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
CCDC reference: 282577
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (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
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-µ
3iodo-tetrakis[(tri-
tert-butylphosphine)copper(I)]
top
Crystal data top
[Cu4I4(C12H27P)4] | Dx = 1.558 Mg m−3 |
Mr = 1571.03 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 9205 reflections |
Hall symbol: -R 3 | θ = 2.4–28.2° |
a = 13.878 (1) Å | µ = 3.22 mm−1 |
c = 60.239 (7) Å | T = 100 K |
V = 10047.7 (16) Å3 | Block, colorless |
Z = 6 | 0.13 × 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 tube | 4891 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
φ and ω scans | θmax = 28.3°, θmin = 1.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −18→18 |
Tmin = 0.624, Tmax = 0.750 | k = −18→17 |
30297 measured reflections | l = −79→78 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.027 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.057 | H-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 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −0.42 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
I1 | 0.6667 | 0.3333 | 0.124796 (4) | 0.01354 (6) | |
I2 | 0.492061 (12) | 0.327202 (12) | 0.069105 (3) | 0.01320 (5) | |
Cu1 | 0.66025 (3) | 0.47848 (3) | 0.095061 (5) | 0.01550 (7) | |
Cu2 | 0.6667 | 0.3333 | 0.047048 (8) | 0.01576 (11) | |
P1 | 0.65672 (5) | 0.62935 (5) | 0.107749 (10) | 0.01192 (12) | |
P2 | 0.6667 | 0.3333 | 0.009673 (17) | 0.0123 (2) | |
C1 | 0.6009 (2) | 0.6873 (2) | 0.08565 (4) | 0.0155 (5) | |
C2 | 0.4739 (2) | 0.6114 (2) | 0.08333 (4) | 0.0199 (5) | |
H2A | 0.4371 | 0.6170 | 0.0968 | 0.030* | |
H2B | 0.4563 | 0.5342 | 0.0813 | 0.030* | |
H2C | 0.4476 | 0.6347 | 0.0704 | 0.030* | |
C3 | 0.6262 (2) | 0.8074 (2) | 0.08903 (4) | 0.0205 (5) | |
H3A | 0.5920 | 0.8277 | 0.0771 | 0.031* | |
H3B | 0.7069 | 0.8577 | 0.0889 | 0.031* | |
H3C | 0.5960 | 0.8133 | 0.1033 | 0.031* | |
C4 | 0.6491 (2) | 0.6777 (2) | 0.06320 (4) | 0.0201 (5) | |
H4A | 0.6307 | 0.6005 | 0.0609 | 0.030* | |
H4B | 0.7301 | 0.7261 | 0.0633 | 0.030* | |
H4C | 0.6171 | 0.7004 | 0.0512 | 0.030* | |
C5 | 0.5637 (2) | 0.5929 (2) | 0.13326 (4) | 0.0152 (5) | |
C6 | 0.4605 (2) | 0.4770 (2) | 0.12918 (4) | 0.0200 (5) | |
H6A | 0.4139 | 0.4531 | 0.1425 | 0.030* | |
H6B | 0.4846 | 0.4233 | 0.1258 | 0.030* | |
H6C | 0.4176 | 0.4814 | 0.1167 | 0.030* | |
C7 | 0.5253 (2) | 0.6759 (2) | 0.13965 (4) | 0.0208 (5) | |
H7A | 0.4817 | 0.6512 | 0.1534 | 0.031* | |
H7B | 0.4794 | 0.6797 | 0.1277 | 0.031* | |
H7C | 0.5906 | 0.7497 | 0.1420 | 0.031* | |
C8 | 0.6224 (2) | 0.5773 (2) | 0.15353 (4) | 0.0179 (5) | |
H8A | 0.6860 | 0.6493 | 0.1578 | 0.027* | |
H8B | 0.6486 | 0.5256 | 0.1497 | 0.027* | |
H8C | 0.5700 | 0.5472 | 0.1660 | 0.027* | |
C9 | 0.8030 (2) | 0.7433 (2) | 0.11575 (4) | 0.0148 (5) | |
C10 | 0.8721 (2) | 0.7979 (2) | 0.09475 (4) | 0.0189 (5) | |
H10A | 0.8424 | 0.8399 | 0.0871 | 0.028* | |
H10B | 0.8681 | 0.7401 | 0.0848 | 0.028* | |
H10C | 0.9497 | 0.8484 | 0.0989 | 0.028* | |
C11 | 0.8606 (2) | 0.6862 (2) | 0.12718 (4) | 0.0183 (5) | |
H11A | 0.8603 | 0.6304 | 0.1172 | 0.027* | |
H11B | 0.8206 | 0.6498 | 0.1408 | 0.027* | |
H11C | 0.9375 | 0.7420 | 0.1308 | 0.027* | |
C12 | 0.8095 (2) | 0.8352 (2) | 0.13095 (4) | 0.0191 (5) | |
H12A | 0.8877 | 0.8910 | 0.1335 | 0.029* | |
H12B | 0.7736 | 0.8027 | 0.1452 | 0.029* | |
H12C | 0.7715 | 0.8706 | 0.1239 | 0.029* | |
C13 | 0.5230 (2) | 0.2292 (2) | −0.00142 (4) | 0.0152 (5) | |
C14 | 0.4434 (2) | 0.2755 (2) | 0.00152 (4) | 0.0195 (5) | |
H14A | 0.3673 | 0.2173 | −0.0020 | 0.029* | |
H14B | 0.4657 | 0.3390 | −0.0085 | 0.029* | |
H14C | 0.4465 | 0.2997 | 0.0169 | 0.029* | |
C15 | 0.4758 (2) | 0.1261 (2) | 0.01369 (4) | 0.0199 (5) | |
H15A | 0.4776 | 0.1487 | 0.0292 | 0.030* | |
H15B | 0.5209 | 0.0902 | 0.0121 | 0.030* | |
H15C | 0.3988 | 0.0736 | 0.0094 | 0.030* | |
C16 | 0.5170 (2) | 0.1934 (2) | −0.02576 (4) | 0.0209 (5) | |
H16A | 0.4392 | 0.1430 | −0.0299 | 0.031* | |
H16B | 0.5597 | 0.1550 | −0.0276 | 0.031* | |
H16C | 0.5484 | 0.2592 | −0.0354 | 0.031* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.01315 (8) | 0.01315 (8) | 0.01434 (12) | 0.00657 (4) | 0.000 | 0.000 |
I2 | 0.01288 (8) | 0.01280 (8) | 0.01346 (8) | 0.00607 (6) | −0.00018 (6) | −0.00027 (6) |
Cu1 | 0.01724 (16) | 0.01329 (14) | 0.01723 (15) | 0.00856 (13) | −0.00067 (12) | −0.00231 (12) |
Cu2 | 0.01739 (16) | 0.01739 (16) | 0.0125 (2) | 0.00869 (8) | 0.000 | 0.000 |
P1 | 0.0116 (3) | 0.0112 (3) | 0.0128 (3) | 0.0055 (2) | −0.0008 (2) | −0.0013 (2) |
P2 | 0.0128 (3) | 0.0128 (3) | 0.0115 (5) | 0.00638 (15) | 0.000 | 0.000 |
C1 | 0.0165 (12) | 0.0169 (12) | 0.0164 (12) | 0.0109 (10) | −0.0017 (9) | −0.0010 (9) |
C2 | 0.0184 (13) | 0.0234 (13) | 0.0202 (12) | 0.0122 (11) | −0.0052 (10) | −0.0029 (10) |
C3 | 0.0230 (13) | 0.0192 (13) | 0.0232 (13) | 0.0135 (11) | −0.0014 (11) | 0.0006 (10) |
C4 | 0.0262 (14) | 0.0253 (14) | 0.0110 (11) | 0.0146 (12) | −0.0016 (10) | −0.0005 (10) |
C5 | 0.0128 (11) | 0.0153 (12) | 0.0153 (11) | 0.0054 (10) | 0.0014 (9) | −0.0028 (9) |
C6 | 0.0139 (12) | 0.0153 (12) | 0.0229 (13) | 0.0014 (10) | 0.0047 (10) | 0.0004 (10) |
C7 | 0.0219 (13) | 0.0227 (14) | 0.0190 (13) | 0.0120 (11) | 0.0002 (10) | −0.0043 (10) |
C8 | 0.0209 (13) | 0.0160 (12) | 0.0134 (11) | 0.0067 (10) | 0.0009 (10) | 0.0000 (9) |
C9 | 0.0129 (11) | 0.0125 (11) | 0.0193 (12) | 0.0064 (9) | −0.0024 (9) | −0.0021 (9) |
C10 | 0.0167 (12) | 0.0156 (12) | 0.0231 (13) | 0.0071 (10) | 0.0019 (10) | 0.0012 (10) |
C11 | 0.0145 (12) | 0.0191 (12) | 0.0221 (12) | 0.0089 (10) | −0.0051 (10) | −0.0028 (10) |
C12 | 0.0174 (12) | 0.0142 (12) | 0.0227 (13) | 0.0057 (10) | −0.0019 (10) | −0.0044 (10) |
C13 | 0.0146 (12) | 0.0152 (12) | 0.0139 (11) | 0.0059 (10) | −0.0022 (9) | −0.0012 (9) |
C14 | 0.0137 (12) | 0.0226 (13) | 0.0211 (12) | 0.0083 (11) | −0.0013 (10) | −0.0002 (10) |
C15 | 0.0159 (12) | 0.0170 (12) | 0.0224 (13) | 0.0050 (10) | −0.0004 (10) | 0.0018 (10) |
C16 | 0.0231 (13) | 0.0239 (13) | 0.0148 (12) | 0.0112 (11) | −0.0048 (10) | −0.0041 (10) |
Geometric parameters (Å, º) top
I1—Cu1 | 2.7300 (4) | C7—H7B | 0.9800 |
I2—Cu1 | 2.7204 (4) | C7—H7C | 0.9800 |
I2—Cu2 | 2.7273 (3) | C8—H8A | 0.9800 |
Cu1—P1 | 2.2522 (7) | C8—H8B | 0.9800 |
Cu1—I2i | 2.7405 (4) | C8—H8C | 0.9800 |
Cu2—P2 | 2.251 (1) | C9—C12 | 1.535 (3) |
P1—C5 | 1.906 (2) | C9—C10 | 1.539 (3) |
P1—C9 | 1.909 (2) | C9—C11 | 1.542 (3) |
P1—C1 | 1.909 (2) | C10—H10A | 0.9800 |
P2—C13 | 1.905 (2) | C10—H10B | 0.9800 |
C1—C3 | 1.535 (3) | C10—H10C | 0.9800 |
C1—C2 | 1.542 (3) | C11—H11A | 0.9800 |
C1—C4 | 1.544 (3) | C11—H11B | 0.9800 |
C2—H2A | 0.9800 | C11—H11C | 0.9800 |
C2—H2B | 0.9800 | C12—H12A | 0.9800 |
C2—H2C | 0.9800 | C12—H12B | 0.9800 |
C3—H3A | 0.9800 | C12—H12C | 0.9800 |
C3—H3B | 0.9800 | C13—C16 | 1.538 (3) |
C3—H3C | 0.9800 | C13—C15 | 1.539 (3) |
C4—H4A | 0.9800 | C13—C14 | 1.542 (3) |
C4—H4B | 0.9800 | C14—H14A | 0.9800 |
C4—H4C | 0.9800 | C14—H14B | 0.9800 |
C5—C7 | 1.541 (3) | C14—H14C | 0.9800 |
C5—C8 | 1.542 (3) | C15—H15A | 0.9800 |
C5—C6 | 1.547 (3) | C15—H15B | 0.9800 |
C6—H6A | 0.9800 | C15—H15C | 0.9800 |
C6—H6B | 0.9800 | C16—H16A | 0.9800 |
C6—H6C | 0.9800 | C16—H16B | 0.9800 |
C7—H7A | 0.9800 | C16—H16C | 0.9800 |
| | | |
Cu1i—I1—Cu1 | 81.62 (1) | H7A—C7—H7B | 109.5 |
Cu1—I2—Cu2 | 81.36 (1) | C5—C7—H7C | 109.5 |
Cu1—I2—Cu1ii | 81.61 (1) | H7A—C7—H7C | 109.5 |
Cu2—I2—Cu1ii | 81.00 (1) | H7B—C7—H7C | 109.5 |
P1—Cu1—I2 | 120.22 (2) | C5—C8—H8A | 109.5 |
P1—Cu1—I1 | 119.15 (2) | C5—C8—H8B | 109.5 |
I2—Cu1—I1 | 98.03 (1) | H8A—C8—H8B | 109.5 |
P1—Cu1—I2i | 118.96 (2) | C5—C8—H8C | 109.5 |
I2—Cu1—I2i | 98.13 (1) | H8A—C8—H8C | 109.5 |
I1—Cu1—I2i | 97.54 (1) | H8B—C8—H8C | 109.5 |
P2—Cu2—I2 | 119.155 (11) | C12—C9—C10 | 108.5 (2) |
I2—Cu2—I2ii | 98.28 (1) | C12—C9—C11 | 109.3 (2) |
C5—P1—C9 | 108.35 (11) | C10—C9—C11 | 105.3 (2) |
C5—P1—C1 | 108.09 (11) | C12—C9—P1 | 115.86 (17) |
C9—P1—C1 | 108.33 (11) | C10—C9—P1 | 110.06 (17) |
C5—P1—Cu1 | 110.69 (8) | C11—C9—P1 | 107.24 (16) |
C9—P1—Cu1 | 110.36 (8) | C9—C10—H10A | 109.5 |
C1—P1—Cu1 | 110.93 (8) | C9—C10—H10B | 109.5 |
C13—P2—C13ii | 108.38 (8) | H10A—C10—H10B | 109.5 |
C13—P2—Cu2 | 110.54 (8) | C9—C10—H10C | 109.5 |
C3—C1—C2 | 108.5 (2) | H10A—C10—H10C | 109.5 |
C3—C1—C4 | 109.6 (2) | H10B—C10—H10C | 109.5 |
C2—C1—C4 | 105.0 (2) | C9—C11—H11A | 109.5 |
C3—C1—P1 | 116.34 (17) | C9—C11—H11B | 109.5 |
C2—C1—P1 | 109.95 (17) | H11A—C11—H11B | 109.5 |
C4—C1—P1 | 106.82 (16) | C9—C11—H11C | 109.5 |
C1—C2—H2A | 109.5 | H11A—C11—H11C | 109.5 |
C1—C2—H2B | 109.5 | H11B—C11—H11C | 109.5 |
H2A—C2—H2B | 109.5 | C9—C12—H12A | 109.5 |
C1—C2—H2C | 109.5 | C9—C12—H12B | 109.5 |
H2A—C2—H2C | 109.5 | H12A—C12—H12B | 109.5 |
H2B—C2—H2C | 109.5 | C9—C12—H12C | 109.5 |
C1—C3—H3A | 109.5 | H12A—C12—H12C | 109.5 |
C1—C3—H3B | 109.5 | H12B—C12—H12C | 109.5 |
H3A—C3—H3B | 109.5 | C16—C13—C15 | 109.5 (2) |
C1—C3—H3C | 109.5 | C16—C13—C14 | 108.1 (2) |
H3A—C3—H3C | 109.5 | C15—C13—C14 | 105.0 (2) |
H3B—C3—H3C | 109.5 | C16—C13—P2 | 116.54 (17) |
C1—C4—H4A | 109.5 | C15—C13—P2 | 107.20 (16) |
C1—C4—H4B | 109.5 | C14—C13—P2 | 109.88 (17) |
H4A—C4—H4B | 109.5 | C13—C14—H14A | 109.5 |
C1—C4—H4C | 109.5 | C13—C14—H14B | 109.5 |
H4A—C4—H4C | 109.5 | H14A—C14—H14B | 109.5 |
H4B—C4—H4C | 109.5 | C13—C14—H14C | 109.5 |
C7—C5—C8 | 108.1 (2) | H14A—C14—H14C | 109.5 |
C7—C5—C6 | 109.3 (2) | H14B—C14—H14C | 109.5 |
C8—C5—C6 | 105.1 (2) | C13—C15—H15A | 109.5 |
C7—C5—P1 | 116.38 (18) | C13—C15—H15B | 109.5 |
C8—C5—P1 | 109.92 (17) | H15A—C15—H15B | 109.5 |
C6—C5—P1 | 107.48 (16) | C13—C15—H15C | 109.5 |
C5—C6—H6A | 109.5 | H15A—C15—H15C | 109.5 |
C5—C6—H6B | 109.5 | H15B—C15—H15C | 109.5 |
H6A—C6—H6B | 109.5 | C13—C16—H16A | 109.5 |
C5—C6—H6C | 109.5 | C13—C16—H16B | 109.5 |
H6A—C6—H6C | 109.5 | H16A—C16—H16B | 109.5 |
H6B—C6—H6C | 109.5 | C13—C16—H16C | 109.5 |
C5—C7—H7A | 109.5 | H16A—C16—H16C | 109.5 |
C5—C7—H7B | 109.5 | H16B—C16—H16C | 109.5 |
Symmetry codes: (i) −x+y+1, −x+1, z; (ii) −y+1, x−y, z. |
Comparison of metrical parameters for R3PMX cubanes topCompound | M—X (Å) | M—P (Å) | X—M—X (°) | X—M—P (°) | M—X—M (°) | Reference |
[Et3PCuI]4 | 2.684 (1) | 2.254 (3) | 109.38 (4) | 109.56 (8) | 66.10 (4) | a |
[Ph3PCuCl]4 | 2.4441 (8) | 2.192 (2) | 94.09 (2) | 122.02 (3) | 85.16 (2) | b |
[t-Bu3PCuBr]4 | 2.5930 (6) | 2.228 (3) | 95.29 (2) | 121.42 (4) | 84.45 (2) | c |
[t-Bu3PCuI]4 | 2.7297 (2) | 2.2519 (7) | 98.090 (4) | 119.30 (1) | 81.472 (4) | d |
[Et3PAgI]4 | 2.9189 (6) | 2.438 (2) | 109.01 (1) | 109.93 (2) | 66.68 (1) | e |
[Ph3PAgCl]4 | 2.653 (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). |