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

The trinuclear triangular cuprate anion of the title compound, tris-[bis-(tri-phenyl-phospho-ranyl-idene)ammonium] tris-(μ2-4-chloro-pyrazolato-κ(2) N:N')-μ3-oxido-tris-[(nitrato-κ(2) O,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 inter-actions, are present.

Chemical context

Trinuclear copper complexes with a triangular arrangement of the n class="Chemical">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 CuII cations in suitable angles to form triangular complexes (Halcrow, 2009 ▸; Viciano-Chumillas et al., 2010 ▸).

Nitrato and n class="Chemical">pyrazolato ligands are commonly studied ligands in CuII coordination chemistry. Simple CuII nitrate complexes are aplenty in the literature and have been studied in detail with respect to their part in the nitro­gen cycle. Triangular trinuclear CuII 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 class="Chemical">N)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 ▸).

Structural commentary

The nine-membered metallacycle n class="Chemical">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 CuII 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.

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.

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)

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

Supra­molecular features

The interstitial water O atom is also located on a threefold n class="Disease">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) .

Figure 2

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

Synthesis and crystallization

4-Cl-pz and the hexa­nuclear n class="Chemical">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.

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 n class="Chemical">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[F 2 > 2σ(F 2)], wR(F 2), 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
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016003741/wm4004sup1.cif

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989016003741/wm4004Isup3.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016003741/wm4004Isup4.hkl

CCDC reference: 1458061

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C36H30P2N)[Cu3(C3H2ClN2)3(NO3)3O]NO3·H2O	Dx = 1.407 Mg m−3
Mr = 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

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

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(Fo2) + (0.0468P)2 + 0.1352P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.088	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.41 e Å−3
7675 reflections	Δρmin = −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)

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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