catena-Poly[[[(diethyl­enetriamine-κ3N,N′,N′′)­copper(II)]-μ-cyanido-κ2C:N] perchlorate]

Corfield, P.W.R.; Yang, S.C.

doi:10.1107/S1600536812023987

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Pages m872-m873

https://doi.org/10.1107/S1600536812023987

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catena-Poly[[[(diethylenetriamine-κ³N,N′,N′′)copper(II)]-μ-cyanido-κ²C:N] perchlorate]

Peter W. R. Corfield ^a ^* and Sylvia C. Yang ^b

^aDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA, and ^bDepartment of Geological Sciences, The Ohio State University, Columbus, Ohio 43210, USA
^*Correspondence e-mail: pcorfield@fordham.edu

(Received 11 April 2012; accepted 25 May 2012; online 13 June 2012)

The structure of the title salt, {[Cu(CN)(C₄H₁₃N₃)]ClO₄}_n, is composed of copper-containing cations and perchlorate 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 diethylenetriamine 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 Cu^I atoms bridged by cyanide ligands, while a smaller number are mixed-valence compounds with cyanide linkages between Cu^I and Cu^II 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 Cu^II 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_r = 292.18
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.031
wR(F²) = 0.085
S = 1.09
1752 reflections
158 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.35 e Å⁻³

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x-1, y, z; (iii) x, y, z+1.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812023987/pk2408sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812023987/pk2408Isup2.hkl

checkCIF report

Comment top

The title compound, [Cu(dien)CN]ClO₄, (Fig. 1), was originally prepared as a simple model for CN^- binding to copper-containing proteins, with the expectation that structural data would supplement information from infra-red studies on cyanide binding to the proteins. (Fager and Alben, 1972) The structure is reported now in light of current interest in cyanide-bridged copper polymers.

The crystal structure consists of cyanidodiethylenetriaminecopper(II) cations and perchlorate anions. The cyanide groups link c-glide related copper atoms to form infinite chains along the c axis, as shown in Fig. 2. The coordination of the copper atoms is square pyramidal, with the terdentate diethylenetriamine ligand and the carbon atom of the cyanide group in equatorial positions, and the nitrogen atom of a symmetry-related cyanide group in the axial position.

Atom O4 of the perchlorate group would occupy the sixth coordination site of the Cu^II atom if the Cu—O4 distance of 2.956 (4) Å represented a chemical bond, making the copper atom octahedrally coordinated. Perchlorate anions rarely coordinate, however, and we prefer the square pyramidal designation, in view of the long Cu—O4 distance, and the displacement of the copper atom by 0.237 (1) Å towards the axial nitrogen atom and away from the perchlorate O4 atom. Furthermore, the O4 atom has similar U_eq values to the other perchlorate oxygen atoms, and is disordered in the same way, whereas bonding to the Cu atom would be expected to localize the atom O4.

The Cu—C—N angle at the cyanide carbon atom is close to linear, at 175.9 (3)°, but the C—N—Cu angle at the bridging cyanide nitrogen atom is 146.5 (2)°, significantly different from 180°. The C—N bond length is 1.139 (4) Å, similar to the terminal bond length of 1.129 Å in K₃Cu(CN)₄, (Roof et al., 1968).

In the diethylenetriamine ligand, the carbon atoms in each chelate ring lie on opposite sides of the corresponding CuN₂ plane. The Cu—N1—C2—C3—N4 chelate ring has the λ conformation, with torsional angle N1—C2—C3—N4 equal to -51.9 (3) °, while the other chelate ring has the δ conformation, with the N4—C5—C6—N7 torsional angle equal to +51.9 (3) °.

Two minor alternative orientations for the perchlorate anion were refined, related to the major orientation by rotation about the Cl—O2 bond, by 34° in one direction, and 25° in the other. (Fig. 3) Each minor site is stabilized by hydrogen bonds to N—H donors from four surrounding cations, while atom O3 of the major perchlorate site forms hydrogen bonds to three of these cations.

Related literature top

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 Cu(I) atoms bridged by cyanide ligands, while a smaller number are mixed-valence compounds with cyanide linkages between Cu(I) and Cu^II 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 Cu^II 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 top

The compound was prepared by addition of stoichiometric amounts of diethylenetriamine and potassium cyanide to a solution of copper(II) perchlorate. Calculated elemental analysis, based upon C₅H₁₃ClCuN₄O₄: C, 20.55%; H, 4.48%; N, 19.18%. Found: C, 20.60, 20.66%; H, 4.98, 4.58%; N, 19.02%. The CN stretching frequency was 2141.4 cm^-1 (Alben and Farrier, 1972).

Structure description top

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 Cu(I) atoms bridged by cyanide ligands, while a smaller number are mixed-valence compounds with cyanide linkages between Cu(I) and Cu^II 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 Cu^II cyanide-bridged linear polymer, similar to the linear polymer reported by Zhan et al. (2007). For the CN stretching frequency, see: Alben & Farrier (1972).

Computing details top

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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the [Cu(dien)CN] cation and the major component of the perchlorate anion, with ellipsoids at the 50% level. Atoms C8' and N8' are C8 and N8 at x, 1/2-y, 1/2+z.
	Fig. 2. Packing of [Cu(dien)CN]ClO₄, viewed down the a axis. The darkened bonds show the Cu-CN-Cu chains along the c axis. Only the major perchlorate component is shown.
	Fig. 3. The disordered perchlorate anion, with ellipsoids drawn at the 25% probability level.

catena-Poly[[[(diethylenetriamine- κ³N,N',N'')copper(II)]-µ-cyanido- κ²C:N] perchlorate] top

Crystal data top

[Cu(CN)(C₄H₁₃N₃)]ClO₄	F(000) = 596
M_r = 292.18	D_x = 1.806 Mg m⁻³ D_m = 1.805 Mg m⁻³ D_m 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

Data collection top

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

Refinement top

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(F_o²) + (0.010P)² + 1.140P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
1752 reflections	Δρ_max = 0.59 e Å⁻³
158 parameters	Δρ_min = −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)

Crystal data top

[Cu(CN)(C₄H₁₃N₃)]ClO₄	V = 1075.2 (2) Å³
M_r = 292.18	Z = 4
Monoclinic, P2₁/c	Cu Kα radiation
a = 6.7767 (8) Å	µ = 5.29 mm⁻¹
b = 21.5081 (16) Å	T = 295 K
c = 8.3635 (12) Å	0.32 × 0.17 × 0.07 mm
β = 118.109 (9)°

Data collection top

Picker four-circle diffractometer	1625 reflections with I > 2σ(I)
Absorption correction: integration (Busing & Levy, 1957a)	R_int = 0.024
T_min = 0.394, T_max = 0.697	6 standard reflections every 200 reflections
3044 measured reflections	intensity decay: none
1752 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.09	Δρ_max = 0.59 e Å⁻³
1752 reflections	Δρ_min = −0.35 e Å⁻³
158 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	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

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

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···O3^iv	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

Symmetry codes: (i) x, −y+1/2, z+1/2; (iii) x−1, y, z; (iv) x, y, z+1.

Experimental details

Crystal data
Chemical formula	[Cu(CN)(C₄H₁₃N₃)]ClO₄
M_r	292.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	6.7767 (8), 21.5081 (16), 8.3635 (12)
β (°)	118.109 (9)
V (Å³)	1075.2 (2)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	5.29
Crystal size (mm)	0.32 × 0.17 × 0.07

Data collection
Diffractometer	Picker four-circle
Absorption correction	Integration (Busing & Levy, 1957a)
T_min, T_max	0.394, 0.697
No. of measured, independent and observed [I > 2σ(I)] reflections	3044, 1752, 1625
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.580

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.085, 1.09
No. of reflections	1752
No. of parameters	158
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.35

Computer programs: locally modified program (Corfield, 1972), 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, local superposition program (Corfield, 1972), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Selected bond lengths (Å) top

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

Symmetry code: (i) x, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3ⁱⁱ	0.90	2.38	3.215 (5)	153.8
N4—H4···O3ⁱⁱⁱ	0.91	2.42	3.214 (5)	145.3
N7—H7A···O3ⁱ	0.90	2.23	3.092 (4)	160.5
N1—H1A···O4'	0.90	2.17	2.771 (17)	123.8
N1—H1B···O3'ⁱⁱ	0.90	2.04	2.913 (15)	163.7
N4—H4···O1'ⁱⁱⁱ	0.91	2.30	3.139 (19)	153.9
N7—H7A···O3'ⁱ	0.90	2.14	3.040 (16)	173.3
N1—H1A···O1''	0.90	2.21	3.06 (4)	155.6
N1—H1B···O4''ⁱⁱ	0.90	2.51	3.21 (3)	135.2
N4—H4···O3''ⁱⁱⁱ	0.91	2.12	2.99 (3)	159.7
N7—H7A···O3''ⁱ	0.90	2.45	3.24 (3)	147.4
N7—H7B···O4''	0.90	2.50	3.04 (3)	118.6

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x−1, y, z; (iii) x, y, z+1.

Acknowledgements

We acknowledge gratefully the provision of a crystalline sample by James O. Alben and N. J. Farrier, as well as partial support from the National Science Foundation through equipment grant GP8534 awarded to the Ohio State University, where the experimental work was carried out.

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