catena-Poly[[[(diethyl-enetriamine-κ³N,N',N'')-copper(II)]-μ-cyanido-κ²C:N] perchlorate].

The structure of the title salt, {[Cu(CN)(C₄H₁₃N₃)]ClO₄}(n), is composed of copper-containing cations and perchlor-ate anions. The Cu(II) atom shows a square-pyramidal coordination, with equatorial positions occupied by the cyanide C atom [Cu-C = 1.990 (3) Å] and the N atoms of the diethyl-enetriamine ligand (average Cu-N = 2.033 Å), while the axial position is occupied by the N atom of a c-glide-related cyanide group. The axial Cu-N distance of 2.340 (3) Å is longer than the equatorial distances, reflecting Jahn-Teller distortion. The Cu(II) cations are linked by the cyanide groups into infinite chains along the c-axis direction. The refinement included a three-component disordered model for the perchlorate ion. Each minor site is stabilized by hydrogen bonds to N-H donors from four surrounding cations, while one O atom of the major perchlorate site forms hydrogen bonds to three of these cations.

Related literature

There is a growing body of literature on self-assembled polymers involving copper cyanide moieties, with many examples of one- two- and three-dimensional networks, see, for example: Roof et al. (1968 ▶); Chestnut et al. (2001 ▶); Kim et al. (2005 ▶); Lim et al. (2008 ▶). Most of these structures involve CuI atoms bridged by cyanide ligands, while a smaller number are mixed-valence compounds with cyanide linkages between CuI and CuII atoms. The present structure was prepared as a model for CN− binding to copper-containing proteins (Fager & Alben, 1972 ▶), and is a rare example of a CuII cyanide-bridged linear polymer, similar to the linear polymer reported by Zhan et al. (2007 ▶). For the CN stretching frequency, see: Alben & Farrier (1972 ▶).

Experimental

Crystal data

[Cu(CN)(C4H13N3)]ClO4

M = 292.18

Monoclinic,

a = 6.7767 (8) Å

b = 21.5081 (16) Å

c = 8.3635 (12) Å

β = 118.109 (9)°

V = 1075.2 (2) Å3

Z = 4

Cu Kα radiation

μ = 5.29 mm−1

T = 295 K

0.32 × 0.17 × 0.07 mm

Data collection

Picker four-circle diffractometer

Absorption correction: integration (Busing & Levy, 1957a ▶) T min = 0.394, T max = 0.697

3044 measured reflections

1752 independent reflections

1625 reflections with I > 2σ(I)

R int = 0.024

6 standard reflections every 200 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.085

S = 1.09

1752 reflections

158 parameters

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.35 e Å−3

Data collection: locally modified program (Corfield, 1972 ▶); cell refinement: locally modified program (Corfield, 1972 ▶); data reduction: cell refinements and data reduction follow procedures in Corfield et al. (1967 ▶) and Corfield & Shore (1973 ▶); standard deviations of intensities include an ignorance factor (Busing & Levy, 1957b ▶) set here to 0.06; program(s) used to solve structure: local superposition program (Corfield, 1972 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023987/pk2408sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023987/pk2408Isup2.hkl

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

[Cu(CN)(C4H13N3)]ClO4	F(000) = 596
Mr = 292.18	Dx = 1.806 Mg m−3Dm = 1.805 Mg m−3Dm measured by flotation in chloroform/bromoform mixtures
Monoclinic, P21/c	Melting point: 471(2) K
Hall symbol: -P 2ybc	Cu Kα radiation, λ = 1.5418 Å
a = 6.7767 (8) Å	Cell parameters from 25 reflections
b = 21.5081 (16) Å	θ = 4–52°
c = 8.3635 (12) Å	µ = 5.29 mm−1
β = 118.109 (9)°	T = 295 K
V = 1075.2 (2) Å3	Plate, dark blue
Z = 4	0.32 × 0.17 × 0.07 mm

Picker four-circle diffractometer	1625 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.024
Oriented graphite 200 reflection monochromator	θmax = 63.3°, θmin = 4.1°
θ/2θ scans	h = −7→6
Absorption correction: integration (Busing & Levy, 1957a)	k = 0→24
Tmin = 0.394, Tmax = 0.697	l = 0→9
3044 measured reflections	6 standard reflections every 200 reflections
1752 independent reflections	intensity decay: none

Refinement on F2	Secondary atom site location: real-space vector search
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031	H-atom parameters constrained
wR(F2) = 0.085	w = 1/[σ2(Fo2) + (0.010P)2 + 1.140P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
1752 reflections	Δρmax = 0.59 e Å−3
158 parameters	Δρmin = −0.35 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: heavy-atom method	Extinction coefficient: 0.0010 (2)

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	Occ. (<1)
Cu	0.15547 (7)	0.322023 (18)	0.63505 (5)	0.03271 (18)
N1	−0.0930 (4)	0.38484 (12)	0.5101 (3)	0.0426 (6)
H1A	−0.0788	0.4034	0.4197	0.051*
H1B	−0.2264	0.3655	0.4620	0.051*
C2	−0.0818 (6)	0.43180 (15)	0.6424 (5)	0.0499 (8)
H2A	−0.1495	0.4157	0.7135	0.075*
H2B	−0.1626	0.4689	0.5799	0.075*
C3	0.1595 (5)	0.44708 (14)	0.7639 (4)	0.0433 (7)
H3A	0.2220	0.4689	0.6965	0.065*
H3B	0.1743	0.4734	0.8632	0.065*
N4	0.2770 (4)	0.38751 (10)	0.8338 (3)	0.0321 (5)
H4	0.2433	0.3746	0.9217	0.038*
C5	0.5219 (5)	0.38908 (15)	0.9155 (4)	0.0410 (7)
H5A	0.5851	0.4108	1.0307	0.061*
H5B	0.5674	0.4104	0.8360	0.061*
C6	0.6010 (6)	0.32285 (15)	0.9427 (5)	0.0481 (8)
H6A	0.7601	0.3214	0.9809	0.072*
H6B	0.5750	0.3034	1.0358	0.072*
N7	0.4756 (4)	0.28942 (12)	0.7688 (4)	0.0430 (6)
H7A	0.4741	0.2484	0.7900	0.052*
H7B	0.5436	0.2949	0.6997	0.052*
C8	0.0609 (5)	0.26492 (13)	0.4243 (4)	0.0344 (6)
N8	0.0196 (4)	0.23248 (12)	0.3050 (3)	0.0428 (6)
Cl	0.30284 (12)	0.40553 (3)	0.28806 (10)	0.0381 (2)
O2	0.4055 (5)	0.45800 (12)	0.2534 (4)	0.0653 (7)
O1	0.0662 (8)	0.4083 (3)	0.1838 (8)	0.0782 (19)	0.70
O3	0.3915 (7)	0.35240 (17)	0.2420 (6)	0.0528 (10)	0.70
O4	0.3631 (8)	0.4055 (2)	0.4760 (6)	0.0593 (12)	0.70
O1'	0.109 (3)	0.3883 (9)	0.125 (3)	0.069 (5)*	0.18
O3'	0.440 (3)	0.3468 (7)	0.349 (2)	0.053 (3)*	0.18
O4'	0.238 (3)	0.4161 (8)	0.419 (2)	0.056 (4)*	0.18
O1''	0.077 (8)	0.421 (2)	0.243 (5)	0.069 (5)*	0.12
O3''	0.286 (4)	0.3518 (13)	0.183 (4)	0.053 (3)*	0.12
O4''	0.413 (5)	0.3815 (12)	0.474 (4)	0.056 (4)*	0.12

	U11	U22	U33	U12	U13	U23
Cu	0.0355 (3)	0.0299 (3)	0.0297 (3)	0.00199 (16)	0.0128 (2)	−0.00357 (15)
N1	0.0402 (14)	0.0407 (14)	0.0389 (14)	0.0040 (11)	0.0121 (12)	−0.0018 (11)
C2	0.0497 (19)	0.0416 (17)	0.052 (2)	0.0151 (15)	0.0190 (16)	−0.0018 (15)
C3	0.0522 (19)	0.0309 (15)	0.0435 (17)	0.0043 (14)	0.0199 (15)	−0.0045 (13)
N4	0.0355 (13)	0.0314 (12)	0.0303 (12)	−0.0007 (10)	0.0163 (10)	−0.0003 (10)
C5	0.0367 (16)	0.0461 (17)	0.0388 (17)	−0.0075 (13)	0.0167 (14)	−0.0099 (14)
C6	0.0366 (17)	0.055 (2)	0.0430 (19)	0.0044 (14)	0.0104 (15)	−0.0033 (14)
N7	0.0421 (14)	0.0380 (14)	0.0494 (15)	0.0046 (11)	0.0218 (12)	−0.0046 (12)
C8	0.0376 (16)	0.0335 (15)	0.0346 (16)	0.0034 (12)	0.0191 (13)	0.0034 (13)
N8	0.0528 (16)	0.0386 (14)	0.0365 (14)	0.0052 (12)	0.0206 (12)	−0.0040 (12)
Cl	0.0391 (4)	0.0397 (4)	0.0381 (4)	−0.0016 (3)	0.0203 (3)	−0.0039 (3)
O2	0.0807 (18)	0.0531 (15)	0.0723 (17)	−0.0186 (13)	0.0446 (15)	0.0014 (13)
O1	0.030 (2)	0.077 (4)	0.095 (5)	0.003 (2)	0.003 (3)	−0.005 (4)
O3	0.068 (3)	0.0388 (19)	0.064 (3)	0.005 (2)	0.041 (3)	−0.0087 (19)
O4	0.069 (3)	0.081 (3)	0.0335 (19)	−0.017 (3)	0.029 (2)	−0.010 (2)

Cu—C8	1.990 (3)	C5—H5B	0.9700
Cu—N1	2.023 (2)	C6—N7	1.480 (4)
Cu—N4	2.034 (2)	C6—H6A	0.9700
Cu—N7	2.040 (3)	C6—H6B	0.9700
Cu—N8i	2.340 (3)	N7—H7A	0.9000
N1—C2	1.474 (4)	N7—H7B	0.9000
N1—H1A	0.9000	C8—N8	1.139 (4)
N1—H1B	0.9000	N8—Cuii	2.340 (3)
C2—C3	1.500 (5)	Cl—O1	1.420 (5)
C2—H2A	0.9700	Cl—O2	1.425 (2)
C2—H2B	0.9700	Cl—O3	1.426 (4)
C3—N4	1.476 (4)	Cl—O4	1.426 (4)
C3—H3A	0.9700	Cl—O1'	1.43 (2)
C3—H3B	0.9700	Cl—O3'	1.507 (15)
N4—C5	1.467 (4)	Cl—O4'	1.376 (16)
N4—H4	0.9100	Cl—O1''	1.44 (5)
C5—C6	1.501 (4)	Cl—O3''	1.42 (3)
C5—H5A	0.9700	Cl—O4''	1.46 (3)
C8—Cu—N1	96.45 (11)	C6—C5—H5A	110.3
C8—Cu—N4	171.38 (11)	N4—C5—H5B	110.3
N1—Cu—N4	82.98 (10)	C6—C5—H5B	110.3
C8—Cu—N7	95.09 (11)	H5A—C5—H5B	108.6
N1—Cu—N7	157.48 (11)	N7—C6—C5	108.3 (3)
N4—Cu—N7	82.73 (10)	N7—C6—H6A	110.0
C8—Cu—N8i	100.04 (10)	C5—C6—H6A	110.0
N1—Cu—N8i	100.27 (11)	N7—C6—H6B	110.0
N4—Cu—N8i	88.51 (9)	C5—C6—H6B	110.0
N7—Cu—N8i	96.66 (10)	H6A—C6—H6B	108.4
C2—N1—Cu	109.50 (19)	C6—N7—Cu	109.98 (19)
C2—N1—H1A	109.8	C6—N7—H7A	109.7
Cu—N1—H1A	109.8	Cu—N7—H7A	109.7
C2—N1—H1B	109.8	C6—N7—H7B	109.7
Cu—N1—H1B	109.8	Cu—N7—H7B	109.7
H1A—N1—H1B	108.2	H7A—N7—H7B	108.2
N1—C2—C3	108.2 (3)	N8—C8—Cu	175.9 (3)
N1—C2—H2A	110.1	C8—N8—Cuii	146.5 (2)
C3—C2—H2A	110.1	O1—Cl—O2	111.1 (3)
N1—C2—H2B	110.1	O1—Cl—O3	111.4 (3)
C3—C2—H2B	110.1	O1—Cl—O4	109.3 (3)
H2A—C2—H2B	108.4	O2—Cl—O3	105.7 (2)
N4—C3—C2	106.9 (2)	O2—Cl—O4	108.1 (2)
N4—C3—H3A	110.3	O3—Cl—O4	111.1 (3)
C2—C3—H3A	110.3	O1'—Cl—O2	109.3 (8)
N4—C3—H3B	110.3	O1'—Cl—O3'	104.4 (10)
C2—C3—H3B	110.3	O1'—Cl—O4'	107.9 (11)
H3A—C3—H3B	108.6	O2—Cl—O3'	116.7 (6)
C5—N4—C3	116.4 (2)	O2—Cl—O4'	113.6 (7)
C5—N4—Cu	109.27 (17)	O3'—Cl—O4'	104.3 (9)
C3—N4—Cu	110.01 (18)	O1''—Cl—O2	108.8 (18)
C5—N4—H4	106.9	O1''—Cl—O3''	105.5 (17)
C3—N4—H4	106.9	O1''—Cl—O4''	108 (2)
Cu—N4—H4	106.9	O2—Cl—O3''	114.8 (11)
N4—C5—C6	107.1 (2)	O2—Cl—O4''	116.1 (12)
N4—C5—H5A	110.3	O3''—Cl—O4''	102.8 (15)
N1—C2—C3—N4	−51.9 (3)	N4—C5—C6—N7	51.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3iii	0.90	2.38	3.215 (5)	154
N4—H4···O3iv	0.91	2.42	3.214 (5)	145
N7—H7A···O3i	0.90	2.23	3.092 (4)	161
N1—H1A···O4′	0.90	2.17	2.771 (17)	124
N1—H1B···O3′iii	0.90	2.04	2.913 (15)	164
N4—H4···O1′iv	0.91	2.30	3.139 (19)	154
N7—H7A···O3′i	0.90	2.14	3.040 (16)	173
N1—H1A···O1′′	0.90	2.21	3.06 (4)	156
N1—H1B···O4′′iii	0.90	2.51	3.21 (3)	135
N4—H4···O3′′iv	0.91	2.12	2.99 (3)	160
N7—H7A···O3′′i	0.90	2.45	3.24 (3)	147
N7—H7B···O4′′	0.90	2.50	3.04 (3)	119

Table 1

Selected bond lengths (Å)

Cu—C8	1.990 (3)
Cu—N1	2.023 (2)
Cu—N4	2.034 (2)
Cu—N7	2.040 (3)
Cu—N8i	2.340 (3)
C8—N8	1.139 (4)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3ii	0.90	2.38	3.215 (5)	154
N4—H4⋯O3iii	0.91	2.42	3.214 (5)	145
N7—H7A⋯O3i	0.90	2.23	3.092 (4)	161
N1—H1A⋯O4′	0.90	2.17	2.771 (17)	124
N1—H1B⋯O3′ii	0.90	2.04	2.913 (15)	164
N4—H4⋯O1′iii	0.91	2.30	3.139 (19)	154
N7—H7A⋯O3′i	0.90	2.14	3.040 (16)	173
N1—H1A⋯O1′′	0.90	2.21	3.06 (4)	156
N1—H1B⋯O4′′ii	0.90	2.51	3.21 (3)	135
N4—H4⋯O3′′iii	0.91	2.12	2.99 (3)	160
N7—H7A⋯O3′′i	0.90	2.45	3.24 (3)	147
N7—H7B⋯O4′′	0.90	2.50	3.04 (3)	119

Symmetry codes: (i) ; (ii) ; (iii) .