Chloro­[N',N'-diethyl-N,N-bis(2-pyri­dyl­methyl)­ethyl­enedi­amine-[kappa]⁴N]copper(II) perchlorate

The title mononuclear copper(II) complex, [CuCl(C₁₈H₂₆N₄)]ClO₄, shows a square-pyramidal coordination with the diethyl­amino N atom at the apical position. Large anisotropies in the displacement parameters of the non-H atoms of the ligand seem to be due to rotational disorder of the ClO₄^- anion.

S1. Comment

DNA degradation by the copper(II) complexes with tripodal ligands has been investigated by one (YN) of the authors (Kobayashi et al., 1996, 1998). The structure of [Cu(Et₂py)Cl]ClO₄ (where py is pyridine), (I), is reported here.

The U_eq values of the perchlorate O1, O2, O3 and O4 atoms are in the range 0.207 (3)–0.349 (6) Ų, suggesting a rotational disorder of the ClO₄^- anion.

S2. Experimental

The ligand and its chlorocopper(II) complex were prepared as described previously (Kobayashi et al., 1998). Crystals of the title compound were grown from an aqueous methanol solution.

S3. Refinement

Positional parameters of all the H atoms were calculated geometrically and fixed with U(H) = 1.2U_eq(parent atom).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

(I)

Crystal data

[CuCl(C18H26N4)]ClO4	Dx = 1.522 Mg m^−3
Mr = 496.88	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/c	Cell parameters from 25 reflections
a = 12.513 (2) Å	θ = 10–15°
b = 14.613 (2) Å	µ = 1.29 mm^−1
c = 12.569 (2) Å	T = 298 K
β = 109.34 (1)°	Plate-like, blue
V = 2168.6 (1) Å^3	0.65 × 0.55 × 0.3 mm
Z = 4

Data collection

Rigaku AFC-5S diffractometer	Rint = 0.025
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→16
Tmin = 0.469, Tmax = 0.701	k = 0→19
5399 measured reflections	l = −16→16
4971 independent reflections	3 standard reflections every 100 reflections
2593 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.064	w = 1/[σ^2(Fo^2) + (0.05(Fo^2 + 2Fc^2)/3)^2]
wR(F^2) = 0.161	(Δ/σ)max = 0.003
S = 1.51	Δρmax = 0.45 e Å^−3
4971 reflections	Δρmin = −0.43 e Å^−3
262 parameters

Special details

Refinement. Refinement using reflections with F² > 0.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.13286 (5)	0.09364 (4)	0.08692 (4)	0.0726 (2)
Cl1	0.0406 (1)	0.1487 (1)	−0.08547 (9)	0.0953 (4)
Cl2	0.6570 (1)	0.1021 (1)	0.4177 (1)	0.0904 (5)
O1	0.6045 (10)	0.0359 (6)	0.343 (1)	0.349 (6)
O2	0.6027 (6)	0.1143 (7)	0.4878 (5)	0.283 (5)
O3	0.6409 (5)	0.1734 (4)	0.3466 (7)	0.207 (3)
O4	0.7669 (5)	0.0787 (6)	0.4624 (5)	0.225 (3)
N1	0.2373 (3)	0.0122 (3)	0.0379 (4)	0.083 (1)
N2	0.2031 (4)	0.0329 (3)	0.2407 (3)	0.107 (2)
N3	0.0124 (4)	0.1289 (4)	0.1526 (4)	0.094 (2)
N4	0.2679 (3)	0.2086 (3)	0.1642 (3)	0.070 (1)
C1	0.2573 (5)	0.0163 (4)	−0.0587 (6)	0.095 (2)
C2	0.3355 (7)	−0.0375 (5)	−0.0822 (8)	0.133 (3)
C3	0.3944 (9)	−0.0989 (8)	−0.003 (1)	0.176 (5)
C4	0.3748 (9)	−0.1041 (7)	0.095 (1)	0.175 (4)
C5	0.2933 (5)	−0.0473 (4)	0.1175 (6)	0.113 (2)
C6	0.2621 (6)	−0.0503 (6)	0.2241 (7)	0.143 (3)
C7	0.1065 (8)	0.0154 (6)	0.2852 (4)	0.133 (3)
C8	0.0206 (7)	0.0882 (5)	0.2473 (6)	0.123 (3)
C9	−0.052 (1)	0.1070 (7)	0.3150 (9)	0.158 (5)
C10	−0.127 (1)	0.1712 (9)	0.270 (1)	0.183 (6)
C11	−0.1431 (6)	0.2142 (6)	0.1692 (9)	0.141 (3)
C12	−0.0694 (6)	0.1909 (5)	0.1128 (6)	0.107 (2)
C13	0.2833 (6)	0.1013 (5)	0.3176 (4)	0.128 (2)
C14	0.3450 (5)	0.1561 (4)	0.2588 (4)	0.106 (2)
C15	0.3259 (5)	0.2324 (3)	0.0805 (4)	0.089 (2)
C16	0.4263 (5)	0.2951 (4)	0.1207 (5)	0.110 (2)
C17	0.2243 (5)	0.2898 (4)	0.2047 (4)	0.092 (2)
C18	0.1487 (6)	0.3488 (4)	0.1148 (6)	0.119 (2)
H1	0.2148	0.0590	−0.1149	0.1136*
H2	0.3488	−0.0323	−0.1529	0.1592*
H3	0.4496	−0.1382	−0.0173	0.2116*
H4	0.4167	−0.1472	0.1508	0.2102*
H5	0.3302	−0.0574	0.2875	0.1710*
H6	0.2135	−0.1020	0.2200	0.1710*
H7	0.0724	−0.0426	0.2576	0.1600*
H8	0.1352	0.0143	0.3661	0.1600*
H9	−0.0457	0.0761	0.3843	0.1894*
H10	−0.1755	0.1895	0.3117	0.2196*
H11	−0.2023	0.2584	0.1395	0.1691*
H12	−0.0773	0.2203	0.0423	0.1282*
H13	0.2402	0.1419	0.3478	0.1539*
H14	0.3372	0.0687	0.3781	0.1539*
H15	0.3896	0.1158	0.2301	0.1276*
H16	0.3940	0.1981	0.3115	0.1276*
H17	0.3509	0.1762	0.0568	0.1071*
H18	0.2709	0.2610	0.0171	0.1071*
H19	0.4835	0.2675	0.1833	0.1316*
H20	0.4561	0.3055	0.0605	0.1316*
H21	0.4034	0.3523	0.1439	0.1316*
H22	0.1826	0.2698	0.2523	0.1104*
H23	0.2878	0.3261	0.2481	0.1104*
H24	0.1242	0.4001	0.1484	0.1422*
H25	0.1891	0.3702	0.0667	0.1422*
H26	0.0839	0.3140	0.0710	0.1422*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0845 (4)	0.0706 (4)	0.0452 (3)	−0.0047 (3)	−0.0022 (2)	0.0046 (3)
Cl1	0.1100 (10)	0.098 (1)	0.0514 (6)	0.0286 (8)	−0.0089 (6)	0.0018 (6)
Cl2	0.1005 (10)	0.101 (1)	0.0743 (8)	0.0337 (8)	0.0350 (7)	0.0212 (8)
O1	0.38 (1)	0.189 (8)	0.39 (2)	0.023 (9)	0.01 (1)	−0.14 (1)
O2	0.198 (7)	0.56 (2)	0.138 (5)	0.118 (8)	0.115 (5)	0.057 (7)
O3	0.160 (5)	0.164 (5)	0.305 (9)	0.063 (4)	0.089 (5)	0.122 (6)
O4	0.137 (4)	0.37 (1)	0.176 (5)	0.129 (6)	0.061 (4)	0.135 (6)
N1	0.081 (3)	0.062 (2)	0.082 (3)	−0.001 (2)	−0.006 (2)	0.002 (2)
N2	0.129 (4)	0.090 (3)	0.059 (2)	−0.036 (3)	−0.024 (2)	0.025 (2)
N3	0.109 (4)	0.097 (3)	0.072 (3)	−0.045 (3)	0.023 (3)	−0.012 (3)
N4	0.078 (2)	0.068 (2)	0.051 (2)	−0.009 (2)	0.006 (2)	0.001 (2)
C1	0.094 (4)	0.067 (3)	0.107 (4)	−0.003 (3)	0.011 (3)	−0.026 (3)
C2	0.103 (5)	0.093 (5)	0.195 (8)	−0.018 (4)	0.040 (5)	−0.066 (5)
C3	0.107 (6)	0.113 (8)	0.28 (2)	0.022 (5)	0.026 (9)	−0.06 (1)
C4	0.103 (6)	0.082 (5)	0.28 (1)	0.023 (5)	−0.021 (8)	0.006 (8)
C5	0.089 (4)	0.063 (3)	0.140 (6)	−0.005 (3)	−0.023 (4)	0.013 (4)
C6	0.134 (6)	0.112 (5)	0.130 (6)	−0.008 (5)	−0.026 (4)	0.069 (5)
C7	0.190 (7)	0.139 (6)	0.055 (3)	−0.107 (6)	0.018 (4)	0.008 (3)
C8	0.156 (7)	0.100 (5)	0.089 (4)	−0.075 (5)	0.009 (4)	−0.007 (4)
C9	0.22 (1)	0.157 (9)	0.124 (7)	−0.122 (8)	0.097 (8)	−0.059 (7)
C10	0.24 (1)	0.18 (1)	0.17 (1)	−0.14 (1)	0.13 (1)	−0.10 (1)
C11	0.114 (5)	0.147 (7)	0.177 (8)	−0.058 (5)	0.070 (6)	−0.083 (7)
C12	0.090 (4)	0.111 (5)	0.117 (5)	−0.029 (4)	0.029 (4)	−0.034 (4)
C13	0.147 (5)	0.138 (5)	0.057 (3)	−0.069 (5)	−0.023 (3)	0.026 (3)
C14	0.108 (4)	0.094 (4)	0.075 (3)	−0.023 (3)	−0.027 (3)	0.016 (3)
C15	0.101 (4)	0.076 (4)	0.084 (3)	−0.017 (3)	0.021 (3)	−0.007 (3)
C16	0.102 (4)	0.106 (4)	0.115 (5)	−0.023 (4)	0.028 (3)	0.009 (4)
C17	0.109 (4)	0.082 (4)	0.081 (3)	−0.013 (3)	0.026 (3)	−0.012 (3)
C18	0.126 (5)	0.077 (4)	0.133 (5)	0.007 (4)	0.016 (4)	−0.006 (4)

Geometric parameters (Å, º)

Cu1—Cl1	2.240 (1)	C6—H6	0.960
Cu1—N1	2.008 (5)	C7—C8	1.47 (1)
Cu1—N2	2.042 (4)	C7—H7	0.960
Cu1—N3	2.011 (5)	C7—H8	0.960
Cu1—N4	2.352 (4)	C8—C9	1.46 (1)
Cl2—O1	1.354 (9)	C9—C10	1.32 (2)
Cl2—O2	1.292 (5)	C9—H9	0.960
Cl2—O3	1.343 (5)	C10—C11	1.37 (1)
Cl2—O4	1.346 (5)	C10—H10	0.960
N1—C1	1.321 (7)	C11—C12	1.379 (9)
N1—C5	1.335 (7)	C11—H11	0.960
N2—C6	1.472 (10)	C12—H12	0.960
N2—C7	1.511 (8)	C13—C14	1.471 (8)
N2—C13	1.517 (7)	C13—H13	0.960
N3—C8	1.304 (8)	C13—H14	0.960
N3—C12	1.334 (8)	C14—H15	0.960
N4—C14	1.474 (6)	C14—H16	0.960
N4—C15	1.503 (6)	C15—C16	1.500 (8)
N4—C17	1.467 (6)	C15—H17	0.960
C1—C2	1.361 (8)	C15—H18	0.960
C1—H1	0.960	C16—H19	0.960
C2—C3	1.36 (1)	C16—H20	0.960
C2—H2	0.960	C16—H21	0.960
C3—C4	1.33 (2)	C17—C18	1.485 (8)
C3—H3	0.960	C17—H22	0.960
C4—C5	1.42 (1)	C17—H23	0.960
C4—H4	0.960	C18—H24	0.960
C5—C6	1.52 (1)	C18—H25	0.960
C6—H5	0.960	C18—H26	0.960
Cl1···C10^i	3.480 (10)	O3···C4^vii	3.35 (1)
Cl1···C7^ii	3.518 (6)	O3···C14	3.504 (9)
O1···C14	3.53 (1)	O4···C7^v	3.337 (9)
O1···C16^iii	3.58 (1)	O4···C9^vi	3.39 (1)
O2···C16^iv	3.443 (8)	O4···C10^vi	3.40 (1)
O2···C6^v	3.575 (9)	C2···C11^ii	3.452 (9)
O2···C14	3.593 (9)	C2···C10^ii	3.48 (1)
O3···C10^vi	3.35 (1)	C3···C11^ii	3.57 (1)
Cl1—Cu1—N1	95.5 (1)	N2—C7—H7	109.3
Cl1—Cu1—N2	173.7 (1)	N2—C7—H8	109.3
Cl1—Cu1—N3	95.1 (2)	C8—C7—H7	109.3
Cl1—Cu1—N4	102.26 (9)	C8—C7—H8	109.3
N1—Cu1—N2	85.0 (2)	H7—C7—H8	109.5
N1—Cu1—N3	158.4 (2)	N3—C8—C7	116.8 (8)
N1—Cu1—N4	95.6 (1)	N3—C8—C9	124.7 (9)
N2—Cu1—N3	82.5 (2)	C7—C8—C9	118.4 (8)
N2—Cu1—N4	84.0 (1)	C8—C9—C10	112 (1)
N3—Cu1—N4	100.4 (1)	C8—C9—H9	123.9
O1—Cl2—O2	108.9 (7)	C10—C9—H9	123.9
O1—Cl2—O3	99.5 (7)	C9—C10—C11	126 (1)
O1—Cl2—O4	107.5 (6)	C9—C10—H10	116.9
O2—Cl2—O3	110.4 (5)	C11—C10—H10	116.9
O2—Cl2—O4	116.5 (4)	C10—C11—C12	116 (1)
O3—Cl2—O4	112.5 (4)	C10—C11—H11	121.8
Cu1—N1—C1	126.6 (4)	C12—C11—H11	121.8
Cu1—N1—C5	112.9 (5)	N3—C12—C11	122.4 (8)
C1—N1—C5	120.4 (6)	N3—C12—H12	118.8
Cu1—N2—C6	107.7 (4)	C11—C12—H12	118.8
Cu1—N2—C7	106.1 (4)	N2—C13—C14	112.7 (5)
Cu1—N2—C13	107.6 (3)	N2—C13—H13	108.7
C6—N2—C7	114.4 (6)	N2—C13—H14	108.7
C6—N2—C13	112.2 (5)	C14—C13—H13	108.7
C7—N2—C13	108.5 (5)	C14—C13—H14	108.7
Cu1—N3—C8	114.6 (6)	H13—C13—H14	109.5
Cu1—N3—C12	127.3 (4)	N4—C14—C13	112.1 (5)
C8—N3—C12	118.1 (7)	N4—C14—H15	108.8
Cu1—N4—C14	98.7 (3)	N4—C14—H16	108.8
Cu1—N4—C15	108.9 (3)	C13—C14—H15	108.8
Cu1—N4—C17	115.0 (3)	C13—C14—H16	108.8
C14—N4—C15	110.2 (4)	H15—C14—H16	109.5
C14—N4—C17	111.1 (4)	N4—C15—C16	116.8 (4)
C15—N4—C17	112.1 (4)	N4—C15—H17	107.6
N1—C1—C2	122.8 (6)	N4—C15—H18	107.6
N1—C1—H1	118.6	C16—C15—H17	107.6
C2—C1—H1	118.6	C16—C15—H18	107.6
C1—C2—C3	118.4 (9)	H17—C15—H18	109.5
C1—C2—H2	120.8	C15—C16—H19	109.5
C3—C2—H2	120.8	C15—C16—H20	109.5
C2—C3—C4	119 (1)	C15—C16—H21	109.5
C2—C3—H3	120.3	H19—C16—H20	109.5
C4—C3—H3	120.3	H19—C16—H21	109.5
C3—C4—C5	121 (1)	H20—C16—H21	109.5
C3—C4—H4	119.4	N4—C17—C18	114.9 (4)
C5—C4—H4	119.4	N4—C17—H22	108.1
N1—C5—C4	117.7 (8)	N4—C17—H23	108.1
N1—C5—C6	117.2 (6)	C18—C17—H22	108.1
C4—C5—C6	125.1 (8)	C18—C17—H23	108.1
N2—C6—C5	112.9 (5)	H22—C17—H23	109.5
N2—C6—H5	108.6	C17—C18—H24	109.5
N2—C6—H6	108.6	C17—C18—H25	109.5
C5—C6—H5	108.6	C17—C18—H26	109.5
C5—C6—H6	108.6	H24—C18—H25	109.5
H5—C6—H6	109.5	H24—C18—H26	109.5
N2—C7—C8	110.3 (5)	H25—C18—H26	109.5

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