(Acetonitrile)[bis­(2-pyridylmeth­yl)amine]bis­(perchlorato)copper(II)

Butcher, R.J.; Tesema, Y.T.; Yisgedu, T.B.; Gultneh, Y.

doi:10.1107/S1600536807067001

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Pages m233-m234

https://doi.org/10.1107/S1600536807067001

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(Acetonitrile)[bis(2-pyridylmethyl)amine]bis(perchlorato)copper(II)

Ray J. Butcher,^a ^* Yohannes T. Tesema,^a Teshome B. Yisgedu ^a and Yilma Gultneh ^a

^aDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 20 November 2007; accepted 14 December 2007; online 21 December 2007)

In the title compound, [Cu(ClO₄)₂(C₁₂H₁₃N₃)(C₂H₃N)], the Cu^II atom is six-coordinate in a Jahn–Teller distorted octahedral geometry, with coordination by the tridentate chelating ligand, an acetonitrile molecule, and two axial perchlorate anions. The tridentate ligand bis(2-pyridylmethyl)amine chelates meridionally and equatorially while an acetonitrile molecule is coordinated at the fourth equatorial site. The two perchlorate anions are disordered with site occupancy factors of 0.72/0.28. The amine H is involved in intramolecular hydrogen bonding to the perchlorate O atoms and there are extensive but weak intermolecular C—H⋯O interactions.

Related literature

For related literature, see: Belle et al. (2002 ); Gultneh et al. (1999 ); Humphreys et al. (2002 ); Palaniandavar et al. (1995 ).

Experimental

Crystal data

[Cu(ClO₄)₂(C₁₂H₁₃N₃)(C₂H₃N)]
M_r = 502.75
Monoclinic, P 2₁ /c
a = 8.3046 (16) Å
b = 31.453 (4) Å
c = 8.4978 (11) Å
β = 118.646 (10)°
V = 1948.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.45 mm⁻¹
T = 293 (2) K
0.45 × 0.21 × 0.07 mm

Data collection

Bruker P4S diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.757, T_max = 0.964 (expected range = 0.709–0.904)
4638 measured reflections
4347 independent reflections
2718 reflections with I > 2σ(I)
R_int = 0.030
3 standard reflections every 97 reflections intensity decay: <2%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.193
S = 1.04
4347 reflections
320 parameters
92 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O22A	0.91	2.45	2.89 (3)	110
N—H0A⋯O23	0.91	2.30	3.084 (12)	144
N—H0A⋯O23ⁱ	0.91	2.50	3.317 (10)	150
C2—H21⋯O13Aⁱⁱ	0.96	2.23	2.98 (2)	133
C2—H22⋯O14ⁱⁱⁱ	0.96	2.36	3.103 (14)	134
C1A—H1AA⋯O12ⁱⁱ	0.93	2.46	3.176 (9)	134
C3A—H3AA⋯O23^iv	0.93	2.53	3.376 (15)	152
C3A—H3AA⋯O23A^iv	0.93	2.29	2.993 (14)	133
C6A—H6AA⋯O21ⁱ	0.97	2.56	3.381 (9)	143
C2B—H2BA⋯O14A^v	0.93	2.35	3.112 (16)	140
C3B—H3BA⋯O11^vi	0.93	2.56	3.429 (10)	156
C4B—H4BA⋯O24A^vii	0.93	2.25	3.06 (3)	145
C6B—H6BA⋯O12	0.97	2.56	3.425 (13)	149
C6B—H6BB⋯O24A^vii	0.97	2.51	3.211 (16)	129
Symmetry codes: (i) -x+2, -y, -z; (ii) x, y, z+1; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+1, -y, -z; (v) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) x+1, y, z; (vii) x, y, z-1.

Data collection: XSCANS (Bruker, 1997 ); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: SHELXTL (Bruker, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807067001/bq2058sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807067001/bq2058Isup2.hkl

checkCIF report

Comment top

Bis(2-pyridylmethyl)amine (L¹) has been used as a chelating ligand for several metal ions, as a single unit, or as two or more units bridged by other groups (such as m-xylyl spaces or aliphatic hydrocarbon chains) through the amine N atom (Gultneh et al., 1999; Palaniandavar et al., 1995; Belle et al., 2002; Humphreys et al., 2002). We report here the structure of the copper (II) complex of the ligand L¹. The complex was synthesized by the reaction of L¹ with Cu(ClO₄)₂.6H₂O in acetonitrile.

The crystal structure shows that Cu^II is six-coordinate in a Jahn-Teller distorted geometry with coordination by the tridentate chelating ligand, an acetonitrile molecule, and two axial perchlorate anions (Fig. 1.). The tridentate ligand L¹ is chelating meridionally and equatorially while an acetonitrile molecule is coordinated at the fourth equatorial site. One axial perchlorate group is at a Cu^II—OClO₃^- distance of 2.455 (9) Å while the other is at 2.828 (5) Å consistent with its expected Jahn-Teller elongation (O—Cu—O angle 169.1 (2)°). The mutually trans Cu—N_py distances are 1.980 (5) Å and 1.984 (5) Å and span an angle of 165.3 (2)°. The Cu—N_amine bond distance is 1.991 (5) Å. The Cu—N_acetonitrile bond distance of 1.980 (5) Å is comparable to the Cu—N distances of the N atoms. The amine H is involved in intramolecular hydrogen bonding to the perchlorate O atoms and there are extensive but weak intermolecular C—H···O interactions. (Table 1.).

Related literature top

For related literature, see: Belle et al. (2002); Gultneh et al. (1999); Humphreys et al. (2002); Palaniandavar et al. (1995).

Experimental top

The title compound, bis(2-pyridylmethyl)amine copper(II) acetonitrile bis(perchlorate), was obtained by refluxing bis(2-pyridylmethyl)amine (2 mmol) and copper(II) perchlorate hexahydrate (2 mmol) in 200 ml of acetonitrile for 1 h. The product deposited on cooling the solution. Suitable crystals suited for crystallographic structure determination were obtained by slow diffusion of diethyl ether into the nitromethane solution of the complex.

Structure description top

For related literature, see: Belle et al. (2002); Gultneh et al. (1999); Humphreys et al. (2002); Palaniandavar et al. (1995).

Computing details top

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS (Bruker, 1997); data reduction: XSCANS (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. The title compound with numbering scheme used. Ellipsoids are drawn at the 20% probability level.
	Fig. 2. The packing arrangement viewed down the c axis showing the intramolecular N—H···O and intermolecular C—H···O interactions in dashed lines.

(Acetonitrile)[bis(2-pyridylmethyl)amine]bis(perchlorato)copper(II) top

Crystal data top

[Cu(ClO₄)₂(C₁₂H₁₃N₃)(C₂H₃N)]	F(000) = 1020
M_r = 502.75	D_x = 1.714 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 54 reflections
a = 8.3046 (16) Å	θ = 2.6–13.1°
b = 31.453 (4) Å	µ = 1.45 mm⁻¹
c = 8.4978 (11) Å	T = 293 K
β = 118.646 (10)°	Plate, blue
V = 1948.0 (5) Å³	0.45 × 0.21 × 0.07 mm
Z = 4

Data collection top

Bruker P4S diffractometer	2718 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 27.5°, θ_min = 2.6°
2θ/ω scans	h = 0→9
Absorption correction: empirical (using intensity measurements) via psi scans (North et al., 1968)	k = −40→0
T_min = 0.757, T_max = 0.964	l = −11→9
4638 measured reflections	3 standard reflections every 97 reflections
4347 independent reflections	intensity decay: <2

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.193	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0863P)² + 3.5739P] where P = (F_o² + 2F_c²)/3
4347 reflections	(Δ/σ)_max = 0.001
320 parameters	Δρ_max = 0.49 e Å⁻³
92 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Cu(ClO₄)₂(C₁₂H₁₃N₃)(C₂H₃N)]	V = 1948.0 (5) Å³
M_r = 502.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3046 (16) Å	µ = 1.45 mm⁻¹
b = 31.453 (4) Å	T = 293 K
c = 8.4978 (11) Å	0.45 × 0.21 × 0.07 mm
β = 118.646 (10)°

Data collection top

Bruker P4S diffractometer	2718 reflections with I > 2σ(I)
Absorption correction: empirical (using intensity measurements) via psi scans (North et al., 1968)	R_int = 0.030
T_min = 0.757, T_max = 0.964	3 standard reflections every 97 reflections
4638 measured reflections	intensity decay: <2
4347 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	92 restraints
wR(F²) = 0.193	H-atom parameters constrained
S = 1.04	Δρ_max = 0.49 e Å⁻³
4347 reflections	Δρ_min = −0.46 e Å⁻³
320 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	0.85396 (9)	0.12165 (2)	−0.01007 (9)	0.0455 (2)
Cl1	0.5466 (2)	0.19134 (7)	−0.4772 (2)	0.0704 (5)
Cl2	1.07924 (18)	0.04196 (5)	0.29953 (18)	0.0480 (4)
O11	0.6293 (8)	0.1760 (2)	−0.2975 (7)	0.104 (2)
O12	0.5827 (15)	0.1680 (3)	−0.5954 (12)	0.107 (4)	0.708 (9)
O13	0.3563 (10)	0.1998 (4)	−0.5489 (12)	0.106 (3)	0.708 (9)
O14	0.6252 (16)	0.2343 (3)	−0.4642 (15)	0.128 (4)	0.708 (9)
O12A	0.412 (3)	0.1546 (6)	−0.561 (3)	0.123 (7)	0.292 (9)
O13A	0.673 (3)	0.1865 (9)	−0.538 (3)	0.121 (8)	0.292 (9)
O14A	0.449 (3)	0.2264 (6)	−0.510 (3)	0.134 (8)	0.292 (9)
O21	1.2524 (7)	0.0234 (2)	0.4056 (8)	0.105 (2)
O22	1.0940 (12)	0.0848 (3)	0.2525 (18)	0.073 (3)	0.73 (3)
O23	0.9968 (17)	0.0176 (3)	0.1363 (12)	0.091 (4)	0.73 (3)
O24	0.9656 (18)	0.0399 (5)	0.378 (2)	0.114 (5)	0.73 (3)
O22A	1.083 (3)	0.0726 (9)	0.180 (4)	0.061 (5)	0.27 (3)
O23A	0.945 (3)	0.0114 (7)	0.200 (4)	0.103 (11)	0.27 (3)
O24A	1.031 (4)	0.0626 (11)	0.422 (3)	0.120 (13)	0.27 (3)
N	0.8033 (7)	0.07655 (17)	−0.1923 (6)	0.0535 (12)
H0A	0.8722	0.0536	−0.1326	0.064*
N1	0.8876 (7)	0.16941 (18)	0.1547 (7)	0.0578 (13)
N1A	0.6448 (6)	0.09486 (15)	0.0037 (6)	0.0437 (10)
N1B	1.0370 (7)	0.14026 (16)	−0.0821 (7)	0.0505 (12)
C1	0.9117 (9)	0.1962 (2)	0.2536 (9)	0.0592 (16)
C2	0.9472 (12)	0.2296 (3)	0.3847 (12)	0.085 (2)
H21	0.9179	0.2194	0.4746	0.127*
H22	0.8726	0.2539	0.3259	0.127*
H23	1.0744	0.2375	0.4402	0.127*
C1A	0.5988 (8)	0.1008 (2)	0.1336 (7)	0.0501 (14)
H1AA	0.6635	0.1206	0.2237	0.060*
C2A	0.4574 (8)	0.0783 (2)	0.1363 (8)	0.0568 (16)
H2AA	0.4302	0.0820	0.2296	0.068*
C3A	0.3585 (8)	0.0508 (2)	0.0004 (9)	0.0579 (16)
H3AA	0.2603	0.0361	−0.0017	0.069*
C4A	0.4043 (8)	0.04453 (19)	−0.1353 (9)	0.0544 (15)
H4AA	0.3383	0.0256	−0.2285	0.065*
C5A	0.5498 (7)	0.06705 (18)	−0.1285 (7)	0.0440 (12)
C6A	0.6090 (8)	0.0636 (2)	−0.2696 (8)	0.0608 (17)
H6AA	0.5946	0.0345	−0.3126	0.073*
H6AB	0.5331	0.0818	−0.3704	0.073*
C1B	1.1723 (8)	0.1693 (2)	0.0060 (9)	0.0613 (17)
H1BA	1.1857	0.1809	0.1123	0.074*
C2B	1.2893 (10)	0.1821 (3)	−0.0557 (13)	0.081 (2)
H2BA	1.3817	0.2018	0.0070	0.097*
C3B	1.2643 (11)	0.1644 (3)	−0.2174 (13)	0.090 (3)
H3BA	1.3384	0.1731	−0.2658	0.108*
C4B	1.1319 (11)	0.1345 (3)	−0.3037 (11)	0.075 (2)
H4BA	1.1176	0.1220	−0.4087	0.090*
C5B	1.0171 (9)	0.1229 (2)	−0.2317 (9)	0.0580 (16)
C6B	0.8664 (10)	0.0902 (2)	−0.3200 (8)	0.0624 (17)
H6BA	0.7647	0.1024	−0.4259	0.075*
H6BB	0.9120	0.0659	−0.3569	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0421 (4)	0.0597 (5)	0.0456 (4)	−0.0037 (3)	0.0299 (3)	−0.0057 (3)
Cl1	0.0599 (10)	0.0979 (14)	0.0629 (10)	0.0036 (9)	0.0371 (9)	−0.0078 (9)
Cl2	0.0430 (7)	0.0613 (9)	0.0422 (7)	−0.0001 (6)	0.0225 (6)	−0.0009 (6)
O11	0.086 (4)	0.151 (6)	0.072 (4)	0.032 (4)	0.036 (3)	0.023 (4)
O12	0.120 (8)	0.114 (8)	0.098 (6)	0.021 (6)	0.061 (6)	−0.035 (5)
O13	0.070 (5)	0.147 (9)	0.101 (6)	0.021 (5)	0.041 (5)	0.001 (6)
O14	0.146 (9)	0.093 (7)	0.154 (9)	−0.027 (6)	0.079 (8)	−0.022 (6)
O12A	0.110 (12)	0.124 (13)	0.105 (11)	−0.020 (11)	0.026 (10)	−0.011 (11)
O13A	0.122 (16)	0.131 (18)	0.163 (16)	0.012 (13)	0.110 (13)	0.011 (14)
O14A	0.122 (13)	0.092 (12)	0.166 (13)	0.027 (12)	0.050 (13)	0.006 (12)
O21	0.066 (3)	0.113 (5)	0.103 (5)	0.021 (3)	0.014 (3)	0.016 (4)
O22	0.070 (4)	0.064 (5)	0.072 (6)	−0.010 (4)	0.023 (4)	−0.004 (4)
O23	0.099 (7)	0.075 (6)	0.057 (5)	−0.009 (5)	0.003 (5)	−0.010 (4)
O24	0.127 (9)	0.137 (11)	0.137 (10)	0.022 (8)	0.111 (9)	0.025 (8)
O22A	0.065 (7)	0.066 (9)	0.065 (9)	0.014 (7)	0.041 (8)	0.020 (7)
O23A	0.101 (19)	0.106 (19)	0.08 (2)	−0.064 (15)	0.026 (15)	−0.010 (14)
O24A	0.22 (4)	0.11 (2)	0.076 (16)	−0.01 (2)	0.11 (2)	−0.034 (16)
N	0.057 (3)	0.071 (3)	0.045 (3)	0.001 (2)	0.035 (2)	−0.003 (2)
N1	0.056 (3)	0.065 (3)	0.065 (3)	−0.009 (3)	0.039 (3)	−0.014 (3)
N1A	0.040 (2)	0.049 (3)	0.050 (3)	0.000 (2)	0.028 (2)	0.000 (2)
N1B	0.049 (3)	0.061 (3)	0.054 (3)	0.013 (2)	0.035 (2)	0.014 (2)
C1	0.049 (3)	0.074 (5)	0.060 (4)	−0.004 (3)	0.030 (3)	−0.005 (3)
C2	0.094 (6)	0.067 (5)	0.100 (6)	−0.017 (4)	0.053 (5)	−0.029 (4)
C1A	0.042 (3)	0.074 (4)	0.042 (3)	−0.002 (3)	0.026 (3)	−0.006 (3)
C2A	0.043 (3)	0.084 (5)	0.054 (4)	0.001 (3)	0.032 (3)	0.007 (3)
C3A	0.039 (3)	0.072 (4)	0.066 (4)	0.001 (3)	0.028 (3)	0.015 (3)
C4A	0.038 (3)	0.049 (3)	0.066 (4)	−0.002 (3)	0.017 (3)	−0.002 (3)
C5A	0.036 (3)	0.048 (3)	0.048 (3)	0.008 (2)	0.020 (2)	−0.002 (2)
C6A	0.049 (3)	0.084 (5)	0.048 (3)	−0.004 (3)	0.023 (3)	−0.016 (3)
C1B	0.047 (3)	0.063 (4)	0.074 (4)	−0.006 (3)	0.030 (3)	0.008 (3)
C2B	0.055 (4)	0.085 (5)	0.118 (7)	0.010 (4)	0.054 (5)	0.030 (5)
C3B	0.076 (5)	0.103 (7)	0.125 (8)	0.024 (5)	0.075 (6)	0.053 (6)
C4B	0.080 (5)	0.093 (6)	0.083 (5)	0.033 (4)	0.064 (4)	0.034 (4)
C5B	0.055 (4)	0.075 (4)	0.061 (4)	0.019 (3)	0.040 (3)	0.023 (3)
C6B	0.074 (4)	0.080 (5)	0.051 (3)	0.014 (4)	0.045 (3)	0.003 (3)

Geometric parameters (Å, º) top

Cu—N1	1.980 (5)	N1B—C1B	1.360 (8)
Cu—N1B	1.980 (5)	C1—C2	1.455 (10)
Cu—N1A	1.984 (4)	C2—H21	0.9600
Cu—N	1.991 (5)	C2—H22	0.9600
Cu—O22A	2.379 (17)	C2—H23	0.9600
Cu—O22	2.455 (9)	C1A—C2A	1.380 (8)
Cu—O11	2.828 (5)	C1A—H1AA	0.9300
Cl1—O14A	1.317 (13)	C2A—C3A	1.360 (9)
Cl1—O12	1.387 (7)	C2A—H2AA	0.9300
Cl1—O13A	1.389 (13)	C3A—C4A	1.390 (9)
Cl1—O13	1.420 (7)	C3A—H3AA	0.9300
Cl1—O11	1.425 (5)	C4A—C5A	1.377 (8)
Cl1—O14	1.483 (8)	C4A—H4AA	0.9300
Cl1—O12A	1.524 (14)	C5A—C6A	1.503 (8)
Cl2—O24	1.394 (7)	C6A—H6AA	0.9700
Cl2—O21	1.406 (5)	C6A—H6AB	0.9700
Cl2—O23A	1.407 (13)	C1B—C2B	1.367 (9)
Cl2—O22A	1.412 (12)	C1B—H1BA	0.9300
Cl2—O22	1.428 (7)	C2B—C3B	1.403 (12)
Cl2—O24A	1.435 (12)	C2B—H2BA	0.9300
Cl2—O23	1.438 (7)	C3B—C4B	1.364 (12)
N—C6A	1.477 (8)	C3B—H3BA	0.9300
N—C6B	1.478 (7)	C4B—C5B	1.405 (8)
N—H0A	0.9100	C4B—H4BA	0.9300
N1—C1	1.137 (8)	C5B—C6B	1.512 (10)
N1A—C5A	1.341 (7)	C6B—H6BA	0.9700
N1A—C1A	1.344 (6)	C6B—H6BB	0.9700
N1B—C5B	1.320 (8)

N1—Cu—N1B	97.2 (2)	C1A—N1A—Cu	126.2 (4)
N1—Cu—N1A	96.40 (19)	C5B—N1B—C1B	119.8 (5)
N1B—Cu—N1A	165.3 (2)	C5B—N1B—Cu	114.5 (4)
N1—Cu—N	175.1 (2)	C1B—N1B—Cu	125.6 (4)
N1B—Cu—N	83.0 (2)	N1—C1—C2	178.1 (8)
N1A—Cu—N	83.01 (19)	C1—C2—H21	109.5
N1—Cu—O22A	102.5 (9)	C1—C2—H22	109.5
N1B—Cu—O22A	85.3 (4)	H21—C2—H22	109.5
N1A—Cu—O22A	97.0 (5)	C1—C2—H23	109.5
N—Cu—O22A	82.4 (9)	H21—C2—H23	109.5
N1—Cu—O22	86.4 (4)	H22—C2—H23	109.5
N1B—Cu—O22	90.6 (3)	N1A—C1A—C2A	121.4 (6)
N1A—Cu—O22	95.6 (3)	N1A—C1A—H1AA	119.3
N—Cu—O22	98.5 (4)	C2A—C1A—H1AA	119.3
O22A—Cu—O22	16.4 (6)	C3A—C2A—C1A	119.0 (6)
N1—Cu—O11	87.9 (2)	C3A—C2A—H2AA	120.5
N1B—Cu—O11	80.84 (18)	C1A—C2A—H2AA	120.5
N1A—Cu—O11	94.23 (19)	C2A—C3A—C4A	120.0 (6)
N—Cu—O11	87.3 (2)	C2A—C3A—H3AA	120.0
O12—Cl1—O13	111.7 (6)	C4A—C3A—H3AA	120.0
O14A—Cl1—O11	116.3 (11)	C5A—C4A—C3A	118.4 (6)
O12—Cl1—O11	115.9 (5)	C5A—C4A—H4AA	120.8
O13A—Cl1—O11	107.6 (10)	C3A—C4A—H4AA	120.8
O13—Cl1—O11	112.9 (5)	N1A—C5A—C4A	121.5 (5)
O12—Cl1—O14	107.2 (6)	N1A—C5A—C6A	115.4 (5)
O13—Cl1—O14	102.8 (6)	C4A—C5A—C6A	123.1 (5)
O11—Cl1—O14	105.1 (5)	N—C6A—C5A	109.3 (5)
O14A—Cl1—O12A	107.3 (12)	N—C6A—H6AA	109.8
O13A—Cl1—O12A	104.8 (12)	C5A—C6A—H6AA	109.8
O24—Cl2—O21	113.2 (6)	N—C6A—H6AB	109.8
O21—Cl2—O23A	112.0 (11)	C5A—C6A—H6AB	109.8
O21—Cl2—O22A	112.0 (9)	H6AA—C6A—H6AB	108.3
O23A—Cl2—O22A	108.6 (10)	N1B—C1B—C2B	122.6 (7)
O24—Cl2—O22	110.2 (6)	N1B—C1B—H1BA	118.7
O21—Cl2—O22	111.8 (4)	C2B—C1B—H1BA	118.7
O21—Cl2—O24A	106.0 (10)	C1B—C2B—C3B	117.4 (8)
O23A—Cl2—O24A	109.1 (12)	C1B—C2B—H2BA	121.3
O22A—Cl2—O24A	108.9 (11)	C3B—C2B—H2BA	121.3
O24—Cl2—O23	108.6 (6)	C4B—C3B—C2B	120.2 (7)
O21—Cl2—O23	105.4 (5)	C4B—C3B—H3BA	119.9
O22—Cl2—O23	107.3 (5)	C2B—C3B—H3BA	119.9
Cl1—O11—Cu	155.4 (4)	C3B—C4B—C5B	119.1 (8)
Cl2—O22—Cu	124.0 (5)	C3B—C4B—H4BA	120.5
Cl2—O22A—Cu	130.1 (12)	C5B—C4B—H4BA	120.5
C6A—N—C6B	116.7 (5)	N1B—C5B—C4B	120.9 (7)
C6A—N—Cu	108.7 (4)	N1B—C5B—C6B	116.8 (5)
C6B—N—Cu	110.3 (4)	C4B—C5B—C6B	122.2 (7)
C6A—N—H0A	106.9	N—C6B—C5B	109.5 (5)
C6B—N—H0A	106.9	N—C6B—H6BA	109.8
Cu—N—H0A	106.9	C5B—C6B—H6BA	109.8
C1—N1—Cu	177.8 (6)	N—C6B—H6BB	109.8
C5A—N1A—C1A	119.6 (5)	C5B—C6B—H6BB	109.8
C5A—N1A—Cu	114.1 (3)	H6BA—C6B—H6BB	108.2

O14A—Cl1—O11—Cu	−174.7 (16)	O22—Cu—N1A—C5A	−109.8 (5)
O12—Cl1—O11—Cu	3.7 (12)	O11—Cu—N1A—C5A	74.8 (4)
O13A—Cl1—O11—Cu	−35.7 (16)	N1—Cu—N1A—C1A	−19.9 (5)
O13—Cl1—O11—Cu	134.3 (10)	N1B—Cu—N1A—C1A	−177.9 (7)
O14—Cl1—O11—Cu	−114.4 (10)	N—Cu—N1A—C1A	165.0 (5)
O12A—Cl1—O11—Cu	72.2 (14)	O22A—Cu—N1A—C1A	83.6 (10)
N1—Cu—O11—Cl1	152.0 (10)	O22—Cu—N1A—C1A	67.1 (6)
N1B—Cu—O11—Cl1	54.3 (10)	O11—Cu—N1A—C1A	−108.2 (5)
N1A—Cu—O11—Cl1	−111.8 (10)	N1—Cu—N1B—C5B	−161.1 (4)
N—Cu—O11—Cl1	−29.0 (10)	N1A—Cu—N1B—C5B	−3.1 (10)
O22A—Cu—O11—Cl1	22 (3)	N—Cu—N1B—C5B	14.0 (4)
O22—Cu—O11—Cl1	93 (2)	O22A—Cu—N1B—C5B	96.9 (10)
O24—Cl2—O22—Cu	−76.8 (8)	O22—Cu—N1B—C5B	112.5 (5)
O21—Cl2—O22—Cu	156.4 (6)	O11—Cu—N1B—C5B	−74.4 (4)
O23A—Cl2—O22—Cu	9.1 (16)	N1—Cu—N1B—C1B	17.1 (5)
O22A—Cl2—O22—Cu	60 (2)	N1A—Cu—N1B—C1B	175.0 (7)
O24A—Cl2—O22—Cu	−99.3 (11)	N—Cu—N1B—C1B	−167.9 (5)
O23—Cl2—O22—Cu	41.3 (8)	O22A—Cu—N1B—C1B	−85.0 (10)
N1—Cu—O22—Cl2	132.1 (10)	O22—Cu—N1B—C1B	−69.4 (6)
N1B—Cu—O22—Cl2	−130.7 (10)	O11—Cu—N1B—C1B	103.7 (5)
N1A—Cu—O22—Cl2	36.0 (10)	C5A—N1A—C1A—C2A	1.2 (9)
N—Cu—O22—Cl2	−47.7 (10)	Cu—N1A—C1A—C2A	−175.6 (4)
O22A—Cu—O22—Cl2	−59.7 (17)	N1A—C1A—C2A—C3A	−2.6 (10)
O11—Cu—O22—Cl2	−169.2 (11)	C1A—C2A—C3A—C4A	2.1 (10)
O24—Cl2—O22A—Cu	−21 (3)	C2A—C3A—C4A—C5A	−0.5 (9)
O21—Cl2—O22A—Cu	−171.5 (18)	C1A—N1A—C5A—C4A	0.5 (8)
O23A—Cl2—O22A—Cu	64 (2)	Cu—N1A—C5A—C4A	177.7 (4)
O22—Cl2—O22A—Cu	−76 (3)	C1A—N1A—C5A—C6A	178.4 (5)
O24A—Cl2—O22A—Cu	−55 (2)	Cu—N1A—C5A—C6A	−4.4 (6)
O23—Cl2—O22A—Cu	86 (2)	C3A—C4A—C5A—N1A	−0.9 (9)
N1—Cu—O22A—Cl2	83 (3)	C3A—C4A—C5A—C6A	−178.6 (6)
N1B—Cu—O22A—Cl2	180 (3)	C6B—N—C6A—C5A	−158.4 (5)
N1A—Cu—O22A—Cl2	−15 (3)	Cu—N—C6A—C5A	−32.9 (6)
N—Cu—O22A—Cl2	−97 (3)	N1A—C5A—C6A—N	25.0 (8)
O22—Cu—O22A—Cl2	71 (2)	C4A—C5A—C6A—N	−157.1 (6)
O11—Cu—O22A—Cl2	−148.2 (9)	C5B—N1B—C1B—C2B	1.1 (10)
N1B—Cu—N—C6A	−150.7 (4)	Cu—N1B—C1B—C2B	−177.0 (5)
N1A—Cu—N—C6A	25.0 (4)	N1B—C1B—C2B—C3B	0.6 (11)
O22A—Cu—N—C6A	123.1 (6)	C1B—C2B—C3B—C4B	−2.2 (11)
O22—Cu—N—C6A	119.7 (5)	C2B—C3B—C4B—C5B	2.2 (11)
O11—Cu—N—C6A	−69.6 (4)	C1B—N1B—C5B—C4B	−1.1 (9)
N1B—Cu—N—C6B	−21.5 (4)	Cu—N1B—C5B—C4B	177.1 (5)
N1A—Cu—N—C6B	154.2 (4)	C1B—N1B—C5B—C6B	178.8 (6)
O22A—Cu—N—C6B	−107.7 (6)	Cu—N1B—C5B—C6B	−3.0 (7)
O22—Cu—N—C6B	−111.1 (5)	C3B—C4B—C5B—N1B	−0.5 (10)
O11—Cu—N—C6B	59.6 (4)	C3B—C4B—C5B—C6B	179.6 (7)
N1—Cu—N1A—C5A	163.1 (4)	C6A—N—C6B—C5B	149.5 (6)
N1B—Cu—N1A—C5A	5.1 (10)	Cu—N—C6B—C5B	24.8 (6)
N—Cu—N1A—C5A	−12.0 (4)	N1B—C5B—C6B—N	−14.8 (8)
O22A—Cu—N1A—C5A	−93.4 (9)	C4B—C5B—C6B—N	165.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O22A	0.91	2.45	2.89 (3)	110
N—H0A···O23	0.91	2.30	3.084 (12)	144
N—H0A···O23ⁱ	0.91	2.50	3.317 (10)	150
C2—H21···O13Aⁱⁱ	0.96	2.23	2.98 (2)	133
C2—H22···O14ⁱⁱⁱ	0.96	2.36	3.103 (14)	134
C1A—H1AA···O12ⁱⁱ	0.93	2.46	3.176 (9)	134
C3A—H3AA···O23^iv	0.93	2.53	3.376 (15)	152
C3A—H3AA···O23A^iv	0.93	2.29	2.993 (14)	133
C6A—H6AA···O21ⁱ	0.97	2.56	3.381 (9)	143
C2B—H2BA···O14A^v	0.93	2.35	3.112 (16)	140
C3B—H3BA···O11^vi	0.93	2.56	3.429 (10)	156
C4B—H4BA···O24A^vii	0.93	2.25	3.06 (3)	145
C6B—H6BA···O12	0.97	2.56	3.425 (13)	149
C6B—H6BB···O24A^vii	0.97	2.51	3.211 (16)	129

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

Experimental details

Crystal data
Chemical formula	[Cu(ClO₄)₂(C₁₂H₁₃N₃)(C₂H₃N)]
M_r	502.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.3046 (16), 31.453 (4), 8.4978 (11)
β (°)	118.646 (10)
V (Å³)	1948.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.45
Crystal size (mm)	0.45 × 0.21 × 0.07

Data collection
Diffractometer	Bruker P4S
Absorption correction	Empirical (using intensity measurements) via psi scans (North et al., 1968)
T_min, T_max	0.757, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	4638, 4347, 2718
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.193, 1.04
No. of reflections	4347
No. of parameters	320
No. of restraints	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.46

Computer programs: XSCANS (Bruker, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O22A	0.91	2.45	2.89 (3)	110.0
N—H0A···O23	0.91	2.30	3.084 (12)	143.7
N—H0A···O23ⁱ	0.91	2.50	3.317 (10)	150.1
C2—H21···O13Aⁱⁱ	0.96	2.23	2.98 (2)	133.3
C2—H22···O14ⁱⁱⁱ	0.96	2.36	3.103 (14)	133.6
C1A—H1AA···O12ⁱⁱ	0.93	2.46	3.176 (9)	134.2
C3A—H3AA···O23^iv	0.93	2.53	3.376 (15)	152.1
C3A—H3AA···O23A^iv	0.93	2.29	2.993 (14)	132.5
C6A—H6AA···O21ⁱ	0.97	2.56	3.381 (9)	143.0
C2B—H2BA···O14A^v	0.93	2.35	3.112 (16)	139.5
C3B—H3BA···O11^vi	0.93	2.56	3.429 (10)	156.3
C4B—H4BA···O24A^vii	0.93	2.25	3.06 (3)	144.9
C6B—H6BA···O12	0.97	2.56	3.425 (13)	149.1
C6B—H6BB···O24A^vii	0.97	2.51	3.211 (16)	129.0

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

Acknowledgements

RJB acknowledges the Laboratory for the Structure of Matter at the Naval Research Laboratory, Washington, DC, USA, for access to their diffractometer.

References

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