[1,6-Bis(2-pyridyl­methyl)-2,5-di­aza­hexane-[kappa]⁴N]­chlorocopper(II) per­chlorate

The title mononuclear copper(II) compound, [CuCl(C₁₆H₂₂­N₄)]­ClO₄, shows a slightly tetrahedrally distorted square-pyramidal coordination with the chlorine ligand at the apical position. The directions of the two N-Me bond axes are syn to the Cu-Cl bond.

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; Kobayashi et al., 1998). The structure of [Cu(mep)Cl]ClO₄, (I), where mep is 1,6-bis(2-pyridylmethyl)-2,5-diazahexane, is reported here.

S2. Experimental

The ligand and its chlorocopper(II) complex were prepared as described previously (Okuno et al., 1997). Crystals of the title compound were grown from a methanol solution.

S3. Refinement

Positional parameters of all the H atoms were calculated geometrically and fixed with U(H) = 1.2U_eq(parent atom). The maximum residual density was located 0.99 Å from the Cu1 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(C16H22N4)]ClO4	Dx = 1.610 Mg m^−3
Mr = 468.83	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/c	Cell parameters from 25 reflections
a = 11.044 (2) Å	θ = 10–15°
b = 11.085 (1) Å	µ = 1.44 mm^−1
c = 15.858 (1) Å	T = 299 K
β = 95.100 (9)°	Prism, blue
V = 1933.8 (4) Å^3	0.6 × 0.5 × 0.2 mm
Z = 4

Data collection

Rigaku AFC-5S diffractometer	Rint = 0.028
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→14
Tmin = 0.365, Tmax = 0.764	k = 0→14
4916 measured reflections	l = −21→21
4445 independent reflections	3 standard reflections every 100 reflections
3426 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.049	w = 1/[σ^2(Fo^2) + (0.05(Fo^2 + 2Fc^2)/3)^2]
wR(F^2) = 0.122	(Δ/σ)max = 0.001
S = 1.51	Δρmax = 0.98 e Å^−3
4445 reflections	Δρmin = −0.68 e Å^−3
244 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	0.71254 (3)	0.16092 (3)	0.27961 (2)	0.02884 (10)
Cl1	0.55658 (8)	0.22147 (8)	0.17090 (5)	0.0431 (2)
Cl2	1.12933 (9)	0.14997 (8)	0.39210 (5)	0.0443 (2)
O1	1.1330 (8)	0.0417 (4)	0.4312 (3)	0.193 (3)
O2	1.0079 (4)	0.1912 (6)	0.3864 (3)	0.147 (2)
O3	1.2025 (4)	0.2331 (4)	0.4416 (2)	0.089 (1)
O4	1.1616 (4)	0.1408 (4)	0.3088 (2)	0.102 (2)
N1	0.7187 (3)	0.3226 (2)	0.3429 (2)	0.0351 (7)
N2	0.6194 (3)	0.1125 (3)	0.3819 (2)	0.0388 (7)
N3	0.7537 (3)	−0.0188 (2)	0.2757 (2)	0.0374 (7)
N4	0.8456 (2)	0.1720 (2)	0.1994 (2)	0.0334 (7)
C1	0.7219 (3)	0.4352 (3)	0.3114 (2)	0.0414 (9)
C2	0.7028 (4)	0.5365 (3)	0.3591 (3)	0.050 (1)
C3	0.6812 (4)	0.5217 (4)	0.4423 (3)	0.058 (1)
C4	0.6774 (4)	0.4067 (4)	0.4761 (2)	0.052 (1)
C5	0.6960 (3)	0.3091 (3)	0.4243 (2)	0.0391 (9)
C6	0.6870 (4)	0.1798 (3)	0.4518 (2)	0.0451 (10)
C7	0.6300 (4)	−0.0196 (3)	0.3956 (2)	0.051 (1)
C8	0.7457 (4)	−0.0652 (3)	0.3630 (2)	0.051 (1)
C9	0.8790 (3)	−0.0306 (3)	0.2500 (2)	0.0429 (9)
C10	0.9022 (3)	0.0669 (3)	0.1882 (2)	0.0369 (8)
C11	0.9808 (4)	0.0515 (4)	0.1257 (3)	0.051 (1)
C12	1.0050 (4)	0.1490 (4)	0.0759 (2)	0.053 (1)
C13	0.9502 (3)	0.2579 (4)	0.0889 (2)	0.048 (1)
C14	0.8690 (3)	0.2653 (3)	0.1499 (2)	0.0414 (9)
C15	0.4893 (4)	0.1493 (4)	0.3745 (3)	0.059 (1)
C16	0.6678 (4)	−0.0813 (3)	0.2130 (2)	0.048 (1)
H1	0.7382	0.4455	0.2533	0.0497*
H2	0.7045	0.6156	0.3346	0.0600*
H3	0.6687	0.5908	0.4770	0.0699*
H4	0.6622	0.3949	0.5342	0.0629*
H5	0.6445	0.1751	0.5019	0.0542*
H6	0.7670	0.1463	0.4632	0.0542*
H7	0.6312	−0.0367	0.4550	0.0611*
H8	0.5617	−0.0593	0.3659	0.0611*
H9	0.7452	−0.1518	0.3623	0.0611*
H10	0.8143	−0.0372	0.3992	0.0611*
H11	0.9362	−0.0237	0.2990	0.0515*
H12	0.8881	−0.1079	0.2240	0.0515*
H13	1.0176	−0.0255	0.1172	0.0608*
H14	1.0597	0.1409	0.0324	0.0632*
H15	0.9681	0.3275	0.0561	0.0570*
H16	0.8276	0.3403	0.1571	0.0497*
H17	0.4834	0.2344	0.3634	0.0703*
H18	0.4461	0.1059	0.3289	0.0703*
H19	0.4545	0.1316	0.4264	0.0703*
H20	0.5866	−0.0740	0.2296	0.0580*
H21	0.6719	−0.0454	0.1582	0.0580*
H22	0.6892	−0.1651	0.2105	0.0580*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0317 (2)	0.0244 (2)	0.0310 (2)	−0.0015 (2)	0.0062 (1)	0.0025 (1)
Cl1	0.0383 (4)	0.0484 (5)	0.0416 (4)	0.0066 (4)	−0.0016 (3)	0.0033 (3)
Cl2	0.0537 (5)	0.0364 (4)	0.0434 (4)	−0.0061 (4)	0.0082 (4)	−0.0042 (3)
O1	0.38 (1)	0.058 (3)	0.124 (4)	−0.043 (4)	−0.067 (5)	0.036 (3)
O2	0.071 (3)	0.254 (7)	0.115 (4)	0.041 (4)	−0.004 (2)	−0.076 (4)
O3	0.089 (3)	0.083 (3)	0.097 (3)	−0.036 (2)	0.022 (2)	−0.043 (2)
O4	0.119 (4)	0.124 (4)	0.070 (2)	−0.023 (3)	0.042 (2)	−0.033 (2)
N1	0.038 (1)	0.031 (1)	0.036 (1)	−0.001 (1)	0.004 (1)	0.000 (1)
N2	0.045 (2)	0.039 (1)	0.033 (1)	−0.003 (1)	0.007 (1)	0.006 (1)
N3	0.039 (1)	0.029 (1)	0.044 (1)	−0.003 (1)	0.004 (1)	0.002 (1)
N4	0.032 (1)	0.032 (1)	0.037 (1)	0.000 (1)	0.005 (1)	0.003 (1)
C1	0.042 (2)	0.031 (2)	0.053 (2)	−0.004 (1)	0.010 (2)	−0.001 (1)
C2	0.051 (2)	0.030 (2)	0.069 (2)	0.001 (2)	0.007 (2)	−0.002 (2)
C3	0.068 (3)	0.043 (2)	0.064 (2)	0.003 (2)	0.008 (2)	−0.019 (2)
C4	0.071 (3)	0.047 (2)	0.040 (2)	0.004 (2)	0.008 (2)	−0.008 (2)
C5	0.044 (2)	0.038 (2)	0.035 (2)	0.002 (1)	0.001 (1)	−0.002 (1)
C6	0.064 (2)	0.040 (2)	0.031 (2)	0.004 (2)	0.004 (2)	0.003 (1)
C7	0.073 (3)	0.037 (2)	0.044 (2)	−0.012 (2)	0.014 (2)	0.008 (1)
C8	0.073 (3)	0.030 (2)	0.050 (2)	0.003 (2)	0.006 (2)	0.012 (1)
C9	0.040 (2)	0.035 (2)	0.054 (2)	0.007 (1)	0.001 (1)	0.004 (1)
C10	0.032 (2)	0.036 (2)	0.042 (2)	0.000 (1)	0.001 (1)	−0.001 (1)
C11	0.039 (2)	0.050 (2)	0.065 (2)	0.009 (2)	0.012 (2)	−0.002 (2)
C12	0.041 (2)	0.066 (3)	0.053 (2)	0.001 (2)	0.018 (2)	−0.002 (2)
C13	0.041 (2)	0.057 (2)	0.046 (2)	−0.006 (2)	0.010 (2)	0.007 (2)
C14	0.044 (2)	0.038 (2)	0.043 (2)	0.000 (2)	0.009 (1)	0.006 (1)
C15	0.042 (2)	0.078 (3)	0.058 (2)	0.001 (2)	0.017 (2)	0.015 (2)
C16	0.051 (2)	0.037 (2)	0.057 (2)	−0.009 (2)	0.004 (2)	−0.007 (2)

Geometric parameters (Å, º)

Cu1—Cl1	2.421 (1)	C4—H4	0.960
Cu1—N1	2.053 (3)	C5—C6	1.504 (5)
Cu1—N2	2.068 (3)	C6—H5	0.960
Cu1—N3	2.046 (3)	C6—H6	0.960
Cu1—N4	2.031 (3)	C7—C8	1.507 (6)
Cl2—O1	1.350 (4)	C7—H7	0.960
Cl2—O2	1.412 (5)	C7—H8	0.960
Cl2—O3	1.417 (3)	C8—H9	0.960
Cl2—O4	1.402 (3)	C8—H10	0.960
N1—C1	1.347 (4)	C9—C10	1.496 (5)
N1—C5	1.345 (4)	C9—H11	0.960
N2—C6	1.481 (4)	C9—H12	0.960
N2—C7	1.484 (5)	C10—C11	1.385 (5)
N2—C15	1.488 (5)	C11—C12	1.379 (6)
N3—C8	1.487 (4)	C11—H13	0.960
N3—C9	1.483 (5)	C12—C13	1.374 (6)
N3—C16	1.485 (5)	C12—H14	0.960
N4—C10	1.341 (4)	C13—C14	1.379 (5)
N4—C14	1.337 (4)	C13—H15	0.960
C1—C2	1.381 (5)	C14—H16	0.960
C1—H1	0.960	C15—H17	0.960
C2—C3	1.371 (6)	C15—H18	0.960
C2—H2	0.960	C15—H19	0.960
C3—C4	1.385 (6)	C16—H20	0.960
C3—H3	0.960	C16—H21	0.960
C4—C5	1.384 (5)	C16—H22	0.960
Cu1···O2	3.556 (5)	O3···C12^iv	3.438 (5)
Cl1···C2^i	3.520 (4)	O3···C3^v	3.465 (5)
O1···C13^ii	3.285 (6)	O3···C15^vi	3.553 (6)
O1···C14^ii	3.322 (6)	O3···C16^vii	3.594 (6)
O1···C8^iii	3.425 (7)	O4···C1^ii	3.304 (5)
O1···C6^iii	3.573 (7)	O4···C2^ii	3.374 (5)
O2···N4	3.333 (5)	O4···C10	3.400 (6)
O2···C13^iv	3.376 (6)	O4···C11	3.517 (6)
O2···C12^iv	3.490 (6)	C1···C11^vii	3.586 (5)
O2···C9	3.494 (7)	C2···C11^vii	3.486 (6)
O2···N1	3.523 (6)	C2···C12^vii	3.528 (6)
O2···C10	3.533 (6)	C6···C13^iv	3.539 (5)
Cl1—Cu1—N1	95.6 (1)	N2—C6—H5	109.9
Cl1—Cu1—N2	105.0 (1)	N2—C6—H6	109.9
Cl1—Cu1—N3	113.3 (1)	C5—C6—H5	109.9
Cl1—Cu1—N4	92.6 (1)	C5—C6—H6	109.9
N1—Cu1—N2	80.8 (1)	H5—C6—H6	109.5
N1—Cu1—N3	150.1 (1)	N2—C7—C8	109.8 (3)
N1—Cu1—N4	105.0 (1)	N2—C7—H7	109.4
N2—Cu1—N3	84.2 (1)	N2—C7—H8	109.4
N2—Cu1—N4	161.0 (1)	C8—C7—H7	109.4
N3—Cu1—N4	82.2 (1)	C8—C7—H8	109.4
O1—Cl2—O2	107.9 (5)	H7—C7—H8	109.5
O1—Cl2—O3	109.4 (3)	N3—C8—C7	109.0 (3)
O1—Cl2—O4	111.6 (4)	N3—C8—H9	109.6
O2—Cl2—O3	108.5 (3)	N3—C8—H10	109.6
O2—Cl2—O4	106.4 (3)	C7—C8—H9	109.6
O3—Cl2—O4	112.9 (2)	C7—C8—H10	109.6
Cu1—N1—C1	128.9 (2)	H9—C8—H10	109.5
Cu1—N1—C5	111.8 (2)	N3—C9—C10	109.5 (3)
C1—N1—C5	118.2 (3)	N3—C9—H11	109.5
Cu1—N2—C6	101.7 (2)	N3—C9—H12	109.5
Cu1—N2—C7	109.4 (2)	C10—C9—H11	109.5
Cu1—N2—C15	114.2 (2)	C10—C9—H12	109.5
C6—N2—C7	111.1 (3)	H11—C9—H12	109.5
C6—N2—C15	109.9 (3)	N4—C10—C9	115.6 (3)
C7—N2—C15	110.2 (3)	N4—C10—C11	122.0 (3)
Cu1—N3—C8	106.1 (2)	C9—C10—C11	122.3 (3)
Cu1—N3—C9	108.1 (2)	C10—C11—C12	118.7 (3)
Cu1—N3—C16	110.1 (2)	C10—C11—H13	120.7
C8—N3—C9	111.1 (3)	C12—C11—H13	120.7
C8—N3—C16	112.0 (3)	C11—C12—C13	119.5 (3)
C9—N3—C16	109.3 (3)	C11—C12—H14	120.3
Cu1—N4—C10	113.7 (2)	C13—C12—H14	120.3
Cu1—N4—C14	127.1 (2)	C12—C13—C14	118.7 (3)
C10—N4—C14	118.5 (3)	C12—C13—H15	120.6
N1—C1—C2	122.6 (3)	C14—C13—H15	120.6
N1—C1—H1	118.7	N4—C14—C13	122.5 (3)
C2—C1—H1	118.7	N4—C14—H16	118.7
C1—C2—C3	118.6 (3)	C13—C14—H16	118.8
C1—C2—H2	120.7	N2—C15—H17	109.5
C3—C2—H2	120.7	N2—C15—H18	109.5
C2—C3—C4	119.7 (3)	N2—C15—H19	109.5
C2—C3—H3	120.1	H17—C15—H18	109.5
C4—C3—H3	120.1	H17—C15—H19	109.5
C3—C4—C5	118.6 (3)	H18—C15—H19	109.5
C3—C4—H4	120.7	N3—C16—H20	109.5
C5—C4—H4	120.7	N3—C16—H21	109.5
N1—C5—C4	122.2 (3)	N3—C16—H22	109.5
N1—C5—C6	114.0 (3)	H20—C16—H21	109.5
C4—C5—C6	123.8 (3)	H20—C16—H22	109.5
N2—C6—C5	107.8 (3)	H21—C16—H22	109.5

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