Chloro­(hist­amine)(1,10-phenanthro­line)copper(II) chloride monohydrate

In the cationic complex present in the title compound, chloro­[2-(4-imidazolyl-κN¹)­ethyl­amine-κN](1,10-phenanthroline-κ²N,N′)copper(II) chloride monohydrate, [CuCl(C₅H₉­N₃)­(C₁₂H₈N₂)]Cl·H₂O, the metal centre adopts a five-coordinate geometry, ligated by the two phenanthroline N atoms, two amine N atoms of the hist­amine ligand (one aliphatic and one from the imidazole ring) and a chloro ligand. The geometry around the Cu atom is a distorted compressed trigonal bipyramid, with one phenanthroline N and one imidazole N atom in the axial positions, and the other phenanthroline N atom, the histamine amine N atom and the chloro ligand in the equatorial positions. The structure includes an uncoordinated water mol­ecule, and a Cl⁻ ion to complete the charge. The water mol­ecule is hydrogen bonded to both Cl⁻ ions (coordinated and uncoordinated), and exhibits a close Cu...H contact in the equatorial plane of the bipyramid.

S1. Comment

Since Sigman and coworkers reported (D'Aurora et al., 1978) that 1,10 phenanthroline-copper complexes can function as artificial nucleases, there has been considerable interest in DNA binding and cleavage by these and other metal-phenanthroline complexes as chemical probes of DNA, because of their potential utility in footprinting techniques. Nucleases are enzymes that catalyse nucleic-acid hydrolysis by cleavage of the phosphodiester linkage. Under physiological conditions, this process has a rate constant of the order of 10⁻⁹ min⁻¹. At these rates of hydrolysis, processes such as replication and transcription are not possible. In the presence of metal ions such as Cu, the hydrolysis rate for phosphodiesters is increased but is still insignificant on the physiological time scale (Sigman et al., 1993).

Many complexes of the phenanthroline ligand with several metals have been synthesized in order to obtain further insights into their nuclease activity (Sakurai et al., 1995; Ramírez-Ramírez et al., 1998). Some researchers have suggested that the mechanism of action of these artificial nucleases could be explained by a partial intercalation of one phenanthroline ligand between the base pairs of DNA (Veal & Rill, 1991). Moreover, it has been determined that substituents on the phenanthroline clearly influence the way in which copper-phenanthroline complexes bind to DNA (Mahadevan & Palaniandavar, 1998; Meadows et al., 1993). Some natural nucleases contain imidazole groups in their structures. The chemistry of imidazole is of special interest because of its wide occurrence in biological compounds, notably as part of the amino acid histidine and metabolites like histamine. Also, it is well known that Cu in living systems is in many cases surrounded by residues of histidine (Baran, 1994).

In this, work we report the synthesis and crystal structure of histamine(1,10-phenanthroline)chlorocopper(II) chloride monohydrate, (I), which contains a mixed-ligand complex with histamine and phenanthroline, and which will be tested as a potential chemical nuclease. Details of the structure of this compound should be helpful in understanding how the chemical nucleases of the copper-phenanthroline system work. \sch

The molecular structure of (I) is shown in Fig. 1. The Cu^II ion displays five-coordinate geometry and can best be described as a compressed trigonal bipyramid (tbp), as can be seen from the distances and angles around the metal (Table 1). Crystal structures of copper(II) complexes with histamine have been reported previously, such as [Cu(histamine)Cl₂] (Główka et al., 1980) and [Cu(histamine)(ClO₄)₂] (Bonnet & Jeannin, 1970), in which a pseudo-octahedral geometry (or, more properly, a distorted square bipyramid) is found for Cu. In the title complex, the coordination is provided by one phenanthroline ligand, one histamine ligand and one coordinated Cl⁻ anion. One phenanthroline and one imidazole N atom, N9 and N1, are located in the axial positions. The other N atom of the phenanthroline, the aliphatic N atom of histamine and the coordinated Cl⁻ form the base of the bipyramid. The Cu^II ion is located in the middle of the base of the tbp, 0.095 Å out of the mean plane (toward N1) formed by the equatorial ligand atoms (N8, N20 and Cl1). The τ descriptor for five-coordinate complexes, expressed here as the difference between the bond angles N8—Cu—Cl1 and N1—Cu—N9 divided by 60, has a value of 0.62, which can be compared with the ideal values of 1 for a tbp and 0 for a square pyramid (Addison et al., 1984).

The equatorial angles Cl1—Cu1—N8, Cl1—Cu1—N20 and N8—Cu1—N20 are 133.99 (6), 119.91 (6) and 105.49 (7)°, respectively. The angles involving Cl⁻ deviate most from the ideal value of 120° for a perfect tbp. The largest equatorial angle gives rise to the cleft in which hydrogen bonding is present, involving the uncoordinated water molecule, the Cl⁻ anion and the coordinated amino group. The axial N1—Cu1—N9 angle [171.01 (8)°] does not deviate greatly from linearity.

The Cu—Cl1 distance is 2.3380 (7) Å, indicative of a relatively strong bond between Cu and the Cl⁻ ligand. This bond is much shorter than is found for an apically coordinated Cl⁻ atom in a five-coordinate tetragonal-pyramidal copper(II) complex such as [Cu(cip)(bipy)(Cl)](NO₃)·2H₂O (cip is ciprofloxacine and bipy is 2,2'-bipyridine), where the bond distance is 2.549 (2) Å (Wallis et al., 1996). In (I), the axial Cu—N bonds (Cu—N1 and Cu—N9) are shorter than the corresponding equatorial bonds (Cu—N8 and Cu—N20), as expected for a trigonal-bipyramidal structure with four N donors (Masood & Hodgson, 1993). The observed geometry must result primarily from electronic factors, since the conformational flexibility of one of the ligands obviates the influence of steric constraints in the complex (Masood & Hodgson, 1993).

Two-dimensional hydrogen-bond networks are present in the structure of (I). The structure includes an uncoordinated water molecule and a Cl⁻ anion, which provide stability through a network of hydrogen-bond interactions (Table 2). The water molecule donates atom H1A to a hydrogen bond with the coordinated Cl⁻. Due to this hydrogen bond, the H atom has a short contact distance to the Cu centre of 2.848 Å [Cu···O1 3.577 (3) Å], somewhat smaller than the sum of the van der Walls radii. It is also interesting that this water molecule is located in the plane of the tbp base (0.0822 Å out of the plane formed by the ligand atoms N8, N20 and Cl1) in a position suggestive of the location of an exiting fourth equatorial ligand (Fig. 2).

In the extended structure of (I), we observe phenanthroline stacking between molecules related by a centre of symmetry. The stacking distance is 3.468 (5) Å for the contact between the molecule at (x,y,z) and that at (1/2 − x, 3/2 − y, 1 − z) (Fig. 2), similar to the distance found in other complexes with this ligand (Mendoza-Díaz et al., 1993). Stacking between the imidazole ring of the coordinated histamine and the phenanthroline ring of the molecule at (x, 1 − y, 1/2 + z) is also observed. However, unlike the stacked phenanthroline groups, which are parallel to each other, the histamine and neighbouring phenanthroline groups form a dihedral angle of 13.48 (13)°, making the stacking less efficient. The perpendicular distance from the centroid of the middle ring of the phenanthroline to the imidazole plane is 3.539 Å. These stacking interactions should favour the stabilization of the tbp geometry over the square pyramid in this case.

S2. Experimental

Into a solution of CuCl₂·2H₂O (1 mmol) dissolved in water (10 ml), 1,10-phenanthroline (1 mmol) dissolved in a 1:1 water-ethanol mixture (30 ml) was added slowly. The solution was warmed up and then histamine hydrochloride (1 mmol) dissolved in water and treated with triethylendiamine (0.4 ml) was added. The reaction mixture was allowed to stand at room temperature overnight and then at 273 K for several days. Blue crystals of (I) suitable for X-ray diffraction formed after several days, and these were filtered off and dried in air.

S3. Refinement

The H atoms of the water molecule were found in difference maps. The remaining H atoms were placed in idealized positions. In the final cycles of the refinement, all H atoms were constrained to ride on their parent atoms, with methylene C—H distances 0.97, aryl C—H 0.93, N—H 0.86, N—H₂ 0.90 and O—H ??Å, and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(O).

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL and PLUTON (Spek, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A view of the molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial view of the two-dimensional hydrogen-bond network in the structure of (I) and the trigonal-bipyramidal geometry around the Cu atom. The stacking of phenanthroline rings with the adjacent molecule [at (1/2 − x, 3/2 − y, 1 − z)] is shown. The view is from [100] with the b axis vertical.

chloro[2-(4-imidazolyl-κN¹)ethylamine-κN](1,10-phenanthroline- κ²N,N')copper(II) chloride monohydrate

Crystal data

[CuCl(C5H9N3)(C12H8N2)]Cl·H2O	F(000) = 1816
Mr = 443.81	Dx = 1.545 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 83 reflections
a = 18.2744 (14) Å	θ = 4.8–12.8°
b = 12.6490 (11) Å	µ = 1.44 mm^−1
c = 17.760 (2) Å	T = 296 K
β = 111.621 (7)°	Prism, green
V = 3816.3 (6) Å^3	0.60 × 0.28 × 0.20 mm
Z = 8

Data collection

Bruker P4 diffractometer	3424 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.023
Graphite monochromator	θmax = 27.5°, θmin = 2.0°
ω scans	h = −23→23
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −16→1
Tmin = 0.611, Tmax = 0.749	l = −21→23
7754 measured reflections	3 standard reflections every 97 reflections
4402 independent reflections	intensity decay: 1.9%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: geom + difmap
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.041P)^2 + 2.422P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
4402 reflections	Δρmax = 0.27 e Å^−3
236 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00084 (10)

Special details

Experimental. 16 ψ scans with XSCANS (Siemens, 1996)

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.244720 (15)	0.46880 (2)	0.627264 (14)	0.04056 (10)
Cl1	0.14405 (3)	0.54257 (5)	0.66187 (4)	0.05477 (16)
Cl2	0.10799 (4)	0.17292 (5)	0.50320 (3)	0.05519 (17)
O1	0.10750 (15)	0.2930 (2)	0.66279 (13)	0.0912 (7)
H1A	0.1247	0.3666	0.6668	0.137*
H1B	0.1029	0.2733	0.6100	0.137*
N1	0.31711 (11)	0.45575 (15)	0.74039 (10)	0.0427 (4)
C2	0.32395 (15)	0.52384 (19)	0.79922 (14)	0.0504 (6)
H2A	0.2885	0.5780	0.7959	0.060*
N3	0.38847 (13)	0.50415 (18)	0.86363 (12)	0.0548 (5)
H3A	0.4040	0.5388	0.9084	0.066*
C4	0.42560 (14)	0.4198 (2)	0.84650 (14)	0.0517 (6)
H4A	0.4723	0.3892	0.8807	0.062*
C5	0.38164 (12)	0.38857 (18)	0.76982 (12)	0.0414 (5)
C6	0.39192 (13)	0.2982 (2)	0.72057 (14)	0.0513 (6)
H6A	0.4251	0.2451	0.7566	0.062*
H6B	0.4186	0.3230	0.6857	0.062*
C7	0.31428 (14)	0.24783 (18)	0.66878 (14)	0.0500 (5)
H7A	0.3242	0.1807	0.6479	0.060*
H7B	0.2832	0.2342	0.7017	0.060*
N8	0.26978 (11)	0.31793 (15)	0.60039 (11)	0.0438 (4)
H8A	0.2239	0.2859	0.5720	0.053*
H8B	0.2972	0.3231	0.5676	0.053*
N9	0.18285 (11)	0.49783 (16)	0.50863 (11)	0.0447 (4)
C10	0.11063 (14)	0.4623 (2)	0.46528 (15)	0.0557 (6)
H10A	0.0856	0.4181	0.4901	0.067*
C11	0.07149 (15)	0.4892 (2)	0.38392 (16)	0.0626 (7)
H11A	0.0215	0.4626	0.3552	0.075*
C12	0.10727 (16)	0.5546 (2)	0.34717 (15)	0.0596 (7)
H12A	0.0817	0.5728	0.2930	0.072*
C13	0.18255 (14)	0.5947 (2)	0.39081 (13)	0.0477 (5)
C14	0.22366 (17)	0.6675 (2)	0.35811 (15)	0.0577 (7)
H14A	0.2002	0.6889	0.3044	0.069*
C15	0.29501 (17)	0.7051 (2)	0.40328 (16)	0.0584 (7)
H15A	0.3197	0.7530	0.3807	0.070*
C16	0.33399 (14)	0.67254 (18)	0.48610 (15)	0.0478 (5)
C17	0.40914 (16)	0.7073 (2)	0.53668 (19)	0.0620 (7)
H17A	0.4374	0.7535	0.5169	0.074*
C18	0.44040 (16)	0.6730 (2)	0.61482 (19)	0.0628 (7)
H18A	0.4905	0.6944	0.6484	0.075*
C19	0.39688 (13)	0.6059 (2)	0.64365 (16)	0.0532 (6)
H19A	0.4186	0.5845	0.6975	0.064*
N20	0.32584 (10)	0.57059 (16)	0.59859 (11)	0.0428 (4)
C21	0.29507 (12)	0.60318 (17)	0.52024 (13)	0.0402 (5)
C22	0.21826 (13)	0.56329 (18)	0.47211 (13)	0.0403 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03727 (15)	0.04680 (17)	0.03433 (15)	0.00099 (11)	0.00933 (11)	0.00221 (11)
Cl1	0.0455 (3)	0.0607 (4)	0.0624 (4)	0.0040 (3)	0.0250 (3)	−0.0018 (3)
Cl2	0.0524 (3)	0.0682 (4)	0.0430 (3)	−0.0150 (3)	0.0153 (2)	−0.0032 (3)
O1	0.1103 (18)	0.0947 (16)	0.0758 (13)	−0.0444 (15)	0.0426 (13)	−0.0186 (13)
N1	0.0442 (10)	0.0448 (10)	0.0363 (9)	0.0026 (8)	0.0115 (8)	0.0003 (8)
C2	0.0573 (14)	0.0474 (13)	0.0430 (12)	0.0017 (11)	0.0144 (11)	−0.0023 (10)
N3	0.0583 (13)	0.0612 (13)	0.0381 (10)	−0.0100 (11)	0.0096 (9)	−0.0068 (9)
C4	0.0429 (12)	0.0621 (15)	0.0428 (12)	−0.0010 (11)	0.0072 (10)	0.0049 (11)
C5	0.0353 (10)	0.0486 (12)	0.0388 (10)	−0.0007 (9)	0.0117 (9)	0.0033 (9)
C6	0.0395 (12)	0.0607 (14)	0.0493 (12)	0.0118 (11)	0.0113 (10)	0.0014 (11)
C7	0.0529 (13)	0.0399 (12)	0.0567 (13)	0.0021 (10)	0.0195 (11)	−0.0028 (10)
N8	0.0384 (9)	0.0510 (11)	0.0414 (9)	−0.0067 (8)	0.0138 (8)	−0.0078 (8)
N9	0.0376 (9)	0.0532 (11)	0.0405 (10)	0.0002 (8)	0.0110 (8)	0.0036 (8)
C10	0.0409 (12)	0.0719 (17)	0.0488 (13)	−0.0052 (12)	0.0102 (10)	0.0029 (12)
C11	0.0408 (13)	0.0833 (19)	0.0510 (14)	0.0045 (13)	0.0019 (11)	−0.0064 (14)
C12	0.0575 (15)	0.0764 (18)	0.0383 (12)	0.0169 (14)	0.0099 (11)	0.0038 (12)
C13	0.0526 (13)	0.0530 (13)	0.0375 (11)	0.0153 (11)	0.0166 (10)	0.0022 (10)
C14	0.0741 (18)	0.0593 (15)	0.0461 (13)	0.0199 (14)	0.0298 (13)	0.0127 (11)
C15	0.0805 (19)	0.0478 (13)	0.0632 (15)	0.0084 (13)	0.0455 (15)	0.0107 (12)
C16	0.0553 (14)	0.0402 (11)	0.0569 (13)	0.0050 (10)	0.0312 (11)	0.0016 (10)
C17	0.0603 (16)	0.0479 (14)	0.092 (2)	−0.0078 (12)	0.0447 (15)	0.0010 (14)
C18	0.0443 (13)	0.0601 (16)	0.0811 (19)	−0.0113 (12)	0.0196 (13)	−0.0030 (14)
C19	0.0412 (12)	0.0554 (14)	0.0573 (14)	−0.0021 (11)	0.0115 (11)	0.0027 (12)
N20	0.0373 (9)	0.0464 (10)	0.0425 (9)	−0.0021 (8)	0.0121 (8)	0.0022 (8)
C21	0.0420 (11)	0.0387 (11)	0.0450 (11)	0.0048 (9)	0.0219 (9)	0.0002 (9)
C22	0.0407 (11)	0.0429 (11)	0.0387 (10)	0.0070 (9)	0.0162 (9)	0.0006 (9)

Geometric parameters (Å, º)

Cu1—N1	1.9634 (18)	N9—C10	1.337 (3)
Cu1—N9	2.0241 (18)	N9—C22	1.354 (3)
Cu1—N8	2.0593 (19)	C10—C11	1.398 (4)
Cu1—N20	2.1613 (19)	C10—H10A	0.9300
Cu1—Cl1	2.3380 (7)	C11—C12	1.362 (4)
O1—H1A	0.9764	C11—H11A	0.9300
O1—H1B	0.9433	C12—C13	1.402 (4)
N1—C2	1.324 (3)	C12—H12A	0.9300
N1—C5	1.390 (3)	C13—C22	1.405 (3)
C2—N3	1.329 (3)	C13—C14	1.439 (4)
C2—H2A	0.9300	C14—C15	1.341 (4)
N3—C4	1.358 (3)	C14—H14A	0.9300
N3—H3A	0.8600	C15—C16	1.438 (3)
C4—C5	1.360 (3)	C15—H15A	0.9300
C4—H4A	0.9300	C16—C21	1.400 (3)
C5—C6	1.493 (3)	C16—C17	1.406 (4)
C6—C7	1.518 (3)	C17—C18	1.362 (4)
C6—H6A	0.9700	C17—H17A	0.9300
C6—H6B	0.9700	C18—C19	1.384 (4)
C7—N8	1.482 (3)	C18—H18A	0.9300
C7—H7A	0.9700	C19—N20	1.326 (3)
C7—H7B	0.9700	C19—H19A	0.9300
N8—H8A	0.9000	N20—C21	1.359 (3)
N8—H8B	0.9000	C21—C22	1.439 (3)
N1—Cu1—N9	171.01 (8)	H8A—N8—H8B	107.2
N1—Cu1—N8	92.05 (7)	C10—N9—C22	118.31 (19)
N9—Cu1—N8	90.77 (8)	C10—N9—Cu1	126.34 (17)
N1—Cu1—N20	91.67 (7)	C22—N9—Cu1	115.29 (14)
N9—Cu1—N20	79.35 (7)	N9—C10—C11	122.3 (3)
N8—Cu1—N20	105.49 (7)	N9—C10—H10A	118.9
N1—Cu1—Cl1	93.63 (6)	C11—C10—H10A	118.9
N9—Cu1—Cl1	90.54 (6)	C12—C11—C10	119.4 (2)
N8—Cu1—Cl1	133.99 (6)	C12—C11—H11A	120.3
N20—Cu1—Cl1	119.91 (6)	C10—C11—H11A	120.3
H1A—O1—H1B	103.4	C11—C12—C13	120.1 (2)
C2—N1—C5	106.30 (19)	C11—C12—H12A	119.9
C2—N1—Cu1	125.80 (16)	C13—C12—H12A	119.9
C5—N1—Cu1	126.48 (15)	C12—C13—C22	117.1 (2)
N1—C2—N3	110.7 (2)	C12—C13—C14	124.1 (2)
N1—C2—H2A	124.7	C22—C13—C14	118.8 (2)
N3—C2—H2A	124.7	C15—C14—C13	121.5 (2)
C2—N3—C4	108.2 (2)	C15—C14—H14A	119.2
C2—N3—H3A	125.9	C13—C14—H14A	119.2
C4—N3—H3A	125.9	C14—C15—C16	121.1 (2)
N3—C4—C5	107.0 (2)	C14—C15—H15A	119.5
N3—C4—H4A	126.5	C16—C15—H15A	119.5
C5—C4—H4A	126.5	C21—C16—C17	116.8 (2)
C4—C5—N1	107.8 (2)	C21—C16—C15	118.9 (2)
C4—C5—C6	130.8 (2)	C17—C16—C15	124.3 (2)
N1—C5—C6	121.35 (18)	C18—C17—C16	119.7 (2)
C5—C6—C7	112.66 (19)	C18—C17—H17A	120.1
C5—C6—H6A	109.1	C16—C17—H17A	120.1
C7—C6—H6A	109.1	C17—C18—C19	119.3 (2)
C5—C6—H6B	109.1	C17—C18—H18A	120.3
C7—C6—H6B	109.1	C19—C18—H18A	120.3
H6A—C6—H6B	107.8	N20—C19—C18	123.5 (2)
N8—C7—C6	110.72 (19)	N20—C19—H19A	118.3
N8—C7—H7A	109.5	C18—C19—H19A	118.3
C6—C7—H7A	109.5	C19—N20—C21	117.4 (2)
N8—C7—H7B	109.5	C19—N20—Cu1	131.47 (16)
C6—C7—H7B	109.5	C21—N20—Cu1	111.17 (14)
H7A—C7—H7B	108.1	N20—C21—C16	123.3 (2)
C7—N8—Cu1	117.80 (14)	N20—C21—C22	116.55 (19)
C7—N8—H8A	107.9	C16—C21—C22	120.1 (2)
Cu1—N8—H8A	107.9	N9—C22—C13	122.8 (2)
C7—N8—H8B	107.9	N9—C22—C21	117.61 (18)
Cu1—N8—H8B	107.9	C13—C22—C21	119.5 (2)
N8—Cu1—N1—C2	−171.0 (2)	C13—C14—C15—C16	1.1 (4)
N20—Cu1—N1—C2	83.5 (2)	C14—C15—C16—C21	−2.1 (4)
Cl1—Cu1—N1—C2	−36.6 (2)	C14—C15—C16—C17	179.0 (2)
N8—Cu1—N1—C5	24.53 (19)	C21—C16—C17—C18	0.1 (4)
N20—Cu1—N1—C5	−81.04 (19)	C15—C16—C17—C18	178.9 (2)
Cl1—Cu1—N1—C5	158.85 (18)	C16—C17—C18—C19	−1.2 (4)
C5—N1—C2—N3	0.1 (3)	C17—C18—C19—N20	1.4 (4)
Cu1—N1—C2—N3	−166.98 (16)	C18—C19—N20—C21	−0.3 (4)
N1—C2—N3—C4	0.0 (3)	C18—C19—N20—Cu1	−178.9 (2)
C2—N3—C4—C5	−0.2 (3)	N1—Cu1—N20—C19	0.7 (2)
N3—C4—C5—N1	0.2 (3)	N9—Cu1—N20—C19	−179.7 (2)
N3—C4—C5—C6	−177.3 (2)	N8—Cu1—N20—C19	−91.9 (2)
C2—N1—C5—C4	−0.2 (3)	Cl1—Cu1—N20—C19	95.9 (2)
Cu1—N1—C5—C4	166.77 (16)	N1—Cu1—N20—C21	−177.99 (15)
C2—N1—C5—C6	177.6 (2)	N9—Cu1—N20—C21	1.59 (15)
Cu1—N1—C5—C6	−15.4 (3)	N8—Cu1—N20—C21	89.42 (15)
C4—C5—C6—C7	142.3 (3)	Cl1—Cu1—N20—C21	−82.84 (15)
N1—C5—C6—C7	−34.9 (3)	C19—N20—C21—C16	−1.0 (3)
C5—C6—C7—N8	72.2 (3)	Cu1—N20—C21—C16	177.89 (17)
C6—C7—N8—Cu1	−56.5 (2)	C19—N20—C21—C22	179.5 (2)
N1—Cu1—N8—C7	11.83 (17)	Cu1—N20—C21—C22	−1.6 (2)
N9—Cu1—N8—C7	−176.70 (16)	C17—C16—C21—N20	1.1 (3)
N20—Cu1—N8—C7	104.14 (16)	C15—C16—C21—N20	−177.8 (2)
Cl1—Cu1—N8—C7	−85.21 (17)	C17—C16—C21—C22	−179.4 (2)
N8—Cu1—N9—C10	75.9 (2)	C15—C16—C21—C22	1.7 (3)
N20—Cu1—N9—C10	−178.5 (2)	C10—N9—C22—C13	−0.4 (3)
Cl1—Cu1—N9—C10	−58.1 (2)	Cu1—N9—C22—C13	−177.77 (17)
N8—Cu1—N9—C22	−106.95 (17)	C10—N9—C22—C21	178.3 (2)
N20—Cu1—N9—C22	−1.34 (16)	Cu1—N9—C22—C21	0.9 (3)
Cl1—Cu1—N9—C22	119.04 (16)	C12—C13—C22—N9	−0.5 (3)
C22—N9—C10—C11	0.9 (4)	C14—C13—C22—N9	177.9 (2)
Cu1—N9—C10—C11	178.0 (2)	C12—C13—C22—C21	−179.1 (2)
N9—C10—C11—C12	−0.7 (4)	C14—C13—C22—C21	−0.8 (3)
C10—C11—C12—C13	−0.2 (4)	N20—C21—C22—N9	0.6 (3)
C11—C12—C13—C22	0.7 (4)	C16—C21—C22—N9	−179.0 (2)
C11—C12—C13—C14	−177.5 (3)	N20—C21—C22—C13	179.3 (2)
C12—C13—C14—C15	178.5 (2)	C16—C21—C22—C13	−0.2 (3)
C22—C13—C14—C15	0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.98	2.26	3.228 (3)	171
O1—H1B···Cl2	0.94	2.31	3.218 (2)	161
N3—H3A···Cl2^i	0.86	2.38	3.169 (2)	154
N8—H8A···Cl2	0.90	2.47	3.3651 (19)	171
N8—H8B···Cl2^ii	0.90	2.49	3.379 (2)	170

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+1/2, −y+1/2, −z+1.