Bis­[1-(p-chloro­phenyl)-5-iso­propyl­biguanide-κ²N²,N⁴]­nickel(II) dichloride di­methyl­form­amide solvate

The asymmetric unit of the title compound, [Ni(C₁₁H₁₆ClN₅)₂]Cl₂·C₃H₇NO, contains one monomeric nickel(II) com­plex cation, two Cl⁻ anions and one di­methyl­form­amide sol­vent mol­ecule. The Ni atom is coordinated to each of two 1-­(p-chloro­phenyl)-5-iso­propyl­biguanide (proguanil) ligands via two N atoms. The complex exhibits a square-planar coordination, with the Ni atom lying 0.021 (2) Å out of the basal plane. The crystal packing is characterized by several hydrogen bonds.

S1. Comment

Proguanil, 1-(p-chlorophenyl)-5-isopropylbiguanide, an antimalarial drug used worldwide, is characterized by different tautomeric forms, one of which is stabilized upon complexation. This fact prompted us to synthesize new complexes of 3 d elements with a view to modulating the pharmacological properties of the free ligand. The asymmetric unit of the title compound, (I), consists of one nickel(II) atom, two proguanil ligands, two Cl⁻anions and one DMF solvent molecule. The Ni^II atom exhibits a square-planar coordination, built from two bidentate chelating proguanil ligands via atoms N2 and N4 in the first ligand (atoms N22 and N24 in the second ligand) from the biguanidyl moiety of each molecule. The same square-planar geometry was observed in [bis(2- guanidinobenzimidazole)nickel(II) dinitrate] (Barba-Behrens et al., 1996) and [bis(biguanidino)nickelate(II):(6,7-dimethoxy-2,4(1H, 3H)quinazolinedione](Bishop et al., 2002). The Ni—N bond lengths are all equivalent [within 2 s.u.; mean 1.864 (3) Å] and the angles at the Ni atom are in the range 89.6 (1)–90.5 (1) °. These values agree with those found in bis(N,N-dimethylbiguanide)nickel(II) salicylate (Lemoine et al., 1996) and bis(N,N-dimethylbiguanide)nickel(II)monohydroxide chloride (Lemoine et al., 1999). The Ni atom is 0.021 (2) Å out of the basal plane [P1; N2/N4/N22/N24]. The N2—C7—N3—C8—N4 and N22—C27—N23—C28—N24 sequences have nearly planar geometries (mean planes P2 and P3, respectively), allowing delocalization of the π electron system along them. The Ni^II atom is displaced 0.244 (4) and −0.459 (4) Å out of planes P2 and P3 and the dihedral angle between these two planes is 32.05 (1)°. The Ni/N2/C7/N3/C8/N4 metalloring may be regarded as having a boat shape, with atoms Ni and N3 on the same side of the N2/C7/C8/N4 (P4) plane [0.234 (5) and 0.018 (5) Å, respectively]. The geometry is the same for the Ni/N22/C27/N23/C28/N24 ring, with atoms Ni and N23 being −0.380 (5) and −0.145 (5) Å, respectively, from plane P5 (N22/C27/C28/N24). These configurations are similar to those described for [bis(2- guanidinobenzimidazole)nickel(II) dinitrate] (Barba-Behrens et al., 1996) The dihedral angle between plane P2 and its attached phenyl ring (C1–C6) is 70.0 (1) ° [the corresponding dihedral angle for P3 and C21–C26 is 76.3 (1)°]. The two halves of each biguanide group are planar, with atom C7 0.011 (4)° out of plane P6 (N1/N2/N3) and atom C8 0.001 (4) Å out of plane P7 (N3/N4/N5) [the corresponding out of plane distance values are 0.002 (4) Å for atom C27 and plane P8 (N21/N22/N23) and 0.011 (4) Å for atom C28 and plane P9 (N23/N24/N25)]. The dihedral angle between planes P6 and P7 is 5.9 (3)° and between planes P8 and P9 is 15.0 (3)°. Thus, the biguanide moiety in each proguanil bidentate chelating agent is almost planar. In contrast, the corresponding dihedral angle between the homologous Ni atoms in the crystal structure of 1-(p-chlorophenyl)-5-isopropylbiguanide hydrochloride (Brown., 1967) is 58.9 °, a value which is characteristic of a non-planar molecule. In the title compound, the corresponding distances in the two proguanil ligands are all equivalent (within 3 s.u.) except for the C9—C11 [1.503 (5) Å] and C29—C31 [1.530 (5) Å] distances in the terminal methyl groups. The C1—N1—C7—N2 [−4.5 (5) °] and C9—N5—C8—N4 [17.0 (6) °] torsion angles in the first ligand, and C21—N21—C27—N22 [−3.3 (7) °] and C29—N25—C28—N24 [−13.0 (6)°] torsion angles in the second proguanil ligand, showed that this conformation remains synperiplanar upon metallation. The same conformation was found for the corresponding atomic set in PdCl₂(proguanil) (Bentefrit et al., 2002) but differed from (proguanil) hydrochloride (Brown, 1967) where the conformation was antiperiplanar (the C—N—C—N torsion angles being 164.1 and 164.5°). The DMF solvent molecule exhibits some disorder in the terminal methyl groups, as shown by its U_eq values. The crystal packing is characterized by several intra- and intermolecular hydrogen bonds, which involve, in particular, the DMF solvate molecule with each ligand of the same complex (table), in contrast to hydrogen bonds observed in [bis(biguanidino)nickelate(II):(6,7-dimethoxy-2,4(1H,3H)quinazolinedione], in which the DMSO solvate acts as a bridging molecule between two neighbouring complexes (Bishop et al., 2002). In (I), atom Cl1 participates in three hydrogen bonds to two chelate entities, while atom Cl2 is involved in five hydrogen bonds belonging to three different complexes.

In addition, the crystalline cohesion is likewise ensured by many van der Waals contacts, the shortest being C26—C52ⁱⁱⁱ = 3.41 (2) Å [symmetry code: (iii) 1/2 + x, 1/2 − y, z].

S2. Experimental

The title compound was obtained by dissolving proguanil hydrochloride in DMF to a concentration of 0.2 mol L⁻¹, (4 × 10⁻⁴ mol) and adding nickel chloride hexahydrate in DMF to a concentration of 0.1 mol L⁻¹, (2 × 10⁻⁴ mol). This hydrochloric mixture was neutralized by a sodium hydroxide solution (4 × 10⁻⁴ mol). After mixing and heating (50°) for a period of 2 h and slow evaporation, yellow crystals were obtained under ambient pressure.

S3. Refinement

All H atoms were placed at their idealized positions as riding atoms (C—H_aromatic=0.93 Å, C—H_methine= 0.93 Å, C—H_methyl=0.96 Å and N—H=0.86 Å). A disordered model for the DMF solvate based on a 60:40 distribution of the N(Me)₂ over two sites related by a pseudo twofold axis was applied.

Computing details

Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A CAMERON (Watkin et al., 1996) drawing of the molecule of (I), showing the atom-numbering system and hydrogen bonding (dashed lines). Displacement ellipsoïds are shown at the 50% probability level for non-H atoms. [Symmetry codes: (i) −x, −y, −z; (ii) −x + 1/2, y + 1/2, −z.]
	Fig. 2. The packing of the unit cell of (I), projected along the c axis.

Bis[1-(p-chlorophenyl)-5-isopropylbiguanide] nickel(II) dichloride dimethylformamide solvate.

Crystal data

[Ni(C11H16ClN5)2]Cl2·C3H7NO	F(000) = 1480
Mr = 710.18	Dx = 1.377 Mg m^−3 Dm = 1.38 Mg m^−3 Dm measured by flotation (CHCl3 / CH2Cl2)
Monoclinic, P21/a	Mo Kα radiation, λ = 0.71069 Å
a = 10.824 (5) Å	Cell parameters from 25 reflections
b = 24.12 (1) Å	θ = 7.0–11.1°
c = 13.180 (3) Å	µ = 0.92 mm^−1
β = 95.42 (3)°	T = 293 K
V = 3426 (2) Å^3	Parallelepipedic, orange
Z = 4	0.45 × 0.37 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer	3270 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.061
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ω – 2θ scans	h = −12→12
Absorption correction: empirical (using intensity measurements) 'multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)'	k = 0→28
Tmin = 0.648, Tmax = 0.883	l = −15→15
11970 measured reflections	3 standard reflections every 60 min
6000 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0724P)^2] where P = (Fo^2 + 2Fc^2)/3
6000 reflections	(Δ/σ)max = 0.001
417 parameters	Δρmax = 0.37 e Å^−3
31 restraints	Δρmin = −0.69 e Å^−3

Special details

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	Occ. (<1)
Ni	0.17718 (4)	0.124941 (15)	0.02731 (3)	0.03747 (14)
N1	0.3256 (3)	−0.03075 (11)	0.0936 (2)	0.0480 (8)
H1	0.3134	−0.0640	0.0714	0.058*
N2	0.2604 (3)	0.06218 (10)	0.0808 (2)	0.0423 (7)
H2	0.3101	0.0679	0.1347	0.051*
N3	0.1791 (2)	−0.00413 (10)	−0.0336 (2)	0.0406 (7)
H3	0.1851	−0.0379	−0.0536	0.049*
N4	0.0777 (3)	0.07998 (10)	−0.0611 (2)	0.0415 (7)
H4	0.0108	0.0953	−0.0880	0.050*
N5	0.0332 (3)	0.00371 (11)	−0.1680 (2)	0.0482 (8)
H5	0.0350	−0.0319	−0.1701	0.058*
N21	0.3881 (3)	0.25224 (12)	0.1615 (3)	0.0597 (9)
H21	0.3991	0.2865	0.1465	0.072*
N22	0.2813 (3)	0.17040 (11)	0.1114 (2)	0.0468 (8)
H22	0.3194	0.1546	0.1638	0.056*
N23	0.2423 (3)	0.25324 (11)	0.0259 (2)	0.0483 (8)
H23	0.2744	0.2846	0.0116	0.058*
N24	0.0939 (3)	0.18774 (10)	−0.0268 (2)	0.0412 (7)
H24	0.0193	0.1823	−0.0535	0.049*
N25	0.0753 (3)	0.28051 (11)	−0.0810 (2)	0.0549 (9)
H25	0.1012	0.3136	−0.0673	0.066*
Cl1	0.15706 (11)	−0.11925 (4)	−0.15644 (9)	0.0699 (3)
Cl2	0.19344 (9)	−0.14532 (4)	0.13548 (8)	0.0559 (3)
Cl4	0.70335 (12)	0.01491 (6)	0.43410 (10)	0.0930 (4)
Cl24	0.69527 (14)	0.16978 (6)	0.52408 (11)	0.1046 (5)
C1	0.4180 (3)	−0.02108 (13)	0.1745 (3)	0.0427 (9)
C2	0.4077 (4)	−0.04429 (15)	0.2688 (3)	0.0531 (10)
H20	0.3409	−0.0672	0.2789	0.064*
C3	0.4962 (4)	−0.03345 (18)	0.3478 (3)	0.0607 (11)
H30	0.4891	−0.0488	0.4117	0.073*
C4	0.5942 (4)	−0.00027 (17)	0.3327 (3)	0.0561 (10)
C5	0.6085 (4)	0.02173 (16)	0.2390 (3)	0.0561 (11)
H50	0.6773	0.0435	0.2292	0.067*
C6	0.5197 (3)	0.01124 (15)	0.1593 (3)	0.0499 (9)
H60	0.5284	0.0260	0.0951	0.060*
C7	0.2551 (3)	0.01135 (13)	0.0494 (3)	0.0382 (8)
C8	0.0939 (3)	0.02861 (13)	−0.0885 (3)	0.0380 (8)
C9	−0.0366 (4)	0.03274 (16)	−0.2522 (3)	0.0522 (10)
H90	−0.1014	0.0547	−0.2240	0.063*
C10	0.0421 (5)	0.0710 (2)	−0.3063 (4)	0.0868 (15)
H101	0.0857	0.0956	−0.2579	0.130*
H102	−0.0092	0.0922	−0.3553	0.130*
H103	0.1009	0.0499	−0.3405	0.130*
C11	−0.0990 (4)	−0.0106 (2)	−0.3212 (3)	0.0817 (15)
H111	−0.0372	−0.0331	−0.3488	0.123*
H112	−0.1490	0.0072	−0.3758	0.123*
H113	−0.1506	−0.0335	−0.2831	0.123*
C21	0.4594 (3)	0.22990 (14)	0.2478 (3)	0.0493 (10)
C22	0.5558 (4)	0.19353 (15)	0.2375 (3)	0.0532 (10)
H220	0.5728	0.1819	0.1730	0.064*
C23	0.6273 (4)	0.17427 (16)	0.3224 (4)	0.0611 (11)
H230	0.6915	0.1494	0.3152	0.073*
C24	0.6034 (4)	0.19192 (18)	0.4170 (3)	0.0622 (11)
C25	0.5072 (4)	0.22774 (18)	0.4283 (3)	0.0665 (12)
H250	0.4908	0.2392	0.4931	0.080*
C26	0.4352 (4)	0.24668 (16)	0.3442 (4)	0.0616 (11)
H260	0.3699	0.2709	0.3521	0.074*
C27	0.3039 (3)	0.22284 (13)	0.1014 (3)	0.0435 (9)
C28	0.1337 (3)	0.23848 (13)	−0.0293 (3)	0.0419 (9)
C29	−0.0282 (4)	0.27375 (16)	−0.1581 (3)	0.0594 (11)
H290	−0.0862	0.2470	−0.1326	0.071*
C30	0.0129 (5)	0.2517 (2)	−0.2553 (4)	0.0996 (18)
H301	0.0692	0.2775	−0.2819	0.149*
H302	−0.0581	0.2467	−0.3039	0.149*
H303	0.0539	0.2168	−0.2426	0.149*
C31	−0.0942 (4)	0.32978 (18)	−0.1709 (4)	0.0894 (16)
H311	−0.1124	0.3433	−0.1054	0.134*
H312	−0.1701	0.3254	−0.2141	0.134*
H313	−0.0415	0.3558	−0.2012	0.134*
C51	0.3507 (4)	0.10755 (15)	0.3792 (4)	0.0579 (11)
H51	0.4171	0.0972	0.4252	0.070*
O50	0.3558 (3)	0.09921 (11)	0.2894 (2)	0.0673 (8)
N50	0.2534 (18)	0.1309 (14)	0.4132 (11)	0.063 (5)	0.61
C52	0.1569 (12)	0.1532 (7)	0.3434 (10)	0.081 (4)	0.61
H52A	0.1691	0.1924	0.3365	0.122*	0.61
H52B	0.0779	0.1465	0.3686	0.122*	0.61
H52C	0.1589	0.1357	0.2781	0.122*	0.61
C53	0.2452 (16)	0.1461 (9)	0.5186 (10)	0.114 (7)	0.61
H53A	0.3110	0.1284	0.5607	0.171*	0.61
H53B	0.1667	0.1343	0.5393	0.171*	0.61
H53C	0.2526	0.1856	0.5258	0.171*	0.61
N50A	0.278 (3)	0.135 (2)	0.4333 (17)	0.080 (9)	0.39
C52A	0.157 (2)	0.1524 (14)	0.3977 (19)	0.140 (13)	0.39
H52D	0.1434	0.1895	0.4207	0.210*	0.39
H52E	0.0973	0.1279	0.4238	0.210*	0.39
H52F	0.1472	0.1515	0.3246	0.210*	0.39
C53A	0.305 (2)	0.1432 (11)	0.5430 (13)	0.084 (7)	0.39
H53D	0.3815	0.1250	0.5659	0.126*	0.39
H53E	0.2388	0.1277	0.5776	0.126*	0.39
H53F	0.3119	0.1821	0.5575	0.126*	0.39

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0510 (3)	0.01572 (19)	0.0442 (3)	−0.0026 (2)	−0.00305 (19)	0.0002 (2)
N1	0.0585 (19)	0.0178 (13)	0.064 (2)	0.0007 (13)	−0.0127 (16)	0.0001 (13)
N2	0.0545 (18)	0.0202 (13)	0.0488 (18)	−0.0033 (13)	−0.0127 (14)	0.0003 (12)
N3	0.0498 (18)	0.0186 (13)	0.0510 (18)	0.0001 (12)	−0.0078 (14)	−0.0069 (12)
N4	0.0415 (17)	0.0236 (14)	0.0571 (18)	0.0036 (12)	−0.0072 (14)	−0.0056 (13)
N5	0.0580 (19)	0.0268 (15)	0.056 (2)	−0.0011 (14)	−0.0136 (15)	−0.0085 (14)
N21	0.072 (2)	0.0232 (15)	0.079 (2)	−0.0127 (15)	−0.0141 (19)	−0.0047 (15)
N22	0.065 (2)	0.0224 (14)	0.0499 (18)	−0.0073 (14)	−0.0109 (15)	0.0027 (13)
N23	0.057 (2)	0.0194 (14)	0.067 (2)	−0.0071 (13)	0.0008 (16)	0.0072 (14)
N24	0.0473 (18)	0.0196 (14)	0.0554 (19)	−0.0028 (12)	−0.0020 (14)	0.0046 (12)
N25	0.067 (2)	0.0222 (15)	0.074 (2)	−0.0010 (14)	−0.0028 (18)	0.0134 (15)
Cl1	0.0910 (8)	0.0285 (5)	0.0928 (8)	−0.0013 (5)	0.0222 (6)	−0.0127 (5)
Cl2	0.0487 (6)	0.0274 (4)	0.0909 (8)	0.0015 (4)	0.0032 (5)	−0.0015 (5)
Cl4	0.0815 (8)	0.1200 (11)	0.0710 (8)	0.0028 (8)	−0.0260 (7)	−0.0133 (7)
Cl24	0.1243 (12)	0.0970 (10)	0.0857 (9)	0.0176 (9)	−0.0265 (8)	0.0027 (8)
C1	0.044 (2)	0.0326 (19)	0.050 (2)	0.0073 (16)	−0.0045 (17)	0.0023 (16)
C2	0.054 (2)	0.040 (2)	0.066 (3)	0.0043 (18)	0.005 (2)	0.0081 (19)
C3	0.063 (3)	0.063 (3)	0.055 (3)	0.013 (2)	−0.003 (2)	0.015 (2)
C4	0.052 (3)	0.058 (3)	0.057 (3)	0.008 (2)	−0.003 (2)	−0.003 (2)
C5	0.048 (2)	0.053 (2)	0.067 (3)	−0.0045 (19)	0.004 (2)	−0.001 (2)
C6	0.052 (2)	0.046 (2)	0.051 (2)	−0.0018 (18)	0.0010 (19)	0.0013 (18)
C7	0.046 (2)	0.0227 (16)	0.045 (2)	−0.0014 (15)	−0.0001 (17)	0.0034 (15)
C8	0.041 (2)	0.0256 (17)	0.047 (2)	−0.0013 (15)	0.0015 (16)	−0.0024 (15)
C9	0.055 (2)	0.052 (2)	0.048 (2)	0.0108 (19)	−0.0044 (19)	−0.0060 (18)
C10	0.113 (4)	0.073 (3)	0.075 (3)	−0.001 (3)	0.011 (3)	0.008 (3)
C11	0.084 (3)	0.089 (4)	0.067 (3)	−0.001 (3)	−0.022 (3)	−0.028 (3)
C21	0.051 (2)	0.0314 (19)	0.064 (3)	−0.0102 (17)	−0.001 (2)	−0.0069 (18)
C22	0.056 (3)	0.041 (2)	0.062 (3)	−0.0069 (19)	0.002 (2)	−0.0155 (19)
C23	0.053 (3)	0.044 (2)	0.086 (3)	−0.0009 (19)	0.002 (2)	−0.010 (2)
C24	0.059 (3)	0.058 (3)	0.068 (3)	−0.002 (2)	−0.003 (2)	0.000 (2)
C25	0.072 (3)	0.063 (3)	0.064 (3)	−0.004 (2)	0.006 (2)	−0.015 (2)
C26	0.054 (3)	0.047 (2)	0.083 (3)	−0.0017 (19)	0.005 (2)	−0.019 (2)
C27	0.058 (2)	0.0196 (16)	0.052 (2)	−0.0057 (16)	0.0008 (18)	−0.0046 (16)
C28	0.051 (2)	0.0263 (18)	0.048 (2)	0.0024 (16)	0.0053 (18)	0.0054 (15)
C29	0.060 (3)	0.042 (2)	0.075 (3)	−0.003 (2)	0.003 (2)	0.025 (2)
C30	0.125 (5)	0.094 (4)	0.077 (4)	−0.005 (4)	−0.001 (3)	0.015 (3)
C31	0.080 (3)	0.056 (3)	0.129 (5)	0.010 (3)	−0.004 (3)	0.041 (3)
C51	0.073 (3)	0.038 (2)	0.061 (3)	−0.003 (2)	−0.009 (2)	0.008 (2)
O50	0.096 (2)	0.0474 (16)	0.0554 (19)	−0.0021 (15)	−0.0098 (16)	0.0012 (14)
N50	0.069 (6)	0.047 (11)	0.075 (6)	0.003 (8)	0.017 (6)	0.000 (6)
C52	0.066 (6)	0.067 (7)	0.114 (10)	0.027 (5)	0.025 (6)	0.023 (8)
C53	0.132 (15)	0.119 (11)	0.092 (11)	0.000 (12)	0.025 (10)	0.017 (9)
N50A	0.12 (2)	0.033 (9)	0.091 (15)	−0.015 (14)	0.026 (12)	−0.017 (12)
C52A	0.127 (19)	0.098 (19)	0.20 (3)	0.010 (15)	0.04 (2)	−0.07 (2)
C53A	0.13 (2)	0.059 (10)	0.067 (11)	−0.007 (12)	0.036 (12)	−0.019 (9)

Geometric parameters (Å, º)

Ni—N4	1.859 (3)	C10—H101	0.9600
Ni—N22	1.861 (3)	C10—H102	0.9600
Ni—N2	1.866 (3)	C10—H103	0.9600
Ni—N24	1.869 (3)	C11—H111	0.9600
N1—C7	1.367 (4)	C11—H112	0.9600
N1—C1	1.411 (4)	C11—H113	0.9600
N1—H1	0.8600	C21—C26	1.382 (5)
N2—C7	1.293 (4)	C21—C22	1.380 (5)
N2—H2	0.8600	C22—C23	1.379 (5)
N3—C7	1.357 (4)	C22—H220	0.9300
N3—C8	1.368 (4)	C23—C24	1.366 (6)
N3—H3	0.8600	C23—H230	0.9300
N4—C8	1.307 (4)	C24—C25	1.371 (6)
N4—H4	0.8600	C25—C26	1.372 (6)
N5—C8	1.327 (4)	C25—H250	0.9300
N5—C9	1.460 (4)	C26—H260	0.9300
N5—H5	0.8600	C29—C30	1.494 (6)
N21—C27	1.351 (4)	C29—C31	1.530 (5)
N21—C21	1.419 (5)	C29—H290	0.9800
N21—H21	0.8600	C30—H301	0.9600
N22—C27	1.298 (4)	C30—H302	0.9600
N22—H22	0.8600	C30—H303	0.9600
N23—C27	1.358 (4)	C31—H311	0.9600
N23—C28	1.370 (4)	C31—H312	0.9600
N23—H23	0.8600	C31—H313	0.9600
N24—C28	1.299 (4)	C51—O50	1.207 (5)
N24—H24	0.8600	C51—N50A	1.289 (13)
N25—C28	1.345 (4)	C51—N50	1.309 (9)
N25—C29	1.449 (5)	C51—H51	0.9300
N25—H25	0.8600	N50—C52	1.430 (14)
Cl4—C4	1.737 (4)	N50—C53	1.449 (12)
Cl24—C24	1.732 (4)	C52—H52A	0.9600
C1—C6	1.379 (5)	C52—H52B	0.9600
C1—C2	1.377 (5)	C52—H52C	0.9600
C2—C3	1.372 (5)	C53—H53A	0.9600
C2—H20	0.9300	C53—H53B	0.9600
C3—C4	1.358 (5)	C53—H53C	0.9600
C3—H30	0.9300	N50A—C52A	1.420 (17)
C4—C5	1.366 (5)	N50A—C53A	1.461 (16)
C5—C6	1.379 (5)	C52A—H52D	0.9600
C5—H50	0.9300	C52A—H52E	0.9600
C6—H60	0.9300	C52A—H52F	0.9600
C9—C10	1.483 (6)	C53A—H53D	0.9600
C9—C11	1.503 (5)	C53A—H53E	0.9600
C9—H90	0.9800	C53A—H53F	0.9600
N4—Ni—N22	177.55 (13)	C9—C11—H111	109.5
N4—Ni—N2	89.65 (12)	C9—C11—H112	109.5
N22—Ni—N2	90.53 (12)	H111—C11—H112	109.5
N4—Ni—N24	90.23 (12)	C9—C11—H113	109.5
N22—Ni—N24	89.58 (13)	H111—C11—H113	109.5
N2—Ni—N24	179.79 (13)	H112—C11—H113	109.5
C7—N1—C1	121.8 (3)	C26—C21—C22	119.1 (4)
C7—N1—H1	119.1	C26—C21—N21	119.4 (4)
C1—N1—H1	119.1	C22—C21—N21	121.5 (4)
C7—N2—Ni	130.0 (2)	C23—C22—C21	120.4 (4)
C7—N2—H2	115.0	C23—C22—H220	119.8
Ni—N2—H2	115.0	C21—C22—H220	119.8
C7—N3—C8	126.5 (3)	C24—C23—C22	119.7 (4)
C7—N3—H3	116.8	C24—C23—H230	120.1
C8—N3—H3	116.8	C22—C23—H230	120.1
C8—N4—Ni	129.9 (2)	C23—C24—C25	120.4 (4)
C8—N4—H4	115.0	C23—C24—Cl24	120.3 (4)
Ni—N4—H4	115.0	C25—C24—Cl24	119.3 (4)
C8—N5—C9	124.4 (3)	C24—C25—C26	120.1 (4)
C8—N5—H5	117.8	C24—C25—H250	120.0
C9—N5—H5	117.8	C26—C25—H250	120.0
C27—N21—C21	123.8 (3)	C25—C26—C21	120.2 (4)
C27—N21—H21	118.1	C25—C26—H260	119.9
C21—N21—H21	118.1	C21—C26—H260	119.9
C27—N22—Ni	128.5 (3)	N22—C27—N21	125.1 (3)
C27—N22—H22	115.7	N22—C27—N23	121.1 (3)
Ni—N22—H22	115.7	N21—C27—N23	113.8 (3)
C27—N23—C28	125.9 (3)	N24—C28—N25	125.6 (3)
C27—N23—H23	117.1	N24—C28—N23	120.1 (3)
C28—N23—H23	117.1	N25—C28—N23	114.3 (3)
C28—N24—Ni	128.6 (3)	N25—C29—C30	111.6 (4)
C28—N24—H24	115.7	N25—C29—C31	107.5 (4)
Ni—N24—H24	115.7	C30—C29—C31	113.1 (4)
C28—N25—C29	124.4 (3)	N25—C29—H290	108.2
C28—N25—H25	117.8	C30—C29—H290	108.2
C29—N25—H25	117.8	C31—C29—H290	108.2
C6—C1—C2	119.7 (3)	C29—C30—H301	109.5
C6—C1—N1	120.2 (3)	C29—C30—H302	109.5
C2—C1—N1	120.2 (3)	H301—C30—H302	109.5
C3—C2—C1	119.8 (4)	C29—C30—H303	109.5
C3—C2—H20	120.1	H301—C30—H303	109.5
C1—C2—H20	120.1	H302—C30—H303	109.5
C4—C3—C2	120.0 (4)	C29—C31—H311	109.5
C4—C3—H30	120.0	C29—C31—H312	109.5
C2—C3—H30	120.0	H311—C31—H312	109.5
C3—C4—C5	121.2 (4)	C29—C31—H313	109.5
C3—C4—Cl4	119.7 (3)	H311—C31—H313	109.5
C5—C4—Cl4	119.1 (3)	H312—C31—H313	109.5
C4—C5—C6	119.1 (4)	O50—C51—N50A	135.5 (12)
C4—C5—H50	120.4	O50—C51—N50	121.3 (8)
C6—C5—H50	120.4	N50A—C51—N50	17 (2)
C1—C6—C5	120.1 (4)	O50—C51—H51	119.4
C1—C6—H60	120.0	N50A—C51—H51	104.5
C5—C6—H60	120.0	N50—C51—H51	119.4
N2—C7—N3	121.6 (3)	C51—N50—C52	120.3 (12)
N2—C7—N1	124.2 (3)	C51—N50—C53	124.1 (12)
N3—C7—N1	114.2 (3)	C52—N50—C53	114.5 (10)
N4—C8—N5	125.3 (3)	C51—N50A—C52A	124.2 (18)
N4—C8—N3	120.1 (3)	C51—N50A—C53A	122.9 (18)
N5—C8—N3	114.5 (3)	C52A—N50A—C53A	112.1 (15)
N5—C9—C10	112.6 (3)	N50A—C52A—H52D	109.5
N5—C9—C11	107.3 (3)	N50A—C52A—H52E	109.5
C10—C9—C11	112.8 (4)	H52D—C52A—H52E	109.5
N5—C9—H90	108.0	N50A—C52A—H52F	109.5
C10—C9—H90	108.0	H52D—C52A—H52F	109.5
C11—C9—H90	108.0	H52E—C52A—H52F	109.5
C9—C10—H101	109.5	N50A—C53A—H53D	109.5
C9—C10—H102	109.5	N50A—C53A—H53E	109.5
H101—C10—H102	109.5	H53D—C53A—H53E	109.5
C9—C10—H103	109.5	N50A—C53A—H53F	109.5
H101—C10—H103	109.5	H53D—C53A—H53F	109.5
H102—C10—H103	109.5	H53E—C53A—H53F	109.5
C1—N1—C7—N2	−4.5 (5)	C21—N21—C27—N22	−3.3 (6)
C9—N5—C8—N4	16.9 (6)	C29—N25—C28—N24	−13.0 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.86	2.54	3.184 (3)	133
N2—H2···O50	0.86	2.19	2.981 (4)	153
N3—H3···Cl1	0.86	2.39	3.212 (3)	161
N4—H4···Cl2^i	0.86	2.54	3.394 (3)	170
N5—H5···Cl1	0.86	2.48	3.253 (3)	149
N21—H21···Cl1^ii	0.86	2.36	3.138 (3)	151
N22—H22···O50	0.86	2.13	2.957 (4)	160
N23—H23···Cl2^ii	0.86	2.62	3.358 (3)	145
N24—H24···Cl2^i	0.86	2.61	3.454 (3)	169
N25—H25···Cl2^ii	0.86	2.67	3.213 (3)	123
N2—H2···O50	0.86	2.19	2.981 (4)	153
N22—H22···O50	0.86	2.13	2.957 (4)	160

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