μ-Cyanido-κ(2) C:N-dicyanido-κ(2) C-bis-(N-ethyl-ethylenedi-amine-κ(2) N,N')copper(II)copper(I).

In the title complex, [Cu(I)Cu(II)(CN)3(C4H12N2)2], the Cu(I) and Cu(II) ions and a bridging cyanide group lie on a twofold rotation axis. The Cu(II) ion is in a slightly-distorted square-pyramidal coordination environment, with the N atoms of the two symmetry-related N-ethyl-ethylenedi-amine ligands occupying the basal positions and an N-bonded cyanide group in the apical position. The Cu(I) ion is in a trigonal-planar coordination environment, bonded to the C atom of the bridging cyanide group and to two terminal cyanide groups. In the crystal, N-H⋯N hydrogen bonds involving two of the symmetry-unique N-H groups of the N-ethyl-ethylenedi-amine ligands and the N atoms of the terminal cyanide ligands link the mol-ecules into strands along [010].

Related literature

The title compound was synthesized as part of our continuing study of structural motifs in mixed-valence copper cyanide complexes containing amine ligands. For descriptions of similar discrete mol­ecular copper cyanide complexes, see: Corfield et al. (2012 ▶); Pretsch et al. (2005 ▶); Pickardt et al. (1999 ▶); Yuge et al. (1998 ▶). For mixed-valence copper cyanide complexes crystallizing as self-assembled polymeric networks, from preparations similar to those used in the present work, see: Williams et al. (1972 ▶); Colacio et al. (2002 ▶); Kim et al. (2005 ▶), and also Corfield & Yang (2012 ▶), although this last one involves only CuII ions.

Experimental

Crystal data

[Cu2(CN)3(C4H12N2)2]

M = 381.45

Monoclinic,

a = 11.425 (1) Å

b = 9.679 (2) Å

c = 15.205 (3) Å

β = 91.52 (1)°

V = 1680.8 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.53 mm−1

T = 301 K

0.33 × 0.30 × 0.30 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: integration (Busing & Levy, 1957 ▶) T min = 0.529, T max = 0.587

3737 measured reflections

1835 independent reflections

1674 reflections with I > 2σ(I)

R int = 0.020

3 standard reflections every 120 min intensity decay: 2.3 (6)%

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.062

S = 1.06

1835 reflections

103 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.25 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1994) ▶; cell refinement: CAD-4 Software; data reduction: data reduction followed procedures in Corfield et al. (1973 ▶); data were averaged with a local version of SORTAV (Blessing, 1989 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) meed, I. DOI: 10.1107/S160053681400172X/lh5680sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681400172X/lh5680Isup2.hkl

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu2(CN)3(C4H12N2)2]	F(000) = 788
Mr = 381.45	Dx = 1.507 Mg m−3Dm = 1.497 (2) Mg m−3Dm measured by Flotation in 1,2-dibromopropane/toluene mixtures. Four independent determinations were made. The observed density measurements were systematically 0.7% low, perhaps due to the presence of occlusions in crystals that were large enough to use for density measurements.
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
a = 11.425 (1) Å	Cell parameters from 25 reflections
b = 9.679 (2) Å	θ = 5.0–19.1°
c = 15.205 (3) Å	µ = 2.53 mm−1
β = 91.52 (1)°	T = 301 K
V = 1680.8 (5) Å3	Block, dark blue
Z = 4	0.33 × 0.30 × 0.30 mm

Enraf–Nonius CAD-4 diffractometer	1674 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 27.0°, θmin = 2.7°
θ/2θ scans	h = −14→14
Absorption correction: integration (Busing & Levy, 1957)	k = −1→12
Tmin = 0.529, Tmax = 0.587	l = −19→19
3737 measured reflections	3 standard reflections every 120 min
1835 independent reflections	intensity decay: 2.3(6)

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.020	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.062	w = 1/[σ2(Fo2) + (0.P)2 + 0.250P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
1835 reflections	Δρmax = 0.22 e Å−3
103 parameters	Δρmin = −0.25 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0078 (4)

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
Cu1	0.5000	−0.29790 (3)	0.2500	0.04340 (12)
Cu2	0.5000	0.24064 (2)	0.2500	0.03031 (11)
C1	0.5000	−0.0984 (3)	0.2500	0.0443 (5)
N1	0.5000	0.0193 (2)	0.2500	0.0501 (5)
C2	0.39932 (15)	−0.40213 (16)	0.32653 (12)	0.0440 (4)
N2	0.34282 (16)	−0.46675 (16)	0.37112 (13)	0.0575 (5)
N3	0.67206 (12)	0.29094 (15)	0.27009 (10)	0.0403 (3)
H3A	0.7170	0.2149	0.2662	0.048*
H3B	0.697 (2)	0.341 (2)	0.2337 (15)	0.061 (7)*
C4	0.68534 (15)	0.35226 (19)	0.35844 (12)	0.0473 (4)
H4A	0.6590	0.4475	0.3574	0.071*
H4B	0.7669	0.3505	0.3778	0.071*
C5	0.61299 (16)	0.2693 (2)	0.41977 (11)	0.0472 (4)
H5A	0.6443	0.1765	0.4254	0.071*
H5B	0.6142	0.3117	0.4776	0.071*
N6	0.49168 (12)	0.26432 (15)	0.38337 (9)	0.0364 (3)
H6	0.4663 (16)	0.342 (2)	0.3875 (12)	0.037 (5)*
C7	0.41570 (17)	0.1642 (2)	0.42882 (12)	0.0498 (4)
H7A	0.4491	0.0726	0.4232	0.075*
H7B	0.3394	0.1633	0.3993	0.075*
C8	0.3996 (2)	0.1943 (3)	0.52557 (13)	0.0670 (6)
H8A	0.4727	0.1814	0.5571	0.101*
H8B	0.3420	0.1326	0.5484	0.101*
H8C	0.3738	0.2880	0.5325	0.101*

	U11	U22	U33	U12	U13	U23
Cu1	0.05315 (19)	0.02439 (17)	0.05233 (19)	0.000	−0.00472 (13)	0.000
Cu2	0.03423 (15)	0.02483 (16)	0.03163 (15)	0.000	−0.00377 (10)	0.000
C1	0.0654 (15)	0.0304 (12)	0.0371 (11)	0.000	0.0031 (10)	0.000
N1	0.0788 (16)	0.0256 (10)	0.0459 (12)	0.000	0.0021 (11)	0.000
C2	0.0481 (9)	0.0245 (7)	0.0590 (10)	0.0064 (6)	−0.0022 (8)	−0.0026 (7)
N2	0.0607 (10)	0.0387 (9)	0.0736 (12)	0.0045 (7)	0.0129 (9)	0.0000 (7)
N3	0.0357 (7)	0.0411 (8)	0.0437 (8)	0.0017 (5)	−0.0054 (6)	0.0045 (6)
C4	0.0412 (8)	0.0456 (10)	0.0543 (10)	−0.0025 (7)	−0.0134 (7)	−0.0085 (7)
C5	0.0468 (10)	0.0560 (10)	0.0381 (8)	0.0080 (8)	−0.0121 (7)	−0.0049 (7)
N6	0.0409 (7)	0.0319 (7)	0.0361 (7)	0.0072 (5)	−0.0033 (5)	−0.0012 (5)
C7	0.0598 (11)	0.0481 (10)	0.0418 (9)	−0.0038 (8)	0.0055 (8)	0.0033 (8)
C8	0.0762 (14)	0.0834 (17)	0.0418 (11)	0.0022 (12)	0.0074 (10)	0.0042 (10)

Cu1—C1	1.931 (3)	C4—H4A	0.9700
Cu1—C2i	1.9406 (18)	C4—H4B	0.9700
Cu1—C2	1.9406 (18)	C5—N6	1.479 (2)
Cu2—N3	2.0403 (14)	C5—H5A	0.9700
Cu2—N3i	2.0403 (14)	C5—H5B	0.9700
Cu2—N6	2.0456 (14)	N6—C7	1.484 (2)
Cu2—N6i	2.0456 (14)	N6—H6	0.81 (2)
Cu2—N1	2.142 (2)	C7—C8	1.516 (3)
C1—N1	1.139 (4)	C7—H7A	0.9700
C2—N2	1.136 (2)	C7—H7B	0.9700
N3—C4	1.473 (2)	C8—H8A	0.9600
N3—H3A	0.9000	C8—H8B	0.9600
N3—H3B	0.79 (2)	C8—H8C	0.9600
C4—C5	1.496 (3)
C1—Cu1—C2i	121.32 (5)	C5—C4—H4B	110.1
C1—Cu1—C2	121.32 (5)	H4A—C4—H4B	108.4
C2i—Cu1—C2	117.35 (9)	N6—C5—C4	108.17 (14)
N3—Cu2—N3i	152.39 (8)	N6—C5—H5A	110.1
N3—Cu2—N6	83.96 (6)	C4—C5—H5A	110.1
N3i—Cu2—N6	92.97 (6)	N6—C5—H5B	110.1
N3—Cu2—N6i	92.97 (6)	C4—C5—H5B	110.1
N3i—Cu2—N6i	83.96 (6)	H5A—C5—H5B	108.4
N6—Cu2—N6i	167.13 (8)	C5—N6—C7	113.62 (14)
N3—Cu2—N1	103.81 (4)	C5—N6—Cu2	107.86 (10)
N3i—Cu2—N1	103.81 (4)	C7—N6—Cu2	115.57 (11)
N6—Cu2—N1	96.43 (4)	C5—N6—H6	106.0 (13)
N6i—Cu2—N1	96.43 (4)	C7—N6—H6	110.8 (13)
N1—C1—Cu1	180.0	Cu2—N6—H6	102.0 (13)
C1—N1—Cu2	180.0	N6—C7—C8	114.45 (17)
N2—C2—Cu1	177.74 (15)	N6—C7—H7A	108.6
C4—N3—Cu2	107.96 (10)	C8—C7—H7A	108.6
C4—N3—H3A	110.1	N6—C7—H7B	108.6
Cu2—N3—H3A	110.1	C8—C7—H7B	108.6
C4—N3—H3B	111.2 (17)	H7A—C7—H7B	107.6
Cu2—N3—H3B	114.1 (18)	C7—C8—H8A	109.5
H3A—N3—H3B	103.4	C7—C8—H8B	109.5
N3—C4—C5	107.87 (14)	H8A—C8—H8B	109.5
N3—C4—H4A	110.1	C7—C8—H8C	109.5
C5—C4—H4A	110.1	H8A—C8—H8C	109.5
N3—C4—H4B	110.1	H8B—C8—H8C	109.5
N3—C4—C5—N6	−54.69 (18)	C5—N6—C7—C8	61.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···N2ii	0.79 (2)	2.49 (2)	3.181 (2)	147 (2)
N6—H6···N2iii	0.81 (2)	2.34 (2)	3.112 (2)	160.9 (17)

Table 1

Selected bond lengths (Å)

Cu1—C1	1.931 (3)
Cu1—C2	1.9406 (18)
Cu2—N3	2.0403 (14)
Cu2—N6	2.0456 (14)
Cu2—N1	2.142 (2)
C1—N1	1.139 (4)
C2—N2	1.136 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯N2i	0.79 (2)	2.49 (2)	3.181 (2)	147 (2)
N6—H6⋯N2ii	0.81 (2)	2.34 (2)	3.112 (2)	160.9 (17)

Symmetry codes: (i) ; (ii) .