0603 (8)	0.4248 (4)	0.041 (2)	0.5
H31	−0.0975	0.1032	0.4245	0.049*	0.5

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0344 (2)	0.0324 (2)	0.01888 (19)	0.0065 (2)	0.00289 (16)	0.00409 (18)
Fe1	0.0389 (13)	0.0173 (4)	0.0198 (4)	−0.0003 (5)	−0.0017 (8)	0.0003 (7)
O1	0.126 (11)	0.023 (3)	0.042 (4)	0.005 (4)	0.004 (6)	−0.001 (3)
O2	0.058 (4)	0.066 (4)	0.046 (3)	0.011 (3)	0.002 (3)	0.012 (3)
N1	0.0343 (16)	0.0327 (17)	0.0184 (13)	0.0077 (13)	0.0020 (12)	0.0013 (12)
N10	0.058 (6)	0.026 (4)	0.051 (8)	0.004 (4)	−0.005 (5)	−0.007 (5)
N2	0.0377 (18)	0.0337 (18)	0.0225 (14)	0.0085 (14)	0.0029 (13)	−0.0008 (12)
N3	0.0329 (16)	0.0299 (16)	0.0219 (13)	0.0018 (13)	0.0045 (12)	0.0005 (12)
N4	0.0327 (15)	0.0280 (16)	0.0170 (12)	0.0004 (13)	0.0038 (11)	0.0025 (11)
N5	0.047 (2)	0.048 (2)	0.0287 (16)	0.0075 (17)	0.0081 (15)	0.0032 (15)
N6	0.042 (5)	0.041 (6)	0.018 (4)	0.003 (4)	−0.003 (3)	−0.003 (3)
N7	0.046 (4)	0.034 (2)	0.0199 (19)	0.000 (2)	0.013 (2)	−0.002 (2)
N6'	0.051 (6)	0.030 (5)	0.034 (5)	0.003 (4)	0.009 (4)	0.008 (4)
N7'	0.046 (4)	0.034 (2)	0.0199 (19)	0.000 (2)	0.013 (2)	−0.002 (2)
N8	0.077 (4)	0.026 (3)	0.030 (2)	0	0.013 (2)	0
N9	0.059 (9)	0.030 (3)	0.024 (2)	−0.002 (3)	−0.011 (6)	0.003 (4)
C1	0.0256 (18)	0.040 (2)	0.0178 (15)	0.0086 (16)	0.0039 (13)	0.0015 (14)
C2	0.0289 (19)	0.047 (2)	0.0215 (16)	0.0100 (17)	0.0068 (14)	0.0053 (15)
C3	0.040 (2)	0.047 (2)	0.0320 (19)	0.0116 (19)	0.0015 (17)	0.0159 (17)
C4	0.050 (3)	0.033 (2)	0.037 (2)	0.0067 (19)	−0.0013 (19)	0.0092 (17)
C5	0.046 (2)	0.036 (2)	0.0258 (18)	0.0053 (18)	0.0026 (16)	0.0016 (15)
C6	0.030 (2)	0.059 (3)	0.0176 (16)	0.0094 (18)	0.0041 (14)	0.0062 (16)
C7	0.0246 (17)	0.040 (2)	0.0202 (15)	0.0106 (16)	0.0047 (13)	0.0003 (15)
C8	0.036 (2)	0.044 (2)	0.0221 (16)	0.0108 (17)	0.0086 (15)	−0.0037 (15)
C9	0.041 (2)	0.053 (3)	0.0297 (19)	0.008 (2)	0.0016 (17)	−0.0131 (18)
C10	0.059 (3)	0.039 (2)	0.041 (2)	0.010 (2)	0.003 (2)	−0.0064 (19)
C11	0.054 (3)	0.032 (2)	0.033 (2)	0.0095 (19)	−0.0014 (18)	−0.0014 (16)
C12	0.0321 (19)	0.061 (3)	0.0177 (15)	0.0105 (19)	0.0051 (14)	−0.0018 (17)
C13	0.0331 (19)	0.0252 (18)	0.0164 (14)	0.0010 (15)	0.0008 (13)	−0.0005 (13)
C14	0.039 (2)	0.0250 (18)	0.0190 (15)	0.0028 (16)	−0.0022 (15)	−0.0023 (13)
C15	0.055 (3)	0.026 (2)	0.0234 (17)	−0.0027 (18)	0.0004 (17)	−0.0010 (14)
C16	0.048 (2)	0.035 (2)	0.0256 (18)	−0.0057 (18)	0.0058 (17)	0.0033 (15)
C17	0.038 (2)	0.035 (2)	0.0246 (17)	0.0030 (17)	0.0047 (15)	0.0024 (15)
C18	0.045 (2)	0.0261 (19)	0.0246 (17)	0.0094 (17)	−0.0070 (16)	−0.0033 (14)
C19	0.0320 (19)	0.0264 (18)	0.0150 (14)	0.0034 (15)	−0.0013 (13)	−0.0016 (13)
C20	0.0333 (19)	0.032 (2)	0.0185 (15)	0.0021 (16)	0.0003 (14)	−0.0050 (14)
C21	0.0302 (19)	0.046 (2)	0.0229 (17)	0.0018 (17)	0.0046 (15)	−0.0065 (15)
C22	0.037 (2)	0.042 (2)	0.0244 (17)	−0.0032 (18)	0.0071 (15)	0.0006 (16)
C23	0.034 (2)	0.033 (2)	0.0197 (16)	0.0007 (16)	0.0023 (14)	0.0022 (14)
C24	0.033 (2)	0.037 (2)	0.0257 (17)	0.0119 (17)	−0.0040 (15)	−0.0038 (15)
C25	0.034 (2)	0.039 (2)	0.0228 (17)	−0.0005 (17)	0.0019 (15)	0.0036 (15)
C26	0.034 (5)	0.015 (4)	0.022 (4)	0.009 (4)	0.000 (4)	−0.003 (3)
C27	0.030 (4)	0.025 (4)	0.011 (3)	0.005 (4)	0.013 (3)	0.002 (3)
C28	0.059 (4)	0.034 (3)	0.014 (2)	0	0.002 (2)	0
C26'	0.040 (6)	0.039 (6)	0.026 (5)	−0.007 (5)	−0.008 (4)	0.007 (4)
C27'	0.033 (5)	0.026 (4)	0.020 (4)	−0.003 (4)	0.018 (4)	0.002 (3)
C29	0.061 (6)	0.032 (5)	0.058 (6)	0.014 (4)	−0.015 (5)	−0.004 (4)
C30	0.072 (8)	0.048 (7)	0.047 (7)	−0.015 (6)	−0.007 (6)	−0.008 (5)
C31	0.048 (5)	0.040 (5)	0.034 (4)	0.010 (4)	−0.002 (4)	0.014 (3)

Geometric parameters (Å, º) top

Cu1—C25	1.964 (4)	C6—C12	1.336 (6)
Cu1—N3	2.011 (3)	C6—H6	0.95
Cu1—N1	2.024 (3)	C7—C8	1.399 (5)
Cu1—N4	2.090 (3)	C8—C9	1.403 (6)
Cu1—N2	2.164 (3)	C8—C12	1.449 (5)
Fe1—N9	1.630 (6)	C9—C10	1.367 (6)
Fe1—C27	1.933 (7)	C9—H9	0.95
Fe1—C26'	1.934 (8)	C10—C11	1.394 (5)
Fe1—C27'	1.937 (7)	C10—H10	0.95
Fe1—C26	1.938 (7)	C11—H11	0.95
Fe1—C28	1.959 (6)	C12—H12	0.95
O1—N9	1.161 (7)	C13—C14	1.403 (5)
O2—C31	1.224 (10)	C13—C19	1.434 (5)
N1—C5	1.322 (5)	C14—C15	1.407 (5)
N1—C1	1.355 (4)	C14—C18	1.425 (5)
N10—C31	1.334 (12)	C15—C16	1.373 (6)
N10—C30	1.430 (15)	C15—H15	0.95
N10—C29	1.442 (13)	C16—C17	1.399 (5)
N2—C11	1.321 (5)	C16—H16	0.95
N2—C7	1.360 (4)	C17—H17	0.95
N3—C17	1.326 (5)	C18—C24	1.350 (5)
N3—C13	1.358 (4)	C18—H18	0.95
N4—C23	1.330 (4)	C19—C20	1.402 (5)
N4—C19	1.367 (4)	C20—C21	1.407 (5)
N5—C25	1.158 (5)	C20—C24	1.427 (5)
N6—C26	1.167 (11)	C21—C22	1.371 (5)
N7—C27	1.147 (9)	C21—H21	0.95
N6'—C26'	1.159 (12)	C22—C23	1.390 (5)
N7'—C27'	1.160 (10)	C22—H22	0.95
N8—C28	1.145 (7)	C23—H23	0.95
C1—C2	1.406 (5)	C24—H24	0.95
C1—C7	1.428 (5)	C29—H29A	0.98
C2—C3	1.397 (6)	C29—H29B	0.98
C2—C6	1.431 (5)	C29—H29C	0.98
C3—C4	1.371 (6)	C30—H30A	0.98
C3—H3	0.95	C30—H30B	0.98
C4—C5	1.390 (5)	C30—H30C	0.98
C4—H4	0.95	C31—H31	0.95
C5—H5	0.95

C25—Cu1—N3	95.49 (13)	C8—C7—C1	119.7 (3)
C25—Cu1—N1	92.01 (13)	C7—C8—C9	117.5 (3)
N3—Cu1—N1	171.89 (11)	C7—C8—C12	119.0 (4)
C25—Cu1—N4	142.30 (13)	C9—C8—C12	123.6 (3)
N3—Cu1—N4	80.91 (11)	C10—C9—C8	119.2 (4)
N1—Cu1—N4	95.03 (11)	C10—C9—H9	120.4
C25—Cu1—N2	124.13 (14)	C8—C9—H9	120.4
N3—Cu1—N2	93.50 (11)	C9—C10—C11	119.6 (4)
N1—Cu1—N2	79.68 (12)	C9—C10—H10	120.2
N4—Cu1—N2	93.58 (11)	C11—C10—H10	120.2
N9—Fe1—C27	93.7 (5)	N2—C11—C10	122.9 (4)
N9—Fe1—C26'	96.3 (7)	N2—C11—H11	118.6
C27—Fe1—C26'	91.1 (5)	C10—C11—H11	118.6
N9—Fe1—C27'	96.4 (5)	C6—C12—C8	120.6 (3)
C27—Fe1—C27'	169.4 (3)	C6—C12—H12	119.7
C26'—Fe1—C27'	90.9 (5)	C8—C12—H12	119.7
N9—Fe1—C26	92.7 (6)	N3—C13—C14	123.7 (3)
C27—Fe1—C26	90.1 (4)	N3—C13—C19	116.8 (3)
C26'—Fe1—C26	170.9 (3)	C14—C13—C19	119.5 (3)
C27'—Fe1—C26	86.3 (4)	C13—C14—C15	116.5 (3)
N9—Fe1—C28	177.7 (4)	C13—C14—C18	119.4 (3)
C27—Fe1—C28	87.9 (3)	C15—C14—C18	124.1 (3)
C26'—Fe1—C28	82.1 (5)	C16—C15—C14	119.5 (3)
C27'—Fe1—C28	82.0 (3)	C16—C15—H15	120.3
C26—Fe1—C28	88.9 (4)	C14—C15—H15	120.3
C5—N1—C1	118.7 (3)	C15—C16—C17	120.1 (4)
C5—N1—Cu1	126.3 (2)	C15—C16—H16	120
C1—N1—Cu1	114.8 (2)	C17—C16—H16	120
C31—N10—C30	120.6 (9)	N3—C17—C16	121.9 (4)
C31—N10—C29	118.9 (8)	N3—C17—H17	119
C30—N10—C29	120.4 (8)	C16—C17—H17	119
C11—N2—C7	118.0 (3)	C24—C18—C14	120.8 (3)
C11—N2—Cu1	131.7 (3)	C24—C18—H18	119.6
C7—N2—Cu1	110.2 (2)	C14—C18—H18	119.6
C17—N3—C13	118.3 (3)	N4—C19—C20	123.3 (3)
C17—N3—Cu1	127.5 (3)	N4—C19—C13	116.7 (3)
C13—N3—Cu1	114.1 (2)	C20—C19—C13	120.0 (3)
C23—N4—C19	117.8 (3)	C19—C20—C21	116.6 (3)
C23—N4—Cu1	130.8 (2)	C19—C20—C24	118.8 (3)
C19—N4—Cu1	111.2 (2)	C21—C20—C24	124.6 (3)
O1—N9—Fe1	175.9 (13)	C22—C21—C20	120.1 (4)
N1—C1—C2	122.1 (3)	C22—C21—H21	120
N1—C1—C7	117.7 (3)	C20—C21—H21	120
C2—C1—C7	120.3 (3)	C21—C22—C23	119.4 (3)
C3—C2—C1	117.5 (3)	C21—C22—H22	120.3
C3—C2—C6	124.0 (3)	C23—C22—H22	120.3
C1—C2—C6	118.5 (4)	N4—C23—C22	122.8 (3)
C4—C3—C2	119.9 (4)	N4—C23—H23	118.6
C4—C3—H3	120	C22—C23—H23	118.6
C2—C3—H3	120	C18—C24—C20	121.5 (3)
C3—C4—C5	118.7 (4)	C18—C24—H24	119.2
C3—C4—H4	120.6	C20—C24—H24	119.2
C5—C4—H4	120.6	N5—C25—Cu1	176.4 (3)
N1—C5—C4	123.1 (3)	N7—C27—Fe1	178.2 (9)
N1—C5—H5	118.5	N8—C28—Fe1	174.28 (7)
C4—C5—H5	118.5	N6'—C26'—Fe1	176.9 (14)
C12—C6—C2	121.9 (3)	N7'—C27'—Fe1	178.7 (9)
C12—C6—H6	119	O2—C31—N10	124.4 (9)
C2—C6—H6	119	O2—C31—H31	117.8
N2—C7—C8	122.8 (4)	N10—C31—H31	117.8
N2—C7—C1	117.4 (3)

Experimental details

Crystal data
Chemical formula	[Cu(CN)(C₁₂H₈N₂)₂]₂[Fe(CN)₅(NO)]·C₃H₇NO
M_r	1188.99
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	150
a, b, c (Å)	11.9235 (16), 10.7836 (16), 19.805 (3)
β (°)	97.252 (3)
V (Å³)	2526.1 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.18
Crystal size (mm)	0.26 × 0.21 × 0.07

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.86, 1
No. of measured, independent and observed [I > 2σ(I)] reflections	26129, 5844, 3739
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.653

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.135, 1.04
No. of reflections	5844
No. of parameters	430
No. of restraints	44
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.59

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu1—C25	1.964 (4)	Fe1—C27	1.933 (7)
Cu1—N3	2.011 (3)	Fe1—C26'	1.934 (8)
Cu1—N1	2.024 (3)	Fe1—C27'	1.937 (7)
Cu1—N4	2.090 (3)	Fe1—C26	1.938 (7)
Cu1—N2	2.164 (3)	Fe1—C28	1.959 (6)
Fe1—N9	1.630 (6)

Acknowledgements

The State Fund for Fundamental Researches of Ukraine (Project 28.3/017) is acknowledged for financial support.

References

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