Poly[tetra­phenyl­phospho­nium copper(I)-di-[mu]₂-dicyanamido]

In the title compound, {(C₂₄H₂₀P)[Cu(C₂N₃)₂]}_n, the copper(I) dicyanamide anion forms a distorted three-dimensional single diamondoid network. Templating tetra­phenyl­phospho­nium cations reside within the cavities of the polymeric anion.

S1. Comment

The dicyanamide pseudohalide anion [N(CN)₂^-, hereinafter abbreviated dca] has become a component of a growing number of coordination polymers because its large variety of bonding modes enables the formation of a wide range of structural types (Miller & Manson, 2001; Batten & Murray, 2003; Manson, 2005). With divalent first row transition elements, neutral binary M(dca)₂ complexes with rutile-like structures form, in which the dca anion is coordinated in a µ_1,3,5 fashion. Long-range magnetic order is observed in the cobalt and nickel compounds, which order ferromagnetically (Manson et al., 1998; Kurmoo & Kepert, 1998), while the vanadium, chromium, manganese and iron analogs possess antiferromagnetic ground states (Kurmoo & Kepert, 1998; Manson et al., 1999, 2001; Kmety et al., 2000; Batten et al., 1999). The isostructural Cu(dca)₂ complex is paramagnetic to temperatures as low as 2 K (Kurmoo & Kepert, 1998, 1999).

There has recently been a rapid increase in the study of anionic dca complexes in which the use of diverse cationic templates has led to an increasing variety of structural types with various dimensionalities. Various trans and cis µ_1,5-dibridged chains have been reported (Raebiger et al., 2001; Jager et al., 2001; Wang et al., 2002). Ladder-type structures represent an intermediate motif between one- and two-dimensional systems (van der Werff, Batten, Jensen, Moubaraki, Murray & Tan, 2001; Wang et al., 2003). Three two-dimensional anionic structural types are known, namely square (Raebiger et al., 2001; van der Werff, Batten, Jensen, Moubaraki & Murray, 2001; van der Werff, Batten, Jensen, Moubaraki, Murray & Tan, 2001; Biswas et al., 2006), hexagonal honeycombs (Batten et al., 2000) and triangular (Schlueter, Geiser & Manson, 2004) Three-dimensional topologies with cubelike (Tong et al., 2003; Schlueter, Manson et al., 2004; Schlueter et al., 2005; van der Werff et al., 2005), triple rutile (Schlueter et al., 2005; van der Werff, Batten, Jensen, Moubaraki & Murray, 2001; van der Werff et al., 2004) and lithium antimonate (Schlueter et al., 2005) packing motifs have also been identified. These various structural types differ in the ratio and arrangement of single and double dca bridges. The vast majority of these complexes contain divalent first row transition elements.

Anionic copper dicyanamide complexes are relatively unknown, but we have recently reported the first three structures that contain anionic copper(II) dicyanamide coordination polymers. The (PPh₄)₃[Cu₄(dca)₁₁] salt possesses a novel triple ladder structure, in which the rungs are comprised of single µ_1,5-dca bridges while the sides are constructed of double µ_1,5-dca bridges (Schlueter, Manson & Geiser, 2006). We have also found that the (PPh₄)Cu(dca)₃H₂O salt contains singly bridged µ_1,5-dca chains that are linked into a two-dimensional network through coordinated water molecules (Schlueter, Manson et al., 2006). Replacement of one of the cation phenyl groups with a butyl group results in the formation of the (PPh₃Bu)₂Cu(dca)₄ salt, which contains doubly-bridged µ_1,5-dca chains (Schlueter, Manson et al., 2006). Only two examples of anionic copper(I) dca salts have been reported to date, namely the [Rb(18-crown-6)]₃Cu₂(dca)₅ salt, which contains both tetrahedrally and triangularly coordinated Cu, forming complex one-dimensional chains (Reference?), while [Tl(18-crown-6)]Cu(dca)₂ contains only tetrahedrally coordinated Cu linked through single µ_1,5-dca bridges into two-dimensional polymeric sheets (Manskaya et al., 1999). Here, we report the first example of a three-dimensional copper(I) dicyanamide network, PPh₄Cu(dca)₂, (I). This salt has been used as a precursor (Wang et al., 1990, 1992) for the electrochemical synthesis of the superconducting charge-transfer salts (BEDT-TTF)₂Cu(dca)X (X is Br or Cl; BEDT-TTF is ? [Please define]) (Williams et al., 1990; Kini et al., 1990). In order to control the electrocrystallization process better, it is necessary to understand more fully the structure of the anionic network in electrolyte precursors.

The atom-numbering scheme of the tetraphenylphosphonium cation and the copper(I) dicyanamide anion of (I) are illustrated in Fig. 1. The geometry of the dca anions in the PPh₄Cu(dca)₂ structure is typical. The nitrile C≡ N bond lengths range from 1.148 (4) to 1.157 (4) Å, the amide N—C bond lengths range from 1.299 (4) to 1.320 (4) Å, the C—N—C bond angles are 120.1 (2) and 123.3 (3)° and the N≡C—N bond angles range from 172.9 (3) to 174.3 (3)°. The displacement ellipsoids of the amide N atoms are elongated, indicating a rocking thermal motion of the dca anion. The coordination about the Cu^I center is distorted tetrahedral, with the N—Cu—N bond angles ranging from 100.5 (1) to 119.0 (1)°. Two of the Cu—N bond lengths are slightly shorter (0.07 Å) than the other two. A polymeric network is formed by two sets of copper dicyanamide chains; one runs along the a axis, while the other runs along the b axis. These zigzag chains wind around 2₁ screw axes. The chain along the a axis has N—Cu—N bond angles of 111.0 (1)°, while for the b axis chain this angle is 110.6 (1)°. As illustrated in Fig. 2, each Cu atom is joined to four equivalent ones through dca linkages, resulting in Cu···Cu separations of 7.9641 (7) and 8.1075 (7) Å, thus forming a highly distorted single diamondoid net.

As seen in Fig. 1, the molecular structure of the tetraphenylphosphonium cation that templates the anionic pores is typical of that commonly described in the literature. The P—C bond lengths range from 1.795 (3) to 1.804 (3) Å with C—P—C bond angles slightly distorted from tetrahedral, ranging from 108.3 (1) to 110.8 (1)°. The C—C distances within the aromatic rings range from 1.375 (4) to 1.396 (4) Å and the C—C—C bond angles range from 119.2 (2) to 120.6 (3)°.

As illustrated in Fig. 3, zigzag chains of PPh₄⁺ cations form along the b axis, with P···P separations of 7.2621 (7) Å. These chains are stabilized through multiple phenyl embraces of both the offset-face-to-face (off) and edge-to-face (ef) types. The most prominent off interaction is between phenyl rings defined by atoms C1–C6 and C13–C18, respectively. The centroid-to-centroid distance between these rings is 4.4080 Å, with a dihedral angle of 15.51° between their respective planes, confirming the presence of π–π interactions (Spek, 2003). The most significant ef interaction is between atom H10 and the phenyl ring defined by atoms C1–C6. The associated H-to-centroid distance is 3.28 Å. This type of concerted supramolecular motif is not one of the modes commonly observed for tetraphenylphosphonium salts (Dance & Scudder, 1996; Scudder & Dance, 1998a,b).

We conclude that, although the three-dimensional Cu(dca)₂^- lattice of the PPh₄⁺ salt breaks down in solution prior to electrocrystallization of (BEDT-TTF)₂Cu(dca)X (X is Br and Cl), the one-dimensional zigzag anionic chain structure is retained in these BEDT-TTF salts. The presence of coordinating Br^- or Cl^- anions and the two-dimensional templating effect of the (BEDT-TTF)₂⁺ cations likely cause the anionic structural transformation.

Related literature

For related literature, see: Batten & Murray (2003); Batten et al. (1999, 2000); Biswas et al. (2006); Dance & Scudder (1996); Jager et al. (2001); Kini et al. (1990); Kmety et al. (2000); Kurmoo & Kepert (1998, 1999); Manskaya et al. (1999); Manson (2005); Manson et al. (1998, 1999, 2001); Miller & Manson (2001); Raebiger et al. (2001); Schlueter et al. (2005); Schlueter, Geiser & Manson (2004); Schlueter, Manson & Geiser (2006); Schlueter, Manson, Hyzer & Geiser (2004, 2006); Scudder & Dance (1998a, 1998b); Spek (2003); Tong et al. (2003); Wang et al. (1990, 1992, 2002, 2003); Werff et al. (2004, 2005); Werff, Batten, Jensen, Moubaraki & Murray (2001); Werff, Batten, Jensen, Moubaraki, Murray & Tan (2001); Williams et al. (1990).

S2. Experimental

Tetraphenylphosphonium copper(I) dicyanamide was prepared according to the literature procedure of Wang et al. (1990). An acetonitrile solution containing CuBr and two equivalents of PPh₄(dca) was refluxed for 16 h. Upon slow cooling, crystals of PPh₄Cu(dca)₂ formed.

S3. Refinement

H atoms on aromatic C atoms were positioned geometrically, with C—H = 0.95 Å, and refined with a riding model, with U_iso(H) = 1.2U_eq(C). [Please check added text]

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003).

Figures

	Fig. 1. The atom-numbering schemes of (a) a unique fragment of the Cu(dca)2^- anion and (b) the molecular structure of the tetraphenylphosphonium cation (different absolute scales). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. An adamantane-type fragment of the polymeric Cu(dca)2^- anion. Twelve dca^- anions and ten Cu^I ions that construct a single cage are illustrated, along with the nitrile N atoms that complete the distorted tetrahedral coordination of the Cu atoms.
	Fig. 3. The PPh4^+ cationic chain running along the b axis. P···P separations are 7.2621 (7) Å. Aromatic interactions of the offset-face-to-face (off) and edge-to-face (ef) types are illustrated with dashed lines. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as spheres of arbitrary radii.

Poly[tetraphenylphosphonium copper(I)-di-µ₂-dicyanamido]

Crystal data

(C24H20P)[Cu(C2N3)2]	Dx = 1.431 Mg m^−3
Mr = 535.01	Melting point: 433 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1784 reflections
a = 12.7929 (12) Å	θ = 2.6–26.2°
b = 13.4006 (12) Å	µ = 0.97 mm^−1
c = 14.4847 (14) Å	T = 150 K
V = 2483.1 (4) Å^3	Rod, colorless
Z = 4	0.40 × 0.06 × 0.06 mm
F(000) = 1096

Data collection

Siemens SMART CCD area-detector diffractometer	5978 independent reflections
Radiation source: fine-focus sealed tube	4855 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ω scans	θmax = 28.3°, θmin = 2.1°
Absorption correction: integration (SHELXTL; Sheldrick, 2001)	h = −16→16
Tmin = 0.787, Tmax = 0.951	k = −17→17
21614 measured reflections	l = −18→19

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)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0308P)^2 + 0.4799P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.022
5978 reflections	Δρmax = 0.89 e Å^−3
325 parameters	Δρmin = −0.63 e Å^−3
0 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.061 (12)

Special details

Experimental. The data collection nominally covered over a hemisphere of reciprocal space by a combination of four sets of exposures; each set had a different φ angle for the crystal and each exposure covered 0.3° in ω. The crystal-to-detector distance was 4.974 cm. Coverage of the unique set was 100% complete to at least 26.3° in θ, 98.3% complete to at least 28.2° in θ.

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
P1	0.54674 (5)	0.59794 (5)	0.66257 (4)	0.02235 (13)
C1	0.4177 (2)	0.62583 (18)	0.70553 (18)	0.0239 (6)
C2	0.3308 (2)	0.5742 (2)	0.67337 (18)	0.0287 (6)
H2	0.3387	0.5240	0.6276	0.034*
C3	0.2326 (2)	0.5960 (2)	0.70824 (18)	0.0315 (6)
H3	0.1730	0.5614	0.6858	0.038*
C4	0.2215 (2)	0.6679 (2)	0.7755 (2)	0.0331 (7)
H4	0.1541	0.6831	0.7992	0.040*
C5	0.3084 (2)	0.7179 (2)	0.8087 (2)	0.0391 (7)
H5	0.3004	0.7665	0.8559	0.047*
C6	0.4065 (2)	0.6978 (2)	0.7738 (2)	0.0359 (7)
H6	0.4658	0.7329	0.7963	0.043*
C7	0.6150 (2)	0.71322 (18)	0.64187 (18)	0.0246 (6)
C8	0.6701 (2)	0.7571 (2)	0.71444 (18)	0.0300 (6)
H8	0.6777	0.7228	0.7714	0.036*
C9	0.7136 (2)	0.8511 (2)	0.7029 (2)	0.0330 (7)
H9	0.7513	0.8812	0.7521	0.040*
C10	0.7024 (2)	0.9008 (2)	0.62045 (19)	0.0329 (6)
H10	0.7312	0.9656	0.6133	0.039*
C11	0.6493 (2)	0.8568 (2)	0.5479 (2)	0.0345 (7)
H11	0.6431	0.8910	0.4907	0.041*
C12	0.6051 (2)	0.7633 (2)	0.55822 (19)	0.0300 (6)
H12	0.5682	0.7335	0.5085	0.036*
C13	0.6184 (2)	0.5281 (2)	0.74723 (18)	0.0267 (6)
C14	0.7242 (2)	0.5086 (2)	0.73136 (19)	0.0309 (6)
H14	0.7578	0.5356	0.6785	0.037*
C15	0.7796 (2)	0.4504 (2)	0.7924 (2)	0.0389 (7)
H15	0.8510	0.4354	0.7810	0.047*
C16	0.7304 (3)	0.4138 (3)	0.8707 (2)	0.0481 (9)
H16	0.7687	0.3742	0.9134	0.058*
C17	0.6266 (3)	0.4343 (3)	0.8873 (2)	0.0490 (9)
H17	0.5940	0.4095	0.9416	0.059*
C18	0.5696 (2)	0.4910 (2)	0.82533 (19)	0.0369 (7)
H18	0.4977	0.5043	0.8362	0.044*
C19	0.5363 (2)	0.52615 (18)	0.55795 (17)	0.0237 (6)
C20	0.5928 (2)	0.4376 (2)	0.5492 (2)	0.0352 (7)
H20	0.6356	0.4151	0.5986	0.042*
C21	0.5864 (3)	0.3824 (2)	0.4684 (2)	0.0433 (8)
H21	0.6239	0.3215	0.4628	0.052*
C22	0.5257 (2)	0.4161 (2)	0.39650 (19)	0.0348 (7)
H22	0.5227	0.3791	0.3407	0.042*
C23	0.4692 (2)	0.50331 (19)	0.40480 (18)	0.0287 (6)
H23	0.4268	0.5254	0.3549	0.034*
C24	0.4737 (2)	0.55907 (19)	0.48554 (17)	0.0252 (6)
H24	0.4345	0.6190	0.4912	0.030*
Cu1	0.50274 (3)	0.09989 (2)	0.39858 (2)	0.03329 (10)
N31	0.5245 (2)	0.17433 (17)	0.27500 (16)	0.0360 (6)
N32	0.5541 (3)	0.27550 (19)	0.13528 (16)	0.0472 (7)
N33	0.53432 (19)	0.45741 (18)	0.12412 (16)	0.0353 (6)
N34	0.4065 (2)	0.1838 (2)	0.4730 (2)	0.0519 (8)
N35	0.3303 (2)	0.3264 (3)	0.5561 (2)	0.0594 (9)
N36	0.1536 (2)	0.3955 (2)	0.54821 (18)	0.0477 (7)
C31	0.5369 (2)	0.2252 (2)	0.2121 (2)	0.0321 (6)
C33	0.5425 (2)	0.3722 (2)	0.13384 (17)	0.0302 (6)
C34	0.3659 (2)	0.2495 (3)	0.5103 (2)	0.0391 (7)
C36	0.2353 (3)	0.3595 (2)	0.54799 (19)	0.0336 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0207 (3)	0.0234 (3)	0.0230 (3)	−0.0017 (3)	−0.0017 (3)	−0.0009 (3)
C1	0.0203 (14)	0.0261 (14)	0.0252 (13)	0.0018 (10)	0.0022 (11)	−0.0016 (11)
C2	0.0265 (14)	0.0322 (15)	0.0273 (13)	−0.0028 (11)	0.0005 (12)	−0.0016 (11)
C3	0.0235 (14)	0.0404 (15)	0.0305 (13)	−0.0052 (14)	−0.0025 (11)	0.0038 (14)
C4	0.0271 (16)	0.0316 (15)	0.0406 (16)	0.0050 (13)	0.0055 (13)	0.0069 (13)
C5	0.0385 (18)	0.0293 (16)	0.0494 (18)	−0.0022 (13)	0.0128 (15)	−0.0139 (13)
C6	0.0297 (17)	0.0340 (16)	0.0439 (18)	−0.0079 (13)	0.0022 (14)	−0.0116 (14)
C7	0.0216 (14)	0.0232 (13)	0.0290 (14)	−0.0031 (11)	0.0023 (11)	−0.0045 (11)
C8	0.0315 (16)	0.0307 (15)	0.0278 (13)	−0.0033 (12)	−0.0030 (12)	−0.0016 (12)
C9	0.0300 (16)	0.0341 (16)	0.0348 (15)	−0.0074 (13)	−0.0055 (13)	−0.0084 (13)
C10	0.0245 (14)	0.0288 (13)	0.0455 (16)	−0.0062 (14)	0.0007 (12)	0.0023 (14)
C11	0.0347 (17)	0.0352 (16)	0.0337 (15)	−0.0090 (13)	0.0007 (13)	0.0049 (13)
C12	0.0294 (16)	0.0340 (15)	0.0267 (14)	−0.0053 (13)	−0.0004 (12)	0.0002 (12)
C13	0.0223 (15)	0.0309 (15)	0.0270 (14)	−0.0019 (12)	−0.0029 (11)	−0.0019 (11)
C14	0.0251 (16)	0.0373 (16)	0.0304 (14)	−0.0023 (13)	0.0008 (12)	−0.0013 (12)
C15	0.0272 (17)	0.0468 (19)	0.0427 (17)	0.0023 (14)	−0.0107 (14)	−0.0026 (14)
C16	0.045 (2)	0.061 (2)	0.0384 (17)	0.0021 (19)	−0.0170 (15)	0.0109 (16)
C17	0.048 (2)	0.070 (2)	0.0287 (17)	0.0017 (18)	−0.0013 (15)	0.0156 (15)
C18	0.0288 (16)	0.0529 (19)	0.0289 (15)	0.0004 (14)	0.0012 (13)	0.0048 (14)
C19	0.0254 (15)	0.0206 (12)	0.0252 (12)	−0.0030 (11)	0.0015 (11)	−0.0044 (10)
C20	0.0410 (18)	0.0258 (13)	0.0387 (17)	0.0084 (13)	−0.0126 (15)	−0.0043 (12)
C21	0.0452 (19)	0.0306 (16)	0.0542 (19)	0.0128 (14)	−0.0090 (15)	−0.0142 (14)
C22	0.0368 (18)	0.0341 (15)	0.0334 (14)	−0.0050 (12)	0.0040 (13)	−0.0130 (12)
C23	0.0294 (16)	0.0318 (13)	0.0249 (13)	−0.0062 (11)	−0.0002 (12)	0.0022 (11)
C24	0.0248 (16)	0.0225 (12)	0.0283 (13)	−0.0023 (10)	−0.0012 (11)	−0.0013 (10)
Cu1	0.02837 (17)	0.02200 (14)	0.0495 (2)	0.00307 (18)	0.00123 (18)	−0.00661 (15)
N31	0.0413 (18)	0.0307 (13)	0.0361 (13)	0.0031 (11)	0.0048 (11)	−0.0019 (10)
N32	0.079 (2)	0.0343 (13)	0.0285 (13)	0.0154 (15)	0.0033 (14)	−0.0008 (11)
N33	0.0323 (15)	0.0364 (13)	0.0371 (13)	−0.0049 (11)	−0.0034 (10)	0.0050 (11)
N34	0.0479 (18)	0.0366 (15)	0.071 (2)	0.0035 (14)	0.0127 (16)	0.0025 (15)
N35	0.0357 (17)	0.084 (2)	0.0585 (18)	0.0054 (16)	0.0031 (15)	−0.0369 (17)
N36	0.0511 (18)	0.0406 (15)	0.0515 (16)	0.0061 (15)	0.0046 (13)	−0.0151 (14)
C31	0.0346 (17)	0.0254 (14)	0.0363 (15)	0.0059 (12)	−0.0043 (13)	−0.0063 (12)
C33	0.0293 (15)	0.0398 (16)	0.0215 (12)	0.0010 (13)	−0.0045 (12)	−0.0003 (11)
C34	0.0346 (18)	0.0452 (19)	0.0376 (16)	0.0026 (15)	0.0049 (14)	0.0037 (15)
C36	0.042 (2)	0.0273 (14)	0.0316 (16)	−0.0087 (14)	0.0090 (15)	−0.0084 (12)

Geometric parameters (Å, º)

P1—C13	1.795 (3)	C15—C16	1.387 (4)
P1—C7	1.800 (3)	C15—H15	0.9500
P1—C19	1.800 (3)	C16—C17	1.377 (5)
P1—C1	1.804 (3)	C16—H16	0.9500
C1—C6	1.390 (4)	C17—C18	1.383 (4)
C1—C2	1.390 (4)	C17—H17	0.9500
C2—C3	1.385 (4)	C18—H18	0.9500
C2—H2	0.9500	C19—C24	1.392 (4)
C3—C4	1.378 (4)	C19—C20	1.395 (4)
C3—H3	0.9500	C20—C21	1.386 (4)
C4—C5	1.384 (4)	C20—H20	0.9500
C4—H4	0.9500	C21—C22	1.376 (4)
C5—C6	1.380 (4)	C21—H21	0.9500
C5—H5	0.9500	C22—C23	1.379 (4)
C6—H6	0.9500	C22—H22	0.9500
C7—C12	1.391 (4)	C23—C24	1.389 (4)
C7—C8	1.395 (4)	C23—H23	0.9500
C8—C9	1.387 (4)	C24—H24	0.9500
C8—H8	0.9500	Cu1—N34	1.985 (3)
C9—C10	1.375 (4)	Cu1—N33^i	1.995 (2)
C9—H9	0.9500	Cu1—N31	2.068 (2)
C10—C11	1.383 (4)	Cu1—N36^ii	2.080 (3)
C10—H10	0.9500	N31—C31	1.148 (4)
C11—C12	1.383 (4)	N32—C33	1.304 (4)
C11—H11	0.9500	N32—C31	1.320 (4)
C12—H12	0.9500	N33—C33	1.156 (3)
C13—C18	1.384 (4)	N34—C34	1.157 (4)
C13—C14	1.396 (4)	N35—C36	1.299 (4)
C14—C15	1.376 (4)	N35—C34	1.307 (4)
C14—H14	0.9500	N36—C36	1.151 (4)
C13—P1—C7	108.28 (13)	C13—C14—H14	120.0
C13—P1—C19	109.53 (12)	C14—C15—C16	119.5 (3)
C7—P1—C19	110.77 (12)	C14—C15—H15	120.3
C13—P1—C1	109.89 (12)	C16—C15—H15	120.3
C7—P1—C1	108.89 (12)	C17—C16—C15	120.6 (3)
C19—P1—C1	109.46 (12)	C17—C16—H16	119.7
C6—C1—C2	120.1 (2)	C15—C16—H16	119.7
C6—C1—P1	118.9 (2)	C16—C17—C18	120.3 (3)
C2—C1—P1	120.9 (2)	C16—C17—H17	119.9
C3—C2—C1	119.9 (3)	C18—C17—H17	119.9
C3—C2—H2	120.1	C17—C18—C13	119.3 (3)
C1—C2—H2	120.1	C17—C18—H18	120.3
C4—C3—C2	119.9 (3)	C13—C18—H18	120.3
C4—C3—H3	120.0	C24—C19—C20	120.0 (2)
C2—C3—H3	120.0	C24—C19—P1	120.53 (19)
C3—C4—C5	120.1 (3)	C20—C19—P1	119.5 (2)
C3—C4—H4	119.9	C21—C20—C19	120.0 (3)
C5—C4—H4	119.9	C21—C20—H20	120.0
C6—C5—C4	120.6 (3)	C19—C20—H20	120.0
C6—C5—H5	119.7	C22—C21—C20	119.8 (3)
C4—C5—H5	119.7	C22—C21—H21	120.1
C5—C6—C1	119.3 (3)	C20—C21—H21	120.1
C5—C6—H6	120.3	C21—C22—C23	120.5 (3)
C1—C6—H6	120.3	C21—C22—H22	119.7
C12—C7—C8	119.9 (2)	C23—C22—H22	119.7
C12—C7—P1	121.0 (2)	C22—C23—C24	120.5 (2)
C8—C7—P1	118.8 (2)	C22—C23—H23	119.8
C9—C8—C7	119.7 (3)	C24—C23—H23	119.8
C9—C8—H8	120.2	C23—C24—C19	119.2 (2)
C7—C8—H8	120.2	C23—C24—H24	120.4
C10—C9—C8	120.1 (3)	C19—C24—H24	120.4
C10—C9—H9	119.9	N34—Cu1—N33^i	118.95 (11)
C8—C9—H9	119.9	N34—Cu1—N31	106.27 (11)
C9—C10—C11	120.4 (3)	N33^i—Cu1—N31	110.54 (10)
C9—C10—H10	119.8	N34—Cu1—N36^ii	110.96 (12)
C11—C10—H10	119.8	N33^i—Cu1—N36^ii	108.09 (11)
C12—C11—C10	120.3 (3)	N31—Cu1—N36^ii	100.46 (11)
C12—C11—H11	119.9	C31—N31—Cu1	172.4 (2)
C10—C11—H11	119.9	C33—N32—C31	120.2 (2)
C11—C12—C7	119.6 (3)	C33—N33—Cu1^iii	171.0 (3)
C11—C12—H12	120.2	C34—N34—Cu1	164.4 (3)
C7—C12—H12	120.2	C36—N35—C34	123.3 (3)
C18—C13—C14	120.3 (3)	C36—N36—Cu1^iv	148.9 (3)
C18—C13—P1	121.0 (2)	N31—C31—N32	174.2 (3)
C14—C13—P1	118.7 (2)	N33—C33—N32	173.8 (3)
C15—C14—C13	119.9 (3)	N34—C34—N35	173.7 (4)
C15—C14—H14	120.0	N36—C36—N35	172.9 (3)
C13—P1—C1—C6	73.3 (3)	C7—P1—C13—C18	128.1 (2)
C7—P1—C1—C6	−45.1 (3)	C19—P1—C13—C18	−111.1 (2)
C19—P1—C1—C6	−166.4 (2)	C1—P1—C13—C18	9.2 (3)
C13—P1—C1—C2	−104.6 (2)	C7—P1—C13—C14	−54.2 (3)
C7—P1—C1—C2	137.0 (2)	C19—P1—C13—C14	66.7 (2)
C19—P1—C1—C2	15.7 (3)	C1—P1—C13—C14	−173.0 (2)
C6—C1—C2—C3	1.3 (4)	C18—C13—C14—C15	1.5 (4)
P1—C1—C2—C3	179.2 (2)	P1—C13—C14—C15	−176.3 (2)
C1—C2—C3—C4	−0.8 (4)	C13—C14—C15—C16	−1.8 (4)
C2—C3—C4—C5	−0.4 (4)	C14—C15—C16—C17	0.7 (5)
C3—C4—C5—C6	1.2 (5)	C15—C16—C17—C18	0.7 (5)
C4—C5—C6—C1	−0.7 (5)	C16—C17—C18—C13	−1.0 (5)
C2—C1—C6—C5	−0.5 (4)	C14—C13—C18—C17	−0.1 (4)
P1—C1—C6—C5	−178.4 (2)	P1—C13—C18—C17	177.6 (2)
C13—P1—C7—C12	154.1 (2)	C13—P1—C19—C24	172.4 (2)
C19—P1—C7—C12	33.9 (3)	C7—P1—C19—C24	−68.2 (2)
C1—P1—C7—C12	−86.5 (2)	C1—P1—C19—C24	51.8 (2)
C13—P1—C7—C8	−32.3 (3)	C13—P1—C19—C20	−8.6 (3)
C19—P1—C7—C8	−152.4 (2)	C7—P1—C19—C20	110.8 (2)
C1—P1—C7—C8	87.2 (2)	C1—P1—C19—C20	−129.1 (2)
C12—C7—C8—C9	0.7 (4)	C24—C19—C20—C21	−0.1 (4)
P1—C7—C8—C9	−173.0 (2)	P1—C19—C20—C21	−179.1 (2)
C7—C8—C9—C10	0.1 (4)	C19—C20—C21—C22	1.1 (5)
C8—C9—C10—C11	−1.2 (4)	C20—C21—C22—C23	−1.5 (5)
C9—C10—C11—C12	1.3 (4)	C21—C22—C23—C24	0.8 (4)
C10—C11—C12—C7	−0.5 (4)	C22—C23—C24—C19	0.2 (4)
C8—C7—C12—C11	−0.5 (4)	C20—C19—C24—C23	−0.6 (4)
P1—C7—C12—C11	173.1 (2)	P1—C19—C24—C23	178.43 (19)

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