Aqua­bis­(2,2′-bi­pyridine-κ2N,N′)chlorido­nickel(II) chloride chloro­form monosolvate hemihydrate

Vasileiadou, E.; Angaridis, P.A.; Raptis, R.G.; Mathivathanan, L.

doi:10.1107/S2414314616018344

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161834

https://doi.org/10.1107/S2414314616018344

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Aquabis(2,2′-bipyridine-κ²N,N′)chloridonickel(II) chloride chloroform monosolvate hemihydrate

Eugenia Vasileiadou,^a,^b Panagiotis A. Angaridis,^b Raphael G. Raptis ^a and Logesh Mathivathanan ^a ^*

^aDepartment of Chemistry and Biochemistry, Florida International University, 11200 SW 8th Street, Miami, FL 33199, USA, and ^bDepartment of Chemistry, Aristotle University of Thessaloniki, University Campus, Thessaloniki, 54124, Greece
^*Correspondence e-mail: logesh.mathivathanan@fiu.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 13 October 2016; accepted 15 November 2016; online 22 November 2016)

The title solvated salt, [NiCl(C₁₀H₈N₂)₂(H₂O)]Cl·CHCl₃·0.5H₂O, contains a mononuclear Ni^II complex cation with 2,2′-bipyridine, chloride and aqua ligands forming a slightly distorted ClN₄O octahedral coordination set. The charge of the cation is balanced by a chloride anion. In the crystal, half a water molecule and a chloroform solvent molecule are present per formula unit. Individual components are held together by O—H⋯Cl hydrogen bonding and π–π interactions.

Keywords: crystal structure; nickel(II); 2,2′-bipyridine; octahedral coordination environment.

CCDC reference: 1517485

Structure description

The Ni^II cation has a distorted octahedral coordination environment with the chlorido and aqua ligands in a cis configuration relative to each other (Fig. 1). The two N,N′-bipyridine ligands are almost perpendicular to each other [dihedral angle 88.73 (16)°]. The Ni—N distances range between 2.059 (3) and 2.102 (3) Å, while the Ni—O(water) and Ni—Cl distances are 2.084 (3) and 2.418 (1) Å, respectively. Similar cis-[M^IICl(2,2′-bipy)₂(H₂O)]⁺ cations are known for M = Mn (Chen et al., 1995 ) and Cd (Lei & Li, 2011 ). A few [NiLL′)₂Cl(OHR)]⁺ complexes are known in the literature where LL′ is a bidentate chelating N-donor ligand such as 2,2′-bipyridine or 1,10-phenanthroline. Examples with R = H or methyl were given by Brewer et al. (2003 ) and Chesnut et al. (1999 ). Interestingly, all except one adopt the cis-configuration. The trans-configuration between Cl and H₂O is known for a tetradentate bis-phenanthroline ligand, viz., 2,2′-bis-(1,10-phenanthroline) (Rice & Anderson, 2000 ), where steric hindrance presumably prevents a cis configuration. In one case, [Ni(2,2′-bipy)₂Cl(OH₂)]⁺ has been formed in situ by reacting [Ni(2,2′-bipy)₃]²⁺ with Cl⁻ and H₂O. The reaction was concentration-sensitive and the [Ni(2,2′-bipy)Cl(OH₂)]⁺ cation forms a three-dimensional hydrogen-bonded network with deprotonated benzene tetracarboxylic acid moieties (Sun et al., 2010 ).

Figure 1
The molecular structure of the cation of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 40% probability level.

The asymmetric unit of the title compound also contains a CHCl₃ solvent molecule and a lattice water molecule located on a twofold rotation axis. The Ni-bound water (O1) molecule forms weak hydrogen bonds with the Cl⁻ counter-anion (Cl5) and the coordinating Cl (Cl1) atom from an adjacent molecule (Table 1, Fig. 2). Although the H atoms of the lattice water molecule could not be located, O⋯Cl distances of 3.231 (3) Å to the counter-anion indicate likewise weak hydrogen bonding. π–π interactions between the pyridyl rings of parallel-stacked 2,2-bipy molecules [C11—C13 = 3.465 (6) Å] are also present in the crystal lattice (Fig. 3). It is worth noting that similar Cl-bridged hetero- and homo-binuclear compounds dominate NiCl₂(LL')₂-chemistry. One example of such heterobinuclear compound, [Ni(2,2′-bipy)₂(μ-Cl)₂CdI₂], has been reported (Chesnut et al., 1999).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl5	0.87 (2)	2.25 (2)	3.115 (3)	171 (5)
O1—H1B⋯Cl1ⁱ	0.87 (2)	2.30 (2)	3.148 (3)	163 (4)
Symmetry code: (i) $[-x+1, y, -z+{\script{3\over 2}}]$ .

Figure 2
Packing diagram of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines.

Figure 3
The intermolecular π–π interactions between the 2,2′-bipy ligands of adjacent complex cations in the title compound.

Synthesis and crystallization

The title compound was isolated when 2,2′-bipyridine was used as an auxiliary ligand for the intended preparation of a Ni-sulfonamide complex. A solution of NiCl₂·6H₂O (34.2 mg, 0.144 mmol) in 10 ml MeOH was added slowly to a solution of N,N-diphenyl-1,2-benzenesulfonamide (60 mg, 0.144 mmol) and 2,2′-bipyridine (25.5 mg, 0.163 mmol) in 8 ml MeOH and 2.2 eq. of NHEt₂, at room temperature. A precipitate formed after 10 min and the reaction was stirred for an additional three hours. The precipitate was filtered off the methanol solution; the yellow–green precipitate was collected and crystals were obtained by diffusion of diethyl ether vapor into a chloroform solution of the compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydrogen atoms of the lattice water molecule could not be modelled satisfactorily and were omitted from the refinement, but are included in the formula.

Table 2
Experimental details

Crystal data
Chemical formula	[NiCl(C₁₀H₈N₂)₂(H₂O)]Cl·CHCl₃·0.5H₂O
M_r	588.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	300
a, b, c (Å)	29.1709 (14), 11.2898 (5), 20.0517 (10)
β (°)	131.163 (1)
V (Å³)	4971.5 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	1.34
Crystal size (mm)	0.14 × 0.07 × 0.06

Data collection
Diffractometer	Bruker D8 Quest CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.692, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	42949, 5141, 3870
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.140, 1.05
No. of reflections	5141
No. of parameters	300
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.71
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT2014 (Sheldrick, 2015 ), ShelXle (Hübschle et al., 2011 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip et al., 2010 ).

Structural data

CCDC reference: 1517485

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018344/wm5333sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616018344/wm5333Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616018344/wm5333Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2015); cell refinement: SAINT (Bruker, 2015); data reduction: SAINT (Bruker, 2015); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015); program(s) used to refine structure: ShelXle (Hübschle et al., 2011) and OLEX2 (Dolomanov et al., 2009); molecular graphics: ShelXle (Hübschle et al., 2011); software used to prepare material for publication: publCIF (Westrip et al., 2010).

Aquabis(2,2'-bipyridine-κ²N,N')chloridonickel(II) chloride chloroform monosolvate hemihydrate top

Crystal data top

[NiCl(C₁₀H₈N₂)₂(H₂O)]Cl·CHCl₃·0.5H₂O	F(000) = 2392
M_r = 588.36	D_x = 1.572 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 29.1709 (14) Å	Cell parameters from 9884 reflections
b = 11.2898 (5) Å	θ = 2.8–26.3°
c = 20.0517 (10) Å	µ = 1.34 mm⁻¹
β = 131.163 (1)°	T = 300 K
V = 4971.5 (4) Å³	Trapezoid, blue
Z = 8	0.14 × 0.07 × 0.06 mm

Data collection top

Bruker D8 Quest CMOS diffractometer	3870 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.048
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θ_max = 26.5°, θ_min = 2.8°
T_min = 0.692, T_max = 0.745	h = −36→36
42949 measured reflections	k = −14→14
5141 independent reflections	l = −25→25

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.140	w = 1/[σ²(F_o²) + (0.0585P)² + 19.6746P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5141 reflections	Δρ_max = 0.56 e Å⁻³
300 parameters	Δρ_min = −0.71 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ni1	0.41761 (2)	0.23752 (4)	0.55719 (3)	0.02914 (15)
Cl1	0.52576 (4)	0.27540 (10)	0.66856 (6)	0.0436 (3)
O1	0.42085 (15)	0.1520 (3)	0.65230 (19)	0.0481 (8)
N1	0.32221 (14)	0.2227 (3)	0.4674 (2)	0.0329 (7)
N2	0.39253 (14)	0.3961 (3)	0.5772 (2)	0.0329 (7)
N3	0.41843 (14)	0.3077 (3)	0.4617 (2)	0.0372 (8)
N4	0.42689 (14)	0.0861 (3)	0.5098 (2)	0.0387 (8)
C1	0.33271 (17)	0.4149 (3)	0.5258 (2)	0.0315 (8)
C2	0.3104 (2)	0.5186 (4)	0.5327 (3)	0.0444 (10)
H2	0.2687	0.5299	0.4980	0.053*
C3	0.3508 (2)	0.6044 (4)	0.5916 (3)	0.0532 (12)
H3	0.3367	0.6746	0.5968	0.064*
C4	0.4116 (2)	0.5858 (4)	0.6421 (3)	0.0494 (11)
H4	0.4395	0.6435	0.6816	0.059*
C5	0.4311 (2)	0.4808 (4)	0.6340 (3)	0.0437 (10)
H5	0.4727	0.4678	0.6694	0.052*
C6	0.29276 (16)	0.3194 (3)	0.4628 (2)	0.0313 (8)
C7	0.23009 (18)	0.3261 (4)	0.4031 (3)	0.0443 (10)
H7	0.2106	0.3939	0.3997	0.053*
C8	0.1965 (2)	0.2306 (4)	0.3481 (3)	0.0497 (11)
H8	0.1542	0.2334	0.3077	0.060*
C9	0.22615 (19)	0.1322 (4)	0.3538 (3)	0.0482 (11)
H9	0.2044	0.0667	0.3180	0.058*
C10	0.28837 (18)	0.1316 (4)	0.4131 (3)	0.0427 (10)
H10	0.3083	0.0648	0.4159	0.051*
C11	0.42223 (18)	0.1021 (4)	0.4384 (3)	0.0451 (11)
C12	0.4180 (2)	0.0055 (6)	0.3914 (4)	0.0672 (15)
H12	0.4138	0.0173	0.3417	0.081*
C13	0.4201 (3)	−0.1054 (6)	0.4185 (5)	0.0789 (18)
H13	0.4173	−0.1702	0.3874	0.095*
C14	0.4263 (2)	−0.1229 (5)	0.4919 (4)	0.0718 (16)
H14	0.4281	−0.1989	0.5113	0.086*
C15	0.4298 (2)	−0.0244 (4)	0.5363 (3)	0.0520 (11)
H15	0.4343	−0.0355	0.5863	0.062*
C16	0.42170 (18)	0.2267 (4)	0.4160 (3)	0.0450 (11)
C17	0.4276 (2)	0.2633 (6)	0.3550 (3)	0.0692 (16)
H17	0.4304	0.2072	0.3237	0.083*
C18	0.4294 (3)	0.3796 (7)	0.3418 (4)	0.0792 (19)
H18	0.4330	0.4040	0.3012	0.095*
C19	0.4259 (2)	0.4610 (6)	0.3881 (3)	0.0709 (16)
H19	0.4274	0.5415	0.3800	0.085*
C20	0.4200 (2)	0.4220 (4)	0.4472 (3)	0.0516 (11)
H20	0.4170	0.4779	0.4783	0.062*
H1A	0.402 (2)	0.088 (3)	0.646 (3)	0.062*
H1B	0.4432 (19)	0.182 (4)	0.7055 (18)	0.062*
Cl2	0.28738 (15)	0.61538 (18)	0.34457 (16)	0.1420 (10)
Cl3	0.23219 (9)	0.83353 (17)	0.25316 (11)	0.1017 (6)
Cl4	0.28069 (7)	0.80694 (13)	0.43133 (10)	0.0766 (4)
C21	0.2434 (3)	0.7354 (5)	0.3311 (4)	0.0801 (17)
H21	0.2039	0.7064	0.3091	0.096*
Cl5	0.36460 (5)	−0.08254 (10)	0.65231 (8)	0.0556 (3)
O2	0.5000	0.8219 (5)	0.7500	0.127 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0288 (3)	0.0340 (3)	0.0255 (2)	0.0032 (2)	0.0182 (2)	0.0000 (2)
Cl1	0.0293 (5)	0.0628 (7)	0.0319 (5)	0.0040 (4)	0.0172 (4)	0.0056 (5)
O1	0.064 (2)	0.0492 (18)	0.0373 (16)	−0.0183 (15)	0.0359 (16)	−0.0078 (14)
N1	0.0319 (16)	0.0323 (17)	0.0328 (16)	0.0022 (13)	0.0206 (15)	0.0001 (13)
N2	0.0335 (17)	0.0348 (17)	0.0306 (16)	−0.0012 (14)	0.0212 (15)	−0.0038 (13)
N3	0.0319 (17)	0.051 (2)	0.0259 (16)	−0.0028 (15)	0.0178 (15)	0.0018 (15)
N4	0.0329 (18)	0.044 (2)	0.0405 (19)	0.0055 (14)	0.0249 (16)	−0.0013 (15)
C1	0.038 (2)	0.0300 (19)	0.0320 (19)	0.0023 (16)	0.0256 (18)	0.0021 (15)
C2	0.047 (2)	0.041 (2)	0.046 (2)	0.0100 (19)	0.031 (2)	0.0027 (19)
C3	0.075 (3)	0.036 (2)	0.058 (3)	0.004 (2)	0.048 (3)	−0.005 (2)
C4	0.063 (3)	0.041 (2)	0.046 (3)	−0.013 (2)	0.037 (2)	−0.014 (2)
C5	0.043 (2)	0.046 (2)	0.040 (2)	−0.0075 (19)	0.026 (2)	−0.0091 (19)
C6	0.034 (2)	0.034 (2)	0.0308 (19)	0.0052 (16)	0.0230 (17)	0.0041 (15)
C7	0.034 (2)	0.048 (3)	0.046 (2)	0.0063 (19)	0.024 (2)	0.002 (2)
C8	0.029 (2)	0.063 (3)	0.045 (2)	−0.002 (2)	0.019 (2)	−0.003 (2)
C9	0.038 (2)	0.048 (3)	0.045 (2)	−0.012 (2)	0.022 (2)	−0.013 (2)
C10	0.039 (2)	0.037 (2)	0.047 (2)	−0.0012 (18)	0.026 (2)	−0.0074 (19)
C11	0.033 (2)	0.068 (3)	0.038 (2)	0.001 (2)	0.025 (2)	−0.010 (2)
C12	0.063 (3)	0.085 (4)	0.070 (3)	−0.007 (3)	0.051 (3)	−0.031 (3)
C13	0.075 (4)	0.075 (4)	0.104 (5)	−0.002 (3)	0.066 (4)	−0.036 (4)
C14	0.064 (3)	0.049 (3)	0.108 (5)	0.011 (2)	0.059 (4)	−0.008 (3)
C15	0.050 (3)	0.051 (3)	0.061 (3)	0.011 (2)	0.039 (2)	0.000 (2)
C16	0.032 (2)	0.075 (3)	0.028 (2)	0.000 (2)	0.0200 (18)	−0.002 (2)
C17	0.066 (3)	0.112 (5)	0.044 (3)	−0.004 (3)	0.043 (3)	−0.006 (3)
C18	0.076 (4)	0.123 (6)	0.049 (3)	−0.010 (4)	0.045 (3)	0.017 (3)
C19	0.065 (3)	0.086 (4)	0.048 (3)	−0.017 (3)	0.032 (3)	0.015 (3)
C20	0.051 (3)	0.061 (3)	0.037 (2)	−0.008 (2)	0.027 (2)	0.004 (2)
Cl2	0.261 (3)	0.0811 (13)	0.1370 (18)	0.0660 (16)	0.154 (2)	0.0285 (12)
Cl3	0.1164 (14)	0.0971 (13)	0.0744 (10)	0.0275 (11)	0.0554 (11)	0.0225 (9)
Cl4	0.0888 (10)	0.0663 (9)	0.0773 (9)	0.0039 (8)	0.0557 (9)	−0.0023 (7)
C21	0.079 (4)	0.073 (4)	0.082 (4)	0.000 (3)	0.050 (4)	−0.003 (3)
Cl5	0.0589 (7)	0.0393 (6)	0.0658 (7)	0.0008 (5)	0.0398 (6)	0.0006 (5)
O2	0.064 (4)	0.053 (4)	0.170 (7)	0.000	0.036 (4)	0.000

Geometric parameters (Å, º) top

Ni1—N4	2.059 (3)	C7—H7	0.9300
Ni1—N2	2.071 (3)	C8—C9	1.365 (6)
Ni1—O1	2.084 (3)	C8—H8	0.9300
Ni1—N3	2.087 (3)	C9—C10	1.366 (6)
Ni1—N1	2.102 (3)	C9—H9	0.9300
Ni1—Cl1	2.4183 (11)	C10—H10	0.9300
O1—H1A	0.872 (19)	C11—C12	1.393 (6)
O1—H1B	0.874 (19)	C11—C16	1.473 (7)
N1—C10	1.343 (5)	C12—C13	1.351 (9)
N1—C6	1.355 (5)	C12—H12	0.9300
N2—C1	1.336 (5)	C13—C14	1.374 (8)
N2—C5	1.338 (5)	C13—H13	0.9300
N3—C20	1.330 (6)	C14—C15	1.385 (7)
N3—C16	1.341 (5)	C14—H14	0.9300
N4—C15	1.337 (6)	C15—H15	0.9300
N4—C11	1.357 (5)	C16—C17	1.407 (6)
C1—C2	1.390 (5)	C17—C18	1.347 (8)
C1—C6	1.476 (5)	C17—H17	0.9300
C2—C3	1.374 (6)	C18—C19	1.356 (9)
C2—H2	0.9300	C18—H18	0.9300
C3—C4	1.361 (7)	C19—C20	1.378 (7)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.370 (6)	C20—H20	0.9300
C4—H4	0.9300	Cl2—C21	1.760 (6)
C5—H5	0.9300	Cl3—C21	1.761 (7)
C6—C7	1.378 (5)	Cl4—C21	1.731 (6)
C7—C8	1.384 (6)	C21—H21	0.9800

N4—Ni1—N2	167.95 (13)	C6—C7—C8	119.2 (4)
N4—Ni1—O1	95.59 (13)	C6—C7—H7	120.4
N2—Ni1—O1	91.87 (12)	C8—C7—H7	120.4
N4—Ni1—N3	78.85 (14)	C9—C8—C7	119.4 (4)
N2—Ni1—N3	93.92 (13)	C9—C8—H8	120.3
O1—Ni1—N3	174.13 (13)	C7—C8—H8	120.3
N4—Ni1—N1	92.32 (12)	C8—C9—C10	118.8 (4)
N2—Ni1—N1	78.32 (12)	C8—C9—H9	120.6
O1—Ni1—N1	89.09 (12)	C10—C9—H9	120.6
N3—Ni1—N1	93.00 (12)	N1—C10—C9	123.2 (4)
N4—Ni1—Cl1	94.88 (9)	N1—C10—H10	118.4
N2—Ni1—Cl1	94.63 (9)	C9—C10—H10	118.4
O1—Ni1—Cl1	89.50 (9)	N4—C11—C12	120.8 (5)
N3—Ni1—Cl1	89.10 (9)	N4—C11—C16	114.9 (4)
N1—Ni1—Cl1	172.76 (9)	C12—C11—C16	124.2 (4)
Ni1—O1—H1A	127 (3)	C13—C12—C11	119.5 (5)
Ni1—O1—H1B	119 (3)	C13—C12—H12	120.2
H1A—O1—H1B	114 (5)	C11—C12—H12	120.2
C10—N1—C6	117.9 (3)	C12—C13—C14	120.2 (5)
C10—N1—Ni1	127.4 (3)	C12—C13—H13	119.9
C6—N1—Ni1	114.6 (2)	C14—C13—H13	119.9
C1—N2—C5	118.9 (3)	C13—C14—C15	118.4 (6)
C1—N2—Ni1	115.9 (2)	C13—C14—H14	120.8
C5—N2—Ni1	125.2 (3)	C15—C14—H14	120.8
C20—N3—C16	119.0 (4)	N4—C15—C14	122.3 (5)
C20—N3—Ni1	126.2 (3)	N4—C15—H15	118.8
C16—N3—Ni1	114.6 (3)	C14—C15—H15	118.8
C15—N4—C11	118.7 (4)	N3—C16—C17	119.9 (5)
C15—N4—Ni1	125.7 (3)	N3—C16—C11	115.7 (4)
C11—N4—Ni1	115.1 (3)	C17—C16—C11	124.3 (4)
N2—C1—C2	121.1 (4)	C18—C17—C16	120.0 (5)
N2—C1—C6	116.0 (3)	C18—C17—H17	120.0
C2—C1—C6	122.9 (3)	C16—C17—H17	120.0
C3—C2—C1	119.1 (4)	C17—C18—C19	119.8 (5)
C3—C2—H2	120.4	C17—C18—H18	120.1
C1—C2—H2	120.4	C19—C18—H18	120.1
C4—C3—C2	119.4 (4)	C18—C19—C20	118.7 (6)
C4—C3—H3	120.3	C18—C19—H19	120.6
C2—C3—H3	120.3	C20—C19—H19	120.6
C3—C4—C5	119.0 (4)	N3—C20—C19	122.6 (5)
C3—C4—H4	120.5	N3—C20—H20	118.7
C5—C4—H4	120.5	C19—C20—H20	118.7
N2—C5—C4	122.5 (4)	Cl4—C21—Cl2	110.1 (4)
N2—C5—H5	118.7	Cl4—C21—Cl3	110.2 (3)
C4—C5—H5	118.7	Cl2—C21—Cl3	108.2 (4)
N1—C6—C7	121.5 (4)	Cl4—C21—H21	109.5
N1—C6—C1	115.0 (3)	Cl2—C21—H21	109.5
C7—C6—C1	123.5 (3)	Cl3—C21—H21	109.5

C5—N2—C1—C2	−2.0 (5)	C15—N4—C11—C12	2.6 (6)
Ni1—N2—C1—C2	−179.4 (3)	Ni1—N4—C11—C12	−169.8 (3)
C5—N2—C1—C6	178.2 (3)	C15—N4—C11—C16	−177.7 (4)
Ni1—N2—C1—C6	0.8 (4)	Ni1—N4—C11—C16	9.9 (4)
N2—C1—C2—C3	2.0 (6)	N4—C11—C12—C13	−1.7 (7)
C6—C1—C2—C3	−178.3 (4)	C16—C11—C12—C13	178.7 (5)
C1—C2—C3—C4	−0.4 (7)	C11—C12—C13—C14	0.1 (8)
C2—C3—C4—C5	−1.1 (7)	C12—C13—C14—C15	0.5 (8)
C1—N2—C5—C4	0.5 (6)	C11—N4—C15—C14	−2.1 (6)
Ni1—N2—C5—C4	177.7 (3)	Ni1—N4—C15—C14	169.5 (4)
C3—C4—C5—N2	1.1 (7)	C13—C14—C15—N4	0.5 (8)
C10—N1—C6—C7	−1.6 (5)	C20—N3—C16—C17	1.0 (6)
Ni1—N1—C6—C7	175.9 (3)	Ni1—N3—C16—C17	−174.8 (3)
C10—N1—C6—C1	178.5 (3)	C20—N3—C16—C11	177.6 (4)
Ni1—N1—C6—C1	−4.0 (4)	Ni1—N3—C16—C11	1.8 (4)
N2—C1—C6—N1	2.2 (5)	N4—C11—C16—N3	−7.7 (5)
C2—C1—C6—N1	−177.6 (4)	C12—C11—C16—N3	171.9 (4)
N2—C1—C6—C7	−177.7 (4)	N4—C11—C16—C17	168.7 (4)
C2—C1—C6—C7	2.5 (6)	C12—C11—C16—C17	−11.7 (7)
N1—C6—C7—C8	1.7 (6)	N3—C16—C17—C18	−0.7 (8)
C1—C6—C7—C8	−178.4 (4)	C11—C16—C17—C18	−177.0 (5)
C6—C7—C8—C9	−0.4 (7)	C16—C17—C18—C19	0.5 (9)
C7—C8—C9—C10	−0.9 (7)	C17—C18—C19—C20	−0.6 (9)
C6—N1—C10—C9	0.2 (6)	C16—N3—C20—C19	−1.1 (6)
Ni1—N1—C10—C9	−177.0 (3)	Ni1—N3—C20—C19	174.1 (3)
C8—C9—C10—N1	1.1 (7)	C18—C19—C20—N3	0.9 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl5	0.87 (2)	2.25 (2)	3.115 (3)	171 (5)
O1—H1B···Cl1ⁱ	0.87 (2)	2.30 (2)	3.148 (3)	163 (4)

Symmetry code: (i) −x+1, y, −z+3/2.

Acknowledgements

REU participant EV was supported by the NSF–REU Site Grant CHE1560375 to FIU.

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