Crystal structure of μ6-chlorido-nona­kis­(μ-4-chloro­pyrazolato)bis-μ3-methoxo-hexa­copper(II)

Shi, K.; Mathivathanan, L.; Raptis, R.G.

doi:10.1107/S2056989017001189

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ISSN: 2056-9890

Volume 73| Part 2| February 2017| Pages 266-269

https://doi.org/10.1107/S2056989017001189

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Crystal structure of μ₆-chlorido-nonakis(μ-4-chloropyrazolato)bis-μ₃-methoxo-hexacopper(II)

Kaige Shi,^a Logesh Mathivathanan ^a and Raphael G. Raptis ^a ^*

^aDepartment of Chemistry and Biochemistry, Florida International University, 11200 SW 8th Street, Miami, FL 33199, USA
^*Correspondence e-mail: raphael.raptis@fiu.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 19 December 2016; accepted 23 January 2017; online 27 January 2017)

The hexanuclear title compound, [{Cu₃(μ₃-OCH₃)(μ-C₃H₂ClN₂)₃}₂(μ-C₃H₂ClN₂)₃(μ₆-Cl)] or [Cu₆(C₃H₂ClN₂)₉(CH₃O)₂Cl], crystallizes in the space group Pbcn, with individual molecules being located on a twofold rotation axis. The molecule adopts a trigonal prismatic shape, with two trinuclear units linked by three 4-chloropyrazolate ligand bridges by encapsulating a Cl⁻ anion in a μ₆-coordination mode. In the crystal, individual molecules are stacked into rods parallel to [1-10] that are arranged in a pseudo-hexagonal packing. Cohesion between molecules is accomplished through weak C—H⋯Cl interactions.

Keywords: crystal structure; trigonal prismatic hexanuclear copper pyrazolate; μ₆-Cl coordination; chloride encapsulation.

CCDC reference: 1529271

1. Chemical context

Multinuclear transition metal ion complexes often have interesting properties, such as magnetic, electrochemical, and catalytic functions. N-donor ligands have coordination plasticity and large affinity for transition metals, and their employment has provided structures of various nuclearities and dimensionalities, which have been shown to be of interest in catalysis, bio-inorganic chemistry and molecular magnetism. There have been several reports concerning multinuclear copper(II) complexes supported by pyrazolato (pz⁻) bridging ligands. In this context, we have investigated a family of redox-active Cu₆-pyrazolato complexes with trigonal prismatic shapes (Mezei et al., 2007 ; Zueva et al., 2009 ), including one with a μ₆-F central ligand (Mathivathanan et al., 2015 ). In connection with our earlier work, the title compound, [{Cu₃(μ₃-OCH₃)(μ-C₃H₂N₂Cl)₃}₂((μ-C₃H₂N₂Cl)₃(μ₆-Cl)], has been prepared recently; it contains an encapsulated μ₆-Cl ligand at the center of the hexanuclear complex.

2. Structural commentary

The crystal structure of the title compound (Fig. 1) consists of two trinuclear [Cu₃(μ₃-OMe)(μ-4-Cl-pz)₃]²⁺ (OMe is a methoxide, 4-Cl-pz a 4-chloropyrazolato ligand) units bridged by three μ-4-Cl-pz⁻ ligands; the complete molecule adopts .2. point group symmetry. The six Cu^II ions form a trigonal prismatic array and a chloride ion is located at the center of the cage, coordinating to the two {Cu}₃ units in a μ₆ mode. All six Cu^II atoms are five-coordinate with distorted square-pyramidal N₃OCl coordination sets with the Cl atom occupying the apical position. Each Cu₃ triangle is capped by an OMe group with the O atom 0.8472 (1) Å above the Cu₃ plane, a somewhat smaller deviation from the Cu₃ plane than the one found in the previously reported structure of [{Cu₃(μ₃-OMe)(μ-pz)₃}₂(μ-pz)₃(μ₆-Cl)], where μ₃-bridging methoxy groups are located ca 1.0 Å above this plane (Kamiyama et al., 2002 ). The distance between two Cu₃ planes is 3.3858 (2) Å. The six Cu—O bond lengths range from 2.033 (2)–2.044 (2) Å, while the Cu—O—Cu angles are in the 102.70 (10)–105.62 (10)° range. The Cu⋯Cu distances within each triangle, 3.1801 (9)–3.2526 (9) Å, are slightly shorter than those between the triangles, 3.356 (2)–3.401 (2) Å). The μ₆-Cl ligand is located close to the center of the trigonal prism defined by the six Cu atoms and non-equidistant from the three pairs of Cu^II ions. The longest Cu—Cl distance of 2.6222 (13) Å (Cu2) is longer than the sum of the ionic radii (2.38 Å), indicating that the two [Cu₃(μ₃-OMe)(μ-4-Cl-pz)₃]²⁺ units are not templated by the encapsulated chloride. The other two Cu—Cl bond lengths are 2.424 (2) (Cu1) and 2.4859 (13) Å.

Figure 1
The molecular structure of the title compound, showing the atom-labeling scheme. H atoms are not shown for clarity. Displacement ellipsoids are drawn at the 40% probability level. Non-labeled atoms are related to the labeled atoms by the symmetry operation (−x, y, −z + $[{1\over 2}]$ ).

Differences in structural parameters between the four known {Cu₆-pyrazolato} complexes with trigonal prismatic shape are compiled in Table 1. The inter-trimer and intra-trimer Cu⋯Cu distances are shorter in the title compound than those in the [Cu₆Cl] compound reported earlier with 4-H-pz as a ligand (Kamiyama et al., 2002), indicating the effect of electron-withdrawing Cl-substitution of the pyrazolato ligands. The Cu—N distances of the pyrazolato ligands connecting the two trimers are longer compared to those in {Cu₆-μ₆-F} (Mathivathanan et al., 2015) or {Cu₆-μ₆-Cl} (Kamiyama et al., 2002). However, the Cu—N distances are similar to those in the empty Cu₆-pyrazolato cage (Mezei et al., 2007).

Table 1
Comparison of selected structural parameters (Å)

	{Cu₆}, PPN^a	{Cu₆Cl}^b	{Cu₆Cl}^c	{Cu₆F}^d
Cu⋯Cu (inter-trimer)	2.975 (3), 2.999, 3.028 (3)	3.3557 (10)–3.4005 (10)	3.621 (1), 3.675 (1)	3.281 (2), 3.335 (2), 3.289 (2)
Cu⋯Cu (intra-trimer)	3.206 (4)–3.279 (5)	3.1801 (9)–3.2526 (9)	3.209 (1), 3.233 (1)	3.234 (2)–3.289 (2)
Cu⋯X	–	2.424 (2), 2.4858 (14), 2.6221 (13) (X = Cl)	2.604 (1), 2.623 (2) (X = Cl)	2.383 (5)–2.605 (5) (X = F)
Cu⋯(μ₃-OR)	1.883 (1)–1.894 (5)	2.003 (2)–2.044 (2)	2.083 (4), 2.085 (6) (R = Me)	2.048 (3)–2.096 (5) (R = H)
Cu—N (inter-trimer)	2.003 (7)–2.056 (6)	2.003 (3)–2.004 (3)	1.990 (5)–1.992 (7)	2.018 (6)–2.047 (6)
Cu—N (intra-trimer)	1.934 (7)–1.964 (7)	1.923 (3)–1.954 (3)	1.931 (5)–1.941 (5)	1.942 (5)–1.979 (6)
Notes: (a) Mezei et al. (2007); (b) this work; (c) Kamiyama et al. (2002); (d) Mathivathanan et al. (2015).

3. Supramolecular features

In the trigonal prismatic molecules, the six pyrazolato ligands of the eclipsed {Cu₃-pyrazolato} trimers exhibit weak π–π stacking interactions, with centroid-to-centroid distances of 3.8489 (6) and 3.6059 (6) Å. These distances are comparable to the ones found in the Cu₆-pyrazolato complex with no encapsulated anion, where the pyrazolato ring centroids are 3.741 (6), 3.700 (6) and 3.680 (6) Å apart (Mezei et al., 2007).

While conventional hydrogen bonds are absent in the structure, there are three weak intermolecular C—H⋯Cl interactions observed in the crystal structure (Fig. 2 and Table 2). Individual {Cu₆-μ₆-Cl}-molecules are stacked in rods parallel to [1 $[\overline{1}]$ 0] that, in turn, are arranged in a pseudo-hexagonal packing (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl4ⁱ	0.93	2.75	3.586 (4)	149
C6—H6⋯Cl3ⁱⁱ	0.93	2.81	3.466 (4)	129
C15—H15A⋯Cl3ⁱⁱⁱ	0.96	2.82	3.651 (4)	146
Symmetry codes: (i) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
Crystal packing diagram viewed along [001], showing hydrogen bonds as blue dashed lines.

Figure 3
Crystal packing diagram viewed along [1 $[\overline{1}]$ 0], highlighting the pseudo-hexagonal rod packing of {Cu₆} molecules.

4. Database survey

Polynuclear complexes with a μ₆-coordinating halide anion are not uncommon. However, they are rarely encountered in a trigonal prismatic environment. According to the Cambridge Structure Database (Groom et al., 2016 ), only three hexanuclear Cu₆-cages with a μ₆-coordinating halide anion have been reported in the literature: [{Cu₃(μ₃-OMe)(μ-pz)₃}₂(μ-pz)₃(μ₆-Cl)] (pz = pyrazole; Kamiyama et al., 2002), [{Cu₃(μ₃-OMe)(μ-3,5-Me₂pz)₃}₂(μ₆-F)(μ₂-OH)] (3,5-Me₂pz⁻ =3,5-dimethylpyrazolato; Cañon-Mancisidor et al., 2014 ) and [{Cu₃(μ₃-OH)(μ-pz)₃}₂(μ-3,5-Ph₂pz)₃(μ₆-F)] (Mathivathanan et al., 2015).

5. Synthesis and crystallization

The complex was formed in an one-pot reaction when CuCl₂·2H₂O (0.06 mmol, 10.2 mg), 4-Cl-pzH (0.09 mmol, 8.9 mg) and ethylamine (0.08 mmol, 11.3 µl) were stirred in 10 ml CH₂Cl₂ for 24 h at ambient temperature. The green solution was transferred to a test tube after filtration. A 4 ml 1:1 mixture of CH₂Cl₂:MeOH (v/v) was layered over the CH₂Cl₂ layer, 1,2-di(4-pyridyl)ethylene (1,2-bpe) (0.01mmol, 1.9 mg) in 4 ml MeOH was added as the third layer on top of the lower two. Suitable crystals for X-ray diffraction were obtained one week later. Yield: 29%. Analysis calculated/found for C₂₉H₂₄Cl₁₀Cu₆N₁₈O₂: C, 25.15/25.22; H,1.75/1.76; N, 18.22/18.17.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were placed in geometrically calculated positions and refined with a riding model. Structure refinement indicates a minimum (−1.56 e Å⁻³) near the μ₆-Cl atom (Cl6), which decreases if the structure is refined with a free site-occupation factor for this atom. This can be explained if some of the Cu₆-cages (< 10%) are vacant. Such a discrepancy is within the experimental error of the CHN elemental analysis, and we decided to refine the model with full occupancy for this Cl atom. In the final cycles, restraints were applied to obtain acceptable U_ij parameters for Cl6.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu₆(C₃H₂ClN₂)₉(CH₃O)₂Cl]
M_r	1392.40
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	299
a, b, c (Å)	16.565 (3), 18.474 (4), 14.606 (3)
V (Å³)	4470.1 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.46
Crystal size (mm)	0.21 × 0.20 × 0.16

Data collection
Diffractometer	Bruker D8 Quest CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2015 )
T_min, T_max	0.671, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	63202, 5726, 4647
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.674

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.119, 1.08
No. of reflections	5726
No. of parameters	296
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −1.59
Computer programs: APEX3 and SAINT (Bruker, 2015), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1529271

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017001189/wm5353sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017001189/wm5353Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017001189/wm5353Isup3.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: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

µ₆-Chlorido-nonakis(µ-4-chloropyrazolato)bis-µ₃-methoxo-hexacopper(II) top

Crystal data top

[Cu₆(C₃H₂ClN₂)₉(CH₃O)₂Cl]	D_x = 2.069 Mg m⁻³
M_r = 1392.40	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 9133 reflections
a = 16.565 (3) Å	θ = 3.0–28.6°
b = 18.474 (4) Å	µ = 3.46 mm⁻¹
c = 14.606 (3) Å	T = 299 K
V = 4470.1 (15) Å³	Cuboctahedron, green
Z = 4	0.21 × 0.20 × 0.16 mm
F(000) = 2736

Data collection top

Bruker D8 Quest CMOS diffractometer	4647 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.026
Absorption correction: multi-scan (SADABS; Bruker, 2015)	θ_max = 28.6°, θ_min = 2.9°
T_min = 0.671, T_max = 0.745	h = −22→22
63202 measured reflections	k = −24→24
5726 independent reflections	l = −19→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.052P)² + 10.494P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
5726 reflections	Δρ_max = 0.75 e Å⁻³
296 parameters	Δρ_min = −1.59 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
Cu1	0.04492 (3)	0.32824 (2)	0.35296 (3)	0.03365 (12)
Cu2	−0.03799 (2)	0.17979 (2)	0.41047 (3)	0.03405 (12)
Cu3	0.13100 (3)	0.17948 (2)	0.29708 (3)	0.03369 (12)
O1	0.07222 (13)	0.22859 (12)	0.40330 (15)	0.0298 (5)
Cl1	0.04787 (7)	−0.11802 (5)	0.36907 (8)	0.0538 (3)
Cl4	0.36310 (7)	0.07485 (7)	0.03389 (9)	0.0601 (3)
Cl2	−0.22199 (7)	0.40543 (7)	0.58300 (9)	0.0641 (3)
Cl3	0.32409 (9)	0.41018 (7)	0.15094 (10)	0.0758 (4)
Cl5	0.000000	0.62857 (8)	0.250000	0.0824 (6)
Cl6	0.000000	0.23354 (16)	0.250000	0.1040 (8)
C5	0.0483 (2)	−0.02467 (18)	0.3635 (2)	0.0358 (7)
N3	0.01229 (17)	0.08926 (15)	0.3792 (2)	0.0345 (6)
N4	0.08520 (17)	0.08802 (15)	0.3377 (2)	0.0349 (6)
N1	−0.04891 (18)	0.33017 (16)	0.4322 (2)	0.0370 (6)
N5	0.1870 (2)	0.27052 (16)	0.2727 (2)	0.0441 (8)
C2	−0.1503 (2)	0.3569 (2)	0.5233 (3)	0.0428 (8)
N7	0.0146 (2)	0.42174 (15)	0.2927 (2)	0.0382 (7)
C12	0.2735 (2)	0.10042 (19)	0.0850 (3)	0.0383 (8)
C4	−0.0109 (2)	0.02073 (18)	0.3944 (3)	0.0382 (8)
H4	−0.059153	0.006471	0.421373	0.046*
N8	0.18357 (18)	0.13431 (16)	0.1875 (2)	0.0362 (6)
C1	−0.0924 (2)	0.3849 (2)	0.4661 (3)	0.0447 (9)
H1	−0.084759	0.433718	0.453080	0.054*
N6	0.1507 (2)	0.33235 (16)	0.2976 (2)	0.0419 (7)
C14	0.000000	0.5358 (3)	0.250000	0.0471 (13)
C8	0.2558 (3)	0.3612 (2)	0.2127 (3)	0.0469 (9)
C6	0.1075 (2)	0.01918 (19)	0.3278 (3)	0.0399 (8)
H6	0.155241	0.003367	0.300986	0.048*
N2	−0.07882 (19)	0.26795 (16)	0.4663 (2)	0.0415 (7)
C11	0.2026 (2)	0.1179 (2)	0.0414 (3)	0.0439 (9)
H11	0.193686	0.115749	−0.021388	0.053*
C3	−0.1403 (2)	0.2838 (2)	0.5216 (3)	0.0515 (10)
H3	−0.171220	0.250424	0.553841	0.062*
C9	0.1920 (3)	0.3877 (2)	0.2616 (3)	0.0504 (10)
H9	0.179311	0.436415	0.268681	0.060*
C10	0.2602 (2)	0.1112 (2)	0.1762 (3)	0.0427 (8)
H10	0.297665	0.103841	0.222717	0.051*
C13	0.0244 (3)	0.4907 (2)	0.3198 (3)	0.0478 (9)
H13	0.044351	0.505543	0.376243	0.057*
C7	0.2509 (3)	0.2874 (2)	0.2207 (3)	0.0587 (12)
H7	0.286269	0.254339	0.194252	0.070*
N9	0.14862 (17)	0.13828 (17)	0.1038 (2)	0.0385 (7)
C15	0.1151 (3)	0.2292 (2)	0.4877 (3)	0.0468 (9)
H15A	0.125602	0.180297	0.506599	0.070*
H15B	0.083328	0.253186	0.533459	0.070*
H15C	0.165302	0.254366	0.479851	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0352 (2)	0.0261 (2)	0.0396 (2)	0.00276 (15)	0.00961 (17)	0.00267 (16)
Cu2	0.0268 (2)	0.0284 (2)	0.0470 (3)	−0.00146 (15)	0.00342 (17)	−0.00153 (17)
Cu3	0.0340 (2)	0.0270 (2)	0.0401 (2)	−0.00140 (15)	0.00890 (17)	−0.00296 (16)
O1	0.0276 (10)	0.0284 (11)	0.0336 (12)	0.0001 (9)	−0.0001 (9)	−0.0004 (9)
Cl1	0.0662 (7)	0.0266 (4)	0.0688 (7)	−0.0019 (4)	−0.0117 (5)	0.0007 (4)
Cl4	0.0496 (6)	0.0620 (7)	0.0687 (7)	0.0247 (5)	0.0180 (5)	0.0044 (5)
Cl2	0.0610 (7)	0.0633 (7)	0.0681 (7)	0.0130 (5)	0.0296 (6)	−0.0109 (6)
Cl3	0.0879 (9)	0.0632 (7)	0.0764 (8)	−0.0382 (7)	0.0455 (7)	−0.0182 (6)
Cl5	0.1185 (17)	0.0253 (7)	0.1034 (15)	0.000	0.0028 (13)	0.000
Cl6	0.113 (2)	0.1012 (18)	0.0981 (17)	0.000	−0.0218 (16)	0.000
C5	0.0441 (19)	0.0259 (15)	0.0375 (18)	−0.0039 (13)	−0.0094 (15)	−0.0016 (13)
N3	0.0322 (14)	0.0303 (13)	0.0410 (16)	−0.0029 (11)	0.0011 (12)	0.0011 (12)
N4	0.0333 (14)	0.0302 (14)	0.0414 (16)	−0.0020 (11)	0.0024 (12)	−0.0034 (12)
N1	0.0376 (15)	0.0319 (14)	0.0415 (16)	0.0044 (11)	0.0089 (13)	0.0007 (12)
N5	0.0413 (16)	0.0302 (14)	0.061 (2)	−0.0016 (13)	0.0199 (15)	−0.0056 (14)
C2	0.0399 (19)	0.045 (2)	0.043 (2)	0.0057 (16)	0.0091 (16)	−0.0078 (16)
N7	0.0451 (17)	0.0255 (13)	0.0439 (16)	0.0009 (12)	0.0064 (14)	0.0003 (12)
C12	0.0344 (17)	0.0342 (17)	0.046 (2)	0.0086 (14)	0.0083 (15)	−0.0036 (15)
C4	0.0390 (18)	0.0315 (17)	0.044 (2)	−0.0054 (14)	−0.0022 (15)	0.0031 (14)
N8	0.0358 (15)	0.0314 (14)	0.0415 (16)	0.0033 (12)	0.0056 (13)	−0.0024 (12)
C1	0.048 (2)	0.0345 (18)	0.051 (2)	0.0058 (16)	0.0153 (18)	−0.0011 (16)
N6	0.0426 (17)	0.0305 (15)	0.0526 (19)	−0.0034 (12)	0.0162 (15)	−0.0010 (13)
C14	0.057 (3)	0.023 (2)	0.061 (4)	0.000	0.008 (3)	0.000
C8	0.049 (2)	0.042 (2)	0.049 (2)	−0.0180 (17)	0.0173 (18)	−0.0066 (17)
C6	0.0395 (18)	0.0318 (17)	0.048 (2)	0.0013 (14)	0.0001 (16)	−0.0071 (15)
N2	0.0365 (15)	0.0312 (14)	0.0569 (19)	0.0008 (12)	0.0148 (14)	−0.0003 (13)
C11	0.0415 (19)	0.049 (2)	0.0410 (19)	0.0118 (16)	0.0019 (16)	−0.0047 (17)
C3	0.043 (2)	0.043 (2)	0.068 (3)	−0.0017 (17)	0.024 (2)	0.0012 (19)
C9	0.053 (2)	0.0336 (18)	0.065 (3)	−0.0082 (17)	0.020 (2)	−0.0008 (18)
C10	0.0385 (19)	0.043 (2)	0.046 (2)	0.0094 (15)	−0.0017 (16)	−0.0017 (16)
C13	0.061 (2)	0.0336 (19)	0.049 (2)	−0.0001 (17)	0.001 (2)	−0.0037 (16)
C7	0.055 (2)	0.042 (2)	0.079 (3)	−0.0071 (19)	0.036 (2)	−0.012 (2)
N9	0.0304 (14)	0.0407 (16)	0.0444 (17)	0.0036 (12)	0.0013 (12)	−0.0019 (13)
C15	0.050 (2)	0.049 (2)	0.041 (2)	0.0018 (17)	−0.0091 (17)	−0.0009 (17)

Geometric parameters (Å, º) top

Cu1—O1	2.033 (2)	N5—C7	1.340 (5)
Cu1—Cl6	2.424 (2)	C2—C1	1.373 (5)
Cu1—N1	1.938 (3)	C2—C3	1.361 (6)
Cu1—N7	2.003 (3)	N7—N7ⁱ	1.337 (6)
Cu1—N6	1.932 (3)	N7—C13	1.344 (5)
Cu2—O1	2.039 (2)	C12—C11	1.375 (5)
Cu2—Cl6	2.6222 (13)	C12—C10	1.365 (6)
Cu2—N3	1.923 (3)	C4—H4	0.9300
Cu2—N2	1.943 (3)	N8—C10	1.350 (5)
Cu2—N9ⁱ	1.998 (3)	N8—N9	1.354 (4)
Cu3—O1	2.044 (2)	C1—H1	0.9300
Cu3—Cl6	2.4859 (13)	N6—C9	1.338 (5)
Cu3—N4	1.945 (3)	C14—C13	1.376 (5)
Cu3—N5	1.954 (3)	C14—C13ⁱ	1.376 (5)
Cu3—N8	2.004 (3)	C8—C9	1.366 (6)
O1—C15	1.422 (4)	C8—C7	1.370 (6)
Cl1—C5	1.726 (4)	C6—H6	0.9300
Cl4—C12	1.726 (3)	N2—C3	1.333 (5)
Cl2—C2	1.724 (4)	C11—H11	0.9300
Cl3—C8	1.707 (4)	C11—N9	1.331 (5)
Cl5—C14	1.714 (5)	C3—H3	0.9300
C5—C4	1.367 (5)	C9—H9	0.9300
C5—C6	1.374 (5)	C10—H10	0.9300
N3—N4	1.352 (4)	C13—H13	0.9300
N3—C4	1.341 (4)	C7—H7	0.9300
N4—C6	1.332 (4)	C15—H15A	0.9600
N1—C1	1.337 (5)	C15—H15B	0.9600
N1—N2	1.347 (4)	C15—H15C	0.9600
N5—N6	1.341 (4)

O1—Cu1—Cl6	68.85 (8)	N6—N5—Cu3	118.1 (2)
N1—Cu1—O1	88.80 (11)	C7—N5—Cu3	132.8 (3)
N1—Cu1—Cl6	97.90 (10)	C7—N5—N6	108.0 (3)
N1—Cu1—N7	92.60 (13)	C1—C2—Cl2	126.4 (3)
N7—Cu1—O1	174.64 (11)	C3—C2—Cl2	127.5 (3)
N7—Cu1—Cl6	105.83 (10)	C3—C2—C1	106.1 (3)
N6—Cu1—O1	89.16 (11)	N7ⁱ—N7—Cu1	120.03 (9)
N6—Cu1—Cl6	92.69 (10)	N7ⁱ—N7—C13	108.5 (2)
N6—Cu1—N1	167.67 (14)	C13—N7—Cu1	131.2 (3)
N6—Cu1—N7	90.55 (13)	C11—C12—Cl4	126.8 (3)
O1—Cu2—Cl6	64.64 (7)	C10—C12—Cl4	126.9 (3)
N3—Cu2—O1	89.11 (11)	C10—C12—C11	106.2 (3)
N3—Cu2—Cl6	90.76 (11)	C5—C4—H4	125.7
N3—Cu2—N2	168.32 (14)	N3—C4—C5	108.7 (3)
N3—Cu2—N9ⁱ	92.22 (13)	N3—C4—H4	125.7
N2—Cu2—O1	87.86 (11)	C10—N8—Cu3	129.7 (3)
N2—Cu2—Cl6	98.10 (11)	C10—N8—N9	108.0 (3)
N2—Cu2—N9ⁱ	92.65 (13)	N9—N8—Cu3	120.8 (2)
N9ⁱ—Cu2—O1	170.36 (11)	N1—C1—C2	108.5 (3)
N9ⁱ—Cu2—Cl6	105.78 (9)	N1—C1—H1	125.8
O1—Cu3—Cl6	67.41 (7)	C2—C1—H1	125.8
N4—Cu3—O1	88.20 (11)	N5—N6—Cu1	119.1 (2)
N4—Cu3—Cl6	95.32 (11)	C9—N6—Cu1	131.2 (3)
N4—Cu3—N5	171.42 (14)	C9—N6—N5	108.4 (3)
N4—Cu3—N8	92.93 (12)	C13ⁱ—C14—Cl5	127.2 (2)
N5—Cu3—O1	88.99 (11)	C13—C14—Cl5	127.2 (2)
N5—Cu3—Cl6	91.07 (12)	C13ⁱ—C14—C13	105.6 (5)
N5—Cu3—N8	90.38 (13)	C9—C8—Cl3	126.8 (3)
N8—Cu3—O1	176.34 (11)	C9—C8—C7	105.5 (3)
N8—Cu3—Cl6	109.00 (9)	C7—C8—Cl3	127.7 (3)
Cu1—O1—Cu2	102.70 (10)	C5—C6—H6	125.5
Cu1—O1—Cu3	103.49 (10)	N4—C6—C5	108.9 (3)
Cu2—O1—Cu3	105.62 (10)	N4—C6—H6	125.5
C15—O1—Cu1	114.7 (2)	N1—N2—Cu2	115.6 (2)
C15—O1—Cu2	113.9 (2)	C3—N2—Cu2	134.8 (3)
C15—O1—Cu3	115.0 (2)	C3—N2—N1	108.5 (3)
Cu1ⁱ—Cl6—Cu1	87.60 (10)	C12—C11—H11	125.6
Cu1ⁱ—Cl6—Cu2	138.95 (6)	N9—C11—C12	108.9 (3)
Cu1—Cl6—Cu2ⁱ	138.95 (6)	N9—C11—H11	125.6
Cu1ⁱ—Cl6—Cu2ⁱ	78.02 (2)	C2—C3—H3	125.6
Cu1—Cl6—Cu2	78.02 (2)	N2—C3—C2	108.8 (3)
Cu1ⁱ—Cl6—Cu3ⁱ	81.39 (2)	N2—C3—H3	125.6
Cu1—Cl6—Cu3	81.39 (2)	N6—C9—C8	109.0 (3)
Cu1—Cl6—Cu3ⁱ	136.85 (6)	N6—C9—H9	125.5
Cu1ⁱ—Cl6—Cu3	136.85 (6)	C8—C9—H9	125.5
Cu2ⁱ—Cl6—Cu2	135.50 (12)	C12—C10—H10	125.7
Cu3ⁱ—Cl6—Cu2	83.43 (5)	N8—C10—C12	108.5 (3)
Cu3ⁱ—Cl6—Cu2ⁱ	79.05 (4)	N8—C10—H10	125.7
Cu3—Cl6—Cu2ⁱ	83.43 (5)	N7—C13—C14	108.7 (4)
Cu3—Cl6—Cu2	79.05 (4)	N7—C13—H13	125.7
Cu3ⁱ—Cl6—Cu3	132.63 (12)	C14—C13—H13	125.7
C4—C5—Cl1	126.5 (3)	N5—C7—C8	109.0 (4)
C4—C5—C6	106.0 (3)	N5—C7—H7	125.5
C6—C5—Cl1	127.6 (3)	C8—C7—H7	125.5
N4—N3—Cu2	120.5 (2)	N8—N9—Cu2ⁱ	120.5 (2)
C4—N3—Cu2	131.1 (3)	C11—N9—Cu2ⁱ	130.8 (3)
C4—N3—N4	108.3 (3)	C11—N9—N8	108.4 (3)
N3—N4—Cu3	118.1 (2)	O1—C15—H15A	109.5
C6—N4—Cu3	133.5 (3)	O1—C15—H15B	109.5
C6—N4—N3	108.2 (3)	O1—C15—H15C	109.5
C1—N1—Cu1	131.9 (3)	H15A—C15—H15B	109.5
C1—N1—N2	108.1 (3)	H15A—C15—H15C	109.5
N2—N1—Cu1	120.0 (2)	H15B—C15—H15C	109.5

Cu1—N1—C1—C2	−176.5 (3)	N4—N3—C4—C5	1.0 (4)
Cu1—N1—N2—Cu2	−12.9 (4)	N1—N2—C3—C2	0.1 (5)
Cu1—N1—N2—C3	177.1 (3)	N5—N6—C9—C8	0.1 (5)
Cu1—N7—C13—C14	174.5 (2)	N7ⁱ—N7—C13—C14	0.6 (5)
Cu1—N6—C9—C8	−166.4 (3)	C12—C11—N9—Cu2ⁱ	173.2 (3)
Cu2—N3—N4—Cu3	−7.5 (4)	C12—C11—N9—N8	0.0 (4)
Cu2—N3—N4—C6	177.2 (2)	C4—C5—C6—N4	0.7 (4)
Cu2—N3—C4—C5	−176.4 (3)	C4—N3—N4—Cu3	174.8 (2)
Cu2—N2—C3—C2	−167.2 (3)	C4—N3—N4—C6	−0.5 (4)
Cu3—N4—C6—C5	−174.5 (3)	C1—N1—N2—Cu2	169.6 (3)
Cu3—N5—N6—Cu1	−1.4 (4)	C1—N1—N2—C3	−0.4 (5)
Cu3—N5—N6—C9	−169.8 (3)	C1—C2—C3—N2	0.3 (5)
Cu3—N5—C7—C8	167.7 (3)	N6—N5—C7—C8	0.4 (5)
Cu3—N8—C10—C12	−165.8 (3)	C6—C5—C4—N3	−1.0 (4)
Cu3—N8—N9—Cu2ⁱ	−6.7 (4)	N2—N1—C1—C2	0.6 (5)
Cu3—N8—N9—C11	167.3 (3)	C11—C12—C10—N8	0.1 (5)
Cl1—C5—C4—N3	178.9 (3)	C3—C2—C1—N1	−0.6 (5)
Cl1—C5—C6—N4	−179.2 (3)	C9—C8—C7—N5	−0.4 (6)
Cl4—C12—C11—N9	−176.8 (3)	C10—C12—C11—N9	0.0 (5)
Cl4—C12—C10—N8	176.9 (3)	C10—N8—N9—Cu2ⁱ	−173.9 (3)
Cl2—C2—C1—N1	−179.4 (3)	C10—N8—N9—C11	0.1 (4)
Cl2—C2—C3—N2	179.1 (3)	C13ⁱ—C14—C13—N7	−0.24 (19)
Cl3—C8—C9—N6	177.6 (3)	C7—N5—N6—Cu1	168.1 (3)
Cl3—C8—C7—N5	−177.8 (4)	C7—N5—N6—C9	−0.3 (5)
Cl5—C14—C13—N7	179.76 (19)	C7—C8—C9—N6	0.2 (6)
N3—N4—C6—C5	−0.1 (4)	N9—N8—C10—C12	−0.1 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl4ⁱⁱ	0.93	2.75	3.586 (4)	149
C6—H6···Cl3ⁱⁱⁱ	0.93	2.81	3.466 (4)	129
C15—H15A···Cl3^iv	0.96	2.82	3.651 (4)	146

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

Comparison of selected structural parameters (Å) top

	{Cu₆}, PPN^a	{Cu₆Cl}^b	{Cu₆Cl}^c	{Cu₆F}^d
Cu···Cu (inter-trimer)	2.975 (3), 2.999, 3.028 (3)	3.3557 (10)–3.4005 (10)	3.621 (1), 3.675 (1)	3.281 (2), 3.335 (2), 3.289 (2)
Cu···Cu (intra-trimer)	3.206 (4)–3.279 (5)	3.1801 (9)–3.2526 (9)	3.209 (1), 3.233 (1)	3.234 (2)–3.289 (2)
Cu···X	–	2.424 (2), 2.4858 (14), 2.6221 (13) X = Cl	2.604 (1), 2.623 (2) (X = Cl)	2.383 (5)–2.605 (5) (X = F)
Cu···(µ₃-OR)	1.883 (1)–1.894 (5)	2.003 (2)–2.044 (2)	2.083 (4), 2.085 (6) (R = Me)	2.048 (3)–2.096 (5) (R = H)
Cu—N (inter-trimer)	2.003 (7)–2.056 (6)	2.003 (3)–2.004 (3)	1.990 (5)–1.992 (7)	2.018 (6)–2.047 (6)
Cu—N (intra-trimer)	1.934 (7)–1.964 (7)	1.923 (3)–1.954 (3)	1.931 (5)–1.941 (5)	1.942 (5)–1.979 (6)

Notes: (a) Mezei et al. (2007); (b) this work; (c) Kamiyama et al. (2002); (d) Mathivathanan et al. (2015). .

Acknowledgements

SK and LM thank NASA and the NSF, respectively, for financial assistance.

Funding information

Funding for this research was provided by: National Science Foundation (award No. CHE 1213683); National Aeronautics and Space Administration (award No. NNX09AV05A).

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