metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 CuII 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 CuII 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[Roof, R. B., Larson, A. C. & Cromer, D. T. (1968). Acta Cryst. B24, 269-273.]); Chestnut et al. (2001[Chestnut, D. J., Plewak, D. & Zubieta, J. (2001). J. Chem. Soc. Dalton Trans. pp. 2567-2580.]); Kim et al. (2005[Kim, D., Koo, J., Hong, C. S., Oh, S. & Do, Y. (2005). Inorg. Chem. 44, 4383-4390.]); Lim et al. (2008[Lim, M. J., Murray, C. A., Tronic, T. A., deKrafft, K. E., Ley, A. N., de Butts, J. C., Pike, R. D., Lu, H. & Patterson, H. H. (2008). Inorg. Chem. 47, 6931-6947.]). 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[Fager, L. Y. & Alben, J. O. (1972). Biochemistry, 11, 4786-4792.]), and is a rare example of a CuII cyanide-bridged linear polymer, similar to the linear polymer reported by Zhan et al. (2007[Zhan, S.-Z., Li, W., Wang, J.-G., Liang, A.-Q. & Deng, Y.-F. (2007). J. Organomet. Chem. 692, 3568-3573.]). For the CN stretching frequency, see: Alben & Farrier (1972[Alben, J. O. & Farrier, N. (1972). Personal communication.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu(CN)(C4H13N3)]ClO4

  • Mr = 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[Busing, W. R. & Levy, H. A. (1957a). Acta Cryst. 10, 180-182.]) Tmin = 0.394, Tmax = 0.697

  • 3044 measured reflections

  • 1752 independent reflections

  • 1625 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.59 e Å−3

  • Δρmin = −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 DA 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[Corfield, P. W. R. (1972). Local versions of standard programs, written at Ohio State University.]); cell refinement: locally modified program (Corfield, 1972[Corfield, P. W. R. (1972). Local versions of standard programs, written at Ohio State University.]); data reduction: cell refinements and data reduction follow procedures in Corfield et al. (1967[Corfield, P. W. R., Doedens, R. J. & Ibers, J. A. (1967). Inorg. Chem. 6, 197-204.]) and Corfield & Shore (1973[Corfield, P. W. R. & Shore, S. G. (1973). J. Am. Chem. Soc. 95, 1480-1487.]); standard deviations of intensities include an ignorance factor (Busing & Levy, 1957b[Busing, W. R. & Levy, H. A. (1957b). J. Chem. Phys. 26, 563-568.]) set here to 0.06; program(s) used to solve structure: local superposition program (Corfield, 1972[Corfield, P. W. R. (1972). Local versions of standard programs, written at Ohio State University.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEPII (Johnson, 1976[Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information


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 CuII 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 Ueq 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 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 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).

Refinement top

All 13 hydrogen atoms of the diethylenetriamine ligand were found unambiguously in a difference Fourier map, and were initially refined freely. In the final refinements, hydrogen atoms were constrained to idealized positions by SHELXL97.

The assignment of C and N atoms in the cyanide group was checked early in the analysis by carrying out a least-squares refinement with the N and C atoms of the cyanide group reversed. The weighted R factor increased significantly from 0.061 to 0.091. There is no evidence of disorder between the C and N atoms of the cyanide group.

Perchlorate ion disorder: Refinement of a single anisotropic perchlorate group converged successfully with wR2=0.1091 for all 1752 reflections. The thermal parameters indicated large librations about the Cl—O2 bond however, and difference Fourier maps indicated two minor alternative orientations for the perchlorate group.

After initial stringent constraints, the three orientations were refined freely, with common Cl and O2 atoms. The main orientation (O1—O4) was refined anisotropically, with an occupancy fixed at 70%. The two minor orientations (O1'-O4') and (O1''-O4'') were given occupancy factors of 18% and 12% respectively, based upon heights found in difference Fourier maps. U values for O1' and O1'', O3' and O3'', and O4' and O4'' were constrained to be equal. This model reduced wR2 significantly from 0.1091 to 0.0847, with the addition of 22 new parameters.

Structure description 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 CuII 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 Ueq 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.

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 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).

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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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)]ClO4F(000) = 596
Mr = 292.18Dx = 1.806 Mg m3
Dm = 1.805 Mg m3
Dm measured by flotation in chloroform/bromoform mixtures
Monoclinic, P21/cMelting point: 471(2) K
Hall symbol: -P 2ybcCu Kα radiation, λ = 1.5418 Å
a = 6.7767 (8) ÅCell parameters from 25 reflections
b = 21.5081 (16) Åθ = 4–52°
c = 8.3635 (12) ŵ = 5.29 mm1
β = 118.109 (9)°T = 295 K
V = 1075.2 (2) Å3Plate, dark blue
Z = 40.32 × 0.17 × 0.07 mm
Data collection top
Picker four-circle
diffractometer
1625 reflections with I > 2σ(I)
Radiation source: sealed X-ray tubeRint = 0.024
Oriented graphite 200 reflection monochromatorθmax = 63.3°, θmin = 4.1°
θ/2θ scansh = 76
Absorption correction: integration
(Busing & Levy, 1957a)
k = 024
Tmin = 0.394, Tmax = 0.697l = 09
3044 measured reflections6 standard reflections every 200 reflections
1752 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: real-space vector search
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031H-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 reflectionsΔρmax = 0.59 e Å3
158 parametersΔρmin = 0.35 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: heavy-atom methodExtinction coefficient: 0.0010 (2)
Crystal data top
[Cu(CN)(C4H13N3)]ClO4V = 1075.2 (2) Å3
Mr = 292.18Z = 4
Monoclinic, P21/cCu Kα radiation
a = 6.7767 (8) ŵ = 5.29 mm1
b = 21.5081 (16) ÅT = 295 K
c = 8.3635 (12) Å0.32 × 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)
Rint = 0.024
Tmin = 0.394, Tmax = 0.6976 standard reflections every 200 reflections
3044 measured reflections intensity decay: none
1752 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.085H-atom parameters constrained
S = 1.09Δρmax = 0.59 e Å3
1752 reflectionsΔρmin = 0.35 e Å3
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
xyzUiso*/UeqOcc. (<1)
Cu0.15547 (7)0.322023 (18)0.63505 (5)0.03271 (18)
N10.0930 (4)0.38484 (12)0.5101 (3)0.0426 (6)
H1A0.07880.40340.41970.051*
H1B0.22640.36550.46200.051*
C20.0818 (6)0.43180 (15)0.6424 (5)0.0499 (8)
H2A0.14950.41570.71350.075*
H2B0.16260.46890.57990.075*
C30.1595 (5)0.44708 (14)0.7639 (4)0.0433 (7)
H3A0.22200.46890.69650.065*
H3B0.17430.47340.86320.065*
N40.2770 (4)0.38751 (10)0.8338 (3)0.0321 (5)
H40.24330.37460.92170.038*
C50.5219 (5)0.38908 (15)0.9155 (4)0.0410 (7)
H5A0.58510.41081.03070.061*
H5B0.56740.41040.83600.061*
C60.6010 (6)0.32285 (15)0.9427 (5)0.0481 (8)
H6A0.76010.32140.98090.072*
H6B0.57500.30341.03580.072*
N70.4756 (4)0.28942 (12)0.7688 (4)0.0430 (6)
H7A0.47410.24840.79000.052*
H7B0.54360.29490.69970.052*
C80.0609 (5)0.26492 (13)0.4243 (4)0.0344 (6)
N80.0196 (4)0.23248 (12)0.3050 (3)0.0428 (6)
Cl0.30284 (12)0.40553 (3)0.28806 (10)0.0381 (2)
O20.4055 (5)0.45800 (12)0.2534 (4)0.0653 (7)
O10.0662 (8)0.4083 (3)0.1838 (8)0.0782 (19)0.70
O30.3915 (7)0.35240 (17)0.2420 (6)0.0528 (10)0.70
O40.3631 (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
U11U22U33U12U13U23
Cu0.0355 (3)0.0299 (3)0.0297 (3)0.00199 (16)0.0128 (2)0.00357 (15)
N10.0402 (14)0.0407 (14)0.0389 (14)0.0040 (11)0.0121 (12)0.0018 (11)
C20.0497 (19)0.0416 (17)0.052 (2)0.0151 (15)0.0190 (16)0.0018 (15)
C30.0522 (19)0.0309 (15)0.0435 (17)0.0043 (14)0.0199 (15)0.0045 (13)
N40.0355 (13)0.0314 (12)0.0303 (12)0.0007 (10)0.0163 (10)0.0003 (10)
C50.0367 (16)0.0461 (17)0.0388 (17)0.0075 (13)0.0167 (14)0.0099 (14)
C60.0366 (17)0.055 (2)0.0430 (19)0.0044 (14)0.0104 (15)0.0033 (14)
N70.0421 (14)0.0380 (14)0.0494 (15)0.0046 (11)0.0218 (12)0.0046 (12)
C80.0376 (16)0.0335 (15)0.0346 (16)0.0034 (12)0.0191 (13)0.0034 (13)
N80.0528 (16)0.0386 (14)0.0365 (14)0.0052 (12)0.0206 (12)0.0040 (12)
Cl0.0391 (4)0.0397 (4)0.0381 (4)0.0016 (3)0.0203 (3)0.0039 (3)
O20.0807 (18)0.0531 (15)0.0723 (17)0.0186 (13)0.0446 (15)0.0014 (13)
O10.030 (2)0.077 (4)0.095 (5)0.003 (2)0.003 (3)0.005 (4)
O30.068 (3)0.0388 (19)0.064 (3)0.005 (2)0.041 (3)0.0087 (19)
O40.069 (3)0.081 (3)0.0335 (19)0.017 (3)0.029 (2)0.010 (2)
Geometric parameters (Å, º) top
Cu—C81.990 (3)C5—H5B0.9700
Cu—N12.023 (2)C6—N71.480 (4)
Cu—N42.034 (2)C6—H6A0.9700
Cu—N72.040 (3)C6—H6B0.9700
Cu—N8i2.340 (3)N7—H7A0.9000
N1—C21.474 (4)N7—H7B0.9000
N1—H1A0.9000C8—N81.139 (4)
N1—H1B0.9000N8—Cuii2.340 (3)
C2—C31.500 (5)Cl—O11.420 (5)
C2—H2A0.9700Cl—O21.425 (2)
C2—H2B0.9700Cl—O31.426 (4)
C3—N41.476 (4)Cl—O41.426 (4)
C3—H3A0.9700Cl—O1'1.43 (2)
C3—H3B0.9700Cl—O3'1.507 (15)
N4—C51.467 (4)Cl—O4'1.376 (16)
N4—H40.9100Cl—O1''1.44 (5)
C5—C61.501 (4)Cl—O3''1.42 (3)
C5—H5A0.9700Cl—O4''1.46 (3)
C8—Cu—N196.45 (11)C6—C5—H5A110.3
C8—Cu—N4171.38 (11)N4—C5—H5B110.3
N1—Cu—N482.98 (10)C6—C5—H5B110.3
C8—Cu—N795.09 (11)H5A—C5—H5B108.6
N1—Cu—N7157.48 (11)N7—C6—C5108.3 (3)
N4—Cu—N782.73 (10)N7—C6—H6A110.0
C8—Cu—N8i100.04 (10)C5—C6—H6A110.0
N1—Cu—N8i100.27 (11)N7—C6—H6B110.0
N4—Cu—N8i88.51 (9)C5—C6—H6B110.0
N7—Cu—N8i96.66 (10)H6A—C6—H6B108.4
C2—N1—Cu109.50 (19)C6—N7—Cu109.98 (19)
C2—N1—H1A109.8C6—N7—H7A109.7
Cu—N1—H1A109.8Cu—N7—H7A109.7
C2—N1—H1B109.8C6—N7—H7B109.7
Cu—N1—H1B109.8Cu—N7—H7B109.7
H1A—N1—H1B108.2H7A—N7—H7B108.2
N1—C2—C3108.2 (3)N8—C8—Cu175.9 (3)
N1—C2—H2A110.1C8—N8—Cuii146.5 (2)
C3—C2—H2A110.1O1—Cl—O2111.1 (3)
N1—C2—H2B110.1O1—Cl—O3111.4 (3)
C3—C2—H2B110.1O1—Cl—O4109.3 (3)
H2A—C2—H2B108.4O2—Cl—O3105.7 (2)
N4—C3—C2106.9 (2)O2—Cl—O4108.1 (2)
N4—C3—H3A110.3O3—Cl—O4111.1 (3)
C2—C3—H3A110.3O1'—Cl—O2109.3 (8)
N4—C3—H3B110.3O1'—Cl—O3'104.4 (10)
C2—C3—H3B110.3O1'—Cl—O4'107.9 (11)
H3A—C3—H3B108.6O2—Cl—O3'116.7 (6)
C5—N4—C3116.4 (2)O2—Cl—O4'113.6 (7)
C5—N4—Cu109.27 (17)O3'—Cl—O4'104.3 (9)
C3—N4—Cu110.01 (18)O1''—Cl—O2108.8 (18)
C5—N4—H4106.9O1''—Cl—O3''105.5 (17)
C3—N4—H4106.9O1''—Cl—O4''108 (2)
Cu—N4—H4106.9O2—Cl—O3''114.8 (11)
N4—C5—C6107.1 (2)O2—Cl—O4''116.1 (12)
N4—C5—H5A110.3O3''—Cl—O4''102.8 (15)
N1—C2—C3—N451.9 (3)N4—C5—C6—N751.9 (3)
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O3iii0.902.383.215 (5)154
N4—H4···O3iv0.912.423.214 (5)145
N7—H7A···O3i0.902.233.092 (4)161
N1—H1A···O40.902.172.771 (17)124
N1—H1B···O3iii0.902.042.913 (15)164
N4—H4···O1iv0.912.303.139 (19)154
N7—H7A···O3i0.902.143.040 (16)173
N1—H1A···O10.902.213.06 (4)156
N1—H1B···O4iii0.902.513.21 (3)135
N4—H4···O3iv0.912.122.99 (3)160
N7—H7A···O3i0.902.453.24 (3)147
N7—H7B···O40.902.503.04 (3)119
Symmetry codes: (i) x, y+1/2, z+1/2; (iii) x1, y, z; (iv) x, y, z+1.

Experimental details

Crystal data
Chemical formula[Cu(CN)(C4H13N3)]ClO4
Mr292.18
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)6.7767 (8), 21.5081 (16), 8.3635 (12)
β (°) 118.109 (9)
V3)1075.2 (2)
Z4
Radiation typeCu Kα
µ (mm1)5.29
Crystal size (mm)0.32 × 0.17 × 0.07
Data collection
DiffractometerPicker four-circle
Absorption correctionIntegration
(Busing & Levy, 1957a)
Tmin, Tmax0.394, 0.697
No. of measured, independent and
observed [I > 2σ(I)] reflections
3044, 1752, 1625
Rint0.024
(sin θ/λ)max1)0.580
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.085, 1.09
No. of reflections1752
No. of parameters158
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—C81.990 (3)Cu—N72.040 (3)
Cu—N12.023 (2)Cu—N8i2.340 (3)
Cu—N42.034 (2)C8—N81.139 (4)
Symmetry code: (i) x, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O3ii0.902.383.215 (5)153.8
N4—H4···O3iii0.912.423.214 (5)145.3
N7—H7A···O3i0.902.233.092 (4)160.5
N1—H1A···O4'0.902.172.771 (17)123.8
N1—H1B···O3'ii0.902.042.913 (15)163.7
N4—H4···O1'iii0.912.303.139 (19)153.9
N7—H7A···O3'i0.902.143.040 (16)173.3
N1—H1A···O1''0.902.213.06 (4)155.6
N1—H1B···O4''ii0.902.513.21 (3)135.2
N4—H4···O3''iii0.912.122.99 (3)159.7
N7—H7A···O3''i0.902.453.24 (3)147.4
N7—H7B···O4''0.902.503.04 (3)118.6
Symmetry codes: (i) x, y+1/2, z+1/2; (ii) x1, 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.

References

First citationAlben, J. O. & Farrier, N. (1972). Personal communication.  Google Scholar
First citationBusing, W. R. & Levy, H. A. (1957a). Acta Cryst. 10, 180–182.  CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationBusing, W. R. & Levy, H. A. (1957b). J. Chem. Phys. 26, 563–568.  CrossRef CAS Web of Science Google Scholar
First citationChestnut, D. J., Plewak, D. & Zubieta, J. (2001). J. Chem. Soc. Dalton Trans. pp. 2567–2580.  Google Scholar
First citationCorfield, P. W. R. (1972). Local versions of standard programs, written at Ohio State University.  Google Scholar
First citationCorfield, P. W. R., Doedens, R. J. & Ibers, J. A. (1967). Inorg. Chem. 6, 197–204.  CSD CrossRef CAS Web of Science Google Scholar
First citationCorfield, P. W. R. & Shore, S. G. (1973). J. Am. Chem. Soc. 95, 1480–1487.  CSD CrossRef CAS Web of Science Google Scholar
First citationFager, L. Y. & Alben, J. O. (1972). Biochemistry, 11, 4786–4792.  CrossRef CAS PubMed Web of Science Google Scholar
First citationJohnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationKim, D., Koo, J., Hong, C. S., Oh, S. & Do, Y. (2005). Inorg. Chem. 44, 4383–4390.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationLim, M. J., Murray, C. A., Tronic, T. A., deKrafft, K. E., Ley, A. N., de Butts, J. C., Pike, R. D., Lu, H. & Patterson, H. H. (2008). Inorg. Chem. 47, 6931–6947.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationRoof, R. B., Larson, A. C. & Cromer, D. T. (1968). Acta Cryst. B24, 269–273.  CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhan, S.-Z., Li, W., Wang, J.-G., Liang, A.-Q. & Deng, Y.-F. (2007). J. Organomet. Chem. 692, 3568–3573.  Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds