Sodium bis-(ethyl-enedi-amine)-copper(II) tetra-cyanido-cuprate(I).

The title compound, Na[Cu(en)2][Cu(CN)4], where en represents ethyl-enedi-amine, NH2CH2CH2NH2, crystallizes as a salt with two distinct cations, Na(+) and [Cu(II)en2](2+), and discrete [Cu(I)(CN)4](3-) anions. The anion geometry is tetra-hedral, with angles at the copper atom ranging from 105.0 (1) to 115.4 (1)°. The Cu-C distances are in the range 1.976 (3) to 1.993 (3) Å. The divalent copper atom is coordinated by four N atoms of the two bidentate en ligands in a slightly distorted square-planar geometry. In the crystal, each sodium ion inter-acts with cyanide N atoms of four different anions, with Na-N distances lying in the narrow range of 2.344 (3) to 2.367 (3) Å, and an approximately tetra-hedral arrangement around the sodium ions. The inter-acting sodium ions and [Cu(I)(CN)4](3-) anions form a three-dimensional network with channels which contain the [Cu(en)2](2+) cations. One of the chelate rings in the cation shows partial disorder between two different conformations and the C atoms were refined with occupancies in the ratio 0.817 (15):0.183 (15).

Related literature

The work presented here continues studies on mixed-valence copper cyanide complexes, see: Corfield et al. (2012 ▶). Studies by others on similar complexes include Colacio et al. (2002 ▶) and Kim et al. (2005 ▶). For other results on the specific system CuI,II—CN—en, see: Williams et al. (1972 ▶) and Weiss et al. (2006 ▶). We are aware of only one other detailed crystal structure describing the discrete [Cu(CN)4]3− anion, that reported for K3Cu(CN)4 in Roof et al. (1968 ▶). For molar conductance, see: Angelici (1977 ▶).

Experimental

Crystal data

Na[Cu(C2H8N2)2][Cu(CN)4]

M = 374.36

Monoclinic,

a = 8.842 (1) Å

b = 10.743 (1) Å

c = 15.268 (3) Å

β = 98.32 (1)°

V = 1435.0 (4) Å3

Z = 4

Cu Kα radiation

μ = 3.94 mm−1

T = 295 K

0.33 × 0.27 × 0.16 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: integration Busing & Levy (1957 ▶) T min = 0.361, T max = 0.576

5288 measured reflections

2679 independent reflections

2614 reflections with I > 2σ(I)

R int = 0.024

3 standard reflections every 120 min intensity decay: 11%

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.087

S = 1.19

2679 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.20 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 Software; 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: locally modified program (Corfield, 1984 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and XABS2 (Parkin et al., 1995 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813012075/lh5608sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012075/lh5608Isup2.hkl

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

Na[Cu(C2H8N2)2][Cu(CN)4]	F(000) = 756
Mr = 374.36	Dx = 1.733 Mg m−3Dm = 1.732 (3) Mg m−3Dm measured by flotation in 1-bromobutane/1,1,4,4-tetrabutane mixtures. Four independent determinations were made.
Monoclinic, P21/c	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.842 (1) Å	θ = 2.7–24.2°
b = 10.743 (1) Å	µ = 3.94 mm−1
c = 15.268 (3) Å	T = 295 K
β = 98.32 (1)°	Block, dark blue
V = 1435.0 (4) Å3	0.33 × 0.27 × 0.16 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	2614 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 70.2°, θmin = 5.1°
θ/2θ scans	h = −10→10
Absorption correction: integration Busing & Levy (1957)	k = 0→11
Tmin = 0.361, Tmax = 0.576	l = 0→18
5288 measured reflections	3 standard reflections every 120 min
2679 independent reflections	intensity decay: 11%

Refinement on F2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.19	w = 1/[σ2(Fo2) + (0.P)2 + 1.160P] where P = (Fo2 + 2Fc2)/3
2679 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Experimental. Diffraction data were collected with Cu Kα radiation. At a later stage, Mo Kα radiation was used in measurements made to obtain improved unit-cell dimensions. Each of the 25 reflections used for cell measurement was determined in four different orientations using the CAD4 SET4 command.

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.

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)
Cu1	0.71472 (4)	−0.04991 (3)	0.31263 (2)	0.03584 (13)
Cu2	0.24744 (4)	0.07238 (3)	0.27612 (2)	0.03475 (13)
Na	0.22615 (12)	−0.26385 (10)	0.40880 (7)	0.0409 (2)
N1	0.9771 (3)	−0.2440 (3)	0.3300 (2)	0.0638 (8)
C1	0.8783 (3)	−0.1771 (2)	0.32825 (17)	0.0371 (5)
N2	0.3881 (3)	−0.1387 (3)	0.33609 (18)	0.0526 (6)
C2	0.5099 (3)	−0.1134 (2)	0.32682 (16)	0.0353 (5)
N3	0.7238 (4)	0.0236 (3)	0.11626 (17)	0.0588 (7)
C3	0.7155 (3)	0.0020 (2)	0.18738 (18)	0.0384 (6)
N4	0.7729 (3)	0.1558 (3)	0.4577 (2)	0.0632 (7)
C4	0.7567 (3)	0.0847 (3)	0.4020 (2)	0.0435 (6)
N5	0.3599 (3)	0.0853 (2)	0.17195 (15)	0.0401 (5)
H5A	0.3405	0.1593	0.1451	0.048*
H5B	0.4612	0.0797	0.1899	0.048*
C6	0.3095 (6)	−0.0168 (5)	0.1094 (3)	0.0489 (14)	0.817 (15)
H6A	0.3605	−0.0937	0.1296	0.073*	0.817 (15)
H6B	0.3348	0.0027	0.0512	0.073*	0.817 (15)
C7	0.1402 (6)	−0.0307 (5)	0.1052 (3)	0.0508 (13)	0.817 (15)
H7A	0.0884	0.0403	0.0752	0.076*	0.817 (15)
H7B	0.1057	−0.1054	0.0726	0.076*	0.817 (15)
C6A	0.257 (3)	0.034 (2)	0.0970 (12)	0.047 (5)*	0.183 (15)
H6A1	0.3137	0.0120	0.0496	0.070*	0.183 (15)
H6A2	0.1804	0.0958	0.0747	0.070*	0.183 (15)
C7A	0.181 (3)	−0.077 (3)	0.1271 (17)	0.055 (6)*	0.183 (15)
H7A1	0.1095	−0.1110	0.0791	0.083*	0.183 (15)
H7A2	0.2567	−0.1401	0.1472	0.083*	0.183 (15)
N8	0.1045 (3)	−0.0388 (2)	0.19709 (16)	0.0446 (5)
H8A	0.1150	−0.1179	0.2164	0.053*
H8B	0.0072	−0.0151	0.1984	0.053*
N9	0.1297 (3)	0.0750 (2)	0.37895 (17)	0.0469 (6)
H9A	0.0287	0.0782	0.3595	0.056*
H9B	0.1493	0.0057	0.4118	0.056*
C10	0.1775 (4)	0.1856 (3)	0.4322 (2)	0.0555 (8)
H10A	0.1477	0.1779	0.4906	0.083*
H10B	0.1295	0.2595	0.4041	0.083*
C11	0.3480 (4)	0.1955 (3)	0.43916 (19)	0.0552 (8)
H11A	0.3830	0.2729	0.4678	0.083*
H11B	0.3963	0.1270	0.4740	0.083*
N12	0.3880 (3)	0.1914 (2)	0.34902 (14)	0.0396 (5)
H12A	0.4855	0.1663	0.3508	0.048*
H12B	0.3789	0.2677	0.3246	0.048*

	U11	U22	U33	U12	U13	U23
Cu1	0.0382 (2)	0.0338 (2)	0.0355 (2)	−0.00035 (15)	0.00530 (16)	−0.00042 (14)
Cu2	0.0366 (2)	0.0353 (2)	0.0331 (2)	−0.00367 (14)	0.00756 (15)	−0.00332 (14)
Na	0.0462 (6)	0.0331 (5)	0.0447 (6)	−0.0020 (4)	0.0107 (4)	−0.0033 (4)
N1	0.0515 (15)	0.0500 (16)	0.091 (2)	0.0087 (13)	0.0137 (14)	0.0131 (15)
C1	0.0375 (13)	0.0344 (14)	0.0385 (13)	−0.0029 (11)	0.0020 (10)	0.0027 (10)
N2	0.0444 (14)	0.0560 (16)	0.0578 (15)	−0.0038 (12)	0.0089 (11)	0.0106 (12)
C2	0.0429 (14)	0.0289 (13)	0.0335 (12)	0.0004 (10)	0.0038 (10)	0.0037 (10)
N3	0.084 (2)	0.0511 (16)	0.0416 (14)	−0.0138 (14)	0.0114 (13)	0.0056 (12)
C3	0.0405 (13)	0.0319 (13)	0.0430 (14)	−0.0007 (11)	0.0062 (11)	0.0026 (11)
N4	0.0684 (18)	0.0588 (18)	0.0638 (17)	−0.0049 (14)	0.0139 (14)	−0.0237 (15)
C4	0.0415 (14)	0.0421 (15)	0.0470 (15)	0.0001 (12)	0.0070 (12)	−0.0039 (12)
N5	0.0438 (12)	0.0387 (12)	0.0395 (11)	0.0005 (9)	0.0112 (9)	0.0028 (9)
C6	0.058 (3)	0.055 (3)	0.0351 (18)	0.003 (2)	0.0101 (16)	−0.0093 (17)
C7	0.059 (2)	0.051 (3)	0.039 (2)	0.000 (2)	−0.0056 (17)	−0.0091 (18)
N8	0.0418 (12)	0.0447 (13)	0.0452 (13)	−0.0075 (10)	−0.0003 (10)	0.0018 (10)
N9	0.0525 (14)	0.0448 (14)	0.0472 (13)	0.0005 (11)	0.0199 (11)	0.0014 (10)
C10	0.077 (2)	0.0510 (18)	0.0426 (15)	0.0078 (16)	0.0224 (15)	−0.0060 (13)
C11	0.077 (2)	0.0523 (18)	0.0336 (14)	−0.0028 (16)	−0.0017 (13)	−0.0027 (13)
N12	0.0427 (12)	0.0343 (12)	0.0404 (11)	−0.0002 (9)	0.0018 (9)	−0.0001 (9)

Cu1—C1	1.979 (3)	C7—N8	1.484 (5)
Cu1—C2	1.976 (3)	C7—H7A	0.9700
Cu1—C3	1.993 (3)	C7—H7B	0.9700
Cu1—C4	1.986 (3)	C6A—C7A	1.47 (3)
Cu2—N5	1.999 (2)	C6A—H6A1	0.9700
Cu2—N8	2.009 (2)	C6A—H6A2	0.9700
Cu2—N9	2.005 (2)	C7A—N8	1.41 (2)
Cu2—N12	2.004 (2)	C7A—H7A1	0.9700
C1—N1	1.129 (4)	C7A—H7A2	0.9700
C2—N2	1.139 (4)	N8—H8A	0.9000
C3—N3	1.123 (4)	N8—H8B	0.9000
C4—N4	1.138 (4)	N9—C10	1.467 (4)
Na—N1i	2.361 (3)	N9—H9A	0.9000
Na—N2	2.356 (3)	N9—H9B	0.9000
Na—N3ii	2.367 (3)	C10—C11	1.499 (5)
Na—N4iii	2.344 (3)	C10—H10A	0.9700
N5—C6A	1.464 (18)	C10—H10B	0.9700
N5—C6	1.480 (5)	C11—N12	1.470 (4)
N5—H5A	0.9000	C11—H11A	0.9700
N5—H5B	0.9000	C11—H11B	0.9700
C6—C7	1.497 (7)	N12—H12A	0.9000
C6—H6A	0.9700	N12—H12B	0.9000
C6—H6B	0.9700
C1—Cu1—C2	114.43 (10)	H6A1—C6A—H6A2	108.3
C1—Cu1—C3	101.82 (11)	C6—C7—N8	108.3 (4)
C1—Cu1—C4	111.06 (11)	C6A—C7A—N8	107 (2)
C2—Cu1—C3	109.40 (10)	C6—C7—H7A	110.0
C2—Cu1—C4	105.04 (11)	C6—C7—H7B	110.0
C3—Cu1—C4	115.42 (12)	C6A—C7A—H7A1	110.3
N5—Cu2—N9	175.03 (10)	C6A—C7A—H7A2	110.3
N5—Cu2—N12	93.29 (9)	N8—C7—H7A	110.0
N9—Cu2—N12	84.65 (10)	N8—C7—H7B	110.0
N5—Cu2—N8	84.59 (10)	N8—C7A—H7A1	110.3
N9—Cu2—N8	97.23 (11)	N8—C7A—H7A2	110.3
N12—Cu2—N8	176.43 (10)	H7A—C7—H7B	108.4
N1i—Na—N2	107.11 (10)	H7A1—C7A—H7A2	108.6
N1i—Na—N3ii	100.77 (11)	C7—N8—Cu2	109.4 (2)
N1i—Na—N4iii	106.49 (12)	C7A—N8—Cu2	107.3 (10)
N2—Na—N3ii	109.50 (11)	C7—N8—H8A	109.8
N2—Na—N4iii	101.61 (11)	C7—N8—H8B	109.8
N3ii—Na—N4iii	129.84 (11)	C7A—N8—H8A	86.4
Cu1—C1—N1	172.9 (3)	C7A—N8—H8B	131.8
Cu1—C2—N2	173.5 (3)	Cu2—N8—H8A	109.8
Cu1—C3—N3	174.5 (3)	Cu2—N8—H8B	109.8
Cu1—C4—N4	173.8 (3)	H8A—N8—H8B	108.3
C1—N1—Naiv	137.0 (3)	Cu2—N9—C10	107.72 (18)
C2—N2—Na	147.6 (2)	Cu2—N9—H9A	110.2
C3—N3—Nav	113.3 (2)	Cu2—N9—H9B	110.2
C4—N4—Naiii	165.3 (3)	C10—N9—H9A	110.2
Cu2—N5—C6	108.9 (2)	C10—N9—H9B	110.2
Cu2—N5—C6A	105.6 (8)	H9A—N9—H9B	108.5
C6—N5—H5A	109.9	N9—C10—C11	107.6 (3)
C6—N5—H5B	109.9	N9—C10—H10A	110.2
C6A—N5—H5A	85.3	N9—C10—H10B	110.2
C6A—N5—H5B	134.0	C11—C10—H10A	110.2
Cu2—N5—H5A	109.9	C11—C10—H10B	110.2
Cu2—N5—H5B	109.9	H10A—C10—H10B	108.5
H5A—N5—H5B	108.3	C10—C11—N12	107.9 (2)
N5—C6—C7	107.9 (4)	C10—C11—H11A	110.1
N5—C6A—C7A	108.6 (19)	C10—C11—H11B	110.1
N5—C6—H6A	110.1	N12—C11—H11A	110.1
N5—C6—H6B	110.1	N12—C11—H11B	110.1
N5—C6A—H6A1	110.0	H11A—C11—H11B	108.4
N5—C6A—H6A2	110.0	C11—N12—Cu2	108.96 (18)
C7—C6—H6A	110.1	C11—N12—H12A	109.9
C7—C6—H6B	110.1	C11—N12—H12B	109.9
C7A—C6A—H6A1	110.0	Cu2—N12—H12A	109.9
C7A—C6A—H6A2	110.0	Cu2—N12—H12B	109.9
H6A—C6—H6B	108.4	H12A—N12—H12B	108.3
N5—C6—C7—N8	−50.3 (6)	N9—C10—C11—N12	53.0 (3)
N5—C6A—C7A—N8	58 (3)