Di-μ-chlorido-bis­[chlorido­(di­methyl­formamide-κN)(3,5-diphenyl-1H-pyrazole-κN2)­copper(II)]

Naugle, M.S.; Keller, B.T.; Zeller, M.; Zaleski, C.M.

doi:10.1107/S2414314618011860

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 8| August 2018| x181186

https://doi.org/10.1107/S2414314618011860

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Di-μ-chlorido-bis[chlorido(dimethylformamide-κN)(3,5-diphenyl-1H-pyrazole-κN²)copper(II)]

Mercedes S. Naugle,^a Brittany T. Keller,^a Matthias Zeller ^b and Curtis M. Zaleski ^a ^*

^aDepartment of Chemistry and Biochemistry, Shippensburg University, 1871 Old Main Dr., Shippensburg, PA 17257, USA, and ^bDepartment of Chemistry, Purdue University, 560 Oval Dr., West Lafayette, IN 47907, USA
^*Correspondence e-mail: cmzaleski@ship.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 12 August 2018; accepted 21 August 2018; online 24 August 2018)

The title compound, [Cu₂Cl₄(C₁₅H₁₂N₂)₂(C₃H₇NO)₂], Cu₂(μ-Cl)₂Cl₂(3,5-diphenyl-1H-pyrazole)₂(DMF)₂, where DMF is N,N-dimethylformamide, crystallizes in the monoclinic space group P2₁/n. The five-coordinate Cu^II ions have a distorted square-pyramidal geometry and are joined via two μ-Cl anions. The coordination environment of each Cu^II ion is completed by a terminal chloride anion, a nitrogen-coordinated 3,5-diphenyl-1H-pyrazole molecule, and a DMF molecule. Two intramolecular hydrogen bonds exist in the molecule as the H atom of the protonated N atom of the 3,5-diphenyl-1H-pyrazole bonds to a terminal chloride anion of the adjacent Cu^II cation. In addition, molecules are linked into a two-dimensional sheet via weak C—H⋯Cl intermolecular hydrogen bonds. Each dimer hydrogen bonds to four neighboring molecules as the H atom of the C atom in the fourth position of the pyrazole ring bonds to a μ-Cl on a neighboring molecule.

Keywords: crystal structure; copper complex; 3,5-diphenyl-1H-pyrazole.

CCDC reference: 1863262

Structure description

Pyrazole-based ligands are ubiquitous in the literature for their ability to build mono-metal complexes and molecules containing multiple metal centers (Mukherjee, 2000 ; Viciano-Chumillas et al., 2010 ; Doidge et al., 2015 ; Castro et al., 2016 ). In particular, 3,5-diphenylpyrazole and its derivatives have been used to form numerous copper complexes with the metal in either the 1+ or 2+ oxidation states (Raptis & Fackler Jr, 1988 ; Mezei et al., 2007 ; Tardito et al., 2011 ; Ahmed et al., 2016 ; Zhang et al., 2017 ). The title compound Cu₂(μ-Cl)₂Cl₂(3,5-diphenyl-1H-pyrazole)₂(DMF)₂ (1), where DMF is N,N-dimethylformamide, reported within relates a dicopper(II) compound with two neutral 3,5-diphenyl-1H-pyrazole ligands, two bridging chloride anions, and two terminal chloride anions. In addition, compound (1) has similar structural features to a number of copper(II)–chloride–pyrazole-based molecules and one copper(II)–chloride–triazole-based molecule: Cu₂(μ-Cl₂)Cl₂(1H-3,5-diethyl-4-methylpyrazole)₄ (Agre et al., 1977 ; Agre et al., 1979 ), Cu₂(μ-Cl₂)Cl₂(3,4-dimethyl-5-phenylpyrazole)₂(4,5-dimethyl-3-phenylpyrazole)₂ (Keij et al., 1991 ), Cu₂(μ-Cl₂)Cl₂(3,5-diphenylpyrazole)₄ (Małecka et al., 1998 ; Mezei & Raptis, 2004 ; Zhu et al., 2011 ), Cu₂(μ-Cl₂)Cl₂(3,5-dimethyl-1H-pyrazole)₄ (Chandrasekhar et al., 2000 ; Giles et al., 2015 ), Cu₂(μ-Cl₂)Cl₂(3-methyl-5-phenyl-1H-pyrazole)₄ (Soltani et al., 2012 ), Cu₂(μ-Cl₂)Cl₂(5-methyl-1H-pyrazole)₄ (Giles et al., 2015; Feng et al., 2016 ), Cu₂(μ-Cl₂)Cl₂(3,4,5-trimethyl-1H-pyrazole)₄ (Vincent et al., 2018 ), and Cu₂(μ-Cl)₂Cl₂(3,5-diphenyl-4-amino-1,2,4-triazole)₂(H₂O)₂ (Bushuev et al., 2006 ).

Compound (1) consists of two Cu^II ions bridged by two μ-Cl anions (Fig. 1). An inversion center exists in the molecule, resulting in identical coordination environments about the copper centers. Thus, only the coordination environment of Cu1 will be discussed. The copper ions are assigned as a 2+ oxidation state based on a bond-valence-sum value of 2.03 (Brese & O'Keeffe, 1991 ; Liu & Thorp, 1993 ) and overall molecular charge considerations. The 3,5-diphenyl-1H-pyrazole ligand is not deprotonated (H atoms are well resolved in difference electron density maps); thus, the ligands have a neutral charge. The four chloride ions necessitate that each identical copper ion has a 2+ charge. Each Cu^II ion is five-coordinate with a distorted square-pyramidal geometry (Fig. 2). This geometry is supported by the calculated τ value of 0.28, where an ideal square-pyramidal geometry is given by τ = 0 and an ideal trigonal–bipyramidal geometry is specified as τ = 1 (Addison et al., 1984 ). The basal atoms of the geometry are comprised of the non-protonated nitrogen atom (N1) of the 3,5-diphenyl-1H-pyrazole ligand, a terminal chloride anion (Cl1), a μ-chloride anion (Cl2), and an oxygen atom (O1) from a DMF molecule. The average bond distance between Cu1 and the basal atoms is 2.133 Å. The coordination is completed by a second μ-chloride anion (Cl2ⁱ) in the apical position [symmetry operator (i): −x + 1, −y + 1, −z]. The bond distance of Cu1 to the apical μ-Cl2ⁱ is elongated with a distance of 2.6693 (6) Å. For comparison, the bond distance of Cu1 to the basal μ-Cl2 is 2.2851 (5) Å. In addition, an intramolecular hydrogen bond exists between the terminal Cl1 anion of Cu1 and the hydrogen atom of N2ⁱ of the 3,5-diphenylpyrazole attached to Cu1ⁱ (Fig. 3 and Table 1). The equivalent intramolecular hydrogen bond exists between Cl1ⁱ and the hydrogen atom of N2. Thus, two intramolecular hydrogen bonds exist in each molecule. Lastly, weak intermolecular hydrogen bonds (C8—H8⋯Cl2ⁱⁱ) connect the molecules into a two-dimensional sheet [Fig. 4; symmetry operator (ii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ]. The hydrogen atom of the carbon atom in the fourth position of the pyrazole ring bonds to a μ-Cl on an adjacent molecule. Since there are two 3,5-diphenyl-1H-pyrazole ligands and two μ-Cl anions per molecule, each individual molecule is hydrogen bonded to four neighboring molecules through this connectivity and a two-dimensional sheet is generated.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯Cl1ⁱ	0.88	2.40	3.2766 (19)	175
C8—H8⋯Cl2ⁱⁱ	0.95	2.79	3.722 (2)	169
Symmetry codes: (i) -x+1, -y+1, -z; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
The molecular structure of (1) with displacement ellipsoids at the 50% probability level [symmetry code: (i) −x + 1, −y + 1, −z). For clarity, H atoms have been omitted. Color scheme: orange – Cu^II, green – Cl, red – oxygen, blue – nitrogen, and gray – carbon. All figures were generated with the program Mercury (Macrae et al., 2006

Figure 2
The distorted square-pyramidal geometry about Cu1 [symmetry code: (i) −x + 1, −y + 1, −z]. See Fig. 1

for display details.

Figure 3
The intramolecular hydrogen bonds present in each molecule of (1) [symmetry code: (i) −x + 1, −y + 1, −z]. Hydrogen atoms are displayed in white. See Fig. 1

for additional display details.

Figure 4
The intermolecular hydrogen bonds present between neighboring molecules of (1) that result in a two-dimensional sheet [symmetry code: (ii) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ]. For clarity only the H atoms (white) involved in the hydrogen bonding are displayed. See Fig. 1

for additional display details.

Synthesis and crystallization

Copper(II) chloride dihydrate was purchased from J. T. Baker Chemical Company, 3,5-diphenyl-1H-pyrazole (>98.0%) was purchased from TCI America, and N,N-dimethylformamide (DMF, ACS grade) was purchased Pharmco–Aaper. All reagents were used as received and without further purification.

Copper(II) chloride dihydrate (1 mmol) and 3,5-diphenyl-1H-pyrazole (1 mmol) were dissolved in 20 ml of DMF resulting in a clear yellow–green solution. The solution was allowed to stir overnight and was then gravity filtered. No precipitate was recovered, and the filtrate had a clear yellow–green color. Slow evaporation of the solvent yielded X-ray quality green plate-like crystals after 30 days. The percent yield of the reaction was 30% based on copper(II) chloride dihydrate.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂Cl₄(C₃H₇NO)₂(C₁₅H₁₂N₂)₂]
M_r	855.60
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	12.004 (1), 9.7942 (4), 17.4116 (8)
β (°)	107.633 (3)
V (Å³)	1950.9 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.40
Crystal size (mm)	0.31 × 0.29 × 0.22

Data collection
Diffractometer	Nonius Kappa CCD
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.612, 0.748
No. of measured, independent and observed [I > 2σ(I)] reflections	12667, 4445, 3976
R_int	0.080
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.107, 1.04
No. of reflections	4445
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.45
Computer programs: COLLECT (Nonius, 1998 ), HKL-3000 (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), shelXle (Hübschle et al., 2011 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1863262

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618011860/lh4039sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618011860/lh4039Isup2.hkl

checkCIF report

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL-3000 (Otwinowski & Minor, 1997); data reduction: HKL-3000 (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) and shelXle (Hübschle et al., 2011); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Di-µ-chlorido-bis[chlorido(dimethylformamide-κN)(3,5-diphenyl-1H-pyrazole-κN²)copper(II)] top

Crystal data top

[Cu₂Cl₄(C₃H₇NO)₂(C₁₅H₁₂N₂)₂]	F(000) = 876
M_r = 855.60	D_x = 1.457 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.004 (1) Å	Cell parameters from 12667 reflections
b = 9.7942 (4) Å	θ = 1.8–27.8°
c = 17.4116 (8) Å	µ = 1.40 mm⁻¹
β = 107.633 (3)°	T = 100 K
V = 1950.9 (2) Å³	Plate, green
Z = 2	0.31 × 0.29 × 0.22 mm

Data collection top

Nonius Kappa CCD diffractometer	4445 independent reflections
Radiation source: fine focus X-ray tube	3976 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.080
ω and φ scans	θ_max = 27.8°, θ_min = 1.8°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −13→15
T_min = 0.612, T_max = 0.748	k = −12→10
12667 measured reflections	l = −22→20

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.0444P)² + 1.0669P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4445 reflections	Δρ_max = 0.49 e Å⁻³
229 parameters	Δρ_min = −0.45 e Å⁻³
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0119 (13)

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.

Refinement. Hydrogen atoms were placed in calculated positions and refined as riding on their carrier atoms with C—H distances of 0.95 Å for sp² carbon atoms, 0.98 Å for methyl carbon atoms, and 0.88 Å for the sp² nitrogen atom. The <ui>U_iso values for hydrogen atoms were set to a multiple of the value of the carrying carbon atom (1.2 times for sp²-hybridized carbon atoms or 1.5 times for methyl carbon atoms).

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

	x	y	z	U_iso*/U_eq
Cu1	0.63919 (2)	0.57447 (2)	0.01853 (2)	0.01123 (12)
Cl2	0.58568 (4)	0.36146 (5)	0.04774 (3)	0.01454 (14)
Cl1	0.68474 (5)	0.49827 (5)	−0.09070 (3)	0.01877 (15)
O1	0.67895 (14)	0.76438 (15)	−0.00269 (9)	0.0167 (3)
N1	0.66061 (15)	0.63626 (17)	0.13178 (10)	0.0128 (3)
N2	0.57490 (16)	0.63696 (18)	0.16782 (10)	0.0130 (3)
H2N	0.5038	0.6053	0.1456	0.016*
N3	0.6447 (2)	0.9468 (2)	−0.08618 (12)	0.0243 (4)
C1	0.9082 (2)	0.6007 (2)	0.12880 (12)	0.0161 (4)
H1	0.8590	0.5251	0.1072	0.019*
C2	1.0193 (2)	0.6081 (2)	0.12018 (12)	0.0179 (4)
H2	1.0460	0.5376	0.0926	0.021*
C3	1.0916 (2)	0.7185 (3)	0.15171 (13)	0.0214 (5)
H3	1.1676	0.7232	0.1457	0.026*
C4	1.0528 (2)	0.8216 (3)	0.19191 (14)	0.0238 (5)
H4	1.1022	0.8971	0.2134	0.029*
C5	0.9413 (2)	0.8147 (2)	0.20085 (14)	0.0205 (5)
H5	0.9150	0.8853	0.2285	0.025*
C6	0.86844 (19)	0.7044 (2)	0.16931 (12)	0.0149 (4)
C7	0.75421 (19)	0.6933 (2)	0.18394 (12)	0.0140 (4)
C8	0.72765 (19)	0.7317 (2)	0.25414 (12)	0.0158 (4)
H8	0.7782	0.7755	0.3003	0.019*
C9	0.61330 (18)	0.6929 (2)	0.24252 (11)	0.0130 (4)
C10	0.54215 (19)	0.7055 (2)	0.29796 (12)	0.0134 (4)
C11	0.6005 (2)	0.7341 (2)	0.37895 (12)	0.0177 (4)
H11	0.6832	0.7431	0.3967	0.021*
C12	0.5374 (2)	0.7494 (2)	0.43331 (13)	0.0220 (5)
H12	0.5775	0.7690	0.4882	0.026*
C13	0.4177 (2)	0.7367 (2)	0.40908 (13)	0.0211 (5)
H13	0.3754	0.7468	0.4469	0.025*
C14	0.3592 (2)	0.7088 (2)	0.32849 (13)	0.0208 (5)
H14	0.2765	0.7004	0.3112	0.025*
C15	0.42102 (19)	0.6930 (2)	0.27315 (12)	0.0171 (4)
H15	0.3804	0.6737	0.2183	0.021*
C16	0.62989 (19)	0.8181 (2)	−0.06975 (12)	0.0165 (4)
H16	0.5795	0.7632	−0.1107	0.020*
C17	0.7246 (3)	1.0358 (3)	−0.02662 (17)	0.0460 (8)
H17A	0.7893	1.0635	−0.0465	0.069*
H17B	0.7554	0.9863	0.0243	0.069*
H17C	0.6822	1.1170	−0.0179	0.069*
C18	0.5865 (3)	1.0043 (3)	−0.16520 (15)	0.0372 (7)
H18A	0.6450	1.0411	−0.1885	0.056*
H18B	0.5338	1.0777	−0.1599	0.056*
H18C	0.5413	0.9328	−0.2005	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01127 (17)	0.01268 (17)	0.00998 (15)	−0.00203 (9)	0.00358 (10)	−0.00140 (8)
Cl2	0.0123 (3)	0.0129 (3)	0.0168 (2)	−0.00006 (18)	0.00204 (18)	0.00201 (17)
Cl1	0.0170 (3)	0.0250 (3)	0.0169 (2)	−0.0054 (2)	0.0089 (2)	−0.00756 (19)
O1	0.0191 (8)	0.0159 (7)	0.0153 (7)	−0.0037 (6)	0.0054 (6)	0.0009 (6)
N1	0.0108 (9)	0.0162 (8)	0.0120 (7)	−0.0017 (7)	0.0044 (6)	−0.0010 (6)
N2	0.0108 (9)	0.0166 (9)	0.0125 (7)	−0.0025 (7)	0.0047 (6)	−0.0021 (7)
N3	0.0344 (12)	0.0161 (9)	0.0199 (9)	−0.0020 (8)	0.0047 (9)	0.0007 (8)
C1	0.0149 (11)	0.0185 (10)	0.0140 (9)	−0.0001 (8)	0.0029 (8)	−0.0008 (8)
C2	0.0157 (11)	0.0231 (11)	0.0156 (9)	0.0029 (9)	0.0057 (8)	−0.0007 (8)
C3	0.0148 (11)	0.0307 (13)	0.0199 (10)	−0.0010 (9)	0.0073 (9)	0.0039 (9)
C4	0.0170 (12)	0.0251 (12)	0.0298 (11)	−0.0084 (9)	0.0078 (9)	−0.0037 (10)
C5	0.0177 (11)	0.0198 (11)	0.0252 (10)	−0.0015 (9)	0.0085 (9)	−0.0047 (9)
C6	0.0141 (10)	0.0177 (10)	0.0131 (8)	0.0001 (8)	0.0043 (8)	0.0013 (8)
C7	0.0152 (10)	0.0129 (9)	0.0135 (8)	−0.0010 (8)	0.0037 (8)	−0.0006 (7)
C8	0.0149 (11)	0.0185 (10)	0.0132 (9)	−0.0014 (8)	0.0030 (8)	−0.0032 (8)
C9	0.0132 (10)	0.0123 (9)	0.0128 (8)	0.0010 (8)	0.0028 (7)	−0.0003 (7)
C10	0.0155 (11)	0.0124 (9)	0.0139 (9)	0.0011 (8)	0.0066 (8)	0.0003 (7)
C11	0.0143 (11)	0.0245 (11)	0.0144 (9)	0.0029 (9)	0.0044 (8)	0.0000 (8)
C12	0.0241 (12)	0.0304 (12)	0.0123 (9)	0.0065 (10)	0.0065 (9)	−0.0003 (9)
C13	0.0221 (12)	0.0254 (11)	0.0201 (10)	0.0019 (9)	0.0129 (9)	−0.0012 (9)
C14	0.0155 (11)	0.0261 (12)	0.0226 (10)	−0.0007 (9)	0.0083 (9)	−0.0017 (9)
C15	0.0170 (11)	0.0193 (11)	0.0151 (9)	−0.0005 (8)	0.0048 (8)	−0.0022 (8)
C16	0.0149 (11)	0.0195 (10)	0.0162 (9)	−0.0038 (8)	0.0063 (8)	−0.0015 (8)
C17	0.071 (2)	0.0207 (13)	0.0338 (14)	−0.0132 (14)	−0.0030 (14)	−0.0007 (12)
C18	0.055 (2)	0.0254 (13)	0.0255 (12)	0.0064 (12)	0.0044 (12)	0.0106 (10)

Geometric parameters (Å, º) top

Cu1—O1	1.9826 (15)	C5—H5	0.9500
Cu1—N1	2.0034 (16)	C6—C7	1.473 (3)
Cu1—Cl1	2.2590 (5)	C7—C8	1.405 (3)
Cu1—Cl2	2.2851 (5)	C8—C9	1.379 (3)
Cu1—Cl2ⁱ	2.6693 (6)	C8—H8	0.9500
Cl2—Cu1ⁱ	2.6693 (6)	C9—C10	1.475 (3)
O1—C16	1.253 (3)	C10—C15	1.391 (3)
N1—C7	1.335 (3)	C10—C11	1.400 (3)
N1—N2	1.358 (2)	C11—C12	1.388 (3)
N2—C9	1.357 (3)	C11—H11	0.9500
N2—H2N	0.8800	C12—C13	1.375 (4)
N3—C16	1.317 (3)	C12—H12	0.9500
N3—C18	1.455 (3)	C13—C14	1.393 (3)
N3—C17	1.467 (3)	C13—H13	0.9500
C1—C2	1.388 (3)	C14—C15	1.391 (3)
C1—C6	1.400 (3)	C14—H14	0.9500
C1—H1	0.9500	C15—H15	0.9500
C2—C3	1.391 (3)	C16—H16	0.9500
C2—H2	0.9500	C17—H17A	0.9800
C3—C4	1.387 (3)	C17—H17B	0.9800
C3—H3	0.9500	C17—H17C	0.9800
C4—C5	1.395 (3)	C18—H18A	0.9800
C4—H4	0.9500	C18—H18B	0.9800
C5—C6	1.393 (3)	C18—H18C	0.9800

O1—Cu1—N1	86.20 (6)	C8—C7—C6	126.82 (19)
O1—Cu1—Cl1	91.13 (4)	C9—C8—C7	106.06 (18)
N1—Cu1—Cl1	159.53 (5)	C9—C8—H8	127.0
O1—Cu1—Cl2	176.18 (5)	C7—C8—H8	127.0
N1—Cu1—Cl2	91.01 (5)	N2—C9—C8	106.62 (17)
Cl1—Cu1—Cl2	92.39 (2)	N2—C9—C10	124.41 (19)
O1—Cu1—Cl2ⁱ	88.16 (5)	C8—C9—C10	128.97 (18)
N1—Cu1—Cl2ⁱ	99.55 (5)	C15—C10—C11	119.17 (19)
Cl1—Cu1—Cl2ⁱ	100.643 (19)	C15—C10—C9	123.19 (18)
Cl2—Cu1—Cl2ⁱ	89.727 (18)	C11—C10—C9	117.63 (19)
Cu1—Cl2—Cu1ⁱ	90.273 (18)	C12—C11—C10	119.9 (2)
C16—O1—Cu1	119.72 (14)	C12—C11—H11	120.0
C7—N1—N2	106.44 (16)	C10—C11—H11	120.0
C7—N1—Cu1	128.82 (14)	C13—C12—C11	121.1 (2)
N2—N1—Cu1	124.55 (13)	C13—C12—H12	119.5
C9—N2—N1	111.11 (17)	C11—C12—H12	119.5
C9—N2—H2N	124.4	C12—C13—C14	119.2 (2)
N1—N2—H2N	124.4	C12—C13—H13	120.4
C16—N3—C18	121.2 (2)	C14—C13—H13	120.4
C16—N3—C17	121.2 (2)	C15—C14—C13	120.5 (2)
C18—N3—C17	117.6 (2)	C15—C14—H14	119.7
C2—C1—C6	120.1 (2)	C13—C14—H14	119.7
C2—C1—H1	120.0	C10—C15—C14	120.1 (2)
C6—C1—H1	120.0	C10—C15—H15	119.9
C1—C2—C3	120.2 (2)	C14—C15—H15	119.9
C1—C2—H2	119.9	O1—C16—N3	123.2 (2)
C3—C2—H2	119.9	O1—C16—H16	118.4
C4—C3—C2	120.0 (2)	N3—C16—H16	118.4
C4—C3—H3	120.0	N3—C17—H17A	109.5
C2—C3—H3	120.0	N3—C17—H17B	109.5
C3—C4—C5	120.0 (2)	H17A—C17—H17B	109.5
C3—C4—H4	120.0	N3—C17—H17C	109.5
C5—C4—H4	120.0	H17A—C17—H17C	109.5
C6—C5—C4	120.2 (2)	H17B—C17—H17C	109.5
C6—C5—H5	119.9	N3—C18—H18A	109.5
C4—C5—H5	119.9	N3—C18—H18B	109.5
C5—C6—C1	119.5 (2)	H18A—C18—H18B	109.5
C5—C6—C7	119.69 (19)	N3—C18—H18C	109.5
C1—C6—C7	120.70 (19)	H18A—C18—H18C	109.5
N1—C7—C8	109.76 (18)	H18B—C18—H18C	109.5
N1—C7—C6	123.32 (18)

C7—N1—N2—C9	−0.4 (2)	N1—N2—C9—C8	1.0 (2)
Cu1—N1—N2—C9	−175.77 (13)	N1—N2—C9—C10	−178.41 (18)
C6—C1—C2—C3	0.0 (3)	C7—C8—C9—N2	−1.2 (2)
C1—C2—C3—C4	0.0 (3)	C7—C8—C9—C10	178.2 (2)
C2—C3—C4—C5	0.1 (4)	N2—C9—C10—C15	−16.5 (3)
C3—C4—C5—C6	−0.2 (4)	C8—C9—C10—C15	164.2 (2)
C4—C5—C6—C1	0.2 (3)	N2—C9—C10—C11	164.8 (2)
C4—C5—C6—C7	175.8 (2)	C8—C9—C10—C11	−14.5 (3)
C2—C1—C6—C5	−0.1 (3)	C15—C10—C11—C12	0.1 (3)
C2—C1—C6—C7	−175.67 (19)	C9—C10—C11—C12	178.8 (2)
N2—N1—C7—C8	−0.3 (2)	C10—C11—C12—C13	0.1 (4)
Cu1—N1—C7—C8	174.72 (14)	C11—C12—C13—C14	−0.4 (4)
N2—N1—C7—C6	176.29 (18)	C12—C13—C14—C15	0.4 (4)
Cu1—N1—C7—C6	−8.6 (3)	C11—C10—C15—C14	−0.1 (3)
C5—C6—C7—N1	148.5 (2)	C9—C10—C15—C14	−178.7 (2)
C1—C6—C7—N1	−35.9 (3)	C13—C14—C15—C10	−0.2 (3)
C5—C6—C7—C8	−35.4 (3)	Cu1—O1—C16—N3	174.50 (17)
C1—C6—C7—C8	140.1 (2)	C18—N3—C16—O1	179.6 (2)
N1—C7—C8—C9	1.0 (2)	C17—N3—C16—O1	2.2 (4)
C6—C7—C8—C9	−175.5 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···Cl1ⁱ	0.88	2.40	3.2766 (19)	175
C8—H8···Cl2ⁱⁱ	0.95	2.79	3.722 (2)	169

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

Acknowledgements

CMZ, MSN, and BTK thank the Chemistry and Biochemistry Department at Shippensburg University for support.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. G. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Agre, V. M., Krol, I. A. & Trunov, V. K. (1977). Proc. Nat. Acad. Sci. USSR, 235, 341. Google Scholar
Agre, V. M., Krol, I. A., Trunov, V. K., Dziomko, V. M. & Ivanov, O. V. (1979). Russ. J. Coord. Chem. 5, 1413. Google Scholar
Ahmed, B. M., Calco, B. & Mezei, G. (2016). Dalton Trans. 45, 8327–8339. Web of Science CSD CrossRef CAS PubMed Google Scholar
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bushuev, M. B., Virovets, A. V., Naumov, D. Y., Shvedenkov, Y. G., Sheludyakova, L. A., Elokhina, V. N., Boguslavsky, E. G. & Lavrenova, L. G. (2006). Russ. J. Coord. Chem. 32, 309–320. CrossRef Google Scholar
Castro, I., Barros, W. P., Calatayud, M. L., Lloret, F., Marino, N., De Munno, G., Stumpf, H. O., Ruiz-García, R. & Julve, M. (2016). Coord. Chem. Rev. 315, 135–152. CrossRef Google Scholar
Chandrasekhar, V., Kingsley, S., Vij, A., Lam, K. C. & Rheingold, A. L. (2000). Inorg. Chem. 39, 3238–3242. Web of Science CSD CrossRef PubMed CAS Google Scholar
Doidge, E. D., Roebuck, J. W., Healy, M. R. & Tasker, P. A. (2015). Coord. Chem. Rev. 288, 98–117. CrossRef Google Scholar
Feng, C., Zhang, D., Chu, Z.-J. & Zhao, H. (2016). Polyhedron, 115, 288–296. CrossRef Google Scholar
Giles, I. D., DePriest, J. C. & Deschamps, J. R. (2015). J. Coord. Chem. 68, 3611–3635. Web of Science CSD CrossRef CAS Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Keij, F. S., Haasnoot, J. G., Oosterling, A. J., Reedijk, J., O'Connor, C. J., Zhang, J. H. & Spek, A. L. (1991). Inorg. Chim. Acta, 181, 185–193. CSD CrossRef CAS Web of Science Google Scholar
Liu, W. & Thorp, H. H. (1993). Inorg. Chem. 32, 4102–4105. CrossRef CAS Web of Science Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Małecka, M., Grabowski, M. J., Olszak, T. A., Kostka, K. & Strawiak, M. (1998). Acta Cryst. C54, 1770–1773. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mezei, G. & Raptis, R. G. (2004). Inorg. Chim. Acta, 357, 3279–3288. Web of Science CSD CrossRef CAS Google Scholar
Mezei, G., Rivera-Carrillo, M. & Raptis, R. G. (2007). Dalton Trans. pp. 37–40. Web of Science CSD CrossRef Google Scholar
Mukherjee, R. (2000). Coord. Chem. Rev. 203, 151–218. Web of Science CrossRef CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Raptis, R. G. & Fackler, J. P. Jr (1988). Inorg. Chem. 27, 4179–4182. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Soltani, B., Sadr, M. H., Engle, J. T., Ziegler, C. J., Joo, S. W. & Hanifehpour, Y. (2012). Transition Met. Chem. 37, 687–694. CrossRef Google Scholar
Tardito, S., Bassanetti, I., Bignardi, C., Elviri, L., Tegoni, M., Mucchino, C., Bussolati, O., Franchi-Gazzola, R. & Marchiò, L. (2011). 133, 6235-6242. Google Scholar
Viciano-Chumillas, M., Tanase, S., de Jongh, L. J. & Reedijk, J. (2010). Eur. J. Inorg. Chem. 2010, 3403–3418. Google Scholar
Vincent, C. J., Giles, I. D. & Deschamps, J. R. (2018). Acta Cryst. E74, 357–362. CrossRef IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, H.-J., Shi, C.-Y., Zhong, F. & Yin, L. (2017). J. Am. Chem. Soc. 139, 2196–2199. CrossRef Google Scholar
Zhu, W.-R., Ding, S.-H., Li, J.-G., Chen, Y., Liu, G.-C., Zhu, Y.-L. & Huang, Z.-Y. (2011). Chin. J. Struct. Chem. 30, 1101–1104. Google Scholar

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