[(Triethyl-ene-tetra-mine)copper(II)]-μ-cyanido-κ(2) N:C-[bis(cyanido-κC)copper(I)].

The title compound, [Cu2(CN)3(C6H18N4)] or [Cu(trien)(CN)Cu(CN)2], where trien is triethyl-ene-tetra-mine, is a mixed-valence complex crystallizing as discrete mol-ecules, with Cu(I) and Cu(II) ions linked by a bridging cyanide group. The Cu(II) ion is in a square-pyramidal coordination environment, with the N atoms of the tetra-dentate trien ligand occupying the basal positions and Cu-N bond lengths in the range 2.028 (4)-2.047 (4) Å. An N-bonded cyanide group is in the apical position, with a slightly longer Cu-N bond length of 2.127 (4) Å. The Cu(I) ion exhibits a trigonal-planar coordination geometry, bonded to the C atoms of the bridging cyanide group and two terminal cyanide groups with Cu-C bond lengths in the range 1.925 (4)-1.948 (5) Å. In the crystal, hydrogen bonding involving the tertiary N-H groups of the trien ligand and N atoms of symmetry-related terminal cyanide groups links mol-ecules into a ribbon extending in the b-axis direction.

Related literature

For mixed-valence copper cyanide complexes crystallizing as one- two- and three-dimensional self-assembled polymeric networks involving cyanide groups bridging copper atoms, see: Williams et al. (1972 ▶); Colacio et al. (2002 ▶); Kim et al. (2005 ▶). For discrete mol­ecules containing terminal cyanide groups which are not involved in any covalent polymeric linkages, see: Yuge et al. (1998 ▶); Pickardt et al. (1999 ▶); Pretsch et al. (2005 ▶). For the structure of a related one-dimensional polymer, see: Corfield & Yang (2012 ▶). For cyanide analysis, see: Cooper & Plane (1966 ▶).

Experimental

Crystal data

[Cu2(CN)3(C6H18N4)]

M = 351.38

Triclinic,

a = 7.363 (3) Å

b = 8.741 (6) Å

c = 11.492 (6) Å

α = 77.84 (3)°

β = 73.78 (3)°

γ = 83.18 (3)°

V = 692.8 (7) Å3

Z = 2

Cu Kα radiation

μ = 3.75 mm−1

T = 295 K

0.7 × 0.2 × 0.1 mm

Data collection

GE 1/4 circle manual diffractometer

Absorption correction: integration (Busing & Levy, 1957 ▶) T min = 0.515, T max = 0.746

2734 measured reflections

2060 independent reflections

1975 reflections with I > 2σ(I)

R int = 0.042

θmax = 60.0°

3 standard reflections every 22 reflections intensity decay: 0.2 (2)%

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.120

S = 1.16

2060 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.56 e Å−3

Data collection: locally modified program (Corfield, 1984 ▶); cell refinements and data reduction followed procedures described by Corfield et al. (1973 ▶); data were averaged with 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) I, global. DOI: 10.1107/S1600536812047745/lh5552sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047745/lh5552Isup2.hkl

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

[Cu2(CN)3(C6H18N4)]	Z = 2
Mr = 351.38	F(000) = 358
Triclinic, P1	Dx = 1.684 Mg m−3Dm = 1.684 (2) Mg m−3Dm measured by flotation in 1,2-dibromoethane/carbon tetrachloride mixtures
Hall symbol: -P 1	Cu Kα radiation, λ = 1.5418 Å
a = 7.363 (3) Å	Cell parameters from 16 reflections
b = 8.741 (6) Å	θ = 23.5–41°
c = 11.492 (6) Å	µ = 3.75 mm−1
α = 77.84 (3)°	T = 295 K
β = 73.78 (3)°	Diamond plate, blue
γ = 83.18 (3)°	0.7 × 0.2 × 0.1 mm
V = 692.8 (7) Å3

GE 1/4 circle manual diffractometer	1975 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.042
None monochromator	θmax = 60.0°, θmin = 4.1°
θ/2θ scans	h = −8→8
Absorption correction: integration (Busing & Levy, 1957)	k = 0→9
Tmin = 0.515, Tmax = 0.746	l = −12→12
2734 measured reflections	3 standard reflections every 22 reflections
2060 independent reflections	intensity decay: 0.2(2)

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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F2) = 0.120	H-atom parameters constrained
S = 1.16	w = 1/[σ2(Fo2) + (0.035P)2 + 1.1P] where P = (Fo2 + 2Fc2)/3
2060 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.56 e Å−3

Experimental. crystal A: 2θ 0–35°; 32–50°; 47–79°. small crystal, showing visible decomposition after data collection, with 13% loss of intensities; no absorption correction. crystal B: 2θ 0–40°; 65–90°; 86–120°. larger crystal, mounted in capillary tube; no fall-off of intensities of standard reflections, but intensities fluctuated with an e.s.d. of 3%.

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	0.40015 (8)	0.09959 (7)	0.66481 (5)	0.0371 (2)
Cu2	0.09442 (7)	0.23562 (6)	0.29634 (5)	0.0288 (2)
N1	0.2352 (5)	0.1692 (4)	0.4395 (3)	0.0419 (9)
C1	0.2989 (6)	0.1424 (5)	0.5210 (4)	0.0361 (9)
N2	0.6787 (7)	0.3236 (5)	0.6847 (4)	0.0591 (11)
C2	0.5694 (6)	0.2419 (5)	0.6797 (4)	0.0367 (9)
N3	0.2855 (6)	−0.1824 (5)	0.8742 (4)	0.0518 (10)
C3	0.3224 (6)	−0.0759 (5)	0.7997 (4)	0.0375 (9)
N4	−0.1840 (5)	0.2330 (4)	0.3945 (3)	0.0388 (8)
H4A	−0.2410	0.1593	0.3758	0.047*
H4B	−0.1926	0.2104	0.4759	0.047*
C5	−0.2766 (6)	0.3882 (5)	0.3625 (4)	0.0442 (10)
H5A	−0.3962	0.4010	0.4231	0.066*
H5B	−0.3011	0.4006	0.2823	0.066*
C6	−0.1434 (7)	0.5083 (6)	0.3605 (5)	0.0487 (11)
H6A	−0.1897	0.6119	0.3264	0.073*
H6B	−0.1388	0.5085	0.4440	0.073*
N7	0.0470 (5)	0.4715 (4)	0.2857 (3)	0.0390 (8)
H7	0.1343	0.5080	0.3138	0.047*
C8	0.0793 (7)	0.5320 (6)	0.1524 (5)	0.0511 (12)
H8A	0.0739	0.6457	0.1359	0.077*
H8B	−0.0171	0.4986	0.1220	0.077*
C9	0.2683 (7)	0.4689 (7)	0.0909 (5)	0.0579 (13)
H9A	0.3649	0.5165	0.1115	0.087*
H9B	0.2873	0.4950	0.0022	0.087*
N10	0.2870 (5)	0.2968 (5)	0.1299 (3)	0.0438 (9)
H10	0.4064	0.2669	0.1376	0.053*
C11	0.2395 (8)	0.2055 (7)	0.0501 (4)	0.0581 (13)
H11A	0.3345	0.2151	−0.0285	0.087*
H11B	0.1175	0.2438	0.0349	0.087*
C12	0.2329 (9)	0.0378 (7)	0.1147 (5)	0.0619 (15)
H12A	0.1878	−0.0240	0.0688	0.093*
H12B	0.3590	−0.0042	0.1199	0.093*
N13	0.1033 (5)	0.0289 (4)	0.2408 (3)	0.0412 (8)
H13A	0.1450	−0.0496	0.2934	0.049*
H13B	−0.0137	0.0092	0.2402	0.049*

	U11	U22	U33	U12	U13	U23
Cu1	0.0395 (4)	0.0409 (4)	0.0366 (4)	−0.0088 (3)	−0.0201 (3)	−0.0029 (3)
Cu2	0.0309 (3)	0.0298 (3)	0.0279 (3)	−0.0016 (2)	−0.0120 (2)	−0.0049 (2)
N1	0.052 (2)	0.040 (2)	0.041 (2)	−0.0007 (16)	−0.0275 (18)	−0.0062 (16)
C1	0.047 (2)	0.028 (2)	0.039 (2)	−0.0068 (17)	−0.020 (2)	−0.0054 (17)
N2	0.064 (3)	0.057 (3)	0.068 (3)	−0.017 (2)	−0.030 (2)	−0.011 (2)
C2	0.040 (2)	0.038 (2)	0.036 (2)	−0.0038 (19)	−0.0168 (18)	−0.0039 (17)
N3	0.054 (2)	0.057 (3)	0.044 (2)	−0.009 (2)	−0.0183 (18)	0.004 (2)
C3	0.034 (2)	0.046 (2)	0.038 (2)	−0.0031 (18)	−0.0189 (18)	−0.007 (2)
N4	0.0410 (19)	0.0398 (19)	0.0367 (18)	−0.0065 (15)	−0.0072 (15)	−0.0113 (15)
C5	0.033 (2)	0.050 (3)	0.050 (3)	0.0004 (19)	−0.0089 (19)	−0.015 (2)
C6	0.050 (3)	0.043 (3)	0.058 (3)	0.007 (2)	−0.017 (2)	−0.020 (2)
N7	0.044 (2)	0.0341 (18)	0.045 (2)	−0.0091 (15)	−0.0206 (16)	−0.0046 (15)
C8	0.062 (3)	0.039 (2)	0.053 (3)	−0.007 (2)	−0.026 (2)	0.009 (2)
C9	0.050 (3)	0.068 (3)	0.047 (3)	−0.023 (2)	−0.009 (2)	0.012 (2)
N10	0.0299 (17)	0.060 (2)	0.0361 (19)	0.0003 (16)	−0.0094 (14)	0.0017 (17)
C11	0.063 (3)	0.077 (4)	0.033 (2)	0.006 (3)	−0.013 (2)	−0.013 (2)
C12	0.082 (4)	0.063 (3)	0.049 (3)	0.025 (3)	−0.028 (3)	−0.032 (3)
N13	0.0366 (18)	0.041 (2)	0.052 (2)	0.0040 (15)	−0.0192 (16)	−0.0150 (17)

Cu1—C1	1.947 (4)	C6—H6B	0.9700
Cu1—C2	1.925 (4)	N7—C8	1.472 (6)
Cu1—C3	1.948 (5)	N7—H7	0.9100
Cu2—N1	2.127 (4)	C8—C9	1.474 (8)
Cu2—N4	2.045 (4)	C8—H8A	0.9700
Cu2—N7	2.034 (4)	C8—H8B	0.9700
Cu2—N10	2.047 (4)	C9—N10	1.478 (7)
Cu2—N13	2.028 (4)	C9—H9A	0.9700
C1—N1	1.131 (6)	C9—H9B	0.9700
C2—N2	1.158 (6)	N10—C11	1.468 (7)
C3—N3	1.126 (6)	N10—H10	0.9100
N4—C5	1.467 (6)	C11—C12	1.497 (8)
N4—H4A	0.9000	C11—H11A	0.9700
N4—H4B	0.9000	C11—H11B	0.9700
C5—C6	1.511 (7)	C12—N13	1.488 (6)
C5—H5A	0.9700	C12—H12A	0.9700
C5—H5B	0.9700	C12—H12B	0.9700
C6—N7	1.464 (6)	N13—H13A	0.9000
C6—H6A	0.9700	N13—H13B	0.9000
C1—Cu1—C2	119.26 (17)	C8—N7—H7	109.4
C2—Cu1—C3	118.75 (17)	Cu2—N7—H7	109.4
C3—Cu1—C1	121.87 (17)	N7—C8—C9	107.4 (4)
N1—Cu2—N4	101.66 (15)	N7—C8—H8A	110.2
N1—Cu2—N7	102.70 (14)	C9—C8—H8A	110.2
N1—Cu2—N10	110.18 (15)	N7—C8—H8B	110.2
N1—Cu2—N13	101.54 (15)	C9—C8—H8B	110.2
N4—Cu2—N7	83.37 (15)	H8A—C8—H8B	108.5
N7—Cu2—N10	83.65 (16)	C8—C9—N10	110.6 (4)
N10—Cu2—N13	84.25 (16)	C8—C9—H9A	109.5
N4—Cu2—N13	95.70 (15)	N10—C9—H9A	109.5
N7—Cu2—N13	155.42 (15)	C8—C9—H9B	109.5
N4—Cu2—N10	147.54 (15)	N10—C9—H9B	109.5
C1—N1—Cu2	174.0 (4)	H9A—C9—H9B	108.1
Cu1—C1—N1	177.9 (4)	C11—N10—C9	115.3 (4)
Cu1—C2—N2	176.5 (4)	C11—N10—Cu2	103.8 (3)
Cu1—C3—N3	176.1 (4)	C9—N10—Cu2	108.3 (3)
C5—N4—Cu2	108.3 (3)	C11—N10—H10	109.7
C5—N4—H4A	110.0	C9—N10—H10	109.7
Cu2—N4—H4A	110.0	Cu2—N10—H10	109.7
C5—N4—H4B	110.0	N10—C11—C12	107.7 (4)
Cu2—N4—H4B	110.0	N10—C11—H11A	110.2
H4A—N4—H4B	108.4	C12—C11—H11A	110.2
N4—C5—C6	107.1 (4)	N10—C11—H11B	110.2
N4—C5—H5A	110.3	C12—C11—H11B	110.2
C6—C5—H5A	110.3	H11A—C11—H11B	108.5
N4—C5—H5B	110.3	N13—C12—C11	109.0 (4)
C6—C5—H5B	110.3	N13—C12—H12A	109.9
H5A—C5—H5B	108.5	C11—C12—H12A	109.9
N7—C6—C5	110.1 (4)	N13—C12—H12B	109.9
N7—C6—H6A	109.6	C11—C12—H12B	109.9
C5—C6—H6A	109.6	H12A—C12—H12B	108.3
N7—C6—H6B	109.6	C12—N13—Cu2	109.1 (3)
C5—C6—H6B	109.6	C12—N13—H13A	109.9
H6A—C6—H6B	108.1	Cu2—N13—H13A	109.9
C6—N7—C8	115.0 (4)	C12—N13—H13B	109.9
C6—N7—Cu2	110.0 (3)	Cu2—N13—H13B	109.9
C8—N7—Cu2	103.4 (3)	H13A—N13—H13B	108.3
C6—N7—H7	109.4
N4—C5—C6—N7	49.9 (5)	N10—C11—C12—N13	53.1 (6)
N7—C8—C9—N10	51.7 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···N2i	0.91	2.14	2.984 (6)	154
N10—H10···N3ii	0.91	2.28	3.178 (6)	171

Table 1

Selected bond lengths (Å)

Cu1—C1	1.947 (4)
Cu1—C2	1.925 (4)
Cu1—C3	1.948 (5)
Cu2—N1	2.127 (4)
Cu2—N4	2.045 (4)
Cu2—N7	2.034 (4)
Cu2—N10	2.047 (4)
Cu2—N13	2.028 (4)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7⋯N2i	0.91	2.14	2.984 (6)	154
N10—H10⋯N3ii	0.91	2.28	3.178 (6)	171

Symmetry codes: (i) ; (ii) .