[N'-Benzoyl-N,N-bis(2-pyridylmethyl-[kappa]N)­ethyl­enedi­amine-[kappa]N]chloro­copper(II) hexa­fluoro­phosphate

The title mononuclear copper(II) complex, [CuCl(C₂₁H₂₂­N₄O)]­PF₆, shows a distorted square-planar coordination and the benzoyl­amino N atom does not coordinate to the Cu atom.

S1. Comment

Crystal structures and catalytic activities of copper(II) complexes containing N,N'-bis(2-pyridylmethyl)-β-alanineamide ligands were reported by Okuna et al. (1997). The copper(II) complexes with similar tripodal ligands containing a peptide group convert supercoiled plasmid DNA into a mixture of nicked and linear forms in the presence of hydrogen peroxide (Kobayashi et al., 1998).

In the crystals of the title compound, [Cu(dpab)Cl]PF₆ [(I), dpab is N'-benzoyl-N,N-bis(2-pyridylmethyl)ethylenediamine], the benzoylamino N4 atom does not coordinate to the Cu atom; Cu···N4 = 2.827 (4) Å. The N4—H1 moiety is incorporated in a bifurcated weak hydrogen bond with the F4 and F5 atoms of PF₆; the N4···F4 and N4···F5 distances are 3.421 (9) and 3.383 (10) Å, respectively.

S2. Experimental

The ligand and its chlorocopper(II) complex were prepared as described previously (Okuna et al., 1997; Kobayashi et al., 1998). Crystals of the title compound were grown from an aqueous methanol/acetonitrile 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(C21H22N4O)]PF6	Dx = 1.631 Mg m^−3
Mr = 590.4	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/n	Cell parameters from 25 reflections
a = 13.064 (3) Å	θ = 10–15°
b = 13.347 (4) Å	µ = 1.16 mm^−1
c = 14.077 (3) Å	T = 296 K
β = 101.52 (2)°	Plate-like, blue
V = 2405.0 (10) Å^3	0.6 × 0.5 × 0.1 mm
Z = 4

Data collection

Rigaku AFC-5S diffractometer	Rint = 0.012
θ–2θ scans	θmax = 27.5°
Absorption correction: integration (Coppens et al., 1965)	h = 0→17
Tmin = 0.868, Tmax = 0.966	k = 0→17
5998 measured reflections	l = −18→18
5513 independent reflections	3 standard reflections every 100 reflections
4029 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.065	w = 1/[σ^2(Fo^2) + (0.1(Fo^2 + 2Fc^2)/3)^2]
wR(F^2) = 0.196	(Δ/σ)max = 0.004
S = 1.38	Δρmax = 0.67 e Å^−3
5513 reflections	Δρmin = −0.84 e Å^−3
316 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	0.96150 (3)	0.08740 (3)	0.08813 (3)	0.0369 (1)
Cl1	1.02592 (10)	−0.06856 (8)	0.11479 (8)	0.0534 (3)
P1	0.61300 (10)	0.07910 (10)	0.3008 (1)	0.0578 (4)
F1	0.5455 (5)	−0.0141 (3)	0.2737 (4)	0.158 (2)
F2	0.5276 (5)	0.1460 (7)	0.3134 (7)	0.227 (4)
F3	0.6461 (7)	0.0420 (6)	0.4038 (4)	0.209 (3)
F4	0.6883 (5)	0.1702 (5)	0.3221 (5)	0.200 (3)
F5	0.7091 (6)	0.0201 (8)	0.2856 (8)	0.249 (5)
F6	0.5806 (7)	0.1122 (4)	0.1936 (4)	0.187 (3)
O1	1.0989 (3)	0.1649 (3)	0.3584 (2)	0.0604 (10)
N1	0.8136 (3)	0.0471 (3)	0.0416 (3)	0.0457 (9)
N2	0.8964 (3)	0.2273 (2)	0.0681 (2)	0.0404 (8)
N3	1.0942 (3)	0.1638 (3)	0.1266 (2)	0.0486 (10)
N4	0.9338 (3)	0.1419 (3)	0.2754 (3)	0.0476 (10)
C1	0.7712 (4)	−0.0415 (4)	0.0502 (4)	0.062 (1)
C2	0.6693 (5)	−0.0640 (6)	0.0052 (6)	0.090 (2)
C3	0.6119 (4)	0.0078 (7)	−0.0518 (5)	0.094 (2)
C4	0.6542 (4)	0.1020 (6)	−0.0601 (4)	0.077 (2)
C5	0.7562 (3)	0.1191 (4)	−0.0112 (3)	0.051 (1)
C6	0.8114 (4)	0.2167 (4)	−0.0183 (3)	0.053 (1)
C7	0.9810 (4)	0.2962 (3)	0.0513 (4)	0.056 (1)
C8	1.0843 (4)	0.2624 (4)	0.1098 (3)	0.055 (1)
C9	1.1658 (5)	0.3280 (5)	0.1407 (4)	0.081 (2)
C10	1.2585 (5)	0.2920 (7)	0.1904 (5)	0.094 (2)
C11	1.2702 (4)	0.1920 (8)	0.2066 (4)	0.090 (2)
C12	1.1856 (3)	0.1287 (5)	0.1754 (3)	0.062 (1)
C13	0.8493 (3)	0.2606 (3)	0.1511 (3)	0.047 (1)
C14	0.9186 (4)	0.2474 (3)	0.2506 (3)	0.048 (1)
C15	1.0231 (3)	0.1099 (3)	0.3358 (3)	0.045 (1)
C16	1.0227 (3)	0.0045 (3)	0.3693 (3)	0.044 (1)
C17	1.1059 (3)	−0.0282 (4)	0.4407 (3)	0.054 (1)
C18	1.1068 (4)	−0.1247 (4)	0.4771 (4)	0.064 (2)
C19	1.0259 (5)	−0.1893 (4)	0.4423 (5)	0.069 (2)
C20	0.9446 (4)	−0.1589 (4)	0.3704 (4)	0.064 (1)
C21	0.9421 (4)	−0.0627 (4)	0.3349 (4)	0.052 (1)
H1	0.8805	0.0943	0.2492	0.0571*
H2	0.8122	−0.0920	0.0888	0.0748*
H3	0.6396	−0.1284	0.0137	0.1082*
H4	0.5424	−0.0071	−0.0860	0.1128*
H5	0.6144	0.1536	−0.0983	0.0920*
H6	0.7630	0.2712	−0.0207	0.0639*
H7	0.8403	0.2172	−0.0759	0.0639*
H8	0.9840	0.2957	−0.0163	0.0677*
H9	0.9664	0.3628	0.0704	0.0677*
H10	1.1571	0.3984	0.1273	0.0966*
H11	1.3153	0.3369	0.2139	0.1123*
H12	1.3361	0.1653	0.2392	0.1081*
H13	1.1929	0.0583	0.1892	0.0743*
H14	0.8325	0.3305	0.1424	0.0563*
H15	0.7865	0.2229	0.1495	0.0563*
H16	0.8864	0.2798	0.2980	0.0579*
H17	0.9853	0.2776	0.2507	0.0579*
H18	1.1628	0.0164	0.4647	0.0644*
H19	1.1640	−0.1465	0.5267	0.0771*
H20	1.0263	−0.2558	0.4684	0.0833*
H21	0.8894	−0.2048	0.3448	0.0764*
H22	0.8841	−0.0415	0.2858	0.0628*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0326 (3)	0.0329 (3)	0.0428 (3)	0.0039 (2)	0.0017 (2)	0.0007 (2)
Cl1	0.0687 (7)	0.0442 (6)	0.0486 (6)	0.0218 (5)	0.0146 (5)	0.0088 (4)
P1	0.0466 (6)	0.0523 (7)	0.0697 (8)	0.0036 (5)	−0.0001 (6)	0.0109 (6)
F1	0.202 (5)	0.077 (3)	0.152 (5)	−0.061 (3)	−0.073 (4)	0.039 (3)
F2	0.138 (5)	0.252 (9)	0.30 (1)	0.074 (6)	0.068 (6)	−0.062 (8)
F3	0.266 (8)	0.231 (7)	0.088 (3)	−0.131 (7)	−0.067 (4)	0.062 (4)
F4	0.163 (5)	0.148 (5)	0.227 (7)	−0.074 (4)	−0.109 (5)	0.084 (5)
F5	0.148 (6)	0.25 (1)	0.37 (1)	0.088 (6)	0.108 (7)	0.028 (9)
F6	0.299 (9)	0.102 (4)	0.112 (4)	−0.078 (5)	−0.074 (5)	0.044 (3)
O1	0.053 (2)	0.068 (2)	0.056 (2)	−0.021 (2)	0.000 (1)	0.004 (2)
N1	0.039 (2)	0.048 (2)	0.050 (2)	−0.002 (1)	0.006 (1)	−0.008 (2)
N2	0.042 (2)	0.034 (2)	0.042 (2)	0.005 (1)	0.001 (1)	0.001 (1)
N3	0.039 (2)	0.066 (2)	0.041 (2)	−0.003 (2)	0.007 (1)	−0.005 (2)
N4	0.050 (2)	0.047 (2)	0.044 (2)	−0.006 (2)	0.005 (1)	0.001 (2)
C1	0.062 (3)	0.057 (3)	0.069 (3)	−0.020 (2)	0.016 (2)	−0.013 (2)
C2	0.073 (4)	0.107 (5)	0.094 (5)	−0.048 (4)	0.026 (4)	−0.041 (4)
C3	0.050 (3)	0.150 (7)	0.078 (4)	−0.031 (4)	0.004 (3)	−0.034 (5)
C4	0.045 (3)	0.118 (5)	0.060 (3)	0.007 (3)	−0.006 (2)	−0.023 (3)
C5	0.040 (2)	0.066 (3)	0.043 (2)	0.008 (2)	0.001 (2)	−0.009 (2)
C6	0.054 (2)	0.054 (3)	0.045 (2)	0.019 (2)	−0.006 (2)	0.000 (2)
C7	0.074 (3)	0.042 (2)	0.054 (3)	−0.008 (2)	0.016 (2)	0.006 (2)
C8	0.057 (3)	0.062 (3)	0.047 (2)	−0.018 (2)	0.017 (2)	−0.006 (2)
C9	0.081 (4)	0.092 (5)	0.073 (4)	−0.043 (3)	0.025 (3)	−0.015 (3)
C10	0.070 (4)	0.146 (7)	0.067 (4)	−0.051 (5)	0.018 (3)	−0.029 (4)
C11	0.039 (3)	0.178 (8)	0.053 (3)	−0.010 (4)	0.007 (2)	−0.024 (4)
C12	0.036 (2)	0.096 (4)	0.052 (3)	0.006 (2)	0.004 (2)	−0.005 (3)
C13	0.053 (2)	0.037 (2)	0.051 (2)	0.010 (2)	0.011 (2)	−0.002 (2)
C14	0.061 (3)	0.042 (2)	0.043 (2)	−0.002 (2)	0.012 (2)	−0.008 (2)
C15	0.045 (2)	0.057 (3)	0.033 (2)	−0.009 (2)	0.008 (2)	−0.003 (2)
C16	0.044 (2)	0.054 (2)	0.035 (2)	0.002 (2)	0.014 (2)	−0.003 (2)
C17	0.049 (2)	0.064 (3)	0.047 (2)	0.005 (2)	0.008 (2)	−0.003 (2)
C18	0.067 (3)	0.069 (3)	0.057 (3)	0.024 (3)	0.013 (2)	0.006 (2)
C19	0.080 (4)	0.049 (3)	0.084 (4)	0.017 (3)	0.028 (3)	0.003 (3)
C20	0.060 (3)	0.047 (3)	0.083 (4)	−0.004 (2)	0.013 (3)	−0.003 (2)
C21	0.050 (2)	0.049 (2)	0.055 (3)	−0.002 (2)	0.005 (2)	−0.001 (2)

Geometric parameters (Å, º)

Cu1—Cl1	2.249 (1)	C6—H6	0.960
Cu1—N1	1.986 (3)	C6—H7	0.960
Cu1—N2	2.048 (3)	C7—C8	1.503 (7)
Cu1—N3	1.991 (4)	C7—H8	0.960
Cu1—N4	2.827 (4)	C7—H9	0.960
P1—F1	1.529 (4)	C8—C9	1.381 (7)
P1—F2	1.467 (6)	C9—C10	1.36 (1)
P1—F3	1.511 (5)	C9—H10	0.960
P1—F4	1.554 (5)	C10—C11	1.36 (1)
P1—F5	1.533 (6)	C10—H11	0.960
P1—F6	1.548 (5)	C11—C12	1.391 (9)
O1—C15	1.223 (5)	C11—H12	0.960
N1—C1	1.322 (6)	C12—H13	0.960
N1—C5	1.348 (6)	C13—C14	1.518 (6)
N2—C6	1.480 (5)	C13—H14	0.960
N2—C7	1.493 (6)	C13—H15	0.960
N2—C13	1.493 (5)	C14—H16	0.960
N3—C8	1.339 (7)	C14—H17	0.960
N3—C12	1.338 (6)	C15—C16	1.484 (6)
N4—C14	1.455 (6)	C16—C17	1.394 (6)
N4—C15	1.367 (6)	C16—C21	1.395 (6)
N4—H1	0.960	C17—C18	1.385 (8)
C1—C2	1.388 (8)	C17—H18	0.960
C1—H2	0.960	C18—C19	1.376 (8)
C2—C3	1.37 (1)	C18—H19	0.960
C2—H3	0.960	C19—C20	1.375 (8)
C3—C4	1.39 (1)	C19—H20	0.960
C3—H4	0.960	C20—C21	1.375 (7)
C4—C5	1.391 (7)	C20—H21	0.960
C4—H5	0.960	C21—H22	0.960
C5—C6	1.502 (7)
Cu1···N4	2.827 (4)	F6···C20^vi	3.184 (7)
Cu1···Cl1^i	2.905 (1)	F6···C3^iii	3.297 (8)
Cl1···N1^i	3.342 (4)	F6···C19^vi	3.399 (8)
Cl1···C6^i	3.379 (5)	O1···C4^vii	3.344 (8)
Cl1···C5^i	3.513 (4)	O1···C6^vii	3.361 (5)
F1···C14^ii	3.246 (7)	O1···C19^v	3.530 (7)
F1···C3^iii	3.381 (8)	C1···C12^i	3.532 (7)
F1···C13^ii	3.386 (7)	C2···C12^i	3.567 (8)
F1···C7^ii	3.598 (7)	C3···C3^iii	3.53 (1)
F2···C11^iv	3.454 (9)	C10···C18^viii	3.399 (8)
F3···C18^v	3.505 (9)	C15···C18^v	3.412 (7)
F3···C17^v	3.534 (8)	C15···C19^v	3.476 (7)
F4···N4	3.421 (9)	C16···C18^v	3.401 (6)
F4···C14	3.513 (9)	C16···C17^v	3.445 (6)
F4···C18^v	3.537 (7)	C17···C21^v	3.554 (7)
F5···C21	3.182 (8)	C17···C17^v	3.585 (9)
F5···N4	3.383 (10)
Cl1—Cu1—N1	96.4 (1)	H6—C6—H7	109.5
Cl1—Cu1—N2	176.7 (1)	N2—C7—C8	109.9 (4)
Cl1—Cu1—N3	98.8 (1)	N2—C7—H8	109.4
N1—Cu1—N2	81.4 (1)	N2—C7—H9	109.4
N1—Cu1—N3	164.8 (2)	C8—C7—H8	109.4
N2—Cu1—N3	83.4 (1)	C8—C7—H9	109.4
F1—P1—F2	96.4 (5)	H8—C7—H9	109.5
F1—P1—F3	90.7 (3)	N3—C8—C7	115.9 (4)
F1—P1—F4	174.7 (5)	N3—C8—C9	121.8 (5)
F1—P1—F5	89.7 (5)	C7—C8—C9	122.3 (5)
F1—P1—F6	87.6 (3)	C8—C9—C10	119.3 (7)
F2—P1—F3	99.4 (6)	C8—C9—H10	120.3
F2—P1—F4	88.1 (5)	C10—C9—H10	120.3
F2—P1—F5	173.4 (6)	C9—C10—C11	119.5 (6)
F2—P1—F6	83.0 (5)	C9—C10—H11	120.2
F3—P1—F4	91.3 (3)	C11—C10—H11	120.2
F3—P1—F5	83.1 (5)	C10—C11—C12	119.3 (6)
F3—P1—F6	177.3 (5)	C10—C11—H12	120.4
F4—P1—F5	85.7 (5)	C12—C11—H12	120.4
F4—P1—F6	90.2 (3)	N3—C12—C11	121.4 (6)
F5—P1—F6	94.7 (5)	N3—C12—H13	119.3
Cu1—N1—C1	127.6 (4)	C11—C12—H13	119.3
Cu1—N1—C5	112.7 (3)	N2—C13—C14	115.1 (3)
C1—N1—C5	119.4 (4)	N2—C13—H14	108.0
Cu1—N2—C6	104.4 (3)	N2—C13—H15	108.0
Cu1—N2—C7	106.4 (3)	C14—C13—H14	108.0
Cu1—N2—C13	112.9 (2)	C14—C13—H15	108.0
C6—N2—C7	112.7 (4)	H14—C13—H15	109.5
C6—N2—C13	108.3 (3)	N4—C14—C13	111.2 (3)
C7—N2—C13	112.0 (3)	N4—C14—H16	109.0
Cu1—N3—C8	114.0 (3)	N4—C14—H17	109.0
Cu1—N3—C12	126.8 (4)	C13—C14—H16	109.0
C8—N3—C12	118.7 (4)	C13—C14—H17	109.0
C14—N4—C15	120.7 (4)	H16—C14—H17	109.5
C14—N4—H1	119.7	O1—C15—N4	121.4 (4)
C15—N4—H1	119.7	O1—C15—C16	122.7 (4)
N1—C1—C2	122.3 (6)	N4—C15—C16	115.9 (4)
N1—C1—H2	118.9	C15—C16—C17	118.3 (4)
C2—C1—H2	118.9	C15—C16—C21	123.3 (4)
C1—C2—C3	118.5 (6)	C17—C16—C21	118.4 (4)
C1—C2—H3	120.8	C16—C17—C18	120.4 (5)
C3—C2—H3	120.8	C16—C17—H18	119.8
C2—C3—C4	120.2 (5)	C18—C17—H18	119.8
C2—C3—H4	119.9	C17—C18—C19	120.1 (5)
C4—C3—H4	119.9	C17—C18—H19	119.9
C3—C4—C5	117.7 (6)	C19—C18—H19	119.9
C3—C4—H5	121.1	C18—C19—C20	120.2 (5)
C5—C4—H5	121.1	C18—C19—H20	119.9
N1—C5—C4	121.9 (5)	C20—C19—H20	119.9
N1—C5—C6	115.7 (4)	C19—C20—C21	120.1 (5)
C4—C5—C6	122.3 (5)	C19—C20—H21	119.9
N2—C6—C5	108.6 (3)	C21—C20—H21	119.9
N2—C6—H6	109.7	C16—C21—C20	120.8 (4)
N2—C6—H7	109.7	C16—C21—H22	119.6
C5—C6—H6	109.7	C20—C21—H22	119.6
C5—C6—H7	109.7

Symmetry codes: (i) −x+2, −y, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1, −y, −z; (iv) x−1, y, z; (v) −x+2, −y, −z+1; (vi) −x+3/2, y+1/2, −z+1/2; (vii) x+1/2, −y+1/2, z+1/2; (viii) −x+5/2, y+1/2, −z+1/2.