Iodidotris(triphenyl­phosphine)copper(I) acetonitrile solvate

The title compound, [CuI(C₁₈H₁₅P)₃]·C₂H₃N, was obtained from the reaction of triphenyl­phosphine and copper(I) iodide in acetonitrile. The monomeric form of the complex has slightly distorted coordination of Cu by the I atom and three P atoms. The crystal structure is stabilized by C—H...π inter­actions between phenyl H atoms and phenyl rings. In addition, the complex mol­ecules exhibit C—H...N hydrogen bonds between phenyl H atoms and acetonitrile N atoms. The crystal used was an inversion twin, with nearly equal component populations of 0.522 (8) and 0.478 (8).

Key indicators

• Single-crystal X-ray study
• T = 115 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.033
• wR factor = 0.068
• Data-to-parameter ratio = 28.5

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  I      -   Cu      ..      17.49 su

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.478
           From the CIF: _refine_ls_abs_structure_Flack_su    0.008
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C1S

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           31.84
           From the CIF: _reflns_number_total              15969
           Count of symmetry unique reflns         8559
           Completeness (_total/calc)            186.58%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      7410
           Fraction of Friedel pairs measured     0.866
           Are heavy atom types Z>Si present        yes
PLAT033_ALERT_2_G Flack Parameter Value Deviates from zero .......       0.48
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Organophosphinecopper (I) halides have widely investigated system due to the formation of varying types of crystal structures (Caulton et al., 1990). Eller et al. (1977) used the organophosphinecopper (I) systems for the direct Cu–SO₂ adduct formation. Recently Hanna et al. (2005) reported the structural and solid state NMR studies of the four coordinate copper (I) complexes with different cations except iodide. During our study on the interaction of heterocyclic thiosemicarbazones with copper (I) halides, we were able to isolate the title compound (1), Venkatraman et al., (2006).

The structure consists of CuI(PPh₃)₃ unit similar to the structure described by Eller et al. (1977) for CuI(PPh₂Me)₃. The asymmetric unit of (1) contains one formula unit of the complex with no crystallographically imposed symmetry (Fig.1), and one acetonitrile solvent molecule. The Cu atom is surrounded by three phosphorus atoms and the iodide atom in a distorted tetrahedral geometry. The three independent Cu—P distances are not grossly different (2.3421 (6), 2.3463 (6), and 2.3295 (7) Å) for P1, P2, and P3, respectively, and the Cu—I distance is 2.6843 (3) Å. The Cu—P bond lengths in compound (1) are similar to values recorded for a range of other [Cu-(PPh3)₃X] complexes [Bowmaker et al., (2000)]. The three P—Cu—I angles are 104.75 (2), 113.66 (2), and 97.69 (2)°, for P1, P2, and P3, respectively, [average 105.2°], and sums to 316.0°. The wide range of P—Cu—P/I angles indicate an irregular tetrahedral structure.

The molecular packing (Fig. 2) is stabilized by CH₂—H···π interactions between the hydrogen of phenyl group and the phenyl ring, with C9—H9···Cg1ⁱ and C40—H40···Cg2ⁱ separations of 2.94 Å (Fig. 2 & Table 1) (Cg1 and Cg2 are the centroids of C1—C6 and C7—C12 phenyl rings, respectively). Further stability comes from weak C—H···N1Sⁱⁱ hydrogen bond in Fig. 2 and Table 1. A l l symmetry codes as in Table 1.

Related literature

For the details of crystal structure of organophosphinecopper(I) halide derivatives, see: Caulton et al., (1990); Bowmaker et al., (2000); Eller et al. (1977); Hamel et al. (2002); Hanna et al. (2005); Venkatraman et al., (2006); Barron et al. (1987); Kräuter & Newmüller (1996).

S2. Experimental

To a solution of copper (I) iodide (Aldrich; 0.190 g, 1 mmol) in acetonitrile (Aldrich; 50 ml) was added solid triphenylphosphine (Aldrich; 0.262 g, 2 mmol) in presence 0.5 ml HCl. The resulting mixture was stirred overnight. The clear solution was filtered and allowed to evaporate at room temperature in the presence of air. A colorless crystalline product suitable for X-ray diffraction was formed (yield ca 70%).

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å for aromatic H atoms and 0.98 Å for methyl H atoms, respectively, and with U_iso(H) = 1.2Ueq(C) for aromatic H atoms and U_iso(H) = 1.5Ueq(C) for methyl H atoms. A torsional parameter was refined for the methyl group. Refinement of the Flack (1983) parameter, using 7443 Friedel pairs indicated that the crystal used was an inversion twin with approximately equal components.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. Numbering scheme and ellipsoids at the 50% level. H atoms are not shown.
	Fig. 2. C—H···N and C—H···π interactions. Geometric parameters and symmetry operations are given in the Table 1.

Iodidotris(triphenylphosphine)copper(I) acetonitrile solvate

Crystal data

[CuI(C18H15P)3]·C2H3N	F(000) = 2072
Mr = 1018.30	Dx = 1.406 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 8935 reflections
a = 18.573 (1) Å	θ = 2.5–31.8°
b = 20.263 (1) Å	µ = 1.23 mm^−1
c = 12.7839 (5) Å	T = 115 K
V = 4811.2 (4) Å^3	Fragment, colorless
Z = 4	0.30 × 0.25 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer (with an Oxford Cryosystems Cryostream cooler)	15969 independent reflections
Radiation source: fine-focus sealed tube	13488 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.000
ω scans with κ offsets	θmax = 31.8°, θmin = 2.8°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −27→27
Tmin = 0.709, Tmax = 0.818	k = −29→30
156685 measured reflections	l = −18→18

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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.068	w = 1/[σ^2(Fo^2) + (0.0253P)^2 + 3.4731P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
15969 reflections	Δρmax = 0.62 e Å^−3
561 parameters	Δρmin = −0.66 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.478 (8)

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
I	0.217564 (7)	0.266851 (6)	0.441186 (16)	0.02077 (3)
Cu	0.240945 (12)	0.397554 (11)	0.44517 (3)	0.01359 (5)
P1	0.13455 (3)	0.44254 (3)	0.51291 (5)	0.01432 (10)
P2	0.33677 (3)	0.42893 (3)	0.55393 (5)	0.01575 (11)
P3	0.25929 (3)	0.41255 (3)	0.26648 (4)	0.01450 (10)
C1	0.13962 (12)	0.45371 (12)	0.65502 (18)	0.0178 (4)
C2	0.12435 (12)	0.51230 (12)	0.70821 (19)	0.0207 (5)
H2	0.1108	0.5506	0.6700	0.025*
C3	0.12884 (14)	0.51494 (14)	0.8170 (2)	0.0273 (6)
H3	0.1185	0.5549	0.8527	0.033*
C4	0.14844 (14)	0.45912 (16)	0.8732 (2)	0.0301 (6)
H4	0.1513	0.4609	0.9473	0.036*
C5	0.16373 (14)	0.40114 (15)	0.8213 (2)	0.0283 (6)
H5	0.1773	0.3630	0.8598	0.034*
C6	0.15930 (14)	0.39828 (13)	0.7130 (2)	0.0217 (5)
H6	0.1698	0.3581	0.6779	0.026*
C7	0.11119 (12)	0.52434 (11)	0.46264 (16)	0.0175 (5)
C8	0.05030 (12)	0.53500 (12)	0.40169 (18)	0.0191 (4)
H8	0.0173	0.4999	0.3900	0.023*
C9	0.03727 (13)	0.59699 (13)	0.3575 (2)	0.0228 (5)
H9	−0.0040	0.6036	0.3148	0.027*
C10	0.08404 (14)	0.64869 (13)	0.3755 (2)	0.0249 (5)
H10	0.0749	0.6908	0.3455	0.030*
C11	0.14434 (11)	0.63916 (10)	0.4375 (3)	0.0234 (4)
H11	0.1760	0.6750	0.4509	0.028*
C12	0.15866 (13)	0.57737 (12)	0.48005 (19)	0.0205 (5)
H12	0.2007	0.5709	0.5211	0.025*
C13	0.04853 (12)	0.39823 (11)	0.50234 (19)	0.0186 (4)
C14	0.03752 (13)	0.35252 (12)	0.4235 (2)	0.0268 (6)
H14	0.0753	0.3423	0.3762	0.032*
C15	−0.02950 (15)	0.32139 (13)	0.4135 (2)	0.0336 (7)
H15	−0.0372	0.2908	0.3584	0.040*
C16	−0.08436 (15)	0.33469 (14)	0.4829 (3)	0.0360 (7)
H16	−0.1295	0.3130	0.4758	0.043*
C17	−0.07363 (14)	0.37963 (15)	0.5628 (2)	0.0337 (6)
H17	−0.1112	0.3885	0.6113	0.040*
C18	−0.00801 (13)	0.41170 (14)	0.5719 (2)	0.0256 (5)
H18	−0.0012	0.4432	0.6261	0.031*
C19	0.42750 (12)	0.41851 (12)	0.49989 (19)	0.0196 (5)
C20	0.48602 (14)	0.45677 (13)	0.5321 (2)	0.0300 (6)
H20	0.4792	0.4912	0.5816	0.036*
C21	0.55453 (14)	0.44453 (15)	0.4916 (3)	0.0359 (7)
H21	0.5939	0.4715	0.5121	0.043*
C22	0.56534 (14)	0.39352 (14)	0.4220 (2)	0.0314 (7)
H22	0.6121	0.3852	0.3950	0.038*
C23	0.50823 (15)	0.35457 (15)	0.3917 (2)	0.0293 (6)
H23	0.5159	0.3191	0.3445	0.035*
C24	0.43900 (12)	0.36709 (12)	0.4301 (2)	0.0230 (5)
H24	0.3998	0.3403	0.4084	0.028*
C25	0.33421 (12)	0.51645 (11)	0.59215 (19)	0.0176 (4)
C26	0.29808 (12)	0.53569 (12)	0.6835 (2)	0.0205 (5)
H26	0.2781	0.5032	0.7284	0.025*
C27	0.29136 (14)	0.60257 (14)	0.7087 (2)	0.0266 (6)
H27	0.2668	0.6153	0.7706	0.032*
C28	0.32047 (15)	0.65019 (13)	0.6435 (2)	0.0313 (6)
H28	0.3166	0.6955	0.6615	0.038*
C29	0.35523 (14)	0.63185 (13)	0.5523 (2)	0.0297 (6)
H29	0.3743	0.6647	0.5070	0.036*
C30	0.36235 (13)	0.56523 (12)	0.5268 (2)	0.0226 (5)
H30	0.3866	0.5529	0.4643	0.027*
C31	0.34799 (14)	0.38716 (13)	0.6806 (2)	0.0192 (5)
C32	0.31740 (14)	0.32518 (13)	0.6941 (2)	0.0232 (5)
H32	0.2918	0.3052	0.6381	0.028*
C33	0.32387 (16)	0.29223 (14)	0.7889 (2)	0.0319 (6)
H33	0.3025	0.2500	0.7977	0.038*
C34	0.36150 (18)	0.32092 (15)	0.8706 (2)	0.0377 (7)
H34	0.3649	0.2989	0.9361	0.045*
C35	0.39419 (18)	0.38161 (14)	0.8570 (2)	0.0372 (7)
H35	0.4210	0.4008	0.9125	0.045*
C36	0.38781 (16)	0.41478 (14)	0.7618 (2)	0.0302 (6)
H36	0.4107	0.4563	0.7524	0.036*
C37	0.18119 (13)	0.38725 (13)	0.18883 (19)	0.0193 (5)
C38	0.18054 (15)	0.33782 (12)	0.1132 (2)	0.0261 (5)
H38	0.2234	0.3143	0.0971	0.031*
C39	0.11603 (19)	0.32291 (14)	0.0607 (2)	0.0367 (7)
H39	0.1155	0.2893	0.0089	0.044*
C40	0.05379 (17)	0.35655 (16)	0.0839 (3)	0.0403 (8)
H40	0.0102	0.3453	0.0492	0.048*
C41	0.05425 (16)	0.40674 (18)	0.1574 (3)	0.0413 (8)
H41	0.0114	0.4305	0.1726	0.050*
C42	0.11817 (14)	0.42195 (16)	0.2089 (2)	0.0303 (6)
H42	0.1187	0.4567	0.2587	0.036*
C43	0.26948 (12)	0.49703 (12)	0.21873 (19)	0.0182 (4)
C44	0.28124 (15)	0.54660 (13)	0.2903 (2)	0.0262 (5)
H44	0.2849	0.5360	0.3625	0.031*
C45	0.28790 (17)	0.61243 (14)	0.2582 (3)	0.0380 (7)
H45	0.2969	0.6462	0.3081	0.046*
C46	0.28136 (16)	0.62768 (15)	0.1545 (3)	0.0367 (7)
H46	0.2858	0.6723	0.1325	0.044*
C47	0.26847 (14)	0.57923 (15)	0.0817 (2)	0.0320 (6)
H47	0.2632	0.5906	0.0100	0.038*
C48	0.26316 (14)	0.51345 (14)	0.1126 (2)	0.0253 (5)
H48	0.2553	0.4799	0.0620	0.030*
C49	0.33584 (14)	0.36919 (13)	0.20742 (19)	0.0182 (5)
C50	0.33779 (14)	0.30007 (13)	0.2073 (2)	0.0228 (5)
H50	0.2983	0.2759	0.2350	0.027*
C51	0.39711 (15)	0.26645 (13)	0.1669 (2)	0.0260 (5)
H51	0.3976	0.2196	0.1663	0.031*
C52	0.45517 (15)	0.30119 (15)	0.1277 (2)	0.0299 (6)
H52	0.4953	0.2783	0.0994	0.036*
C53	0.45462 (15)	0.36930 (15)	0.1297 (2)	0.0299 (6)
H53	0.4950	0.3932	0.1042	0.036*
C54	0.39532 (13)	0.40330 (13)	0.1690 (2)	0.0218 (5)
H54	0.3955	0.4502	0.1696	0.026*
N1S	0.0790 (2)	0.23273 (17)	0.8365 (3)	0.0715 (12)
C1S	0.05774 (19)	0.22818 (15)	0.7540 (3)	0.0409 (7)
C2S	0.0311 (2)	0.22160 (19)	0.6481 (3)	0.0474 (8)
H21S	0.0714	0.2250	0.5989	0.071*
H22S	−0.0038	0.2567	0.6338	0.071*
H23S	0.0077	0.1786	0.6400	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
I	0.02420 (6)	0.01553 (5)	0.02259 (6)	−0.00050 (5)	−0.00066 (8)	0.00298 (8)
Cu	0.01321 (10)	0.01381 (10)	0.01374 (10)	0.00034 (8)	−0.00041 (14)	0.00155 (13)
P1	0.0120 (2)	0.0155 (2)	0.0155 (2)	−0.0003 (2)	−0.0003 (2)	0.0000 (2)
P2	0.0126 (2)	0.0172 (3)	0.0174 (3)	−0.0001 (2)	−0.0028 (2)	0.0018 (2)
P3	0.0143 (2)	0.0160 (2)	0.0132 (2)	0.0010 (2)	0.0002 (2)	0.0014 (2)
C1	0.0116 (10)	0.0240 (11)	0.0179 (11)	−0.0007 (8)	0.0006 (8)	−0.0002 (9)
C2	0.0157 (10)	0.0236 (12)	0.0230 (12)	−0.0015 (9)	0.0021 (9)	−0.0027 (9)
C3	0.0206 (12)	0.0366 (15)	0.0249 (13)	−0.0027 (10)	0.0038 (10)	−0.0104 (11)
C4	0.0241 (13)	0.0509 (18)	0.0154 (12)	−0.0049 (12)	0.0013 (10)	−0.0033 (11)
C5	0.0244 (13)	0.0401 (15)	0.0206 (12)	0.0013 (11)	−0.0017 (10)	0.0055 (11)
C6	0.0206 (12)	0.0228 (12)	0.0218 (12)	−0.0005 (10)	−0.0002 (10)	0.0006 (10)
C7	0.0169 (9)	0.0173 (9)	0.0185 (14)	0.0015 (7)	0.0008 (8)	0.0002 (8)
C8	0.0177 (10)	0.0211 (11)	0.0185 (10)	0.0006 (9)	−0.0022 (8)	−0.0024 (9)
C9	0.0200 (12)	0.0283 (13)	0.0203 (11)	0.0055 (9)	−0.0036 (9)	0.0039 (10)
C10	0.0249 (12)	0.0218 (12)	0.0280 (13)	0.0035 (10)	0.0030 (10)	0.0092 (10)
C11	0.0222 (9)	0.0189 (9)	0.0291 (11)	−0.0037 (7)	0.0009 (13)	0.0022 (13)
C12	0.0157 (10)	0.0226 (11)	0.0232 (11)	−0.0019 (9)	−0.0031 (8)	0.0029 (9)
C13	0.0150 (10)	0.0178 (10)	0.0230 (12)	−0.0018 (8)	−0.0027 (9)	0.0026 (9)
C14	0.0248 (11)	0.0211 (10)	0.0346 (18)	−0.0005 (9)	−0.0096 (11)	−0.0008 (10)
C15	0.0322 (14)	0.0226 (12)	0.0459 (19)	−0.0054 (10)	−0.0181 (12)	0.0014 (11)
C16	0.0229 (14)	0.0332 (14)	0.0518 (18)	−0.0130 (11)	−0.0144 (12)	0.0186 (13)
C17	0.0171 (12)	0.0432 (17)	0.0407 (16)	−0.0053 (11)	0.0000 (11)	0.0120 (13)
C18	0.0177 (11)	0.0324 (13)	0.0267 (13)	−0.0043 (10)	−0.0006 (10)	0.0006 (10)
C19	0.0142 (10)	0.0236 (11)	0.0209 (12)	0.0029 (8)	−0.0005 (8)	0.0045 (9)
C20	0.0173 (11)	0.0271 (13)	0.0456 (17)	0.0003 (10)	−0.0036 (11)	−0.0096 (12)
C21	0.0156 (11)	0.0315 (14)	0.061 (2)	−0.0016 (10)	−0.0024 (12)	−0.0061 (13)
C22	0.0188 (11)	0.0398 (14)	0.0358 (19)	0.0023 (10)	0.0044 (10)	−0.0006 (12)
C23	0.0265 (13)	0.0368 (15)	0.0247 (13)	0.0042 (11)	0.0009 (10)	−0.0074 (11)
C24	0.0200 (10)	0.0278 (11)	0.0211 (13)	−0.0018 (8)	−0.0040 (10)	−0.0030 (11)
C25	0.0142 (10)	0.0173 (10)	0.0215 (11)	−0.0003 (8)	−0.0056 (8)	0.0005 (9)
C26	0.0177 (11)	0.0200 (11)	0.0240 (12)	−0.0007 (8)	−0.0041 (9)	−0.0008 (9)
C27	0.0230 (13)	0.0271 (14)	0.0297 (14)	0.0015 (10)	−0.0045 (10)	−0.0076 (11)
C28	0.0274 (13)	0.0167 (12)	0.0500 (18)	0.0026 (10)	−0.0110 (12)	−0.0033 (11)
C29	0.0251 (13)	0.0199 (12)	0.0442 (16)	−0.0019 (10)	−0.0048 (11)	0.0080 (11)
C30	0.0181 (11)	0.0213 (11)	0.0283 (13)	−0.0004 (9)	−0.0017 (9)	0.0027 (10)
C31	0.0204 (12)	0.0199 (12)	0.0173 (11)	0.0055 (9)	−0.0024 (9)	0.0031 (9)
C32	0.0242 (13)	0.0236 (12)	0.0218 (12)	0.0003 (10)	−0.0057 (10)	0.0040 (10)
C33	0.0407 (16)	0.0260 (13)	0.0291 (14)	−0.0029 (12)	−0.0073 (12)	0.0101 (11)
C34	0.0523 (19)	0.0359 (16)	0.0248 (14)	0.0049 (14)	−0.0123 (13)	0.0097 (12)
C35	0.055 (2)	0.0293 (15)	0.0269 (14)	0.0028 (13)	−0.0216 (14)	−0.0001 (11)
C36	0.0380 (15)	0.0233 (13)	0.0292 (14)	−0.0009 (11)	−0.0147 (13)	0.0009 (11)
C37	0.0191 (12)	0.0250 (12)	0.0139 (11)	−0.0024 (9)	−0.0014 (9)	0.0040 (9)
C38	0.0346 (14)	0.0217 (12)	0.0221 (12)	−0.0049 (10)	−0.0064 (11)	0.0021 (10)
C39	0.0541 (19)	0.0272 (14)	0.0288 (15)	−0.0167 (13)	−0.0190 (13)	0.0082 (11)
C40	0.0323 (15)	0.0476 (18)	0.0408 (17)	−0.0187 (13)	−0.0207 (13)	0.0226 (15)
C41	0.0196 (13)	0.062 (2)	0.0425 (18)	0.0019 (13)	−0.0091 (12)	0.0101 (16)
C42	0.0207 (12)	0.0451 (17)	0.0250 (13)	0.0064 (12)	−0.0041 (10)	−0.0021 (12)
C43	0.0148 (10)	0.0194 (11)	0.0206 (11)	0.0020 (8)	0.0017 (8)	0.0049 (9)
C44	0.0335 (14)	0.0195 (11)	0.0257 (13)	−0.0020 (10)	0.0028 (11)	0.0022 (9)
C45	0.0489 (18)	0.0183 (12)	0.0467 (19)	−0.0020 (12)	0.0093 (15)	0.0025 (12)
C46	0.0321 (15)	0.0252 (15)	0.053 (2)	0.0040 (12)	0.0123 (14)	0.0181 (14)
C47	0.0240 (13)	0.0397 (16)	0.0324 (15)	0.0034 (11)	0.0027 (11)	0.0208 (12)
C48	0.0224 (12)	0.0327 (14)	0.0209 (12)	0.0016 (10)	−0.0015 (9)	0.0092 (10)
C49	0.0180 (11)	0.0224 (12)	0.0141 (11)	0.0052 (9)	0.0027 (9)	0.0012 (9)
C50	0.0251 (12)	0.0241 (13)	0.0193 (12)	0.0030 (10)	0.0008 (9)	0.0009 (10)
C51	0.0329 (14)	0.0241 (12)	0.0209 (12)	0.0097 (11)	0.0000 (10)	0.0006 (10)
C52	0.0266 (13)	0.0379 (15)	0.0252 (13)	0.0155 (11)	0.0063 (10)	0.0027 (11)
C53	0.0222 (12)	0.0368 (15)	0.0308 (14)	0.0056 (11)	0.0082 (10)	0.0077 (12)
C54	0.0184 (11)	0.0246 (12)	0.0224 (12)	0.0034 (9)	0.0043 (10)	0.0053 (10)
N1S	0.106 (3)	0.055 (2)	0.053 (2)	0.026 (2)	−0.039 (2)	−0.0197 (17)
C1S	0.0500 (19)	0.0309 (15)	0.0418 (18)	0.0090 (13)	−0.0135 (15)	−0.0073 (13)
C2S	0.054 (2)	0.052 (2)	0.0363 (18)	−0.0011 (16)	−0.0160 (15)	0.0016 (15)

Geometric parameters (Å, º)

Cu—I	2.6843 (3)	C26—C27	1.398 (4)
Cu—P1	2.3421 (6)	C26—H26	0.9500
Cu—P2	2.3463 (6)	C27—C28	1.385 (4)
Cu—P3	2.3295 (7)	C27—H27	0.9500
P1—C7	1.830 (2)	C28—C29	1.384 (4)
P1—C1	1.833 (2)	C28—H28	0.9500
P1—C13	1.838 (2)	C29—C30	1.395 (4)
P2—C19	1.833 (2)	C29—H29	0.9500
P2—C31	1.839 (3)	C30—H30	0.9500
P2—C25	1.840 (2)	C31—C32	1.389 (4)
P3—C43	1.827 (2)	C31—C36	1.392 (4)
P3—C37	1.831 (3)	C32—C33	1.389 (4)
P3—C49	1.834 (3)	C32—H32	0.9500
C1—C6	1.394 (3)	C33—C34	1.385 (4)
C1—C2	1.397 (3)	C33—H33	0.9500
C2—C3	1.395 (4)	C34—C35	1.383 (4)
C2—H2	0.9500	C34—H34	0.9500
C3—C4	1.388 (4)	C35—C36	1.395 (4)
C3—H3	0.9500	C35—H35	0.9500
C4—C5	1.378 (4)	C36—H36	0.9500
C4—H4	0.9500	C37—C42	1.389 (4)
C5—C6	1.389 (4)	C37—C38	1.392 (4)
C5—H5	0.9500	C38—C39	1.406 (4)
C6—H6	0.9500	C38—H38	0.9500
C7—C8	1.390 (3)	C39—C40	1.374 (5)
C7—C12	1.408 (3)	C39—H39	0.9500
C8—C9	1.399 (3)	C40—C41	1.385 (5)
C8—H8	0.9500	C40—H40	0.9500
C9—C10	1.380 (4)	C41—C42	1.392 (4)
C9—H9	0.9500	C41—H41	0.9500
C10—C11	1.385 (4)	C42—H42	0.9500
C10—H10	0.9500	C43—C44	1.376 (4)
C11—C12	1.391 (3)	C43—C48	1.402 (3)
C11—H11	0.9500	C44—C45	1.401 (4)
C12—H12	0.9500	C44—H44	0.9500
C13—C14	1.384 (3)	C45—C46	1.367 (5)
C13—C18	1.403 (4)	C45—H45	0.9500
C14—C15	1.401 (3)	C46—C47	1.374 (5)
C14—H14	0.9500	C46—H46	0.9500
C15—C16	1.377 (4)	C47—C48	1.394 (4)
C15—H15	0.9500	C47—H47	0.9500
C16—C17	1.383 (5)	C48—H48	0.9500
C16—H16	0.9500	C49—C54	1.393 (4)
C17—C18	1.386 (4)	C49—C50	1.401 (4)
C17—H17	0.9500	C50—C51	1.395 (4)
C18—H18	0.9500	C50—H50	0.9500
C19—C24	1.388 (4)	C51—C52	1.382 (4)
C19—C20	1.397 (3)	C51—H51	0.9500
C20—C21	1.396 (4)	C52—C53	1.380 (4)
C20—H20	0.9500	C52—H52	0.9500
C21—C22	1.378 (4)	C53—C54	1.393 (4)
C21—H21	0.9500	C53—H53	0.9500
C22—C23	1.378 (4)	C54—H54	0.9500
C22—H22	0.9500	N1S—C1S	1.130 (5)
C23—C24	1.400 (3)	C1S—C2S	1.447 (5)
C23—H23	0.9500	C2S—H21S	0.9800
C24—H24	0.9500	C2S—H22S	0.9800
C25—C30	1.396 (3)	C2S—H23S	0.9800
C25—C26	1.402 (3)
P1—Cu—P2	108.39 (2)	C30—C25—P2	120.9 (2)
P3—Cu—P1	115.80 (2)	C26—C25—P2	120.1 (2)
P3—Cu—P2	115.77 (2)	C27—C26—C25	120.3 (2)
P1—Cu—I	104.75 (2)	C27—C26—H26	119.9
P2—Cu—I	113.66 (2)	C25—C26—H26	119.9
P3—Cu—I	97.69 (2)	C28—C27—C26	120.1 (3)
C7—P1—C1	104.4 (1)	C28—C27—H27	119.9
C7—P1—C13	102.2 (1)	C26—C27—H27	119.9
C1—P1—C13	100.2 (1)	C29—C28—C27	120.1 (3)
C7—P1—Cu	115.01 (7)	C29—C28—H28	119.9
C1—P1—Cu	111.79 (8)	C27—C28—H28	119.9
C13—P1—Cu	121.07 (8)	C28—C29—C30	120.1 (3)
C19—P2—C31	100.1 (1)	C28—C29—H29	120.0
C19—P2—C25	103.6 (1)	C30—C29—H29	120.0
C31—P2—C25	102.3 (1)	C29—C30—C25	120.7 (2)
C19—P2—Cu	116.27 (8)	C29—C30—H30	119.7
C31—P2—Cu	118.89 (9)	C25—C30—H30	119.7
C25—P2—Cu	113.51 (7)	C32—C31—C36	119.2 (2)
C43—P3—C37	99.4 (1)	C32—C31—P2	118.7 (2)
C43—P3—C49	103.4 (1)	C36—C31—P2	122.1 (2)
C37—P3—C49	104.9 (1)	C33—C32—C31	120.5 (3)
C43—P3—Cu	117.71 (8)	C33—C32—H32	119.7
C37—P3—Cu	112.29 (8)	C31—C32—H32	119.7
C49—P3—Cu	117.04 (8)	C34—C33—C32	120.0 (3)
C6—C1—C2	118.6 (2)	C34—C33—H33	120.0
C6—C1—P1	116.1 (2)	C32—C33—H33	120.0
C2—C1—P1	125.2 (2)	C35—C34—C33	120.0 (3)
C3—C2—C1	120.4 (2)	C35—C34—H34	120.0
C3—C2—H2	119.8	C33—C34—H34	120.0
C1—C2—H2	119.8	C34—C35—C36	120.1 (3)
C4—C3—C2	120.0 (2)	C34—C35—H35	120.0
C4—C3—H3	120.0	C36—C35—H35	120.0
C2—C3—H3	120.0	C31—C36—C35	120.1 (3)
C5—C4—C3	120.0 (2)	C31—C36—H36	119.9
C5—C4—H4	120.0	C35—C36—H36	119.9
C3—C4—H4	120.0	C42—C37—C38	119.0 (2)
C4—C5—C6	120.2 (3)	C42—C37—P3	115.2 (2)
C4—C5—H5	119.9	C38—C37—P3	125.8 (2)
C6—C5—H5	119.9	C37—C38—C39	119.5 (3)
C5—C6—C1	120.8 (2)	C37—C38—H38	120.2
C5—C6—H6	119.6	C39—C38—H38	120.2
C1—C6—H6	119.6	C40—C39—C38	120.5 (3)
C8—C7—C12	118.7 (2)	C40—C39—H39	119.7
C8—C7—P1	122.0 (2)	C38—C39—H39	119.7
C12—C7—P1	119.2 (2)	C39—C40—C41	120.3 (3)
C7—C8—C9	120.4 (2)	C39—C40—H40	119.8
C7—C8—H8	119.8	C41—C40—H40	119.8
C9—C8—H8	119.8	C40—C41—C42	119.3 (3)
C10—C9—C8	120.3 (2)	C40—C41—H41	120.4
C10—C9—H9	119.8	C42—C41—H41	120.4
C8—C9—H9	119.8	C37—C42—C41	121.3 (3)
C9—C10—C11	119.9 (2)	C37—C42—H42	119.4
C9—C10—H10	120.0	C41—C42—H42	119.4
C11—C10—H10	120.0	C44—C43—C48	118.9 (2)
C10—C11—C12	120.3 (2)	C44—C43—P3	118.6 (2)
C10—C11—H11	119.9	C48—C43—P3	122.5 (2)
C12—C11—H11	119.9	C43—C44—C45	121.0 (3)
C11—C12—C7	120.4 (2)	C43—C44—H44	119.5
C11—C12—H12	119.8	C45—C44—H44	119.5
C7—C12—H12	119.8	C46—C45—C44	119.4 (3)
C14—C13—C18	118.8 (2)	C46—C45—H45	120.3
C14—C13—P1	120.6 (2)	C44—C45—H45	120.3
C18—C13—P1	120.6 (2)	C45—C46—C47	120.7 (3)
C13—C14—C15	119.9 (3)	C45—C46—H46	119.6
C13—C14—H14	120.1	C47—C46—H46	119.6
C15—C14—H14	120.1	C46—C47—C48	120.2 (3)
C16—C15—C14	120.7 (3)	C46—C47—H47	119.9
C16—C15—H15	119.6	C48—C47—H47	119.9
C14—C15—H15	119.6	C47—C48—C43	119.7 (3)
C15—C16—C17	119.8 (2)	C47—C48—H48	120.1
C15—C16—H16	120.1	C43—C48—H48	120.1
C17—C16—H16	120.1	C54—C49—C50	118.4 (2)
C16—C17—C18	119.9 (3)	C54—C49—P3	121.5 (2)
C16—C17—H17	120.1	C50—C49—P3	120.0 (2)
C18—C17—H17	120.1	C51—C50—C49	120.6 (2)
C17—C18—C13	120.9 (3)	C51—C50—H50	119.7
C17—C18—H18	119.6	C49—C50—H50	119.7
C13—C18—H18	119.6	C52—C51—C50	120.1 (2)
C24—C19—C20	119.1 (2)	C52—C51—H51	119.9
C24—C19—P2	118.0 (2)	C50—C51—H51	119.9
C20—C19—P2	122.7 (2)	C53—C52—C51	119.8 (2)
C21—C20—C19	120.1 (3)	C53—C52—H52	120.1
C21—C20—H20	120.0	C51—C52—H52	120.1
C19—C20—H20	120.0	C52—C53—C54	120.5 (2)
C22—C21—C20	120.4 (3)	C52—C53—H53	119.8
C22—C21—H21	119.8	C54—C53—H53	119.8
C20—C21—H21	119.8	C49—C54—C53	120.6 (2)
C23—C22—C21	119.9 (2)	C49—C54—H54	119.7
C23—C22—H22	120.0	C53—C54—H54	119.7
C21—C22—H22	120.0	N1S—C1S—C2S	179.3 (4)
C22—C23—C24	120.3 (2)	C1S—C2S—H21S	109.5
C22—C23—H23	119.8	C1S—C2S—H22S	109.5
C24—C23—H23	119.8	H21S—C2S—H22S	109.5
C19—C24—C23	120.2 (2)	C1S—C2S—H23S	109.5
C19—C24—H24	119.9	H21S—C2S—H23S	109.5
C23—C24—H24	119.9	H22S—C2S—H23S	109.5
C30—C25—C26	118.7 (2)
P3—Cu—P1—C7	−41.42 (8)	C19—C20—C21—C22	−1.9 (5)
P2—Cu—P1—C7	90.62 (8)	C20—C21—C22—C23	0.4 (5)
I—Cu—P1—C7	−147.73 (8)	C21—C22—C23—C24	0.9 (4)
P3—Cu—P1—C1	−160.21 (9)	C20—C19—C24—C23	−0.9 (4)
P2—Cu—P1—C1	−28.18 (9)	P2—C19—C24—C23	−176.1 (2)
I—Cu—P1—C1	93.47 (9)	C22—C23—C24—C19	−0.6 (4)
P3—Cu—P1—C13	82.11 (9)	C19—P2—C25—C30	43.1 (2)
P2—Cu—P1—C13	−145.85 (9)	C31—P2—C25—C30	146.78 (19)
I—Cu—P1—C13	−24.20 (9)	Cu—P2—C25—C30	−83.89 (19)
P3—Cu—P2—C19	−32.45 (9)	C19—P2—C25—C26	−142.59 (19)
P1—Cu—P2—C19	−164.50 (9)	C31—P2—C25—C26	−38.9 (2)
I—Cu—P2—C19	79.49 (9)	Cu—P2—C25—C26	90.42 (19)
P3—Cu—P2—C31	−152.11 (10)	C30—C25—C26—C27	−0.8 (3)
P1—Cu—P2—C31	75.84 (10)	P2—C25—C26—C27	−175.18 (18)
I—Cu—P2—C31	−40.17 (10)	C25—C26—C27—C28	−0.1 (4)
P3—Cu—P2—C25	87.57 (9)	C26—C27—C28—C29	1.1 (4)
P1—Cu—P2—C25	−44.48 (9)	C27—C28—C29—C30	−1.3 (4)
I—Cu—P2—C25	−160.49 (8)	C28—C29—C30—C25	0.5 (4)
P1—Cu—P3—C43	63.46 (9)	C26—C25—C30—C29	0.6 (3)
P2—Cu—P3—C43	−65.03 (9)	P2—C25—C30—C29	174.95 (19)
I—Cu—P3—C43	173.98 (8)	C19—P2—C31—C32	−105.8 (2)
P1—Cu—P3—C37	−51.02 (10)	C25—P2—C31—C32	147.8 (2)
P2—Cu—P3—C37	−179.52 (9)	Cu—P2—C31—C32	21.9 (2)
I—Cu—P3—C37	59.50 (9)	C19—P2—C31—C36	72.3 (3)
P1—Cu—P3—C49	−172.41 (10)	C25—P2—C31—C36	−34.1 (3)
P2—Cu—P3—C49	59.10 (10)	Cu—P2—C31—C36	−160.0 (2)
I—Cu—P3—C49	−61.89 (10)	C36—C31—C32—C33	2.6 (4)
C7—P1—C1—C6	−177.91 (18)	P2—C31—C32—C33	−179.3 (2)
C13—P1—C1—C6	76.6 (2)	C31—C32—C33—C34	−0.5 (5)
Cu—P1—C1—C6	−53.0 (2)	C32—C33—C34—C35	−1.6 (5)
C7—P1—C1—C2	3.1 (2)	C33—C34—C35—C36	1.6 (5)
C13—P1—C1—C2	−102.4 (2)	C32—C31—C36—C35	−2.7 (4)
Cu—P1—C1—C2	128.07 (19)	P2—C31—C36—C35	179.3 (2)
C6—C1—C2—C3	0.0 (3)	C34—C35—C36—C31	0.6 (5)
P1—C1—C2—C3	178.94 (19)	C43—P3—C37—C42	−63.8 (2)
C1—C2—C3—C4	−0.1 (4)	C49—P3—C37—C42	−170.4 (2)
C2—C3—C4—C5	0.3 (4)	Cu—P3—C37—C42	61.5 (2)
C3—C4—C5—C6	−0.3 (4)	C43—P3—C37—C38	115.7 (2)
C4—C5—C6—C1	0.2 (4)	C49—P3—C37—C38	9.1 (3)
C2—C1—C6—C5	0.0 (4)	Cu—P3—C37—C38	−119.0 (2)
P1—C1—C6—C5	−179.1 (2)	C42—C37—C38—C39	−1.6 (4)
C1—P1—C7—C8	−122.92 (19)	P3—C37—C38—C39	178.9 (2)
C13—P1—C7—C8	−18.9 (2)	C37—C38—C39—C40	−0.2 (4)
Cu—P1—C7—C8	114.23 (18)	C38—C39—C40—C41	1.6 (4)
C1—P1—C7—C12	61.5 (2)	C39—C40—C41—C42	−1.1 (5)
C13—P1—C7—C12	165.52 (19)	C38—C37—C42—C41	2.2 (4)
Cu—P1—C7—C12	−61.40 (19)	P3—C37—C42—C41	−178.3 (2)
C12—C7—C8—C9	0.9 (3)	C40—C41—C42—C37	−0.8 (5)
P1—C7—C8—C9	−174.72 (18)	C37—P3—C43—C44	135.0 (2)
C7—C8—C9—C10	−1.3 (4)	C49—P3—C43—C44	−117.1 (2)
C8—C9—C10—C11	0.2 (4)	Cu—P3—C43—C44	13.6 (2)
C9—C10—C11—C12	1.2 (4)	C37—P3—C43—C48	−42.6 (2)
C10—C11—C12—C7	−1.5 (4)	C49—P3—C43—C48	65.2 (2)
C8—C7—C12—C11	0.4 (4)	Cu—P3—C43—C48	−164.05 (17)
P1—C7—C12—C11	176.2 (2)	C48—C43—C44—C45	−0.9 (4)
C7—P1—C13—C14	104.3 (2)	P3—C43—C44—C45	−178.6 (2)
C1—P1—C13—C14	−148.4 (2)	C43—C44—C45—C46	1.1 (4)
Cu—P1—C13—C14	−25.1 (2)	C44—C45—C46—C47	−0.1 (5)
C7—P1—C13—C18	−73.6 (2)	C45—C46—C47—C48	−1.2 (4)
C1—P1—C13—C18	33.7 (2)	C46—C47—C48—C43	1.4 (4)
Cu—P1—C13—C18	157.04 (17)	C44—C43—C48—C47	−0.3 (4)
C18—C13—C14—C15	0.9 (4)	P3—C43—C48—C47	177.28 (19)
P1—C13—C14—C15	−177.04 (19)	C43—P3—C49—C54	18.8 (2)
C13—C14—C15—C16	−1.4 (4)	C37—P3—C49—C54	122.4 (2)
C14—C15—C16—C17	0.5 (4)	Cu—P3—C49—C54	−112.4 (2)
C15—C16—C17—C18	0.8 (4)	C43—P3—C49—C50	−166.1 (2)
C16—C17—C18—C13	−1.3 (4)	C37—P3—C49—C50	−62.4 (2)
C14—C13—C18—C17	0.5 (4)	Cu—P3—C49—C50	62.8 (2)
P1—C13—C18—C17	178.4 (2)	C54—C49—C50—C51	−1.8 (4)
C31—P2—C19—C24	98.0 (2)	P3—C49—C50—C51	−177.1 (2)
C25—P2—C19—C24	−156.6 (2)	C49—C50—C51—C52	0.9 (4)
Cu—P2—C19—C24	−31.4 (2)	C50—C51—C52—C53	0.7 (4)
C31—P2—C19—C20	−77.0 (2)	C51—C52—C53—C54	−1.4 (4)
C25—P2—C19—C20	28.4 (2)	C50—C49—C54—C53	1.2 (4)
Cu—P2—C19—C20	153.61 (19)	P3—C49—C54—C53	176.4 (2)
C24—C19—C20—C21	2.1 (4)	C52—C53—C54—C49	0.4 (4)
P2—C19—C20—C21	177.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···Cg1^i	0.95	2.94	3.732	141
C40—H40···Cg2^i	0.95	2.94	3.696	137
C39—H39···N1S^ii	0.95	2.58	3.468 (4)	157

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