A [Cu3(μ3-O)]–pyrazolate metallacycle with terminal nitrate ligands exhibiting point group symmetry 3

Mathivathanan, L.; Cruz, R.; Raptis, R.G.

doi:10.1107/S2056989016003741

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 72| Part 4| April 2016| Pages 492-494

https://doi.org/10.1107/S2056989016003741

Open

access

A [Cu₃(μ₃-O)]–pyrazolate metallacycle with terminal nitrate ligands exhibiting point group symmetry 3

Logesh Mathivathanan,^a ^*‡ Raquel Cruz ^a and Raphael G. Raptis ^a ‡

^aDepartment of Chemistry, University of Puerto Rico – Rio Piedras, San Juan 00936, Puerto Rico, USA
^*Correspondence e-mail: logesh.mathivathanan@fiu.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 23 December 2015; accepted 4 March 2016; online 15 March 2016)

The trinuclear triangular cuprate anion of the title compound, tris[bis(triphenylphosphoranylidene)ammonium] tris(μ₂-4-chloropyrazolato-κ²N:N′)-μ₃-oxido-tris[(nitrato-κ²O,O′)cuprate(II)] nitrate monohydrate, (C₃₆H₃₀P₂N)[Cu₃(C₃H₂ClN₂)₃(NO₃)₃O]NO₃·H₂O, has point group symmetry 3., with the μ₃-O atom located on the threefold rotation axis. The distorted square-pyramidal coordination sphere of the Cu^II atom is completed by two N atoms of trans-bridging pyrazolate groups and a chelating nitrate anion. The complex anion is slightly bent, with the nitrate and pyrazolate groups occupying positions above and below the Cu₃ plane, respectively. In the crystal, weak O—H⋯O and C—H⋯O hydrogen bonds, as well as π–π interactions, are present.

Keywords: crystal structure; copper–pyrazolate complex; terminal nitrate ligands.

CCDC reference: 1458061

1. Chemical context

Trinuclear copper complexes with a triangular arrangement of the copper(II) cations are of importance in terms of their magnetic and redox properties (Rivera-Carrillo et al., 2008 ). Moreover, Cu₃(μ₃-O/OH) moieties make up the active sites of several multicopper oxidase enzymes (Solomon et al., 2014 ). Pyrazolate anions as ligands are of bidentate chelating nature and are able to bind to the the Cu^II cations in suitable angles to form triangular complexes (Halcrow, 2009 ; Viciano-Chumillas et al., 2010 ).

Nitrato and pyrazolato ligands are commonly studied ligands in Cu^II coordination chemistry. Simple Cu^II nitrate complexes are aplenty in the literature and have been studied in detail with respect to their part in the nitrogen cycle. Triangular trinuclear Cu^II complexes with terminal nitrate ligands, however, are scarcer (Alsalme et al., 2014 ). Nitrates, being good hydrogen-bonding acceptors, are able to form Cu₃(μ₃-OH) complexes, with hydrogen bonds to the μ₃-OH group and to ancilliary ligands and water molecules.

In this communication we describe the accidental synthesis and the structure of a trinuclear Cu–pyrazolato complex, viz. (PPN)₃[Cu₃(μ₃-O)(μ-4-Clpz)₃(NO₃)₃](NO₃)·H₂O, where PPN = bis(triphenylphosphoranylidene)ammonium; 4-Cl-pz = 4-chloropyrazolate. A related Cu₃-pyrazolato complex was reported by Angaridis et al. (2002 ).

2. Structural commentary

The nine-membered metallacycle Cu₃N₆ in the cuprate anion (Fig. 1) is strung together by a μ₃-O group located at the center of the triangle (point group symmetry of the complete molecule 3.), forming an almost planar Cu₃(μ₃-O)-core, where the μ₃-O atom O1 is located 0.122 (7) Å above the Cu₃ plane. The distorted square-pyramidal geometry of the Cu^II atom is completed by the two N atoms of symmetry-related trans-bridging pyrazolato ligands, and a terminal nitrato ligand that is bound to the metal in a chelating fashion (Table 1). The complex is slightly bent with the nitrate and pyrazolato groups occupying positions above and below the Cu₃ plane, respectively. The Cl atom of the pyrazole anion is located approximately 1.28 Å below the Cu₃ plane. The non-coordinating nitrate counter-anion is located about a special position with the nitrogen atom on the threefold rotation axis.

Table 1
Selected bond lengths (Å)

Cu1—O1	1.8816 (7)	Cu1—O2	2.059 (3)
Cu1—N2	1.952 (4)	Cu1—O3	2.483 (4)
Cu1—N1	1.960 (4)

Figure 1
The molecular structure of the trinuclear pyrazolatocuprate anion in the title compound showing the atom-labeling scheme for the symmetry-independent atoms. Non-H atoms are shown as displacement ellipsoids at the 30% probability level.

The triphenylphosphene groups in the PPN cation are staggered around the central N atom [P—N—P angle 139.5 (2)°] and show bond lengths and angles characteristic for this unit (Beckett et al., 2010 ).

3. Supramolecular features

The interstitial water O atom is also located on a threefold rotation axis which consequently results in disordered H atoms of this moiety. Although these H atoms could not be located, three O⋯O distances to the chelating nitrate anions of 3.367 (6) Å point to weak O—H⋯O hydrogen bonds in the structure. This nitrate O atom is additionally involved in weak non-classical hydrogen-bonding interactions with one of the C–H groups of the PPN cation (Table 2). The latter shows also π–π interactions [3.902 (7) Å] with one of the pyrazolate rings, leading to an overall three-dimensional network. The packing of the molecular units is shown in Fig. 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O3ⁱ	0.93	2.53	3.410 (11)	157
Symmetry code: (i) $[-x+y+{\script{4\over 3}}, -x+{\script{2\over 3}}, z-{\script{1\over 3}}]$ .

Figure 2
The crystal packing diagram for the title compound shown down [001].

4. Synthesis and crystallization

4-Cl-pz and the hexanuclear Cu₆-pyrazolato complex (PPN)[{Cu₃(μ₃-O)(μ-4-Cl-pz)₃}₂(μ-3,5-Ph₂pz)₃], were synthesized by published procedures (Maresca et al., 1997 ; Mezei et al., 2007 ). (NH₄)₂Ce(NO₃)₆ (2 eq.) was dissolved in 5 ml of acetonitrile and was layered over a CH₂Cl₂ solution of the hexanuclear copper(II) complex (1 eq.). Slow mixing of the reactants and solvent evaporation over a few weeks yielded dark-blue crystals of the title compound.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The C-bound H atoms were placed geometrically, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The isolated water solvent O atom, O1W, was refined isotropically. H atoms bound to the water oxygen atom could not be placed satisfactorily with agreeable occupancy as O1W resides on a threefold rotation axis, resulting in crystallographically disordered H atoms. These H atoms were not modelled but are included in the formula of the title compound.

Table 3
Experimental details

Crystal data
Chemical formula	(C₃₆H₃₀P₂N)[Cu₃(C₃H₂ClN₂)₃(NO₃)₃O]NO₃·H₂O
M_r	2390.85
Crystal system, space group	Trigonal, R3
Temperature (K)	296
a, c (Å)	23.038 (2), 18.4214 (17)
V (Å³)	8466.9 (17)
Z	3
Radiation type	Mo Kα
μ (mm⁻¹)	0.79
Crystal size (mm)	0.23 × 0.14 × 0.13

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005 )
T_min, T_max	0.840, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	30414, 7675, 6428
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.03
No. of reflections	7675
No. of parameters	468
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.29
Absolute structure	Flack x determined using 2750 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.004 (5)
Computer programs: APEX2 and SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1458061

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016003741/wm4004sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S2056989016003741/wm4004Isup3.cdx

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016003741/wm4004Isup4.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Tris[bis(triphenylphosphoranylidene)ammonium] tris(µ₂-4-chloropyrazolato-κ²N:N')-µ₃-oxido-tris[(nitrato-κ²O,O')cuprate(II)] nitrate monohydrate top

Crystal data top

(C₃₆H₃₀P₂N)[Cu₃(C₃H₂ClN₂)₃(NO₃)₃O]NO₃·H₂O	D_x = 1.407 Mg m⁻³
M_r = 2390.85	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 9882 reflections
a = 23.038 (2) Å	θ = 2.3–26.0°
c = 18.4214 (17) Å	µ = 0.79 mm⁻¹
V = 8466.9 (17) Å³	T = 296 K
Z = 3	Polygon, blue
F(000) = 3687	0.23 × 0.14 × 0.13 mm

Data collection top

Bruker APEXII CCD diffractometer	7675 independent reflections
Radiation source: sealed tube	6428 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
φ and ω scans	θ_max = 26.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −28→28
T_min = 0.840, T_max = 0.905	k = −28→28
30414 measured reflections	l = −22→22

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.034	w = 1/[σ²(F_o²) + (0.0468P)² + 0.1352P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.41 e Å⁻³
7675 reflections	Δρ_min = −0.29 e Å⁻³
468 parameters	Absolute structure: Flack x determined using 2750 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.004 (5)

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
O1W	0.0000	1.0000	0.3698 (7)	0.141 (4)*
Cu1	0.57819 (3)	0.31688 (3)	0.88140 (3)	0.04893 (15)
O1	0.6667	0.3333	0.8748 (4)	0.0691 (18)
O2	0.48058 (17)	0.29648 (18)	0.8736 (2)	0.0619 (9)
N1	0.54504 (18)	0.22155 (19)	0.8997 (2)	0.0504 (9)
N2	0.61014 (18)	0.41208 (18)	0.8960 (2)	0.0493 (9)
N3	0.4670 (2)	0.28251 (19)	0.8087 (3)	0.0582 (10)
C1	0.4851 (2)	0.1710 (2)	0.9186 (3)	0.0590 (12)
H1	0.4465	0.1738	0.9249	0.071*
C2	0.4893 (3)	0.1144 (2)	0.9272 (3)	0.0570 (12)
C3	0.5783 (3)	0.4455 (3)	0.9126 (3)	0.0582 (12)
H3	0.5321	0.4274	0.9141	0.070*
Cl1	0.42537 (8)	0.03570 (7)	0.95132 (10)	0.0859 (5)
O3	0.5141 (2)	0.2937 (2)	0.7664 (2)	0.0753 (10)
O4	0.4095 (2)	0.2572 (3)	0.7874 (3)	0.1105 (17)
P1	0.81315 (5)	0.23893 (5)	0.23155 (5)	0.0379 (2)
P2	0.78221 (5)	0.16748 (5)	0.37198 (5)	0.0392 (2)
N4	0.78666 (18)	0.21790 (18)	0.31150 (18)	0.0461 (8)
C4	0.7627 (2)	0.1937 (2)	0.4558 (2)	0.0440 (10)
C5	0.7353 (2)	0.2344 (2)	0.4544 (2)	0.0487 (11)
H5	0.7293	0.2500	0.4101	0.058*
C6	0.7165 (3)	0.2526 (3)	0.5183 (3)	0.0625 (13)
H6	0.6978	0.2803	0.5167	0.075*
C7	0.7254 (3)	0.2299 (3)	0.5829 (3)	0.0754 (17)
H7	0.7129	0.2424	0.6256	0.090*
C8	0.7527 (3)	0.1887 (3)	0.5860 (3)	0.0788 (17)
H8	0.7584	0.1732	0.6305	0.095*
C9	0.7717 (3)	0.1703 (3)	0.5224 (3)	0.0615 (13)
H9	0.7904	0.1427	0.5242	0.074*
C10	0.8593 (2)	0.1669 (2)	0.3837 (2)	0.0463 (10)
C11	0.9135 (2)	0.2251 (3)	0.4090 (3)	0.0610 (12)
H11	0.9081	0.2606	0.4241	0.073*
C12	0.9761 (3)	0.2304 (4)	0.4120 (3)	0.0801 (18)
H12	1.0128	0.2696	0.4289	0.096*
C13	0.9836 (3)	0.1783 (4)	0.3899 (3)	0.0796 (18)
H13	1.0257	0.1819	0.3922	0.095*
C14	0.9302 (3)	0.1205 (4)	0.3645 (4)	0.0833 (18)
H14	0.9363	0.0855	0.3490	0.100*
C15	0.8679 (3)	0.1139 (3)	0.3617 (3)	0.0629 (13)
H15	0.8315	0.0743	0.3451	0.075*
C16	0.7162 (2)	0.0829 (2)	0.3546 (2)	0.0467 (10)
C17	0.6790 (2)	0.0681 (3)	0.2917 (3)	0.0569 (12)
H17	0.6875	0.1021	0.2589	0.068*
C18	0.6291 (3)	0.0032 (3)	0.2771 (3)	0.0732 (15)
H18	0.6053	−0.0064	0.2338	0.088*
C19	0.6146 (3)	−0.0466 (3)	0.3259 (4)	0.0771 (17)
H19	0.5810	−0.0902	0.3158	0.093*
C20	0.6493 (3)	−0.0327 (3)	0.3896 (4)	0.0807 (18)
H20	0.6381	−0.0665	0.4236	0.097*
C21	0.7012 (3)	0.0315 (3)	0.4039 (3)	0.0737 (16)
H21	0.7260	0.0403	0.4465	0.088*
C22	0.8529 (2)	0.1956 (2)	0.1928 (2)	0.0414 (9)
C23	0.8160 (2)	0.1331 (2)	0.1628 (3)	0.0532 (11)
H23	0.7698	0.1141	0.1578	0.064*
C24	0.8467 (3)	0.0979 (3)	0.1398 (3)	0.0678 (14)
H24	0.8214	0.0559	0.1185	0.081*
C25	0.9149 (3)	0.1251 (3)	0.1483 (3)	0.0666 (14)
H25	0.9355	0.1010	0.1339	0.080*
C26	0.9520 (3)	0.1870 (3)	0.1778 (3)	0.0630 (13)
H26	0.9980	0.2055	0.1828	0.076*
C27	0.9219 (2)	0.2228 (2)	0.2003 (3)	0.0505 (10)
H27	0.9477	0.2652	0.2204	0.061*
C28	0.7444 (2)	0.2268 (2)	0.1749 (2)	0.0415 (9)
C29	0.6909 (2)	0.2287 (2)	0.2075 (3)	0.0526 (11)
H29	0.6902	0.2334	0.2575	0.063*
C30	0.6394 (2)	0.2237 (3)	0.1659 (3)	0.0674 (14)
H30	0.6037	0.2250	0.1880	0.081*
C31	0.6397 (3)	0.2167 (3)	0.0916 (3)	0.0738 (16)
H31	0.6048	0.2140	0.0636	0.089*
C32	0.6910 (3)	0.2138 (3)	0.0599 (3)	0.0698 (15)
H32	0.6906	0.2081	0.0098	0.084*
C33	0.7439 (3)	0.2192 (3)	0.1000 (2)	0.0578 (12)
H33	0.7791	0.2176	0.0772	0.069*
C34	0.8736 (2)	0.3267 (2)	0.2287 (3)	0.0468 (10)
C35	0.8897 (3)	0.3652 (3)	0.2894 (4)	0.0845 (19)
H35	0.8686	0.3462	0.3331	0.101*
C36	0.9372 (5)	0.4322 (3)	0.2866 (5)	0.123 (3)
H36	0.9495	0.4580	0.3287	0.147*
C37	0.9664 (4)	0.4611 (3)	0.2211 (5)	0.106 (3)
H37	0.9980	0.5065	0.2190	0.127*
C38	0.9497 (3)	0.4245 (3)	0.1612 (4)	0.0813 (18)
H38	0.9697	0.4445	0.1173	0.098*
C39	0.9028 (3)	0.3568 (2)	0.1633 (3)	0.0632 (13)
H39	0.8908	0.3316	0.1208	0.076*
N5	0.6667	0.3333	0.3566 (5)	0.069 (2)
O5	0.6275 (3)	0.2721 (2)	0.3545 (3)	0.1083 (16)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0436 (3)	0.0458 (3)	0.0582 (3)	0.0230 (3)	0.0029 (3)	0.0017 (3)
O1	0.044 (2)	0.044 (2)	0.119 (6)	0.0220 (10)	0.000	0.000
O2	0.058 (2)	0.069 (2)	0.065 (2)	0.0356 (18)	0.0048 (17)	−0.0040 (18)
N1	0.044 (2)	0.046 (2)	0.060 (2)	0.0217 (18)	0.0012 (17)	−0.0010 (17)
N2	0.049 (2)	0.048 (2)	0.054 (2)	0.0268 (19)	0.0061 (17)	0.0045 (17)
N3	0.054 (3)	0.048 (2)	0.073 (3)	0.025 (2)	−0.011 (2)	0.007 (2)
C1	0.047 (3)	0.053 (3)	0.069 (3)	0.019 (2)	0.005 (2)	−0.002 (2)
C2	0.059 (3)	0.045 (3)	0.051 (3)	0.014 (2)	−0.001 (2)	0.005 (2)
C3	0.060 (3)	0.061 (3)	0.062 (3)	0.037 (3)	0.011 (2)	0.014 (2)
Cl1	0.0748 (10)	0.0513 (8)	0.0996 (11)	0.0075 (7)	0.0071 (8)	0.0112 (7)
O3	0.084 (3)	0.078 (3)	0.064 (2)	0.040 (2)	0.008 (2)	0.0030 (19)
O4	0.068 (3)	0.129 (4)	0.118 (4)	0.037 (3)	−0.030 (3)	0.004 (3)
P1	0.0386 (6)	0.0401 (6)	0.0386 (5)	0.0224 (5)	0.0019 (4)	0.0017 (4)
P2	0.0378 (5)	0.0423 (6)	0.0376 (5)	0.0200 (5)	−0.0016 (4)	0.0010 (4)
N4	0.053 (2)	0.055 (2)	0.0393 (18)	0.0341 (19)	0.0026 (16)	0.0058 (16)
C4	0.038 (2)	0.044 (2)	0.040 (2)	0.0136 (19)	−0.0028 (17)	−0.0008 (18)
C5	0.046 (2)	0.050 (3)	0.046 (3)	0.021 (2)	0.0003 (19)	−0.0051 (19)
C6	0.055 (3)	0.063 (3)	0.064 (3)	0.025 (3)	0.010 (2)	−0.008 (3)
C7	0.068 (4)	0.094 (4)	0.054 (3)	0.033 (3)	0.009 (3)	−0.020 (3)
C8	0.083 (4)	0.100 (5)	0.036 (3)	0.033 (4)	0.001 (2)	0.007 (3)
C9	0.071 (3)	0.076 (3)	0.043 (3)	0.041 (3)	−0.003 (2)	0.003 (2)
C10	0.041 (2)	0.057 (3)	0.044 (2)	0.027 (2)	0.0013 (18)	0.008 (2)
C11	0.048 (3)	0.065 (3)	0.066 (3)	0.026 (3)	−0.007 (2)	−0.005 (3)
C12	0.042 (3)	0.103 (5)	0.078 (4)	0.023 (3)	−0.008 (3)	0.005 (3)
C13	0.057 (4)	0.120 (6)	0.077 (4)	0.056 (4)	0.006 (3)	0.027 (4)
C14	0.081 (4)	0.098 (5)	0.099 (5)	0.066 (4)	0.006 (4)	0.009 (4)
C15	0.059 (3)	0.061 (3)	0.080 (3)	0.038 (3)	0.004 (3)	0.008 (3)
C16	0.040 (2)	0.046 (2)	0.054 (3)	0.022 (2)	0.0006 (19)	0.000 (2)
C17	0.048 (3)	0.059 (3)	0.056 (3)	0.022 (2)	−0.009 (2)	−0.003 (2)
C18	0.055 (3)	0.079 (4)	0.071 (3)	0.023 (3)	−0.013 (3)	−0.020 (3)
C19	0.051 (3)	0.055 (3)	0.105 (5)	0.011 (3)	−0.001 (3)	−0.022 (3)
C20	0.073 (4)	0.048 (3)	0.103 (5)	0.017 (3)	−0.004 (3)	0.009 (3)
C21	0.069 (3)	0.055 (3)	0.077 (4)	0.016 (3)	−0.015 (3)	0.011 (3)
C22	0.041 (2)	0.046 (2)	0.042 (2)	0.026 (2)	0.0018 (17)	0.0011 (18)
C23	0.044 (2)	0.046 (3)	0.067 (3)	0.021 (2)	0.002 (2)	−0.006 (2)
C24	0.067 (3)	0.050 (3)	0.090 (4)	0.032 (3)	0.005 (3)	−0.016 (3)
C25	0.069 (4)	0.063 (3)	0.087 (4)	0.047 (3)	0.020 (3)	0.005 (3)
C26	0.045 (3)	0.068 (3)	0.085 (4)	0.035 (3)	0.012 (2)	0.008 (3)
C27	0.042 (2)	0.047 (3)	0.065 (3)	0.025 (2)	0.002 (2)	−0.001 (2)
C28	0.044 (2)	0.042 (2)	0.043 (2)	0.0243 (19)	0.0007 (17)	0.0019 (17)
C29	0.053 (3)	0.062 (3)	0.052 (3)	0.036 (2)	0.002 (2)	0.000 (2)
C30	0.049 (3)	0.077 (4)	0.086 (4)	0.038 (3)	−0.006 (3)	−0.004 (3)
C31	0.069 (4)	0.079 (4)	0.082 (4)	0.044 (3)	−0.026 (3)	−0.001 (3)
C32	0.080 (4)	0.088 (4)	0.049 (3)	0.047 (3)	−0.013 (3)	0.004 (3)
C33	0.064 (3)	0.076 (3)	0.045 (3)	0.043 (3)	0.001 (2)	0.006 (2)
C34	0.046 (2)	0.038 (2)	0.059 (3)	0.023 (2)	0.004 (2)	−0.0018 (19)
C35	0.089 (4)	0.055 (3)	0.077 (4)	0.011 (3)	0.013 (3)	−0.009 (3)
C36	0.157 (8)	0.054 (4)	0.106 (6)	0.015 (4)	0.015 (5)	−0.025 (4)
C37	0.084 (5)	0.045 (3)	0.166 (8)	0.015 (3)	0.029 (5)	0.000 (4)
C38	0.074 (4)	0.055 (3)	0.118 (5)	0.035 (3)	0.035 (4)	0.021 (4)
C39	0.064 (3)	0.049 (3)	0.074 (3)	0.026 (3)	0.017 (3)	0.009 (2)
N5	0.065 (3)	0.065 (3)	0.077 (5)	0.0327 (16)	0.000	0.000
O5	0.090 (3)	0.074 (3)	0.150 (5)	0.032 (3)	0.020 (3)	0.000 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.8816 (7)	C10—C15	1.393 (7)
Cu1—N2	1.952 (4)	C11—C12	1.385 (8)
Cu1—N1	1.960 (4)	C12—C13	1.360 (9)
Cu1—O2	2.059 (3)	C13—C14	1.366 (9)
Cu1—O3	2.483 (4)	C14—C15	1.367 (8)
O1—Cu1ⁱ	1.8816 (7)	C16—C17	1.379 (6)
O1—Cu1ⁱⁱ	1.8816 (7)	C16—C21	1.391 (7)
O2—N3	1.237 (5)	C17—C18	1.382 (7)
N1—C1	1.334 (6)	C18—C19	1.362 (9)
N1—N2ⁱ	1.345 (5)	C19—C20	1.365 (9)
N2—C3	1.337 (6)	C20—C21	1.386 (8)
N2—N1ⁱⁱ	1.345 (5)	C22—C23	1.371 (6)
N3—O4	1.215 (6)	C22—C27	1.393 (6)
N3—O3	1.253 (6)	C23—C24	1.382 (7)
C1—C2	1.364 (7)	C24—C25	1.379 (8)
C2—C3ⁱ	1.368 (7)	C25—C26	1.356 (8)
C2—Cl1	1.727 (5)	C26—C27	1.381 (6)
C3—C2ⁱⁱ	1.368 (7)	C28—C33	1.389 (6)
P1—N4	1.575 (4)	C28—C29	1.391 (6)
P1—C34	1.794 (4)	C29—C30	1.368 (7)
P1—C28	1.799 (4)	C30—C31	1.379 (8)
P1—C22	1.805 (4)	C31—C32	1.350 (8)
P2—N4	1.576 (4)	C32—C33	1.378 (7)
P2—C10	1.795 (4)	C34—C35	1.358 (7)
P2—C4	1.795 (4)	C34—C39	1.386 (7)
P2—C16	1.802 (4)	C35—C36	1.376 (9)
C4—C5	1.366 (6)	C36—C37	1.379 (11)
C4—C9	1.397 (6)	C37—C38	1.323 (10)
C5—C6	1.391 (7)	C38—C39	1.384 (8)
C6—C7	1.356 (8)	N5—O5ⁱ	1.238 (5)
C7—C8	1.379 (9)	N5—O5	1.238 (5)
C8—C9	1.388 (8)	N5—O5ⁱⁱ	1.238 (5)
C10—C11	1.378 (7)

O1—Cu1—N2	91.18 (12)	C8—C9—C4	119.5 (5)
O1—Cu1—N1	90.73 (12)	C11—C10—C15	119.6 (4)
N2—Cu1—N1	162.20 (16)	C11—C10—P2	117.0 (4)
O1—Cu1—O2	172.2 (2)	C15—C10—P2	123.2 (4)
N2—Cu1—O2	91.22 (15)	C10—C11—C12	119.8 (5)
N1—Cu1—O2	89.25 (14)	C13—C12—C11	119.8 (6)
Cu1—O1—Cu1ⁱ	119.59 (5)	C12—C13—C14	120.8 (5)
Cu1—O1—Cu1ⁱⁱ	119.59 (5)	C13—C14—C15	120.4 (6)
Cu1ⁱ—O1—Cu1ⁱⁱ	119.59 (5)	C14—C15—C10	119.6 (6)
N3—O2—Cu1	103.4 (3)	C17—C16—C21	118.6 (4)
C1—N1—N2ⁱ	108.1 (4)	C17—C16—P2	120.0 (4)
C1—N1—Cu1	132.6 (3)	C21—C16—P2	121.4 (4)
N2ⁱ—N1—Cu1	119.3 (3)	C16—C17—C18	120.6 (5)
C3—N2—N1ⁱⁱ	108.3 (4)	C19—C18—C17	120.3 (5)
C3—N2—Cu1	132.1 (3)	C18—C19—C20	120.1 (5)
N1ⁱⁱ—N2—Cu1	118.9 (3)	C19—C20—C21	120.4 (6)
O4—N3—O2	120.7 (5)	C20—C21—C16	119.9 (5)
O4—N3—O3	121.5 (5)	C23—C22—C27	118.8 (4)
O2—N3—O3	117.9 (4)	C23—C22—P1	121.4 (3)
N1—C1—C2	109.1 (4)	C27—C22—P1	119.4 (3)
C1—C2—C3ⁱ	105.8 (4)	C22—C23—C24	120.6 (4)
C1—C2—Cl1	127.0 (4)	C25—C24—C23	120.0 (5)
C3ⁱ—C2—Cl1	127.2 (4)	C26—C25—C24	119.9 (5)
N2—C3—C2ⁱⁱ	108.6 (4)	C25—C26—C27	120.6 (5)
N4—P1—C34	109.7 (2)	C26—C27—C22	120.1 (5)
N4—P1—C28	108.61 (19)	C33—C28—C29	118.8 (4)
C34—P1—C28	106.6 (2)	C33—C28—P1	123.1 (3)
N4—P1—C22	115.14 (19)	C29—C28—P1	118.1 (3)
C34—P1—C22	106.8 (2)	C30—C29—C28	120.1 (5)
C28—P1—C22	109.62 (19)	C29—C30—C31	120.6 (5)
N4—P2—C10	113.0 (2)	C32—C31—C30	119.5 (5)
N4—P2—C4	107.2 (2)	C31—C32—C33	121.3 (5)
C10—P2—C4	108.3 (2)	C32—C33—C28	119.7 (5)
N4—P2—C16	112.4 (2)	C35—C34—C39	118.9 (5)
C10—P2—C16	108.4 (2)	C35—C34—P1	121.2 (4)
C4—P2—C16	107.4 (2)	C39—C34—P1	119.9 (4)
P1—N4—P2	139.5 (2)	C34—C35—C36	120.4 (6)
C5—C4—C9	119.3 (4)	C35—C36—C37	119.7 (7)
C5—C4—P2	119.6 (3)	C38—C37—C36	120.5 (6)
C9—C4—P2	121.0 (4)	C37—C38—C39	120.6 (6)
C4—C5—C6	120.8 (5)	C38—C39—C34	119.8 (5)
C7—C6—C5	119.7 (5)	O5ⁱ—N5—O5	119.91 (5)
C6—C7—C8	120.7 (5)	O5ⁱ—N5—O5ⁱⁱ	119.90 (6)
C7—C8—C9	119.8 (5)	O5—N5—O5ⁱⁱ	119.91 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O3ⁱⁱⁱ	0.93	2.53	3.410 (11)	157

Symmetry code: (iii) −x+y+4/3, −x+2/3, z−1/3.

Footnotes

‡Present address: Department of Chemistry and Biochemistry, Florida International University, 11200 SW 8th Street, Miami, FL 33199, USA.

Acknowledgements

RC thanks NSF–CREST at UPR–Mayaguez for an undergraduate research fellowship. LM thanks NSF–IFN for a graduate student fellowship.

References

Alsalme, A., Ghazzali, M., Khan, R. A., Al-Farhan, K. & Reedijk, J. (2014). Polyhedron, 75, 64–67. Web of Science CSD CrossRef CAS Google Scholar
Angaridis, P. A., Baran, P., Boča, R., Cervantes-Lee, F., Haase, W., Mezei, G., Raptis, R. G. & Werner, R. (2002). Inorg. Chem. 41, 2219–2228. Web of Science CSD CrossRef PubMed CAS Google Scholar
Beckett, M. A., Horton, P. N., Hursthouse, M. B. & Timmis, J. L. (2010). Acta Cryst. E66, o319. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Halcrow, M. A. (2009). Dalton Trans. pp. 2059–2073. Web of Science CrossRef 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
Maresca, K. P., Rose, D. J. & Zubieta, J. (1997). Inorg. Chim. Acta, 260, 83–88. CSD CrossRef CAS Web of Science Google Scholar
Mezei, G., Rivera-Carrillo, M. & Raptis, R. G. (2007). Dalton Trans. pp. 37–40. Web of Science CSD CrossRef Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rivera-Carrillo, M., Chakraborty, I., Mezei, G., Webster, R. D. & Raptis, R. G. (2008). Inorg. Chem. 47, 7644–7650. Web of Science PubMed CAS 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
Solomon, E. I., Heppner, D. E., Johnston, E. M., Ginsbach, J. W., Cirera, J., Qayyum, M., Kieber-Emmons, M. T., Kjaergaard, C. H., Hadt, R. G. & Tian, L. (2014). Chem. Rev. 114, 3659–3853. Web of Science CrossRef CAS PubMed Google Scholar
Viciano-Chumillas, M., Tanase, S., de Jongh, L. J. & Reedijk, J. (2010). Eur. J. Inorg. Chem. pp. 3403–3418. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.