A square-pyramidal copper(II) complex with strong intra­molecular hydrogen bonds: diaqua­(N,N′-di­methyl­formamide-κO)bis­[2-(diphenyl­phosphor­yl)benzoato-κO]copper(II)

In the title Cu^II complex, [Cu(C₁₉H₁₄O₃P)₂(C₃H₇NO)(H₂O)₂], the mol­ecule is bis­ected by a twofold axis relating the two 2-(di­phenyl­phosphor­yl)benzoate (ODPPB) ligands. The asym­­metric unit consists of a Cu^II metal centre on the sym­metry axis, an ODPPB ligand, one water ligand and one dimethyl­formamide (DMF) ligand (disordered around the twofold axis). The Cu^II ion has fivefold coordination provided by two carboxyl­ate O atoms from two ODPPB ligands, two O atoms from two coordinated water mol­ecules and another O atom from a (disordered) DMF mol­ecule, giving a CuO₅ square-pyramidal coordination geometry. The ODPPB ligand adopts a terminal monocoordinated mode with two free O atoms forming two strong intra­molecular hydrogen bonds with the coordinated water mol­ecules, which may play a key role in the stability of the mol­ecular structure, as shown by the higher release temperature for the coordinated water mol­ecules than for the coordinated DMF mol­ecule. The optical absorption properties of powder samples of the title compound have also been studied.

S1. Comment

Copper(II)-containing proteins play an improtant role in many organisms due to the oxygen-carrying capacity of the copper(II) centre (Cuff et al., 1998) and, moreover, to their copper-catalyzed substrate oxygenation (Klinman, 1996; Solomon et al., 1996). Copper-active sites often present a mononuclear, dinuclear or trinuclear character (Klinman, 1996; Gerdemann et al., 2002). Enzyme-catalyzed reactions have attracted attention as a result of their intrinsic high efficiency and excellent specificity compared to those promoted by general chemical catalysts. In consideration of the energy conservation and emission reduction, increased efforts have been made recently with regard to biomimetic catalysts by artificially constructing some novel complexes (Bruijnincx et al., 2008). As for copper-catalyzed substrate oxygenation, great progress has been made in many aspects, such as catalytic mechnisms around the copper-active sites, structural-model studies and functional-model syntheses (Cramer & Tolman, 2007; Solomon et al., 2007). Since the formation of the 1:1 Cu/O₂ adduct is an important first step in copper-promoted aerobic oxidations (Donoghue et al., 2010), a suitable and accessible coordinating site for O₂ should be a key point in the molecular structure during the design of a new model for copper(II)-based oxidase. As far as mononuclear copper-active sites adopting a square-pyramid geometry is concerned, the axial coordinating site of copper(II) in the model should be empty or occupied by a weak ligand so that O₂ can approach the axial site and the essential 1:1 Cu/O₂ adduct thus be produced easily. In relative terms, four facially coordinating atoms should bind to copper in a square-pyramidal structure. Of course, the thermostability of the model compound also needs to be taken into account because the stability of a metal complex is critical for its use as a catalyst. In this work, we assembled the carboxylate ligand 2-(diphenylphosphoryl)benzoate (ODPPB) with a copper(II) salt and successfully obtained the mononuclear complex [Cu(ODPPB)₂(DMF)(H₂O)₂] (DMF is dimethylformamide), (I), with the Cu^II atom adopting a square-pyramidal geometry and the weak DMF ligand occupying the axial site.

The mononuclear neutral title molecule, (I) (Fig. 1), consists of two ODPPB ligands, two coordinated water molecules and one coordinated DMF molecule (disordered around the twofold axis) and one copper(II) cation on the symmetry element. The Cu^II atom exhibits a square-pyramidal coordination geometry, which is constructed from two carboxylate O atoms from two ODPPB ligands, two O atoms from two coordinated water molecules and an O atom from a DMF ligand. In this CuO₅ square pyramid, the Cu1—O distances (Table 1) are similar to those reported in similar complexes in the literature (Chen et al., 1990; Yang et al., 2011; He et al., 2012). The ODPPB ligand adopts a monocoordinated terminal mode, contrasting with the bridging mode via the carboxylate and phosphoryl groups seen in dinuclear structures (Barbaro et al., 1998; Yeh et al., 2006). On the other hand, it has been found that carbonyl and carboxyl O atoms can effectively coordinate with phosphorus to give a trigonal–bipyramidal (TBP) geometry in various organic phosphorus compounds (Chandrasekaran et al., 2001, 2002, 2003). They also had found that the relative strengths of the P—O donor-accepting interactions are related with the P—O donor distances and percent displacement toward a trigonal bipyramid (%TBP). In (I), the P—O donor distance (P1—O2) is 2.842 (2) Å, which represents a weak P—O donor-accepting interaction. This donor-accepting interaction should weaken the coordination of carboxylate atom O2 with the Cu1 ccentre and, in fact, the Cu1—O2 bond length is indeed somewhat longer than the coordinating bond from water (Cu1—O5). As to the remaining two O atoms of the ODPPB ligand, there are no obvious coordinating interactions to copper or phosphorus, but there are instead two sets of strong O—H···O hydrogen bonds. The O5—H5A···O1ⁱ [symmetry code: (i) -x+1, y, -z+1/2] and O5—H5B···O3 hydrogen bonds effectively fuse two ODPPB ligands and two water ligands to form a firm base of the CuO₅ square pyramid (Fig. 2). The hydrogen-bonding data are in the range of standard examples (Desiraju & Steiner, 1999). On the axial site of the CuO₅ square pyramid, the DMF ligand is disordered, partially occupying two equivalent sites and thus complying with the space-group symmetry only on average. Contrasting with similar complexes in the literature (Chai et al., 2009; Chai, Lin et al., 2010; Chai, Song et al., 2010). there are no obvious intermolecular supramolecular interactions in the structure of (I) (Fig. 3).

For investigating the thermal stability of compound (I), simultaneous thermogravimetric (TG) and differential scanning calorimetry (DSC) measurements were carried out on the as-synthesized powder sample. As show in Fig. 4, there are three obvious weight-loss steps. The weight loss in the range 398–433 K (9%) corresponds to the release of the coordinated solvent DMF (calculated value 9.0%).

The second step (433–498 K) corresponds to the release of the water and carboxylate groups of ODPPB (Observed weight loss, of about 15%; calculated value 15.2%), and the exothermic signal shown in the DSC curve also agrees with the decarboxylation reaction. This difference in the release temperatures of the coordinated water and DMF molecules is rather unusual, and the special stability of the former could be attributed to the restraint introduced by the strong intramolecular hydrogen bonds. The third step began at 498 K and was complete at about 753 K, during which the organic ligand was fully released. The final weight loss of about 92.5% was consistent with a residual of cuprous oxide (expected loss 92.2%).

The UV–Vis diffuse-reflectance spectrum of (I) was measured on a powder sample and is plotted in Fig. 5 as an F(R)² versus photo wavelength, according to the Kubelka–Munk function (Chai et al., 2007a,b). As can be seen, there are two obvious absorption bands in the spectrum. One strong band located in the region 200–350 nm can be assigned to the transition of ligands between different energy levels. The remaining very weak band above 550 nm (λ_max = 820 nm) is assigned to the d–d transition of the Cu^II centre with square-pyramidal geometry. This optical absorption transition is consistent with the pale-green colour of the compound: in the family of copper(II) complexes, the common colour is blue rather than green. The present pale-green colour means that the ligands around the Cu^II centre are weak-field ligands and which could only induce weak-ligand field splitting (Schläfer & Gliemann, 1969).

Related literature

For related literature, see: Barbaro et al. (1998); Bruijnincx et al. (2008); Chai et al. (2007a, 2007b, 2009); Chai, Lin, Song, Shu, Qin, Shi & Guo (2010); Chai, Song, Shu, Qin & Shi (2010); Chandrasekaran et al. (2001, 2002, 2003); Chen et al. (1990); Cramer & Tolman (2007); Cuff et al. (1998); Desiraju & Steiner (1999); Donoghue et al. (2010); Gerdemann et al. (2002); He et al. (2012); Klinman (1996); Schläfer & Gliemann (1969); Solomon et al. (1996, 2007); Yang et al. (2011); Yeh et al. (2006).

S2. Experimental

The title compound, (I), was synthesized by a solution reaction of [Cu(CH₃CN)₄]PF₆ [OK?] (37 mg, 0.1 mmol), carbazole (17 mg, 0.1 mmol) and 2-(diphenylphosphoryl)benzoic acid (62 mg, 0.2 mmol) in dichloromethane (6 ml) and DMF (4 ml) at room temperature. The filtered solution was placed in a tube and covered by a layer of propan-2-ol. After several days, pale-green crystals of (I) were obtained in a yield of 57% (47 mg). Analysis calculated for C₄₁H₃₉CuNO₉P₂ (%): C 60.40, H 4.82, N 1.72, O 17.66; found: C 60.93, H 4.15, N 1.54, O 17.97. Samples suitable for single-crystal X-ray diffraction were selected directly from the obtained crop.

S3. Refinement

All H atoms bonded to C atoms were added at calculated positions (C—H = 0.99 Å) and refined using a riding model, with U_iso(H) = 1.2U_eq(C). Those pertaining to the coordinating water molecule were located from difference Fourier peaks and refined isotropically restrained O—H distances of 0.85 (2) Å. The coordinating DMF molecule was refined in the isolation fashion.

Computing details

Data collection: CrysAlis PRO (Oxford Diffraction, 2011); cell refinement: CrysAlis PRO (Oxford Diffraction, 2011); data reduction: CrysAlis PRO (Oxford Diffraction, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The copper coordination basal plane of (I), showing the intramolecular hydrogen-bonding interactions (dashed lines).
	Fig. 3. A packing diagram for (I), viewed along the b direction, showing the lack of any significant intermolecular interactions.
	Fig. 4. The simultaneous TG and DSC curves of (I), recorded on a polycrystalline sample under an argon atmosphere.
	Fig. 5. A plot of F(R)^2 versus wavelength for compound (I). The inset shows the spectrum feature of the d–d transition for clarity.

Diaqua(N,N'-dimethylformamide-κO)bis[2-(diphenylphosphoryl)benzoato-κO]copper(II)

Crystal data

[Cu(C19H14O3P)2(C3H7NO)(H2O)2]	F(000) = 1692
Mr = 815.21	Dx = 1.402 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -C 2yc	Cell parameters from 2887 reflections
a = 19.0469 (11) Å	θ = 3.2–29.1°
b = 8.7313 (4) Å	µ = 0.71 mm^−1
c = 23.6080 (15) Å	T = 293 K
β = 100.450 (6)°	Block, light green
V = 3861.0 (4) Å^3	0.35 × 0.28 × 0.23 mm
Z = 4

Data collection

Oxford Xcalibur Gemini ultra diffractometer	3773 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2899 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 10.3592 pixels mm^-1	θmax = 26.0°, θmin = 3.2°
ω scans	h = −23→23
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
Tmin = 0.790, Tmax = 0.855	l = −19→29
7985 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0374P)^2 + 1.7477P] where P = (Fo^2 + 2Fc^2)/3
3773 reflections	(Δ/σ)max < 0.001
273 parameters	Δρmax = 0.26 e Å^−3
2 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. IR (KBr, cm^-1): 3418 m, 3054 m, 3021 m, 2989 m, 2962 m, 2937 m, 2900 m, 1665 m, 1610 m, 1583 m, 1555 m, 1436 m, 1382 s, 1153 sh, 1117 m, 754 ms, 728 sh, 693 m, 547 sh.

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.5000	0.68748 (4)	0.2500	0.04778 (15)
P1	0.29432 (3)	0.61293 (6)	0.13903 (3)	0.03567 (16)
O1	0.31125 (8)	0.53308 (17)	0.19585 (7)	0.0450 (4)
O2	0.44481 (8)	0.63981 (19)	0.17292 (7)	0.0483 (4)
O3	0.52932 (10)	0.5691 (3)	0.12567 (9)	0.0817 (7)
O5	0.59180 (10)	0.6750 (2)	0.22459 (9)	0.0593 (5)
H5A	0.6220 (13)	0.623 (3)	0.2464 (11)	0.071*
H5B	0.5834 (16)	0.630 (3)	0.1933 (9)	0.071*
C1	0.30939 (12)	0.8170 (2)	0.14218 (10)	0.0384 (5)
C2	0.34550 (13)	0.8969 (3)	0.10572 (11)	0.0495 (6)
H2	0.3645	0.8446	0.0777	0.059*
C3	0.35356 (15)	1.0549 (3)	0.11067 (14)	0.0628 (8)
H3	0.3782	1.1081	0.0863	0.075*
C4	0.32483 (16)	1.1322 (3)	0.15192 (14)	0.0657 (8)
H4	0.3301	1.2379	0.1554	0.079*
C5	0.28873 (18)	1.0547 (3)	0.18760 (14)	0.0706 (9)
H5	0.2689	1.1078	0.2150	0.085*
C6	0.28133 (15)	0.8979 (3)	0.18344 (12)	0.0573 (7)
H6	0.2573	0.8459	0.2085	0.069*
C7	0.19932 (12)	0.5965 (2)	0.11218 (10)	0.0391 (5)
C8	0.16312 (14)	0.6945 (3)	0.07057 (12)	0.0535 (7)
H8	0.1874	0.7749	0.0569	0.064*
C9	0.09132 (15)	0.6733 (3)	0.04936 (13)	0.0643 (8)
H9	0.0677	0.7379	0.0208	0.077*
C10	0.05493 (15)	0.5574 (4)	0.07026 (14)	0.0693 (8)
H10	0.0064	0.5449	0.0564	0.083*
C11	0.08929 (15)	0.4601 (4)	0.11132 (14)	0.0697 (8)
H11	0.0643	0.3812	0.1251	0.084*
C12	0.16157 (14)	0.4789 (3)	0.13247 (12)	0.0555 (7)
H12	0.1849	0.4123	0.1604	0.067*
C13	0.33548 (11)	0.5298 (2)	0.08165 (10)	0.0360 (5)
C14	0.29065 (13)	0.4671 (3)	0.03398 (11)	0.0479 (6)
H14	0.2415	0.4739	0.0318	0.058*
C15	0.31673 (15)	0.3952 (3)	−0.01026 (11)	0.0556 (7)
H15	0.2853	0.3559	−0.0417	0.067*
C16	0.38885 (15)	0.3820 (3)	−0.00756 (12)	0.0577 (7)
H16	0.4068	0.3332	−0.0369	0.069*
C17	0.43433 (14)	0.4416 (3)	0.03892 (11)	0.0514 (6)
H17	0.4833	0.4314	0.0407	0.062*
C18	0.40958 (12)	0.5168 (2)	0.08349 (10)	0.0379 (5)
C19	0.46612 (12)	0.5802 (3)	0.13098 (11)	0.0440 (6)
O4	0.4885 (4)	0.9310 (4)	0.2624 (3)	0.0662 (16)	0.50
N1	0.5189 (7)	1.1726 (5)	0.2422 (4)	0.078 (3)	0.50
C20	0.5253 (4)	1.0211 (6)	0.2420 (3)	0.0584 (17)	0.50
H20A	0.5613	0.9808	0.2246	0.070*	0.50
C21	0.5684 (6)	1.2681 (15)	0.2186 (6)	0.108 (4)	0.50
H21A	0.6005	1.2047	0.2020	0.163*	0.50
H21B	0.5952	1.3295	0.2488	0.163*	0.50
H21C	0.5425	1.3337	0.1895	0.163*	0.50
C22	0.4703 (7)	1.2443 (16)	0.2735 (7)	0.114 (5)	0.50
H22A	0.4447	1.1672	0.2903	0.171*	0.50
H22B	0.4373	1.3065	0.2477	0.171*	0.50
H22C	0.4965	1.3074	0.3033	0.171*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0490 (3)	0.0357 (2)	0.0519 (3)	0.000	−0.0088 (2)	0.000
P1	0.0398 (3)	0.0315 (3)	0.0353 (3)	0.0013 (2)	0.0058 (2)	0.0016 (2)
O1	0.0536 (10)	0.0425 (8)	0.0371 (9)	−0.0002 (8)	0.0037 (7)	0.0050 (7)
O2	0.0409 (9)	0.0540 (10)	0.0463 (11)	0.0079 (8)	−0.0022 (8)	−0.0094 (8)
O3	0.0408 (11)	0.150 (2)	0.0550 (13)	−0.0087 (12)	0.0108 (9)	−0.0131 (13)
O5	0.0497 (11)	0.0721 (13)	0.0502 (12)	−0.0139 (10)	−0.0070 (9)	0.0180 (10)
C1	0.0403 (12)	0.0348 (11)	0.0389 (13)	0.0023 (10)	0.0037 (10)	0.0022 (10)
C2	0.0534 (15)	0.0433 (13)	0.0543 (17)	0.0056 (12)	0.0167 (12)	0.0079 (12)
C3	0.0621 (17)	0.0446 (15)	0.082 (2)	−0.0038 (14)	0.0138 (16)	0.0221 (15)
C4	0.076 (2)	0.0344 (13)	0.081 (2)	0.0027 (14)	−0.0005 (17)	−0.0011 (14)
C5	0.097 (2)	0.0424 (15)	0.076 (2)	0.0078 (16)	0.0247 (19)	−0.0096 (14)
C6	0.0755 (19)	0.0433 (14)	0.0586 (18)	0.0023 (13)	0.0265 (15)	−0.0032 (12)
C7	0.0411 (12)	0.0365 (11)	0.0409 (14)	0.0021 (10)	0.0103 (10)	0.0003 (10)
C8	0.0469 (15)	0.0540 (15)	0.0601 (18)	0.0049 (12)	0.0111 (12)	0.0150 (13)
C9	0.0471 (16)	0.0763 (19)	0.067 (2)	0.0155 (15)	0.0042 (14)	0.0081 (16)
C10	0.0380 (14)	0.096 (2)	0.072 (2)	−0.0058 (16)	0.0048 (14)	−0.0051 (18)
C11	0.0554 (18)	0.076 (2)	0.078 (2)	−0.0233 (16)	0.0131 (16)	0.0032 (17)
C12	0.0581 (17)	0.0520 (15)	0.0553 (17)	−0.0055 (13)	0.0068 (13)	0.0080 (13)
C13	0.0385 (12)	0.0305 (11)	0.0382 (13)	0.0007 (10)	0.0051 (10)	0.0013 (9)
C14	0.0424 (14)	0.0520 (14)	0.0477 (16)	−0.0028 (12)	0.0036 (11)	−0.0073 (12)
C15	0.0626 (17)	0.0579 (16)	0.0448 (16)	−0.0062 (14)	0.0058 (13)	−0.0144 (13)
C16	0.0686 (19)	0.0580 (16)	0.0512 (17)	−0.0003 (14)	0.0235 (14)	−0.0149 (13)
C17	0.0483 (14)	0.0556 (15)	0.0526 (17)	0.0040 (12)	0.0157 (12)	−0.0045 (13)
C18	0.0419 (13)	0.0358 (11)	0.0362 (13)	−0.0002 (10)	0.0072 (10)	0.0038 (10)
C19	0.0400 (14)	0.0492 (13)	0.0418 (15)	0.0016 (11)	0.0048 (11)	0.0091 (11)
O4	0.087 (5)	0.0351 (17)	0.079 (6)	0.004 (3)	0.020 (3)	−0.010 (2)
N1	0.146 (12)	0.033 (3)	0.050 (6)	−0.002 (4)	0.004 (5)	0.002 (3)
C20	0.087 (5)	0.038 (3)	0.049 (4)	−0.001 (3)	0.009 (3)	0.006 (3)
C21	0.154 (12)	0.061 (5)	0.106 (8)	−0.022 (7)	0.012 (8)	0.012 (5)
C22	0.118 (11)	0.057 (7)	0.168 (13)	0.005 (8)	0.026 (9)	−0.025 (7)

Geometric parameters (Å, º)

Cu1—O2^i	1.9737 (16)	C9—C10	1.368 (4)
Cu1—O2	1.9737 (16)	C9—H9	0.9300
Cu1—O4^i	2.163 (4)	C10—C11	1.364 (4)
Cu1—O4	2.163 (4)	C10—H10	0.9300
Cu1—O5^i	1.952 (2)	C11—C12	1.387 (4)
Cu1—O5	1.952 (2)	C11—H11	0.9300
P1—O1	1.4941 (16)	C12—H12	0.9300
P1—C1	1.804 (2)	C13—C14	1.395 (3)
P1—C7	1.811 (2)	C13—C18	1.409 (3)
P1—C13	1.833 (2)	C14—C15	1.386 (3)
O2—C19	1.250 (3)	C14—H14	0.9300
O3—C19	1.237 (3)	C15—C16	1.368 (4)
O5—H5A	0.835 (17)	C15—H15	0.9300
O5—H5B	0.828 (17)	C16—C17	1.371 (4)
C1—C2	1.384 (3)	C16—H16	0.9300
C1—C6	1.387 (3)	C17—C18	1.393 (3)
C2—C3	1.391 (3)	C17—H17	0.9300
C2—H2	0.9300	C18—C19	1.511 (3)
C3—C4	1.377 (4)	O4—C20	1.211 (6)
C3—H3	0.9300	N1—C20	1.328 (7)
C4—C5	1.361 (4)	N1—C22	1.427 (12)
C4—H4	0.9300	N1—C21	1.445 (12)
C5—C6	1.377 (4)	C20—H20A	0.9300
C5—H5	0.9300	C21—H21A	0.9600
C6—H6	0.9300	C21—H21B	0.9600
C7—C12	1.388 (3)	C21—H21C	0.9600
C7—C8	1.388 (3)	C22—H22A	0.9600
C8—C9	1.381 (4)	C22—H22B	0.9600
C8—H8	0.9300	C22—H22C	0.9600
O5—Cu1—O5^i	173.60 (12)	C8—C9—H9	120.0
O5^i—Cu1—O2^i	93.55 (7)	C11—C10—C9	120.5 (3)
O5—Cu1—O2^i	85.10 (7)	C11—C10—H10	119.7
O5^i—Cu1—O2	85.10 (7)	C9—C10—H10	119.7
O5—Cu1—O2	93.55 (7)	C10—C11—C12	119.9 (3)
O2—Cu1—O2^i	155.65 (10)	C10—C11—H11	120.0
O5^i—Cu1—O4^i	102.40 (15)	C12—C11—H11	120.0
O5—Cu1—O4^i	83.98 (15)	C11—C12—C7	120.4 (3)
O2^i—Cu1—O4^i	106.4 (2)	C11—C12—H12	119.8
O2—Cu1—O4^i	97.6 (2)	C7—C12—H12	119.8
O5^i—Cu1—O4	83.98 (15)	C14—C13—C18	117.2 (2)
O4—Cu1—O5	102.40 (15)	C14—C13—P1	118.04 (17)
O2^i—Cu1—O4	97.6 (2)	C18—C13—P1	124.70 (17)
O2—Cu1—O4	106.4 (2)	C15—C14—C13	122.4 (2)
O4^i—Cu1—O4	21.1 (2)	C15—C14—H14	118.8
O1—P1—C1	114.65 (10)	C13—C14—H14	118.8
O1—P1—C7	108.45 (10)	C16—C15—C14	119.8 (2)
C1—P1—C7	103.53 (10)	C16—C15—H15	120.1
O1—P1—C13	115.28 (9)	C14—C15—H15	120.1
C1—P1—C13	109.58 (10)	C15—C16—C17	119.2 (2)
C7—P1—C13	104.12 (10)	C15—C16—H16	120.4
C19—O2—Cu1	128.54 (15)	C17—C16—H16	120.4
Cu1—O5—H5A	113 (2)	C16—C17—C18	122.1 (2)
Cu1—O5—H5B	105 (2)	C16—C17—H17	118.9
H5A—O5—H5B	107 (3)	C18—C17—H17	118.9
C2—C1—C6	118.6 (2)	C17—C18—C13	119.3 (2)
C2—C1—P1	124.46 (17)	C17—C18—C19	116.1 (2)
C6—C1—P1	116.97 (17)	C13—C18—C19	124.6 (2)
C1—C2—C3	120.5 (2)	O3—C19—O2	125.1 (2)
C1—C2—H2	119.7	O3—C19—C18	118.2 (2)
C3—C2—H2	119.7	O2—C19—C18	116.7 (2)
C4—C3—C2	119.6 (3)	C20—O4—Cu1	120.4 (3)
C4—C3—H3	120.2	C20—N1—C22	120.5 (7)
C2—C3—H3	120.2	C20—N1—C21	120.4 (8)
C5—C4—C3	120.3 (2)	C22—N1—C21	118.4 (5)
C5—C4—H4	119.9	O4—C20—N1	125.8 (6)
C3—C4—H4	119.9	O4—C20—H20A	117.1
C4—C5—C6	120.5 (3)	N1—C20—H20A	117.1
C4—C5—H5	119.8	N1—C21—H21A	109.5
C6—C5—H5	119.8	N1—C21—H21B	109.5
C5—C6—C1	120.6 (3)	H21A—C21—H21B	109.5
C5—C6—H6	119.7	N1—C21—H21C	109.5
C1—C6—H6	119.7	H21A—C21—H21C	109.5
C12—C7—C8	118.6 (2)	H21B—C21—H21C	109.5
C12—C7—P1	119.02 (18)	N1—C22—H22A	109.5
C8—C7—P1	122.37 (18)	N1—C22—H22B	109.5
C9—C8—C7	120.4 (2)	H22A—C22—H22B	109.5
C9—C8—H8	119.8	N1—C22—H22C	109.5
C7—C8—H8	119.8	H22A—C22—H22C	109.5
C10—C9—C8	120.1 (3)	H22B—C22—H22C	109.5
C10—C9—H9	120.0

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5B···O3	0.83 (2)	1.82 (2)	2.592 (3)	156 (3)
O5—H5A···O1^i	0.84 (2)	1.86 (2)	2.686 (2)	170 (3)
C17—H17···O3	0.93	2.37	2.714 (3)	102

Symmetry code: (i) −x+1, y, −z+1/2.