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Acta Cryst. (2010). E66, m432-m433    [ doi:10.1107/S1600536810010196 ]

Bis(isopropyltriphenylphosphonium) di-[mu]-iodido-bis[iodidocopper(I)]

E. Jalilian and S. Lidin

Abstract top

The title compound, (C21H22P)2[Cu2I4], prepared from reaction between copper powder, iodine and isopropyl triphenylphosphonium iodide in hydroxyacetone (acetol), shows an already known Cu2I42- anion with a planar conformation [Cu-I range = 2.5108 (3)-2.5844 (3) Å and I-Cu-I range = 110.821 (10)-125.401 (10)°].

Comment top

Copper halide complexes have been of great interested due to their wide structural variation. The copper atoms can be in trigonal or tetrahedral geometry and this is the main reason for so many structure variations.

A search in Cambridge Structural Database shows 20 different structures containing [Cu2I4]2- as the anion, the major difference between these are that different cations are employed in the structures. [Cu2I4]-2 unit can be in two different forms, planar or bent.

For being able to crystallize [Cu2I4]2- unit the cations needs to be large and bulky such as [N/P-R4]+ or [AsR4]+ (where R= alkyl /phenyl). Hartl et al. (1985) and Pfitzner & Schmitz (1997) discuss the different modification of [Cu2I4]2- unit with tetra phenylphosphonium as the cation.

By reacting copper powder, iodine and isopropyltriphenylphosphonium iodide in hydoxyacetone under nitrogen atmosphere and reflux colorless parallelepiped crystals are formed. X-ray crystallography shows that the mentioned crystals contain the well known [Cu2I4]2- as the anion and isopropyltriphenylphosphonium as the cation.

The anion shows some variation in the Cu–I distance 2.5108 (3)–2.5844 (3) Å and large variation in I–Cu–I angle 110.821 (19)–125.401 (10)°. The counter ion is a typical isopropyltriphenylphosphonium with P–C range 1.7909 (17)–1.8242 (17) Å, C–C (in isopropyl chain) range 1.387 (3)–1.400 (2) Å and (in phenyl rings) 1.536 (2)–1.539 (2) Å, The angles are in range C–P–C 107.29 (7)–110.57 (8)° and (P/)C–C–C 109.88 (11)–120.63 (16)°.

Related literature top

For structurally fully characterized units containing a planar [Cu2I4]2- ion included in the Cambridge Structural Database (CSD; Allen, 2002), see: Asplund et al. (1982); Asplund & Jagner (1984a); Hartl et al. (1985); Basu et al. (1987); Canty et al. (1987); Cunningham et al. (1990); Bhaduri et al. (1991); Pfitzner & Schmitz (1997); Allen et al. (1998); Su et al. (2002); Feng et al. (2006); Bowmaker et al. (2007); Cariati et al. (2007); Kia et al. (2007); Liu et al. (2007); Herres-Pawlis et al. (2008); Mishra et al. (2008). For those structures in the CSD containing a bent [Cu2I4]2- ion, see: Asplund & Jagner (1984b); Ramaprabhu et al. (1994); Hoyer & Hartl (1992). For the extinction correction see: Becker & Coppens (1974).

Experimental top

Isopropyl triphenylphosphonium iodide (2.711 mmol), iodine (5.011 mmol) and copper powder (20.056 mmol) were mixed and heated under reflux in hydroxyacetone (50 ml) under a nitrogen atmosphere. After 3 hours the solution became pale yellow. The mixture was filtered while hot and solution was kept at 6°C. Well shaped parallelepiped crystals formed over the course of several days.

Refinement top

The structures were solved by charge-flipping, giving the I, Cu, P and main part of the C positions. The remaining C positions were found using difference Fourier analysis. All non-hydrogen positions were refined using full matrix least squares. The hydrogen atoms were located by geometrical methods and were allowed to ride, with C–H = 1.00Å and Ueq = 1.2Uiso(C).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SUPERFLIP (Oszlányi & Sütő, 2004); program(s) used to refine structure: JANA2000 (Petricek et al., 2000); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: JANA2000 (Petricek et al., 2000).

Figures top
[Figure 1] Fig. 1. Molecular structure and atom-labelling scheme for the anion and cation respectively in (I). Non-H atoms are shown as 50% probability displacement ellipsoids.
Bis(isopropyltriphenylphosphonium) di-µ-iodido-bis[iodidocopper(I)] top
Crystal data top
(C21H22P)2[Cu2I4]F(000) = 1192
Mr = 1245.4Dx = 1.923 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 35772 reflections
a = 11.5503 (1) Åθ = 4.3–32.2°
b = 12.2422 (1) ŵ = 3.96 mm−1
c = 15.2619 (1) ÅT = 100 K
β = 94.91 (1)°Parallelepiped, colorless
V = 2150.14 (3) Å30.34 × 0.24 × 0.11 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur3
diffractometer with a Sapphire-3 CCD detector		7235 independent reflections
Radiation source: Enhance (Mo) X-ray source5970 reflections with I > 3σ(I)
graphiteRint = 0.028
Detector resolution: 16.5467 pixels mm-1θmax = 32.3°, θmin = 4.3°
ω scansh = −16→16
Absorption correction: gaussian
(CrysAlis RED; Oxford Diffraction, 2008)		k = −18→17
Tmin = 0.425, Tmax = 0.720l = −22→22
59726 measured reflections
Refinement top
Refinement on F2Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.0025I2]
R[F2 > 2σ(F2)] = 0.021(Δ/σ)max = 0.048
wR(F2) = 0.059Δρmax = 0.42 e Å−3
S = 0.85Δρmin = −0.34 e Å−3
7235 reflectionsExtinction correction: B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)
227 parametersExtinction coefficient: 64 (4)
H-atom parameters constrained
Crystal data top
(C21H22P)2[Cu2I4]V = 2150.14 (3) Å3
Mr = 1245.4Z = 2
Monoclinic, P21/nMo Kα radiation
a = 11.5503 (1) ŵ = 3.96 mm−1
b = 12.2422 (1) ÅT = 100 K
c = 15.2619 (1) Å0.34 × 0.24 × 0.11 mm
β = 94.91 (1)°
Data collection top
Oxford Diffraction Xcalibur3
diffractometer with a Sapphire-3 CCD detector		7235 independent reflections
Absorption correction: gaussian
(CrysAlis RED; Oxford Diffraction, 2008)		5970 reflections with I > 3σ(I)
Tmin = 0.425, Tmax = 0.720Rint = 0.028
59726 measured reflectionsθmax = 32.3°
Refinement top
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.059Δρmax = 0.42 e Å−3
S = 0.85Δρmin = −0.34 e Å−3
7235 reflectionsAbsolute structure: ?
227 parametersFlack parameter: ?
? restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.157523 (11)0.779996 (10)0.067564 (7)0.01803 (4)
I20.088940 (10)0.420511 (9)0.109927 (7)0.01722 (4)
Cu0.05477 (2)0.60384 (2)0.027808 (15)0.01978 (7)
P0.64953 (4)0.37043 (4)0.21738 (3)0.00966 (10)
C1p10.74345 (15)0.33415 (13)0.31293 (10)0.0109 (4)
C2p10.69514 (16)0.31940 (15)0.39296 (10)0.0143 (4)
C3p10.76541 (17)0.28472 (15)0.46633 (11)0.0173 (5)
C4p10.88223 (17)0.26343 (15)0.45940 (11)0.0176 (5)
C5p10.93029 (17)0.27634 (15)0.37964 (12)0.0167 (5)
C6p10.86142 (15)0.31277 (14)0.30603 (10)0.0135 (4)
C1p20.54471 (14)0.46880 (14)0.24661 (10)0.0112 (4)
C2p20.57038 (16)0.53997 (14)0.31737 (11)0.0144 (4)
C3p20.49367 (16)0.62306 (15)0.33355 (11)0.0170 (5)
C4p20.39280 (16)0.63785 (15)0.27840 (12)0.0175 (5)
C5p20.36630 (16)0.56700 (15)0.20803 (12)0.0160 (5)
C6p20.44136 (15)0.48239 (14)0.19229 (10)0.0134 (4)
C1p30.57856 (14)0.24771 (13)0.17715 (9)0.0109 (4)
C2p30.63395 (15)0.18004 (14)0.11953 (10)0.0129 (4)
C3p30.58422 (16)0.08039 (14)0.09410 (11)0.0158 (5)
C4p30.48000 (16)0.04790 (15)0.12623 (11)0.0164 (5)
C5p30.42538 (16)0.11456 (15)0.18379 (11)0.0163 (5)
C6p30.47469 (16)0.21450 (14)0.21023 (11)0.0141 (4)
C10.79164 (16)0.53620 (14)0.16800 (11)0.0153 (4)
C20.73307 (15)0.43027 (13)0.13327 (10)0.0116 (4)
C30.65453 (16)0.45208 (16)0.04843 (11)0.0163 (5)
H2p10.6106190.3336640.3974950.0171*
H3p10.7316770.2751480.5240390.0207*
H4p10.9323410.2385560.5123220.0211*
H5p11.0142780.2594810.3750660.0201*
H6p10.8959320.3235650.2487560.0162*
H2p20.6439910.5308560.3561760.0173*
H3p20.5109370.6725960.3851130.0204*
H4p20.3390480.69950.2892340.021*
H5p20.2931240.5772680.1689350.0192*
H6p20.4219470.4310030.1422510.0161*
H2p30.7088140.2033520.0968680.0154*
H3p30.6231050.0319340.0527660.019*
H4p30.444416−0.0238180.1076940.0197*
H5p30.3505590.0908240.2063070.0196*
H6p30.4362580.2620440.2524510.0169*
H110.8450370.5196820.2214170.0184*
H120.8371360.5686420.1215540.0184*
H130.7308750.5892580.1836350.0184*
H310.6202050.3816510.0254230.0196*
H320.5907440.5032850.0614060.0196*
H330.7016250.4854510.0033630.0196*
H20.7947090.3774090.1189670.014*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01934 (7)0.01958 (7)0.01576 (6)0.00147 (4)0.00501 (4)0.00177 (4)
I20.01794 (7)0.01351 (6)0.02015 (6)−0.00133 (4)0.00141 (4)0.00095 (4)
Cu0.01934 (12)0.02089 (12)0.01968 (10)0.00260 (9)0.00502 (8)0.00201 (8)
P0.00942 (19)0.00998 (19)0.00955 (15)0.00068 (14)0.00067 (13)−0.00029 (13)
C1p10.0118 (7)0.0095 (7)0.0110 (6)−0.0001 (6)−0.0015 (5)−0.0001 (5)
C2p10.0144 (8)0.0142 (8)0.0143 (7)−0.0009 (6)0.0012 (6)0.0014 (6)
C3p10.0222 (9)0.0170 (8)0.0121 (7)−0.0025 (7)−0.0015 (6)0.0016 (6)
C4p10.0215 (9)0.0143 (8)0.0155 (7)−0.0017 (7)−0.0070 (6)0.0021 (6)
C5p10.0141 (8)0.0133 (8)0.0219 (8)0.0006 (6)−0.0032 (6)0.0010 (6)
C6p10.0141 (8)0.0111 (7)0.0152 (7)0.0001 (6)0.0004 (6)0.0003 (6)
C1p20.0101 (7)0.0118 (7)0.0116 (6)0.0017 (6)0.0009 (5)−0.0011 (5)
C2p20.0140 (8)0.0131 (8)0.0159 (7)0.0007 (6)0.0003 (6)−0.0036 (6)
C3p20.0173 (9)0.0143 (8)0.0197 (7)0.0004 (7)0.0025 (6)−0.0063 (6)
C4p20.0142 (8)0.0150 (8)0.0234 (8)0.0016 (7)0.0024 (6)−0.0038 (6)
C5p20.0118 (8)0.0163 (8)0.0197 (7)0.0019 (6)−0.0007 (6)−0.0014 (6)
C6p20.0119 (8)0.0138 (8)0.0142 (6)0.0006 (6)0.0000 (5)−0.0024 (6)
C1p30.0120 (8)0.0101 (7)0.0103 (6)0.0018 (6)0.0000 (5)−0.0002 (5)
C2p30.0136 (8)0.0123 (7)0.0127 (6)0.0013 (6)0.0013 (5)−0.0001 (5)
C3p30.0205 (9)0.0126 (8)0.0138 (7)0.0035 (6)−0.0017 (6)−0.0025 (6)
C4p30.0191 (9)0.0112 (8)0.0180 (7)−0.0006 (6)−0.0042 (6)0.0009 (6)
C5p30.0141 (8)0.0163 (8)0.0186 (7)−0.0028 (7)0.0017 (6)0.0030 (6)
C6p30.0150 (8)0.0141 (8)0.0134 (7)0.0010 (6)0.0031 (6)0.0003 (5)
C10.0153 (8)0.0128 (8)0.0180 (7)−0.0013 (6)0.0020 (6)0.0016 (6)
C20.0116 (8)0.0111 (7)0.0124 (6)0.0005 (6)0.0021 (5)0.0008 (5)
C30.0183 (9)0.0190 (9)0.0115 (6)−0.0004 (7)0.0002 (6)0.0024 (6)
Geometric parameters (Å, °) top
I1—Cu2.5108 (3)C4p2—H4p21.0000
I2—Cu2.5844 (3)C5p2—C6p21.385 (3)
P—C1p11.7972 (15)C5p2—H5p21.0000
P—C1p21.7909 (17)C6p2—H6p21.0000
P—C1p31.7944 (17)C1p3—C2p31.402 (2)
P—C21.8242 (17)C1p3—C6p31.401 (3)
C1p1—C2p11.397 (2)C2p3—C3p31.390 (2)
C1p1—C6p11.400 (2)C2p3—H2p31.0000
C2p1—C3p11.392 (2)C3p3—C4p31.396 (3)
C2p1—H2p11.0000C3p3—H3p31.0000
C3p1—C4p11.387 (3)C4p3—C5p31.389 (3)
C3p1—H3p11.0000C4p3—H4p31.0000
C4p1—C5p11.390 (3)C5p3—C6p31.395 (3)
C4p1—H4p11.0000C5p3—H5p31.0000
C5p1—C6p11.393 (2)C6p3—H6p31.0000
C5p1—H5p11.0000C1—C21.536 (2)
C6p1—H6p11.0000C1—H111.0000
C1p2—C2p21.399 (2)C1—H121.0000
C1p2—C6p21.404 (2)C1—H131.0000
C2p2—C3p21.385 (3)C2—C31.539 (2)
C2p2—H2p21.0000C2—H21.0000
C3p2—C4p21.390 (3)C3—H311.0000
C3p2—H3p21.0000C3—H321.0000
C4p2—C5p21.394 (3)C3—H331.0000
Cu—I2—Cui69.179 (8)C4p2—C5p2—H5p2120.01
Cui—I2—Cu69.179 (8)C6p2—C5p2—H5p2120.01
I1—Cu—I2125.401 (10)C1p2—C6p2—C5p2119.97 (15)
I2i—Cu—I2110.821 (10)C1p2—C6p2—H6p2120.02
C1p1—P—C1p2109.76 (7)C5p2—C6p2—H6p2120.01
C1p1—P—C1p3107.29 (7)P—C1p3—C2p3119.33 (13)
C1p1—P—C2110.57 (8)P—C1p3—C6p3119.99 (12)
C1p2—P—C1p3110.45 (8)C2p3—C1p3—C6p3120.35 (15)
C1p2—P—C2108.34 (8)C1p3—C2p3—C3p3119.62 (16)
C1p3—P—C2110.43 (7)C1p3—C2p3—H2p3120.19
P—C1p1—C2p1118.87 (13)C3p3—C2p3—H2p3120.19
P—C1p1—C6p1120.59 (12)C2p3—C3p3—C4p3120.02 (16)
C2p1—C1p1—C6p1120.36 (14)C2p3—C3p3—H3p3119.99
C1p1—C2p1—C3p1119.58 (17)C4p3—C3p3—H3p3119.99
C1p1—C2p1—H2p1120.21C3p3—C4p3—C5p3120.44 (17)
C3p1—C2p1—H2p1120.21C3p3—C4p3—H4p3119.78
C2p1—C3p1—C4p1120.01 (16)C5p3—C4p3—H4p3119.78
C2p1—C3p1—H3p1120.00C4p3—C5p3—C6p3120.12 (17)
C4p1—C3p1—H3p1120.00C4p3—C5p3—H5p3119.94
C3p1—C4p1—C5p1120.63 (16)C6p3—C5p3—H5p3119.94
C3p1—C4p1—H4p1119.69C1p3—C6p3—C5p3119.44 (16)
C5p1—C4p1—H4p1119.69C1p3—C6p3—H6p3120.28
C4p1—C5p1—C6p1119.97 (17)C5p3—C6p3—H6p3120.28
C4p1—C5p1—H5p1120.02C2—C1—H11109.47
C6p1—C5p1—H5p1120.02C2—C1—H12109.47
C1p1—C6p1—C5p1119.44 (16)C2—C1—H13109.47
C1p1—C6p1—H6p1120.28H11—C1—H12109.47
C5p1—C6p1—H6p1120.28H11—C1—H13109.47
P—C1p2—C2p2120.52 (12)H12—C1—H13109.47
P—C1p2—C6p2119.43 (12)P—C2—C1109.88 (11)
C2p2—C1p2—C6p2119.68 (16)P—C2—C3110.64 (12)
C1p2—C2p2—C3p2119.89 (15)P—C2—H2108.84
C1p2—C2p2—H2p2120.06C1—C2—C3110.75 (14)
C3p2—C2p2—H2p2120.06C1—C2—H2108.72
C2p2—C3p2—C4p2120.25 (16)C3—C2—H2107.94
C2p2—C3p2—H3p2119.88C2—C3—H31109.47
C4p2—C3p2—H3p2119.88C2—C3—H32109.47
C3p2—C4p2—C5p2120.20 (17)C2—C3—H33109.47
C3p2—C4p2—H4p2119.90H31—C3—H32109.47
C5p2—C4p2—H4p2119.90H31—C3—H33109.47
C4p2—C5p2—C6p2119.97 (16)H32—C3—H33109.47
Symmetry codes: (i) −x, −y+1, −z.
Acknowledgements top

Financial support from the Swedish Research Council is gratefully acknowledged.

references
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