Download citation
Download citation
link to html
The title compound, [Cu4I4(C12H27P)4], recovered from an attempt to prepare triisopropyl­silylthiol­ato(tri-tert-butyl­phosphine)copper(I), is found to be tetra­meric with a distorted heterocubane structure, one of the body diagonals of the cube being a crystallographic threefold rotation axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805021744/om6250sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805021744/om6250Isup2.hkl
Contains datablock I

CCDC reference: 282577

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.027
  • wR factor = 0.057
  • Data-to-parameter ratio = 28.4

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT601_ALERT_2_A Structure Contains Solvent Accessible VOIDS of . 419.00 A   3
Author Response: As noted in the Experimental section, solvent of crystallization (benzene and/or pentane) was found but was so severely disordered about the 3-fold axis that its identity could not be confidently determined nor could it be modeled in any satisfactory manner. The disordered electron density was therefore removed with PLATON SQUEEZE.

Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) I1 - Cu1 .. 14.27 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) I2 - Cu1 .. 12.29 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) I2 - Cu2 .. 14.14 su PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) I2 - Cu1_a .. 15.32 su
1 ALERT level A = In general: serious problem 4 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXL97.

Tetra-µ3iodo-tetrakis[(tri-tert-butylphosphine)copper(I)] top
Crystal data top
[Cu4I4(C12H27P)4]Dx = 1.558 Mg m3
Mr = 1571.03Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 9205 reflections
Hall symbol: -R 3θ = 2.4–28.2°
a = 13.878 (1) ŵ = 3.22 mm1
c = 60.239 (7) ÅT = 100 K
V = 10047.7 (16) Å3Block, colorless
Z = 60.13 × 0.09 × 0.09 mm
F(000) = 4704
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
5477 independent reflections
Radiation source: fine-focus sealed tube4891 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
φ and ω scansθmax = 28.3°, θmin = 1.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)
h = 1818
Tmin = 0.624, Tmax = 0.750k = 1817
30297 measured reflectionsl = 7978
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.057H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0186P)2 + 41.1166P]
where P = (Fo2 + 2Fc2)/3
5477 reflections(Δ/σ)max = 0.003
193 parametersΔρmax = 0.77 e Å3
0 restraintsΔρmin = 0.42 e Å3
Special details top

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 (Å2) top
xyzUiso*/Ueq
I10.66670.33330.124796 (4)0.01354 (6)
I20.492061 (12)0.327202 (12)0.069105 (3)0.01320 (5)
Cu10.66025 (3)0.47848 (3)0.095061 (5)0.01550 (7)
Cu20.66670.33330.047048 (8)0.01576 (11)
P10.65672 (5)0.62935 (5)0.107749 (10)0.01192 (12)
P20.66670.33330.009673 (17)0.0123 (2)
C10.6009 (2)0.6873 (2)0.08565 (4)0.0155 (5)
C20.4739 (2)0.6114 (2)0.08333 (4)0.0199 (5)
H2A0.43710.61700.09680.030*
H2B0.45630.53420.08130.030*
H2C0.44760.63470.07040.030*
C30.6262 (2)0.8074 (2)0.08903 (4)0.0205 (5)
H3A0.59200.82770.07710.031*
H3B0.70690.85770.08890.031*
H3C0.59600.81330.10330.031*
C40.6491 (2)0.6777 (2)0.06320 (4)0.0201 (5)
H4A0.63070.60050.06090.030*
H4B0.73010.72610.06330.030*
H4C0.61710.70040.05120.030*
C50.5637 (2)0.5929 (2)0.13326 (4)0.0152 (5)
C60.4605 (2)0.4770 (2)0.12918 (4)0.0200 (5)
H6A0.41390.45310.14250.030*
H6B0.48460.42330.12580.030*
H6C0.41760.48140.11670.030*
C70.5253 (2)0.6759 (2)0.13965 (4)0.0208 (5)
H7A0.48170.65120.15340.031*
H7B0.47940.67970.12770.031*
H7C0.59060.74970.14200.031*
C80.6224 (2)0.5773 (2)0.15353 (4)0.0179 (5)
H8A0.68600.64930.15780.027*
H8B0.64860.52560.14970.027*
H8C0.57000.54720.16600.027*
C90.8030 (2)0.7433 (2)0.11575 (4)0.0148 (5)
C100.8721 (2)0.7979 (2)0.09475 (4)0.0189 (5)
H10A0.84240.83990.08710.028*
H10B0.86810.74010.08480.028*
H10C0.94970.84840.09890.028*
C110.8606 (2)0.6862 (2)0.12718 (4)0.0183 (5)
H11A0.86030.63040.11720.027*
H11B0.82060.64980.14080.027*
H11C0.93750.74200.13080.027*
C120.8095 (2)0.8352 (2)0.13095 (4)0.0191 (5)
H12A0.88770.89100.13350.029*
H12B0.77360.80270.14520.029*
H12C0.77150.87060.12390.029*
C130.5230 (2)0.2292 (2)0.00142 (4)0.0152 (5)
C140.4434 (2)0.2755 (2)0.00152 (4)0.0195 (5)
H14A0.36730.21730.00200.029*
H14B0.46570.33900.00850.029*
H14C0.44650.29970.01690.029*
C150.4758 (2)0.1261 (2)0.01369 (4)0.0199 (5)
H15A0.47760.14870.02920.030*
H15B0.52090.09020.01210.030*
H15C0.39880.07360.00940.030*
C160.5170 (2)0.1934 (2)0.02576 (4)0.0209 (5)
H16A0.43920.14300.02990.031*
H16B0.55970.15500.02760.031*
H16C0.54840.25920.03540.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.01315 (8)0.01315 (8)0.01434 (12)0.00657 (4)0.0000.000
I20.01288 (8)0.01280 (8)0.01346 (8)0.00607 (6)0.00018 (6)0.00027 (6)
Cu10.01724 (16)0.01329 (14)0.01723 (15)0.00856 (13)0.00067 (12)0.00231 (12)
Cu20.01739 (16)0.01739 (16)0.0125 (2)0.00869 (8)0.0000.000
P10.0116 (3)0.0112 (3)0.0128 (3)0.0055 (2)0.0008 (2)0.0013 (2)
P20.0128 (3)0.0128 (3)0.0115 (5)0.00638 (15)0.0000.000
C10.0165 (12)0.0169 (12)0.0164 (12)0.0109 (10)0.0017 (9)0.0010 (9)
C20.0184 (13)0.0234 (13)0.0202 (12)0.0122 (11)0.0052 (10)0.0029 (10)
C30.0230 (13)0.0192 (13)0.0232 (13)0.0135 (11)0.0014 (11)0.0006 (10)
C40.0262 (14)0.0253 (14)0.0110 (11)0.0146 (12)0.0016 (10)0.0005 (10)
C50.0128 (11)0.0153 (12)0.0153 (11)0.0054 (10)0.0014 (9)0.0028 (9)
C60.0139 (12)0.0153 (12)0.0229 (13)0.0014 (10)0.0047 (10)0.0004 (10)
C70.0219 (13)0.0227 (14)0.0190 (13)0.0120 (11)0.0002 (10)0.0043 (10)
C80.0209 (13)0.0160 (12)0.0134 (11)0.0067 (10)0.0009 (10)0.0000 (9)
C90.0129 (11)0.0125 (11)0.0193 (12)0.0064 (9)0.0024 (9)0.0021 (9)
C100.0167 (12)0.0156 (12)0.0231 (13)0.0071 (10)0.0019 (10)0.0012 (10)
C110.0145 (12)0.0191 (12)0.0221 (12)0.0089 (10)0.0051 (10)0.0028 (10)
C120.0174 (12)0.0142 (12)0.0227 (13)0.0057 (10)0.0019 (10)0.0044 (10)
C130.0146 (12)0.0152 (12)0.0139 (11)0.0059 (10)0.0022 (9)0.0012 (9)
C140.0137 (12)0.0226 (13)0.0211 (12)0.0083 (11)0.0013 (10)0.0002 (10)
C150.0159 (12)0.0170 (12)0.0224 (13)0.0050 (10)0.0004 (10)0.0018 (10)
C160.0231 (13)0.0239 (13)0.0148 (12)0.0112 (11)0.0048 (10)0.0041 (10)
Geometric parameters (Å, º) top
I1—Cu12.7300 (4)C7—H7B0.9800
I2—Cu12.7204 (4)C7—H7C0.9800
I2—Cu22.7273 (3)C8—H8A0.9800
Cu1—P12.2522 (7)C8—H8B0.9800
Cu1—I2i2.7405 (4)C8—H8C0.9800
Cu2—P22.251 (1)C9—C121.535 (3)
P1—C51.906 (2)C9—C101.539 (3)
P1—C91.909 (2)C9—C111.542 (3)
P1—C11.909 (2)C10—H10A0.9800
P2—C131.905 (2)C10—H10B0.9800
C1—C31.535 (3)C10—H10C0.9800
C1—C21.542 (3)C11—H11A0.9800
C1—C41.544 (3)C11—H11B0.9800
C2—H2A0.9800C11—H11C0.9800
C2—H2B0.9800C12—H12A0.9800
C2—H2C0.9800C12—H12B0.9800
C3—H3A0.9800C12—H12C0.9800
C3—H3B0.9800C13—C161.538 (3)
C3—H3C0.9800C13—C151.539 (3)
C4—H4A0.9800C13—C141.542 (3)
C4—H4B0.9800C14—H14A0.9800
C4—H4C0.9800C14—H14B0.9800
C5—C71.541 (3)C14—H14C0.9800
C5—C81.542 (3)C15—H15A0.9800
C5—C61.547 (3)C15—H15B0.9800
C6—H6A0.9800C15—H15C0.9800
C6—H6B0.9800C16—H16A0.9800
C6—H6C0.9800C16—H16B0.9800
C7—H7A0.9800C16—H16C0.9800
Cu1i—I1—Cu181.62 (1)H7A—C7—H7B109.5
Cu1—I2—Cu281.36 (1)C5—C7—H7C109.5
Cu1—I2—Cu1ii81.61 (1)H7A—C7—H7C109.5
Cu2—I2—Cu1ii81.00 (1)H7B—C7—H7C109.5
P1—Cu1—I2120.22 (2)C5—C8—H8A109.5
P1—Cu1—I1119.15 (2)C5—C8—H8B109.5
I2—Cu1—I198.03 (1)H8A—C8—H8B109.5
P1—Cu1—I2i118.96 (2)C5—C8—H8C109.5
I2—Cu1—I2i98.13 (1)H8A—C8—H8C109.5
I1—Cu1—I2i97.54 (1)H8B—C8—H8C109.5
P2—Cu2—I2119.155 (11)C12—C9—C10108.5 (2)
I2—Cu2—I2ii98.28 (1)C12—C9—C11109.3 (2)
C5—P1—C9108.35 (11)C10—C9—C11105.3 (2)
C5—P1—C1108.09 (11)C12—C9—P1115.86 (17)
C9—P1—C1108.33 (11)C10—C9—P1110.06 (17)
C5—P1—Cu1110.69 (8)C11—C9—P1107.24 (16)
C9—P1—Cu1110.36 (8)C9—C10—H10A109.5
C1—P1—Cu1110.93 (8)C9—C10—H10B109.5
C13—P2—C13ii108.38 (8)H10A—C10—H10B109.5
C13—P2—Cu2110.54 (8)C9—C10—H10C109.5
C3—C1—C2108.5 (2)H10A—C10—H10C109.5
C3—C1—C4109.6 (2)H10B—C10—H10C109.5
C2—C1—C4105.0 (2)C9—C11—H11A109.5
C3—C1—P1116.34 (17)C9—C11—H11B109.5
C2—C1—P1109.95 (17)H11A—C11—H11B109.5
C4—C1—P1106.82 (16)C9—C11—H11C109.5
C1—C2—H2A109.5H11A—C11—H11C109.5
C1—C2—H2B109.5H11B—C11—H11C109.5
H2A—C2—H2B109.5C9—C12—H12A109.5
C1—C2—H2C109.5C9—C12—H12B109.5
H2A—C2—H2C109.5H12A—C12—H12B109.5
H2B—C2—H2C109.5C9—C12—H12C109.5
C1—C3—H3A109.5H12A—C12—H12C109.5
C1—C3—H3B109.5H12B—C12—H12C109.5
H3A—C3—H3B109.5C16—C13—C15109.5 (2)
C1—C3—H3C109.5C16—C13—C14108.1 (2)
H3A—C3—H3C109.5C15—C13—C14105.0 (2)
H3B—C3—H3C109.5C16—C13—P2116.54 (17)
C1—C4—H4A109.5C15—C13—P2107.20 (16)
C1—C4—H4B109.5C14—C13—P2109.88 (17)
H4A—C4—H4B109.5C13—C14—H14A109.5
C1—C4—H4C109.5C13—C14—H14B109.5
H4A—C4—H4C109.5H14A—C14—H14B109.5
H4B—C4—H4C109.5C13—C14—H14C109.5
C7—C5—C8108.1 (2)H14A—C14—H14C109.5
C7—C5—C6109.3 (2)H14B—C14—H14C109.5
C8—C5—C6105.1 (2)C13—C15—H15A109.5
C7—C5—P1116.38 (18)C13—C15—H15B109.5
C8—C5—P1109.92 (17)H15A—C15—H15B109.5
C6—C5—P1107.48 (16)C13—C15—H15C109.5
C5—C6—H6A109.5H15A—C15—H15C109.5
C5—C6—H6B109.5H15B—C15—H15C109.5
H6A—C6—H6B109.5C13—C16—H16A109.5
C5—C6—H6C109.5C13—C16—H16B109.5
H6A—C6—H6C109.5H16A—C16—H16B109.5
H6B—C6—H6C109.5C13—C16—H16C109.5
C5—C7—H7A109.5H16A—C16—H16C109.5
C5—C7—H7B109.5H16B—C16—H16C109.5
Symmetry codes: (i) x+y+1, x+1, z; (ii) y+1, xy, z.
Comparison of metrical parameters for R3PMX cubanes top
CompoundM—X (Å)M—P (Å)X—M—X (°)X—M—P (°)M—X—M (°)Reference
[Et3PCuI]42.684 (1)2.254 (3)109.38 (4)109.56 (8)66.10 (4)a
[Ph3PCuCl]42.4441 (8)2.192 (2)94.09 (2)122.02 (3)85.16 (2)b
[t-Bu3PCuBr]42.5930 (6)2.228 (3)95.29 (2)121.42 (4)84.45 (2)c
[t-Bu3PCuI]42.7297 (2)2.2519 (7)98.090 (4)119.30 (1)81.472 (4)d
[Et3PAgI]42.9189 (6)2.438 (2)109.01 (1)109.93 (2)66.68 (1)e
[Ph3PAgCl]42.653 (1)2.382 (2)92.72 (3)122.35 (4)86.48 (3)f
References: (a) Churchill & Kalra (1974b); (b) Churchill & Kalra (1974a); (c) Goel & Beauchamp (1983); (d) this work; (e) Teo & Calabrese (1976a); (f) Churchill & DeBoer (1975).
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds