Bis­[μ-bis(4-nitro­phenyl) phosphato-κ²O:O]­bis­[(4,4′-di­methyl-2,2′-bi­pyridine)­nitratocopper(II)]

The title dimeric complex, [Cu₂(L)₂(BNPP)₂(NO₃)₂], is formed between 4,4′-methyl-2,2′-bi­pyridine (L, C₁₂H₁₂N₂), copper(II), and the substrate BNPP [bis-(4-nitro­phenyl)­phosphate, C₁₂H₈N₂O₈P], with the two subunits, [Cu(L)(BNPP)NO₃)] related by a center of inversion. The coordination geometry about the Cu atoms is square pyramidal, with phosphate O atoms occupying both an in-plane and an out-of-plane sites. While the dimeric scheme is similar to other five-coordinate copper(II) complexes of bi­pyridine, the alternating in-plane and out-of-plane bridging of the copper(II) centers by BNPP is unusual.

Key indicators

• Single-crystal X-ray study
• T = 198 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.036
• wR factor = 0.096
• Data-to-parameter ratio = 10.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



THETM_01  Alert B The value of sine(theta_max)/wavelength is less than 0.575
          Calculated sin(theta_max)/wavelength =    0.5506

Author response: The range of 2-theta is restricted when our low temperature Device is used on the P4 diffractometer.

 Alert Level C:



PLAT_213  Alert C Atom O6      has ADP max/min Ratio ...........       3.20 prolate


 0 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The role of metal ions in the enhanced hydrolysis of phosphate esters has long been known and the mechanism of these reactions extensively investigated. We have been exploring ways to incorporate these active homogeneous catalytic systems into insoluble polymers in order to take advantage of both the fast rates of homogeneous catalysis, as well as the ease of handling of inhomogeneous systems (Lu et al., 2000; Singh et al., 2000; Deschamps, 2002; Hartshorn et al., 2002).

In early research in this field, it was shown that 2,2'-bipyridyl (bpy) copper(II) complexes are among the most efficient in hydrolyzing selected phosphorofluoridates, a class of compounds closely related to phosphate esters (Courtney et al., 1957). A more recent report comprehensively detailed the hydrolysis of other phosphate esters with bpy–Cu^II (Morrow & Trogler, 1988). Since copper bipyridyl complexes are so effective across a wide range of substrates, we have sought to functionalize a 4,4'-dimethyl-2,2'-bipyridine in order to incorporate it into polymers using a cross-linker, such as trimethylolpropane trimethacrylate (TRIM). The resulting insoluble polymers are even more effective than the soluble monomer catalytic complexes, with catalytic rates up to 6.7 × 10⁵ times faster than the uncatalyzed rates for methyl parathion, a phosphotriester (Hartshorn et al., 2002).

A potential approach for further improving the catalytic properties of these enhanced polymeric catalysts would be to make imprinted nano-cavities within the polymers that can be customized to accommodate individual active metal-ion complexes and their targeted substrate. To this end, we have prepared a complex with copper coordinated to the dimethyl bpy molecule and a phosphodiester substrate. The complex serves as a prototype template for imprinting and also as a model to better understand the geometrical dimensions and constraints that would be necessary for making imprinted sites within polymers.

We report here the crystal structure, (I), of a Cu^II complex of 4,4'-dimethyl-2,2'-bipyridine (L) coupled to bis(4-nitrophenyl) phosphate, BNPP, a model phosphodiester. The structure is based on a dimeric complex, [Cu₂(L)₂(BNPP)₂(NO₃)₂] (Fig. 1), with the two identical subunits, [Cu(L)(BNPP)NO₃)], related by a center of inversion. The dimeric nature of the crystal unit is reminiscent of other mixed-ligand systems based on bpy with phosphomonoesters (Aoki, 1978; Fischer & Bau, 1978; Glowiak et al., 1986; Kovari & Kramer, 1996). Interestingly, despite being a phosphodiester, two O atoms in BNPP act as a bridge between the Cu ions, just as in the phosphomonoesters. In this case, however, the two bridging P—O bond lengths of 1.466 (2) and 1.486 (2) Å (Table 1) are much shorter than that of a standard P—O single bond (1.64 Å; Cruickshank, 1961), or the bridging P—O bonds of a monophospate (e.g. Fischer & Bau, 1978). A further difference is found for BNPP, which bridges the two Cu^II centers with alternate square-planar and axial positions. This is in contrast to the usual planar positions occupied by bridging monophosphate complexes (Aoki, 1978; Fischer & Bau, 1978; Kovari & Kramer, 1996).

The subunit [Cu(L)(BNPP)NO₃)] (Fig. 2) is square pyramidal, with BNPP in both one axial and one basal position (not shown). The subunit exhibits some in-plane asymmetry, with one of the Cu—N bonds [i.e. Cu1—N12 2.011 (3) Å] longer than the other, and C—O lengths of 1.961 (2) and 1.975 (2) Å. This is in contrast to the simpler [CuL(NO₃)₂] complex, where the two Cu—N bonds are of equal length (unpublished data). While the Cu—O bond with nitrate forms part of the base, the rest of the nitrate ion, with a Cu—O—N angle of 111.2 (2)°, is located below the plane.

The axial phosphate C—O bond is much longer at 2.149 (2) Å, although still shorter than the average Cu—O(water) distance of 2.455 Å (Glowiak et al., 1986). The P—O bonds that connect the nitrophenyls to the phosphate group are about the same length, at 1.598 (2) and 1.608 (2) Å, while the nitrophenyl rings are approximately at right angles to each other [92.05 (13)°].

In summary, the ternary complex, [Cu(L)(BNPP)(NO₃)]₂, exhibits the characteristic features, such as a five-coordinate square-pyramidal geometry, typical of previously reported mixed-ligand copper(II) complexes with monophosphate compounds. Similarly, the crystallization of the complex as a dimer conforms to the trend, even to the extent of BNPP playing the role of a bridge between the two Cu^II ions. The existence of a stable nitrato complex of CuLBNPP is promising for both preparing imprinted polymers and for incorporating binuclear complexes into polymers.

S2. Experimental

All reagents and solvents were purchased from commercial sources and used as received. To prepare the title complex, Cu(NO₃)₂·2.5H₂O, mbpy, and BNPP were mixed in ethanol in an equimolar ratio. The resulting solution was allowed to slowly evaporate, producing blue crystals suitable for single-crystal X-ray diffraction analysis.

Computing details

Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. View of (I). Displacement ellipsoids are shown at the 20% probability level, H atoms have been omitted for clarity and only atoms coordinated to the Cu atom are labeled.
	Fig. 2. A view of the [Cu(L)(BNPP)NO3)] subunit, showing the square-pyramidal coordination around the Cu atom and BNPP in the axial position. Displacement ellipsoids are shown at the 30% probability level.

Bis[µ-bis(4-nitrophenyl) phosphate-κ²O:O]bis[(4,4'-dimethyl-2,2'-bipyridine)nitratocopper(II)]

Crystal data

[Cu2(C12H8N2O8P)2(C12H12N2)2(NO3)2]	Z = 1
Mr = 1297.92	F(000) = 662
Triclinic, P1	Dx = 1.568 Mg m^−3
a = 10.9572 (5) Å	Cu Kα radiation, λ = 1.54178 Å
b = 11.5226 (6) Å	Cell parameters from 26 reflections
c = 12.0697 (11) Å	θ = 3.7–27.5°
α = 96.159 (5)°	µ = 2.29 mm^−1
β = 96.421 (7)°	T = 198 K
γ = 113.044 (4)°	Plate, blue
V = 1374.32 (16) Å^3	0.22 × 0.14 × 0.08 mm

Data collection

Bruker P4 diffractometer	3333 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.017
Graphite monochromator	θmax = 58.1°, θmin = 3.7°
2θ/ω scans	h = −1→11
Absorption correction: integration (XPREP; Bruker, 1997)	k = −12→11
Tmin = 0.702, Tmax = 0.856	l = −13→13
4685 measured reflections	3 standard reflections every 97 reflections
3829 independent reflections	intensity decay: random variation of 2

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.096	w = 1/[σ^2(Fo^2) + (0.0358P)^2 + 1.4102P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3829 reflections	Δρmax = 0.27 e Å^−3
380 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00044 (12)

Special details

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
Cu1	0.01873 (4)	0.21729 (4)	0.06005 (3)	0.03153 (16)
N1	0.0010 (2)	0.2724 (2)	−0.0882 (2)	0.0328 (6)
C2	−0.0677 (3)	0.1937 (3)	−0.1851 (3)	0.0431 (8)
H2A	−0.1149	0.1051	−0.1839	0.052*
C3	−0.0716 (4)	0.2380 (4)	−0.2862 (3)	0.0500 (9)
H3A	−0.1208	0.1798	−0.3535	0.060*
C4	−0.0047 (4)	0.3662 (3)	−0.2905 (3)	0.0460 (9)
C4A	−0.0091 (5)	0.4185 (4)	−0.3988 (3)	0.0684 (12)
H4AA	−0.0660	0.3489	−0.4604	0.103*
H4AB	0.0822	0.4577	−0.4160	0.103*
H4AC	−0.0464	0.4830	−0.3908	0.103*
C5	0.0690 (3)	0.4459 (3)	−0.1906 (3)	0.0420 (8)
H5A	0.1177	0.5347	−0.1903	0.050*
C6	0.0723 (3)	0.3969 (3)	−0.0907 (2)	0.0318 (7)
C7	0.1534 (3)	0.4723 (3)	0.0191 (2)	0.0323 (7)
C8	0.2300 (3)	0.6025 (3)	0.0381 (3)	0.0398 (8)
H8A	0.2316	0.6498	−0.0220	0.048*
C9	0.3043 (3)	0.6651 (3)	0.1436 (3)	0.0397 (8)
C9A	0.3850 (4)	0.8074 (3)	0.1657 (3)	0.0549 (10)
H9AA	0.4323	0.8341	0.2441	0.082*
H9AB	0.3247	0.8506	0.1532	0.082*
H9AC	0.4507	0.8303	0.1143	0.082*
C10	0.3006 (3)	0.5912 (3)	0.2270 (3)	0.0461 (8)
H10A	0.3516	0.6301	0.3003	0.055*
C11	0.2236 (3)	0.4620 (3)	0.2046 (3)	0.0432 (8)
H11A	0.2233	0.4130	0.2631	0.052*
N12	0.1483 (3)	0.4019 (2)	0.1026 (2)	0.0337 (6)
P1	0.22037 (8)	0.05933 (7)	−0.03628 (6)	0.0316 (2)
O1	0.2369 (2)	0.05876 (19)	−0.16615 (17)	0.0389 (5)
C13	0.2592 (3)	0.1605 (3)	−0.2253 (3)	0.0367 (7)
C14	0.2110 (4)	0.1279 (4)	−0.3396 (3)	0.0524 (9)
H14A	0.1611	0.0407	−0.3728	0.063*
C15	0.2355 (4)	0.2224 (4)	−0.4058 (3)	0.0641 (11)
H15A	0.2036	0.2013	−0.4849	0.077*
C16	0.3063 (4)	0.3466 (4)	−0.3558 (3)	0.0550 (10)
N16	0.3308 (5)	0.4477 (5)	−0.4273 (4)	0.0913 (13)
O7	0.3757 (7)	0.5550 (4)	−0.3818 (4)	0.170 (3)
O8	0.3009 (5)	0.4164 (4)	−0.5281 (3)	0.1309 (17)
C17	0.3520 (4)	0.3802 (4)	−0.2422 (4)	0.0604 (11)
H17A	0.3997	0.4677	−0.2096	0.073*
C18	0.3290 (4)	0.2867 (3)	−0.1749 (3)	0.0513 (9)
H18A	0.3604	0.3088	−0.0957	0.062*
O2	0.1566 (2)	0.1440 (2)	0.00081 (19)	0.0475 (6)
O3	0.3772 (2)	0.1192 (2)	0.01844 (17)	0.0394 (5)
C19	0.4243 (3)	0.1295 (3)	0.1326 (3)	0.0353 (7)
C20	0.5500 (3)	0.1308 (3)	0.1590 (3)	0.0457 (8)
H20A	0.6007	0.1262	0.1011	0.055*
C21	0.6022 (4)	0.1388 (4)	0.2709 (3)	0.0588 (10)
H21A	0.6886	0.1389	0.2912	0.071*
C22	0.5259 (4)	0.1467 (4)	0.3515 (3)	0.0588 (11)
N22	0.5809 (5)	0.1548 (4)	0.4712 (4)	0.0962 (15)
O5	0.5160 (5)	0.1678 (5)	0.5427 (3)	0.1358 (18)
O6	0.6864 (5)	0.1492 (6)	0.4928 (4)	0.162 (2)
C23	0.4017 (4)	0.1469 (4)	0.3269 (3)	0.0588 (10)
H23A	0.3518	0.1518	0.3854	0.071*
C24	0.3493 (4)	0.1397 (4)	0.2154 (3)	0.0497 (9)
H24A	0.2637	0.1416	0.1960	0.060*
O4	0.1626 (2)	−0.0768 (2)	−0.02068 (18)	0.0415 (5)
N25	−0.0143 (4)	0.2094 (3)	0.2799 (2)	0.0580 (9)
O9	0.0513 (2)	0.1724 (2)	0.20940 (18)	0.0436 (6)
O10	−0.0770 (3)	0.2699 (3)	0.2473 (3)	0.0767 (9)
O11	−0.0074 (4)	0.1804 (3)	0.3743 (2)	0.1007 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0381 (3)	0.0315 (3)	0.0266 (3)	0.0150 (2)	0.00322 (19)	0.01049 (18)
N1	0.0360 (14)	0.0341 (14)	0.0303 (14)	0.0160 (12)	0.0021 (11)	0.0103 (11)
C2	0.048 (2)	0.0409 (19)	0.0351 (18)	0.0146 (16)	−0.0023 (16)	0.0085 (15)
C3	0.058 (2)	0.056 (2)	0.0288 (18)	0.0182 (19)	−0.0041 (16)	0.0092 (16)
C4	0.058 (2)	0.059 (2)	0.0312 (18)	0.0314 (19)	0.0094 (16)	0.0188 (16)
C4A	0.098 (3)	0.077 (3)	0.034 (2)	0.037 (3)	0.005 (2)	0.0267 (19)
C5	0.055 (2)	0.0410 (19)	0.0368 (19)	0.0228 (17)	0.0111 (16)	0.0164 (15)
C6	0.0363 (17)	0.0381 (18)	0.0306 (16)	0.0224 (15)	0.0096 (13)	0.0125 (13)
C7	0.0354 (17)	0.0355 (17)	0.0325 (16)	0.0189 (14)	0.0095 (13)	0.0104 (13)
C8	0.045 (2)	0.0392 (19)	0.0423 (19)	0.0196 (16)	0.0156 (16)	0.0164 (15)
C9	0.0352 (18)	0.0350 (17)	0.047 (2)	0.0114 (15)	0.0109 (15)	0.0054 (15)
C9A	0.054 (2)	0.0375 (19)	0.064 (2)	0.0072 (17)	0.0162 (19)	0.0075 (17)
C10	0.044 (2)	0.045 (2)	0.0370 (18)	0.0080 (17)	0.0007 (15)	0.0015 (15)
C11	0.051 (2)	0.043 (2)	0.0301 (17)	0.0143 (17)	0.0035 (15)	0.0094 (15)
N12	0.0394 (15)	0.0334 (14)	0.0301 (14)	0.0161 (12)	0.0044 (11)	0.0093 (11)
P1	0.0320 (4)	0.0362 (4)	0.0285 (4)	0.0150 (4)	0.0043 (3)	0.0101 (3)
O1	0.0529 (14)	0.0360 (12)	0.0291 (11)	0.0182 (11)	0.0070 (10)	0.0101 (9)
C13	0.0359 (18)	0.0411 (19)	0.0369 (18)	0.0162 (15)	0.0100 (14)	0.0159 (14)
C14	0.069 (3)	0.049 (2)	0.0347 (19)	0.0184 (19)	0.0060 (17)	0.0131 (16)
C15	0.083 (3)	0.075 (3)	0.037 (2)	0.031 (2)	0.011 (2)	0.023 (2)
C16	0.061 (2)	0.060 (3)	0.054 (2)	0.027 (2)	0.0188 (19)	0.033 (2)
N16	0.114 (4)	0.078 (3)	0.085 (3)	0.030 (3)	0.026 (3)	0.053 (3)
O7	0.282 (7)	0.069 (3)	0.138 (4)	0.038 (4)	0.028 (4)	0.063 (3)
O8	0.177 (4)	0.129 (3)	0.079 (3)	0.040 (3)	0.021 (3)	0.071 (3)
C17	0.064 (3)	0.042 (2)	0.074 (3)	0.0177 (19)	0.010 (2)	0.0194 (19)
C18	0.063 (2)	0.043 (2)	0.044 (2)	0.0176 (18)	0.0051 (18)	0.0119 (16)
O2	0.0533 (15)	0.0620 (15)	0.0436 (13)	0.0381 (13)	0.0119 (11)	0.0152 (11)
O3	0.0307 (12)	0.0493 (13)	0.0347 (12)	0.0123 (10)	0.0045 (9)	0.0089 (10)
C19	0.0337 (18)	0.0312 (16)	0.0356 (18)	0.0095 (14)	−0.0004 (14)	0.0038 (13)
C20	0.0349 (19)	0.047 (2)	0.051 (2)	0.0130 (16)	0.0028 (16)	0.0099 (16)
C21	0.040 (2)	0.058 (2)	0.069 (3)	0.0133 (18)	−0.011 (2)	0.016 (2)
C22	0.059 (3)	0.054 (2)	0.039 (2)	0.005 (2)	−0.0166 (19)	0.0055 (17)
N22	0.088 (3)	0.105 (3)	0.054 (3)	0.006 (3)	−0.032 (2)	0.016 (2)
O5	0.144 (4)	0.188 (5)	0.040 (2)	0.040 (3)	−0.012 (2)	0.010 (2)
O6	0.098 (3)	0.255 (6)	0.095 (3)	0.043 (4)	−0.048 (3)	0.056 (3)
C23	0.061 (3)	0.074 (3)	0.033 (2)	0.023 (2)	0.0014 (18)	−0.0006 (18)
C24	0.048 (2)	0.062 (2)	0.0385 (19)	0.0249 (19)	−0.0003 (16)	0.0007 (17)
O4	0.0414 (13)	0.0391 (12)	0.0401 (12)	0.0113 (10)	0.0009 (10)	0.0171 (10)
N25	0.071 (2)	0.0431 (18)	0.0361 (18)	−0.0032 (17)	0.0148 (16)	0.0056 (14)
O9	0.0504 (14)	0.0495 (14)	0.0322 (12)	0.0202 (12)	0.0058 (11)	0.0149 (10)
O10	0.082 (2)	0.0611 (19)	0.098 (2)	0.0324 (17)	0.0453 (19)	0.0160 (17)
O11	0.132 (3)	0.091 (2)	0.0327 (16)	−0.005 (2)	0.0198 (17)	0.0101 (15)

Geometric parameters (Å, º)

Cu1—O9	1.961 (2)	P1—O1	1.598 (2)
Cu1—O4^i	1.975 (2)	P1—O3	1.608 (2)
Cu1—N1	1.976 (2)	O1—C13	1.392 (4)
Cu1—N12	2.011 (3)	C13—C14	1.376 (5)
Cu1—O2	2.149 (2)	C13—C18	1.381 (5)
N1—C2	1.341 (4)	C14—C15	1.379 (5)
N1—C6	1.344 (4)	C14—H14A	0.9500
C2—C3	1.374 (4)	C15—C16	1.362 (6)
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.378 (5)	C16—C17	1.364 (5)
C3—H3A	0.9500	C16—N16	1.482 (5)
C4—C5	1.384 (5)	N16—O7	1.178 (6)
C4—C4A	1.501 (4)	N16—O8	1.201 (5)
C4A—H4AA	0.9800	C17—C18	1.380 (5)
C4A—H4AB	0.9800	C17—H17A	0.9500
C4A—H4AC	0.9800	C18—H18A	0.9500
C5—C6	1.387 (4)	O3—C19	1.391 (4)
C5—H5A	0.9500	C19—C20	1.372 (4)
C6—C7	1.479 (4)	C19—C24	1.387 (5)
C7—N12	1.353 (4)	C20—C21	1.386 (5)
C7—C8	1.380 (4)	C20—H20A	0.9500
C8—C9	1.385 (5)	C21—C22	1.370 (6)
C8—H8A	0.9500	C21—H21A	0.9500
C9—C10	1.380 (5)	C22—C23	1.360 (6)
C9—C9A	1.503 (4)	C22—N22	1.480 (5)
C9A—H9AA	0.9800	N22—O6	1.185 (6)
C9A—H9AB	0.9800	N22—O5	1.211 (6)
C9A—H9AC	0.9800	C23—C24	1.384 (5)
C10—C11	1.371 (5)	C23—H23A	0.9500
C10—H10A	0.9500	C24—H24A	0.9500
C11—N12	1.348 (4)	O4—Cu1^i	1.975 (2)
C11—H11A	0.9500	N25—O10	1.220 (4)
P1—O2	1.466 (2)	N25—O11	1.224 (4)
P1—O4	1.486 (2)	N25—O9	1.311 (4)
O9—Cu1—O4^i	92.94 (9)	C7—N12—Cu1	114.6 (2)
O9—Cu1—O2	90.56 (9)	O2—P1—O4	119.96 (14)
O9—Cu1—N1	175.44 (10)	O2—P1—O1	111.88 (12)
O9—Cu1—N12	95.33 (10)	O4—P1—O1	106.35 (12)
O4^i—Cu1—O2	106.98 (9)	O2—P1—O3	110.80 (13)
O4^i—Cu1—N1	91.58 (9)	O4—P1—O3	107.31 (12)
O4^i—Cu1—N12	153.94 (10)	O1—P1—O3	98.25 (11)
N1—Cu1—O2	87.52 (9)	C13—O1—P1	126.6 (2)
N1—Cu1—N12	80.83 (10)	C14—C13—C18	121.2 (3)
N12—Cu1—O2	97.62 (10)	C14—C13—O1	115.8 (3)
C2—N1—C6	119.0 (3)	C18—C13—O1	123.0 (3)
C2—N1—Cu1	124.8 (2)	C13—C14—C15	119.6 (4)
C6—N1—Cu1	115.95 (19)	C13—C14—H14A	120.2
N1—C2—C3	121.8 (3)	C15—C14—H14A	120.2
N1—C2—H2A	119.1	C16—C15—C14	118.9 (4)
C3—C2—H2A	119.1	C16—C15—H15A	120.6
C2—C3—C4	120.4 (3)	C14—C15—H15A	120.6
C2—C3—H3A	119.8	C15—C16—C17	121.9 (3)
C4—C3—H3A	119.8	C15—C16—N16	118.6 (4)
C3—C4—C5	117.3 (3)	C17—C16—N16	119.5 (4)
C3—C4—C4A	122.0 (3)	O7—N16—O8	123.3 (4)
C5—C4—C4A	120.7 (3)	O7—N16—C16	118.0 (5)
C4—C4A—H4AA	109.5	O8—N16—C16	118.6 (5)
C4—C4A—H4AB	109.5	C16—C17—C18	119.9 (4)
H4AA—C4A—H4AB	109.5	C16—C17—H17A	120.0
C4—C4A—H4AC	109.5	C18—C17—H17A	120.0
H4AA—C4A—H4AC	109.5	C17—C18—C13	118.4 (3)
H4AB—C4A—H4AC	109.5	C17—C18—H18A	120.8
C4—C5—C6	120.3 (3)	C13—C18—H18A	120.8
C4—C5—H5A	119.8	P1—O2—Cu1	163.66 (16)
C6—C5—H5A	119.8	C19—O3—P1	123.85 (19)
N1—C6—C5	121.0 (3)	C20—C19—C24	121.7 (3)
N1—C6—C7	114.4 (2)	C20—C19—O3	116.4 (3)
C5—C6—C7	124.6 (3)	C24—C19—O3	121.9 (3)
N12—C7—C8	121.3 (3)	C19—C20—C21	119.4 (3)
N12—C7—C6	114.0 (3)	C19—C20—H20A	120.3
C8—C7—C6	124.8 (3)	C21—C20—H20A	120.3
C7—C8—C9	120.8 (3)	C22—C21—C20	118.1 (3)
C7—C8—H8A	119.6	C22—C21—H21A	120.9
C9—C8—H8A	119.6	C20—C21—H21A	120.9
C10—C9—C8	117.1 (3)	C23—C22—C21	123.2 (3)
C10—C9—C9A	121.8 (3)	C23—C22—N22	118.4 (4)
C8—C9—C9A	121.1 (3)	C21—C22—N22	118.4 (4)
C9—C9A—H9AA	109.5	O6—N22—O5	123.0 (5)
C9—C9A—H9AB	109.5	O6—N22—C22	118.8 (5)
H9AA—C9A—H9AB	109.5	O5—N22—C22	118.2 (5)
C9—C9A—H9AC	109.5	C22—C23—C24	119.0 (4)
H9AA—C9A—H9AC	109.5	C22—C23—H23A	120.5
H9AB—C9A—H9AC	109.5	C24—C23—H23A	120.5
C11—C10—C9	120.3 (3)	C23—C24—C19	118.5 (3)
C11—C10—H10A	119.9	C23—C24—H24A	120.7
C9—C10—H10A	119.9	C19—C24—H24A	120.7
N12—C11—C10	122.5 (3)	P1—O4—Cu1^i	134.24 (13)
N12—C11—H11A	118.8	O10—N25—O11	124.8 (4)
C10—C11—H11A	118.8	O10—N25—O9	118.2 (3)
C11—N12—C7	118.0 (3)	O11—N25—O9	117.1 (4)
C11—N12—Cu1	127.3 (2)	N25—O9—Cu1	111.2 (2)

Symmetry code: (i) −x, −y, −z.