Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013551/ya6052sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013551/ya6052Isup2.hkl |
CCDC reference: 172197
A solution of n-BuLi (3.00 mmol) in 1.2 ml of hexane was added at ambient temperature to DmpI (1.07 g, 3.00 mmol) in 20 ml of toluene. After 2 h, CuOtBu (0.41 g, 3.00 mmol) was added via a solid-addition tube and stirring was continued for 14 h. The resulting amber solution was concentrated under reduced pressure. Cooling in a 248 K freezer afforded colorless crystals of (CuDmp)2 in 55% yield. All volatile materials were removed from the mother liquor and the residue was redissolved in a small amount of diethyl ether. After cooling to 248 K, colorless needles of (I) were obtained in ca 3% yield. The origin of the CuI content in (I) can be explained by the presence of LiI impurities (formed by a side reaction from nBuLi and nBuI) followed by an exchange reaction with CuOtBu. M.p.: crystals change color to orange > 353 K and decompose to a black liquid at 497–501 K. IR (Nujol, cm-1): 1610 (m), 1358 (m), 1173 (m), 1080 (w), 1028 (m), 1014 (w), 942 (m), 845 (s), 801 (ms), 770 (w), 740 (s), 716 (ms), 625 (m), 589 (w), 570 (m), 545 (w), 506 (w), 385 (w). EI—MS (70 eV): m/z (%) 1078.3 (0.003%) [M+ with 63Cu].
The H atoms were placed in the idealized positions and refined in a riding-model approximation, including free rotation for methyl groups. For most H atoms the assigned Ueq was allowed to refine freely. Isotropic displacement parameters being larger than 0.15 were constrained to 1.2 Ueq of the parent atom.
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL.
[Cu4(C24H25)2(C4H9O)I] | F(000) = 1096 |
Mr = 1081.05 | Dx = 1.503 Mg m−3 |
Triclinic, P1 | Melting point: crystals change color to orange at ca 353 K and decompose to a black liquid at 497-501 K K |
a = 12.3307 (14) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.6105 (10) Å | Cell parameters from 37 reflections |
c = 16.3613 (12) Å | θ = 11.5–12.5° |
α = 89.734 (6)° | µ = 2.44 mm−1 |
β = 80.137 (7)° | T = 173 K |
γ = 72.592 (9)° | Needle, colorless |
V = 2388.8 (4) Å3 | 0.70 × 0.15 × 0.05 mm |
Z = 2 |
Siemens P4 diffractometer | 5430 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.050 |
Graphite monochromator | θmax = 26.0°, θmin = 2.0° |
ω scans | h = −15→15 |
Absorption correction: ψ scan (North et al., 1968) | k = −14→15 |
Tmin = 0.280, Tmax = 0.888 | l = −19→20 |
9829 measured reflections | 2 standard reflections every 198 reflections |
9372 independent reflections | intensity decay: none |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.059 | Only H-atom displacement parameters refined |
S = 0.72 | w = 1/[σ2(Fo2) + (0.0129P)2] where P = (Fo2 + 2Fc2)/3 |
9372 reflections | (Δ/σ)max = 0.002 |
594 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
[Cu4(C24H25)2(C4H9O)I] | γ = 72.592 (9)° |
Mr = 1081.05 | V = 2388.8 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 12.3307 (14) Å | Mo Kα radiation |
b = 12.6105 (10) Å | µ = 2.44 mm−1 |
c = 16.3613 (12) Å | T = 173 K |
α = 89.734 (6)° | 0.70 × 0.15 × 0.05 mm |
β = 80.137 (7)° |
Siemens P4 diffractometer | 5430 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.050 |
Tmin = 0.280, Tmax = 0.888 | 2 standard reflections every 198 reflections |
9829 measured reflections | intensity decay: none |
9372 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.059 | Only H-atom displacement parameters refined |
S = 0.72 | Δρmax = 0.63 e Å−3 |
9372 reflections | Δρmin = −0.36 e Å−3 |
594 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.08158 (5) | 0.13506 (5) | 0.79467 (3) | 0.02608 (13) | |
Cu2 | 0.09458 (5) | 0.13644 (5) | 0.64811 (3) | 0.03205 (15) | |
Cu3 | 0.24573 (5) | 0.25757 (5) | 0.63380 (3) | 0.03069 (14) | |
Cu4 | 0.23489 (5) | 0.26779 (5) | 0.78012 (3) | 0.02564 (13) | |
I | 0.17975 (3) | 0.19354 (3) | 0.515577 (18) | 0.03773 (9) | |
O | 0.1557 (3) | 0.1998 (2) | 0.86031 (16) | 0.0307 (7) | |
C1 | −0.0005 (4) | 0.0647 (4) | 0.7314 (2) | 0.0244 (10) | |
C2 | 0.0401 (4) | −0.0447 (4) | 0.6921 (2) | 0.0267 (10) | |
C3 | −0.0377 (4) | −0.0973 (4) | 0.6734 (3) | 0.0370 (12) | |
H3A | −0.0092 | −0.1701 | 0.6477 | 0.052 (15)* | |
C4 | −0.1542 (4) | −0.0466 (4) | 0.6911 (3) | 0.0376 (12) | |
H4A | −0.2058 | −0.0825 | 0.6755 | 0.060 (16)* | |
C5 | −0.1969 (4) | 0.0578 (4) | 0.7321 (3) | 0.0323 (11) | |
H5A | −0.2780 | 0.0918 | 0.7470 | 0.029 (12)* | |
C6 | −0.1218 (4) | 0.1122 (3) | 0.7513 (2) | 0.0236 (10) | |
C7 | 0.1678 (4) | −0.1080 (4) | 0.6693 (3) | 0.0287 (11) | |
C8 | 0.2336 (4) | −0.1473 (4) | 0.7309 (3) | 0.0320 (11) | |
C9 | 0.3492 (4) | −0.2081 (4) | 0.7068 (3) | 0.0371 (12) | |
H9A | 0.3939 | −0.2345 | 0.7487 | 0.018 (11)* | |
C10 | 0.4015 (4) | −0.2316 (4) | 0.6254 (3) | 0.0375 (12) | |
C11 | 0.3332 (4) | −0.1944 (4) | 0.5649 (3) | 0.0419 (14) | |
H11A | 0.3676 | −0.2100 | 0.5080 | 0.034 (12)* | |
C12 | 0.2173 (4) | −0.1355 (4) | 0.5850 (3) | 0.0340 (12) | |
C13 | 0.1819 (5) | −0.1281 (5) | 0.8226 (3) | 0.0468 (14) | |
H13A | 0.2169 | −0.1936 | 0.8524 | 0.062 (17)* | |
H13B | 0.0983 | −0.1154 | 0.8300 | 0.11 (3)* | |
H13C | 0.1969 | −0.0628 | 0.8447 | 0.061 (17)* | |
C14 | 0.5285 (4) | −0.2938 (5) | 0.5997 (4) | 0.0585 (17) | |
H14A | 0.5399 | −0.3411 | 0.5497 | 0.10 (2)* | |
H14B | 0.5557 | −0.3402 | 0.6447 | 0.07 (2)* | |
H14C | 0.5722 | −0.2404 | 0.5881 | 0.08 (2)* | |
C15 | 0.1504 (5) | −0.1053 (5) | 0.5152 (3) | 0.0493 (15) | |
H15A | 0.2031 | −0.1010 | 0.4641 | 0.070 (18)* | |
H15B | 0.0914 | −0.0329 | 0.5289 | 0.038 (14)* | |
H15C | 0.1131 | −0.1621 | 0.5072 | 0.09 (2)* | |
C16 | −0.1758 (4) | 0.2207 (4) | 0.8022 (2) | 0.0271 (10) | |
C17 | −0.2182 (4) | 0.2166 (4) | 0.8876 (3) | 0.0319 (11) | |
C18 | −0.2731 (4) | 0.3147 (4) | 0.9351 (3) | 0.0391 (12) | |
H18A | −0.2986 | 0.3107 | 0.9929 | 0.056 (16)* | |
C19 | −0.2920 (4) | 0.4172 (4) | 0.9018 (3) | 0.0417 (13) | |
C20 | −0.2525 (4) | 0.4208 (4) | 0.8173 (3) | 0.0422 (13) | |
H20A | −0.2659 | 0.4910 | 0.7928 | 0.058 (16)* | |
C21 | −0.1944 (4) | 0.3256 (4) | 0.7677 (3) | 0.0332 (11) | |
C22 | −0.2071 (5) | 0.1058 (4) | 0.9263 (3) | 0.0433 (13) | |
H22A | −0.2213 | 0.1165 | 0.9869 | 0.058 (16)* | |
H22B | −0.1291 | 0.0554 | 0.9073 | 0.039 (14)* | |
H22C | −0.2638 | 0.0737 | 0.9098 | 0.075 (19)* | |
C23 | −0.3514 (5) | 0.5233 (5) | 0.9551 (4) | 0.0715 (19) | |
H23A | −0.3707 | 0.5048 | 1.0130 | 0.11 (3)* | |
H23B | −0.4223 | 0.5641 | 0.9354 | 0.134* | |
H23C | −0.2997 | 0.5696 | 0.9516 | 0.10 (2)* | |
C24 | −0.1533 (5) | 0.3367 (4) | 0.6758 (3) | 0.0455 (13) | |
H24A | −0.1504 | 0.2697 | 0.6444 | 0.035 (13)* | |
H24B | −0.0760 | 0.3459 | 0.6678 | 0.067 (19)* | |
H24C | −0.2069 | 0.4018 | 0.6561 | 0.11 (3)* | |
C25 | 0.3363 (4) | 0.3262 (3) | 0.6992 (2) | 0.0235 (10) | |
C26 | 0.3118 (4) | 0.4350 (4) | 0.6694 (2) | 0.0286 (10) | |
C27 | 0.4005 (4) | 0.4770 (4) | 0.6335 (3) | 0.0352 (12) | |
H27A | 0.3827 | 0.5493 | 0.6123 | 0.025 (11)* | |
C28 | 0.5146 (5) | 0.4134 (4) | 0.6289 (3) | 0.0427 (13) | |
H28A | 0.5747 | 0.4418 | 0.6035 | 0.080 (19)* | |
C29 | 0.5419 (4) | 0.3085 (4) | 0.6608 (3) | 0.0364 (12) | |
H29A | 0.6205 | 0.2667 | 0.6592 | 0.035 (13)* | |
C30 | 0.4543 (4) | 0.2643 (4) | 0.6953 (2) | 0.0274 (10) | |
C31 | 0.1884 (4) | 0.5086 (4) | 0.6808 (3) | 0.0319 (11) | |
C32 | 0.1336 (5) | 0.5537 (4) | 0.7613 (3) | 0.0409 (13) | |
C33 | 0.0156 (5) | 0.6088 (5) | 0.7751 (4) | 0.068 (2) | |
H33A | −0.0221 | 0.6364 | 0.8298 | 0.051 (15)* | |
C34 | −0.0474 (5) | 0.6245 (5) | 0.7137 (5) | 0.067 (2) | |
C35 | 0.0099 (5) | 0.5883 (4) | 0.6340 (4) | 0.0590 (17) | |
H35A | −0.0327 | 0.6029 | 0.5899 | 0.042 (14)* | |
C36 | 0.1275 (5) | 0.5315 (4) | 0.6154 (3) | 0.0384 (12) | |
C37 | 0.2029 (5) | 0.5453 (5) | 0.8316 (3) | 0.0600 (18) | |
H37A | 0.1523 | 0.5867 | 0.8813 | 0.12 (2)* | |
H37B | 0.2665 | 0.5767 | 0.8145 | 0.08 (2)* | |
H37C | 0.2342 | 0.4670 | 0.8438 | 0.018 (11)* | |
C38 | −0.1752 (5) | 0.6793 (6) | 0.7282 (5) | 0.114 (3) | |
H38A | −0.1979 | 0.7305 | 0.7773 | 0.040 (16)* | |
H38B | −0.2150 | 0.6225 | 0.7372 | 0.13 (3)* | |
H38C | −0.1966 | 0.7208 | 0.6796 | 0.159* | |
C39 | 0.1881 (5) | 0.5034 (5) | 0.5258 (3) | 0.0533 (15) | |
H39A | 0.2438 | 0.4287 | 0.5213 | 0.059 (17)* | |
H39B | 0.2288 | 0.5577 | 0.5078 | 0.061 (17)* | |
H39C | 0.1309 | 0.5057 | 0.4904 | 0.09 (2)* | |
C40 | 0.4835 (3) | 0.1563 (4) | 0.7380 (2) | 0.0242 (10) | |
C41 | 0.5020 (4) | 0.0542 (4) | 0.6966 (2) | 0.0269 (10) | |
C42 | 0.5254 (4) | −0.0418 (4) | 0.7407 (3) | 0.0333 (11) | |
H42A | 0.5406 | −0.1114 | 0.7120 | 0.044 (14)* | |
C43 | 0.5273 (4) | −0.0397 (4) | 0.8251 (3) | 0.0375 (12) | |
C44 | 0.5122 (4) | 0.0615 (4) | 0.8646 (3) | 0.0368 (12) | |
H44A | 0.5154 | 0.0640 | 0.9221 | 0.022 (11)* | |
C45 | 0.4922 (4) | 0.1598 (4) | 0.8227 (3) | 0.0328 (11) | |
C46 | 0.4979 (5) | 0.0442 (4) | 0.6052 (2) | 0.0371 (12) | |
H46A | 0.4265 | 0.0288 | 0.5986 | 0.063 (17)* | |
H46B | 0.5645 | −0.0166 | 0.5782 | 0.11 (2)* | |
H46C | 0.5001 | 0.1141 | 0.5794 | 0.043 (14)* | |
C47 | 0.5462 (5) | −0.1465 (4) | 0.8723 (3) | 0.0556 (16) | |
H47A | 0.6078 | −0.1529 | 0.9045 | 0.08 (2)* | |
H47B | 0.5682 | −0.2106 | 0.8328 | 0.060 (17)* | |
H47C | 0.4747 | −0.1444 | 0.9101 | 0.12 (3)* | |
C48 | 0.4809 (4) | 0.2674 (4) | 0.8670 (3) | 0.0392 (13) | |
H48A | 0.4762 | 0.2566 | 0.9267 | 0.066 (17)* | |
H48B | 0.4106 | 0.3239 | 0.8573 | 0.056 (16)* | |
H48C | 0.5483 | 0.2920 | 0.8460 | 0.028 (12)* | |
C49 | 0.1058 (4) | 0.2462 (4) | 0.9406 (2) | 0.0362 (13) | |
C50 | 0.1961 (6) | 0.2675 (7) | 0.9836 (3) | 0.080 (2) | |
H50A | 0.2554 | 0.1970 | 0.9882 | 0.07 (2)* | |
H50B | 0.1601 | 0.3015 | 1.0392 | 0.082* | |
H50C | 0.2318 | 0.3179 | 0.9513 | 0.045 (15)* | |
C51 | 0.0129 (5) | 0.3598 (5) | 0.9329 (3) | 0.0630 (18) | |
H51A | −0.0513 | 0.3463 | 0.9111 | 0.056 (17)* | |
H51B | 0.0478 | 0.4058 | 0.8950 | 0.076 (19)* | |
H51C | −0.0159 | 0.3985 | 0.9877 | 0.076 (18)* | |
C52 | 0.0479 (5) | 0.1718 (5) | 0.9897 (3) | 0.0539 (16) | |
H52A | −0.0153 | 0.1642 | 0.9635 | 0.035 (13)* | |
H52B | 0.0170 | 0.2039 | 1.0464 | 0.064 (17)* | |
H52C | 0.1041 | 0.0984 | 0.9913 | 0.10 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0287 (3) | 0.0282 (3) | 0.0226 (3) | −0.0117 (3) | −0.0025 (2) | −0.0018 (2) |
Cu2 | 0.0368 (4) | 0.0390 (4) | 0.0236 (3) | −0.0189 (3) | −0.0007 (3) | 0.0006 (3) |
Cu3 | 0.0359 (4) | 0.0367 (4) | 0.0244 (3) | −0.0179 (3) | −0.0062 (3) | 0.0003 (2) |
Cu4 | 0.0255 (3) | 0.0305 (3) | 0.0217 (3) | −0.0107 (3) | −0.0020 (2) | −0.0006 (2) |
I | 0.0481 (2) | 0.0543 (2) | 0.01965 (14) | −0.02876 (19) | −0.00603 (13) | 0.00254 (14) |
O | 0.0354 (19) | 0.036 (2) | 0.0253 (16) | −0.0183 (17) | −0.0054 (14) | −0.0001 (14) |
C1 | 0.028 (3) | 0.027 (3) | 0.020 (2) | −0.013 (2) | −0.0006 (18) | 0.0029 (18) |
C2 | 0.032 (3) | 0.028 (3) | 0.020 (2) | −0.010 (2) | −0.0017 (19) | 0.0013 (18) |
C3 | 0.043 (3) | 0.031 (3) | 0.037 (3) | −0.012 (3) | −0.006 (2) | −0.012 (2) |
C4 | 0.031 (3) | 0.039 (3) | 0.046 (3) | −0.017 (3) | −0.002 (2) | −0.011 (2) |
C5 | 0.025 (3) | 0.034 (3) | 0.038 (3) | −0.009 (2) | −0.004 (2) | 0.000 (2) |
C6 | 0.026 (3) | 0.023 (2) | 0.022 (2) | −0.009 (2) | −0.0026 (18) | −0.0014 (18) |
C7 | 0.033 (3) | 0.020 (2) | 0.031 (2) | −0.009 (2) | 0.001 (2) | −0.0010 (19) |
C8 | 0.030 (3) | 0.025 (3) | 0.037 (3) | −0.007 (2) | 0.003 (2) | −0.005 (2) |
C9 | 0.035 (3) | 0.033 (3) | 0.045 (3) | −0.011 (2) | −0.011 (2) | 0.003 (2) |
C10 | 0.026 (3) | 0.023 (3) | 0.057 (3) | −0.006 (2) | 0.008 (2) | −0.012 (2) |
C11 | 0.053 (4) | 0.033 (3) | 0.035 (3) | −0.020 (3) | 0.018 (3) | −0.010 (2) |
C12 | 0.036 (3) | 0.026 (3) | 0.038 (3) | −0.013 (2) | 0.007 (2) | −0.007 (2) |
C13 | 0.051 (4) | 0.046 (4) | 0.033 (3) | −0.002 (3) | −0.004 (3) | 0.007 (3) |
C14 | 0.034 (3) | 0.047 (4) | 0.088 (5) | −0.012 (3) | 0.009 (3) | −0.009 (4) |
C15 | 0.072 (4) | 0.044 (4) | 0.025 (3) | −0.008 (3) | −0.006 (3) | −0.006 (2) |
C16 | 0.023 (3) | 0.028 (3) | 0.028 (2) | −0.004 (2) | −0.0060 (19) | −0.0075 (19) |
C17 | 0.028 (3) | 0.036 (3) | 0.033 (2) | −0.012 (2) | −0.006 (2) | −0.002 (2) |
C18 | 0.035 (3) | 0.051 (4) | 0.031 (3) | −0.013 (3) | −0.002 (2) | −0.010 (2) |
C19 | 0.034 (3) | 0.036 (3) | 0.053 (3) | −0.011 (3) | 0.000 (2) | −0.020 (3) |
C20 | 0.044 (3) | 0.028 (3) | 0.058 (3) | −0.016 (3) | −0.007 (3) | 0.001 (2) |
C21 | 0.033 (3) | 0.034 (3) | 0.035 (3) | −0.014 (2) | −0.003 (2) | −0.004 (2) |
C22 | 0.049 (4) | 0.054 (4) | 0.028 (3) | −0.020 (3) | −0.005 (2) | 0.004 (2) |
C23 | 0.072 (5) | 0.053 (4) | 0.084 (5) | −0.021 (4) | 0.003 (4) | −0.032 (4) |
C24 | 0.052 (4) | 0.037 (3) | 0.043 (3) | −0.009 (3) | −0.005 (3) | 0.009 (3) |
C25 | 0.024 (2) | 0.024 (3) | 0.025 (2) | −0.013 (2) | −0.0005 (18) | −0.0053 (18) |
C26 | 0.036 (3) | 0.025 (3) | 0.024 (2) | −0.010 (2) | 0.000 (2) | −0.0066 (18) |
C27 | 0.039 (3) | 0.024 (3) | 0.044 (3) | −0.016 (2) | −0.001 (2) | 0.000 (2) |
C28 | 0.041 (3) | 0.035 (3) | 0.051 (3) | −0.018 (3) | 0.006 (3) | −0.001 (2) |
C29 | 0.020 (3) | 0.040 (3) | 0.048 (3) | −0.010 (2) | −0.001 (2) | −0.002 (2) |
C30 | 0.027 (3) | 0.029 (3) | 0.025 (2) | −0.010 (2) | −0.0002 (19) | −0.0054 (19) |
C31 | 0.035 (3) | 0.027 (3) | 0.034 (2) | −0.014 (2) | 0.002 (2) | 0.004 (2) |
C32 | 0.044 (3) | 0.027 (3) | 0.041 (3) | −0.001 (3) | 0.004 (2) | 0.007 (2) |
C33 | 0.056 (4) | 0.046 (4) | 0.077 (5) | 0.000 (3) | 0.028 (4) | 0.023 (3) |
C34 | 0.042 (4) | 0.035 (4) | 0.107 (6) | 0.001 (3) | 0.013 (4) | 0.033 (4) |
C35 | 0.045 (4) | 0.038 (3) | 0.103 (5) | −0.013 (3) | −0.038 (4) | 0.036 (3) |
C36 | 0.047 (3) | 0.024 (3) | 0.049 (3) | −0.015 (3) | −0.013 (3) | 0.011 (2) |
C37 | 0.086 (5) | 0.042 (4) | 0.035 (3) | −0.002 (4) | 0.005 (3) | −0.012 (3) |
C38 | 0.052 (5) | 0.044 (4) | 0.212 (10) | 0.012 (4) | 0.023 (5) | 0.061 (6) |
C39 | 0.076 (4) | 0.040 (4) | 0.045 (3) | −0.013 (4) | −0.022 (3) | 0.011 (3) |
C40 | 0.012 (2) | 0.030 (3) | 0.028 (2) | −0.004 (2) | −0.0020 (17) | −0.0035 (19) |
C41 | 0.018 (2) | 0.034 (3) | 0.025 (2) | −0.003 (2) | −0.0017 (18) | 0.000 (2) |
C42 | 0.031 (3) | 0.035 (3) | 0.029 (2) | −0.007 (2) | 0.001 (2) | 0.003 (2) |
C43 | 0.032 (3) | 0.042 (3) | 0.032 (3) | −0.001 (3) | −0.004 (2) | 0.005 (2) |
C44 | 0.026 (3) | 0.052 (3) | 0.027 (2) | −0.005 (3) | −0.001 (2) | −0.005 (2) |
C45 | 0.027 (3) | 0.038 (3) | 0.035 (2) | −0.011 (2) | −0.006 (2) | −0.005 (2) |
C46 | 0.053 (4) | 0.032 (3) | 0.025 (2) | −0.011 (3) | −0.005 (2) | −0.005 (2) |
C47 | 0.063 (4) | 0.047 (4) | 0.048 (3) | −0.002 (3) | −0.014 (3) | 0.017 (3) |
C48 | 0.035 (3) | 0.046 (3) | 0.034 (3) | −0.004 (3) | −0.014 (2) | −0.009 (2) |
C49 | 0.040 (3) | 0.063 (4) | 0.017 (2) | −0.033 (3) | −0.006 (2) | 0.008 (2) |
C50 | 0.065 (5) | 0.153 (8) | 0.031 (3) | −0.050 (6) | −0.001 (3) | −0.014 (4) |
C51 | 0.066 (4) | 0.064 (4) | 0.051 (4) | −0.022 (4) | 0.016 (3) | −0.013 (3) |
C52 | 0.060 (4) | 0.073 (5) | 0.033 (3) | −0.030 (4) | −0.003 (3) | 0.004 (3) |
Cu1—C1 | 1.946 (4) | C25—C26 | 1.417 (6) |
Cu1—O | 1.856 (3) | C25—C30 | 1.421 (6) |
Cu2—C1 | 2.031 (4) | C26—C27 | 1.395 (5) |
Cu2—I | 2.4457 (6) | C26—C31 | 1.508 (6) |
Cu3—C25 | 2.033 (4) | C27—C28 | 1.384 (6) |
Cu3—I | 2.4499 (6) | C27—H27A | 0.9500 |
Cu4—O | 1.861 (3) | C28—C29 | 1.387 (6) |
Cu4—C25 | 1.957 (4) | C28—H28A | 0.9500 |
Cu1—Cu2 | 2.3761 (7) | C29—C30 | 1.394 (5) |
Cu1—Cu4 | 2.8578 (8) | C29—H29A | 0.9500 |
Cu2—Cu3 | 2.7227 (8) | C30—C40 | 1.502 (6) |
Cu3—Cu4 | 2.3766 (7) | C31—C36 | 1.391 (6) |
O—C49 | 1.400 (5) | C31—C32 | 1.410 (6) |
C1—C6 | 1.414 (6) | C32—C33 | 1.391 (7) |
C1—C2 | 1.433 (6) | C32—C37 | 1.531 (7) |
C2—C3 | 1.393 (5) | C33—C34 | 1.351 (8) |
C2—C7 | 1.518 (6) | C33—H33A | 0.9500 |
C3—C4 | 1.366 (6) | C34—C35 | 1.380 (8) |
C3—H3A | 0.9500 | C34—C38 | 1.497 (8) |
C4—C5 | 1.391 (6) | C35—C36 | 1.392 (7) |
C4—H4A | 0.9500 | C35—H35A | 0.9500 |
C5—C6 | 1.383 (5) | C36—C39 | 1.518 (6) |
C5—H5A | 0.9500 | C37—H37A | 0.9800 |
C6—C16 | 1.511 (5) | C37—H37B | 0.9800 |
C7—C8 | 1.398 (6) | C37—H37C | 0.9800 |
C7—C12 | 1.407 (5) | C38—H38A | 0.9800 |
C8—C9 | 1.390 (6) | C38—H38B | 0.9800 |
C8—C13 | 1.517 (6) | C38—H38C | 0.9800 |
C9—C10 | 1.368 (6) | C39—H39A | 0.9800 |
C9—H9A | 0.9500 | C39—H39B | 0.9800 |
C10—C11 | 1.398 (7) | C39—H39C | 0.9800 |
C10—C14 | 1.513 (6) | C40—C41 | 1.396 (6) |
C11—C12 | 1.381 (6) | C40—C45 | 1.410 (5) |
C11—H11A | 0.9500 | C41—C42 | 1.387 (6) |
C12—C15 | 1.504 (6) | C41—C46 | 1.512 (5) |
C13—H13A | 0.9800 | C42—C43 | 1.386 (6) |
C13—H13B | 0.9800 | C42—H42A | 0.9500 |
C13—H13C | 0.9800 | C43—C44 | 1.380 (6) |
C14—H14A | 0.9800 | C43—C47 | 1.526 (6) |
C14—H14B | 0.9800 | C44—C45 | 1.391 (6) |
C14—H14C | 0.9800 | C44—H44A | 0.9500 |
C15—H15A | 0.9800 | C45—C48 | 1.499 (6) |
C15—H15B | 0.9800 | C46—H46A | 0.9800 |
C15—H15C | 0.9800 | C46—H46B | 0.9800 |
C16—C21 | 1.406 (6) | C46—H46C | 0.9800 |
C16—C17 | 1.412 (5) | C47—H47A | 0.9800 |
C17—C18 | 1.385 (6) | C47—H47B | 0.9800 |
C17—C22 | 1.510 (6) | C47—H47C | 0.9800 |
C18—C19 | 1.371 (7) | C48—H48A | 0.9800 |
C18—H18A | 0.9500 | C48—H48B | 0.9800 |
C19—C20 | 1.391 (6) | C48—H48C | 0.9800 |
C19—C23 | 1.514 (6) | C49—C52 | 1.494 (6) |
C20—C21 | 1.381 (6) | C49—C50 | 1.502 (6) |
C20—H20A | 0.9500 | C49—C51 | 1.564 (7) |
C21—C24 | 1.523 (6) | C50—H50A | 0.9800 |
C22—H22A | 0.9800 | C50—H50B | 0.9800 |
C22—H22B | 0.9800 | C50—H50C | 0.9800 |
C22—H22C | 0.9800 | C51—H51A | 0.9800 |
C23—H23A | 0.9800 | C51—H51B | 0.9800 |
C23—H23B | 0.9800 | C51—H51C | 0.9800 |
C23—H23C | 0.9800 | C52—H52A | 0.9800 |
C24—H24A | 0.9800 | C52—H52B | 0.9800 |
C24—H24B | 0.9800 | C52—H52C | 0.9800 |
C24—H24C | 0.9800 | ||
O—Cu1—C1 | 176.84 (14) | H24A—C24—H24C | 109.5 |
O—Cu1—Cu2 | 128.17 (9) | H24B—C24—H24C | 109.5 |
C1—Cu1—Cu2 | 54.98 (11) | C26—C25—C30 | 117.4 (4) |
O—Cu1—Cu4 | 39.81 (8) | C26—C25—Cu4 | 127.3 (3) |
C1—Cu1—Cu4 | 143.34 (11) | C30—C25—Cu4 | 111.5 (3) |
Cu2—Cu1—Cu4 | 88.38 (2) | C26—C25—Cu3 | 101.3 (3) |
C1—Cu2—Cu1 | 51.69 (11) | C30—C25—Cu3 | 115.6 (3) |
C1—Cu2—I | 160.42 (11) | Cu4—C25—Cu3 | 73.07 (13) |
Cu1—Cu2—I | 147.87 (3) | C27—C26—C25 | 121.0 (4) |
C1—Cu2—Cu3 | 143.29 (11) | C27—C26—C31 | 119.5 (4) |
Cu1—Cu2—Cu3 | 91.60 (2) | C25—C26—C31 | 119.5 (4) |
I—Cu2—Cu3 | 56.284 (18) | C28—C27—C26 | 120.0 (5) |
C25—Cu3—Cu4 | 51.99 (11) | C28—C27—H27A | 120.0 |
C25—Cu3—I | 160.20 (11) | C26—C27—H27A | 120.0 |
Cu4—Cu3—I | 147.75 (3) | C27—C28—C29 | 120.7 (5) |
C25—Cu3—Cu2 | 143.45 (11) | C27—C28—H28A | 119.7 |
Cu4—Cu3—Cu2 | 91.63 (2) | C29—C28—H28A | 119.7 |
I—Cu3—Cu2 | 56.137 (18) | C28—C29—C30 | 120.0 (5) |
O—Cu4—C25 | 172.67 (16) | C28—C29—H29A | 120.0 |
O—Cu4—Cu3 | 127.93 (9) | C30—C29—H29A | 120.0 |
C25—Cu4—Cu3 | 54.94 (11) | C29—C30—C25 | 120.8 (4) |
O—Cu4—Cu1 | 39.69 (8) | C29—C30—C40 | 119.9 (4) |
C25—Cu4—Cu1 | 142.90 (11) | C25—C30—C40 | 118.9 (4) |
Cu3—Cu4—Cu1 | 88.33 (2) | C36—C31—C32 | 119.7 (5) |
Cu2—I—Cu3 | 67.58 (2) | C36—C31—C26 | 122.3 (4) |
C49—O—Cu1 | 123.5 (3) | C32—C31—C26 | 118.0 (4) |
C49—O—Cu4 | 123.8 (3) | C33—C32—C31 | 118.6 (5) |
Cu1—O—Cu4 | 100.51 (13) | C33—C32—C37 | 120.6 (5) |
C6—C1—C2 | 116.1 (4) | C31—C32—C37 | 120.8 (5) |
C6—C1—Cu1 | 112.7 (3) | C34—C33—C32 | 122.5 (6) |
C2—C1—Cu1 | 127.6 (3) | C34—C33—H33A | 118.7 |
C6—C1—Cu2 | 120.0 (3) | C32—C33—H33A | 118.7 |
C2—C1—Cu2 | 97.4 (3) | C33—C34—C35 | 117.8 (6) |
Cu1—C1—Cu2 | 73.33 (14) | C33—C34—C38 | 123.2 (7) |
C3—C2—C1 | 120.5 (4) | C35—C34—C38 | 119.0 (7) |
C3—C2—C7 | 117.3 (4) | C34—C35—C36 | 123.0 (6) |
C1—C2—C7 | 122.2 (4) | C34—C35—H35A | 118.5 |
C4—C3—C2 | 121.5 (4) | C36—C35—H35A | 118.5 |
C4—C3—H3A | 119.3 | C31—C36—C35 | 117.9 (5) |
C2—C3—H3A | 119.3 | C31—C36—C39 | 121.4 (5) |
C3—C4—C5 | 119.6 (4) | C35—C36—C39 | 120.5 (5) |
C3—C4—H4A | 120.2 | C32—C37—H37A | 109.5 |
C5—C4—H4A | 120.2 | C32—C37—H37B | 109.5 |
C6—C5—C4 | 120.1 (4) | H37A—C37—H37B | 109.5 |
C6—C5—H5A | 119.9 | C32—C37—H37C | 109.5 |
C4—C5—H5A | 119.9 | H37A—C37—H37C | 109.5 |
C5—C6—C1 | 122.1 (4) | H37B—C37—H37C | 109.5 |
C5—C6—C16 | 116.3 (4) | C34—C38—H38A | 109.5 |
C1—C6—C16 | 121.3 (4) | C34—C38—H38B | 109.5 |
C8—C7—C12 | 120.0 (4) | H38A—C38—H38B | 109.5 |
C8—C7—C2 | 120.8 (4) | C34—C38—H38C | 109.5 |
C12—C7—C2 | 119.0 (4) | H38A—C38—H38C | 109.5 |
C9—C8—C7 | 118.6 (4) | H38B—C38—H38C | 109.5 |
C9—C8—C13 | 119.4 (5) | C36—C39—H39A | 109.5 |
C7—C8—C13 | 122.0 (4) | C36—C39—H39B | 109.5 |
C10—C9—C8 | 122.9 (5) | H39A—C39—H39B | 109.5 |
C10—C9—H9A | 118.5 | C36—C39—H39C | 109.5 |
C8—C9—H9A | 118.5 | H39A—C39—H39C | 109.5 |
C9—C10—C11 | 117.5 (5) | H39B—C39—H39C | 109.5 |
C9—C10—C14 | 122.5 (5) | C41—C40—C45 | 119.7 (4) |
C11—C10—C14 | 120.0 (5) | C41—C40—C30 | 122.2 (4) |
C12—C11—C10 | 122.2 (4) | C45—C40—C30 | 118.1 (4) |
C12—C11—H11A | 118.9 | C42—C41—C40 | 118.9 (4) |
C10—C11—H11A | 118.9 | C42—C41—C46 | 118.7 (4) |
C11—C12—C7 | 118.7 (5) | C40—C41—C46 | 122.4 (4) |
C11—C12—C15 | 117.8 (4) | C43—C42—C41 | 122.4 (5) |
C7—C12—C15 | 123.5 (5) | C43—C42—H42A | 118.8 |
C8—C13—H13A | 109.5 | C41—C42—H42A | 118.8 |
C8—C13—H13B | 109.5 | C44—C43—C42 | 118.0 (5) |
H13A—C13—H13B | 109.5 | C44—C43—C47 | 121.3 (4) |
C8—C13—H13C | 109.5 | C42—C43—C47 | 120.7 (5) |
H13A—C13—H13C | 109.5 | C43—C44—C45 | 121.9 (4) |
H13B—C13—H13C | 109.5 | C43—C44—H44A | 119.0 |
C10—C14—H14A | 109.5 | C45—C44—H44A | 119.0 |
C10—C14—H14B | 109.5 | C44—C45—C40 | 119.0 (4) |
H14A—C14—H14B | 109.5 | C44—C45—C48 | 120.3 (4) |
C10—C14—H14C | 109.5 | C40—C45—C48 | 120.7 (4) |
H14A—C14—H14C | 109.5 | C41—C46—H46A | 109.5 |
H14B—C14—H14C | 109.5 | C41—C46—H46B | 109.5 |
C12—C15—H15A | 109.5 | H46A—C46—H46B | 109.5 |
C12—C15—H15B | 109.5 | C41—C46—H46C | 109.5 |
H15A—C15—H15B | 109.5 | H46A—C46—H46C | 109.5 |
C12—C15—H15C | 109.5 | H46B—C46—H46C | 109.5 |
H15A—C15—H15C | 109.5 | C43—C47—H47A | 109.5 |
H15B—C15—H15C | 109.5 | C43—C47—H47B | 109.5 |
C21—C16—C17 | 118.1 (4) | H47A—C47—H47B | 109.5 |
C21—C16—C6 | 123.3 (4) | C43—C47—H47C | 109.5 |
C17—C16—C6 | 118.4 (4) | H47A—C47—H47C | 109.5 |
C18—C17—C16 | 119.7 (4) | H47B—C47—H47C | 109.5 |
C18—C17—C22 | 120.2 (4) | C45—C48—H48A | 109.5 |
C16—C17—C22 | 120.0 (4) | C45—C48—H48B | 109.5 |
C19—C18—C17 | 122.5 (5) | H48A—C48—H48B | 109.5 |
C19—C18—H18A | 118.8 | C45—C48—H48C | 109.5 |
C17—C18—H18A | 118.8 | H48A—C48—H48C | 109.5 |
C18—C19—C20 | 117.6 (4) | H48B—C48—H48C | 109.5 |
C18—C19—C23 | 121.5 (5) | O—C49—C52 | 110.8 (4) |
C20—C19—C23 | 120.9 (5) | O—C49—C50 | 110.0 (4) |
C21—C20—C19 | 122.1 (5) | C52—C49—C50 | 110.5 (4) |
C21—C20—H20A | 119.0 | O—C49—C51 | 108.0 (4) |
C19—C20—H20A | 119.0 | C52—C49—C51 | 108.7 (4) |
C20—C21—C16 | 119.9 (4) | C50—C49—C51 | 108.7 (5) |
C20—C21—C24 | 118.8 (5) | C49—C50—H50A | 109.5 |
C16—C21—C24 | 121.2 (4) | C49—C50—H50B | 109.5 |
C17—C22—H22A | 109.5 | H50A—C50—H50B | 109.5 |
C17—C22—H22B | 109.5 | C49—C50—H50C | 109.5 |
H22A—C22—H22B | 109.5 | H50A—C50—H50C | 109.5 |
C17—C22—H22C | 109.5 | H50B—C50—H50C | 109.5 |
H22A—C22—H22C | 109.5 | C49—C51—H51A | 109.5 |
H22B—C22—H22C | 109.5 | C49—C51—H51B | 109.5 |
C19—C23—H23A | 109.5 | H51A—C51—H51B | 109.5 |
C19—C23—H23B | 109.5 | C49—C51—H51C | 109.5 |
H23A—C23—H23B | 109.5 | H51A—C51—H51C | 109.5 |
C19—C23—H23C | 109.5 | H51B—C51—H51C | 109.5 |
H23A—C23—H23C | 109.5 | C49—C52—H52A | 109.5 |
H23B—C23—H23C | 109.5 | C49—C52—H52B | 109.5 |
C21—C24—H24A | 109.5 | H52A—C52—H52B | 109.5 |
C21—C24—H24B | 109.5 | C49—C52—H52C | 109.5 |
H24A—C24—H24B | 109.5 | H52A—C52—H52C | 109.5 |
C21—C24—H24C | 109.5 | H52B—C52—H52C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | [Cu4(C24H25)2(C4H9O)I] |
Mr | 1081.05 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 12.3307 (14), 12.6105 (10), 16.3613 (12) |
α, β, γ (°) | 89.734 (6), 80.137 (7), 72.592 (9) |
V (Å3) | 2388.8 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.44 |
Crystal size (mm) | 0.70 × 0.15 × 0.05 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.280, 0.888 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9829, 9372, 5430 |
Rint | 0.050 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.059, 0.72 |
No. of reflections | 9372 |
No. of parameters | 594 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.63, −0.36 |
Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1998), SHELXTL.
Cu1—C1 | 1.946 (4) | Cu4—O | 1.861 (3) |
Cu1—O | 1.856 (3) | Cu4—C25 | 1.957 (4) |
Cu2—C1 | 2.031 (4) | Cu1—Cu2 | 2.3761 (7) |
Cu2—I | 2.4457 (6) | Cu1—Cu4 | 2.8578 (8) |
Cu3—C25 | 2.033 (4) | Cu2—Cu3 | 2.7227 (8) |
Cu3—I | 2.4499 (6) | Cu3—Cu4 | 2.3766 (7) |
O—Cu1—C1 | 176.84 (14) | Cu2—I—Cu3 | 67.58 (2) |
C1—Cu2—I | 160.42 (11) | Cu1—O—Cu4 | 100.51 (13) |
C25—Cu3—I | 160.20 (11) | Cu1—C1—Cu2 | 73.33 (14) |
O—Cu4—C25 | 172.67 (16) | Cu4—C25—Cu3 | 73.07 (13) |
The preparation of organocopper compounds of the type RCu usually involves the reaction of a copper(I) halide with an organolithium or -magnesium reagent in donor solvents like Et2O, THF or DMS (van Koten et al., 1995). A commonly encountered problem of this method is the contamination of the desired copper compounds with lithium or magnesium halides and the formation of stable mixed organocopper copper halide aggregates (Jansson et al., 1996, and references cited within). The use of copper tert-butoxide as an alternative halide-free starting material has recently permitted the preparation of the copper aryls CuC6H3Ph2-2,6 and CuC6H3Mes2-2,6 which are trimeric and dimeric, respectively, in the solid state (Niemeyer, 1998). As by-product of the synthesis of the latter compound the title complex, (I), has now been isolated in small yield.
The molecular structure of (I) shows a tetranuclear copper aggregate (Fig. 1) which consists of two trans-arylcopper moieties and one copper iodide and copper tert-butoxide unit, respectively. The almost planar central Cu4C2IO ring (Fig. 2) [the largest deviations from planarity are 0.075 (2) Å for Cu4 and 0.059 (3) Å for C25] features two-coordinate Cu atoms with an approximately linear environment [O—Cu1—C1 176.84 (14), C1—Cu2—I 160.42 (11), C25—Cu3—I 160.20 (11) and O—Cu4—C25 172.67 (16)°]. There are two different sets of Cu—C bond lengths. Shorter Cu1—C1 and Cu4—C25 distances [1.946 (4) and 1.957 (4) Å] and larger Cu1—C1···C4 and Cu4—C25···C28 angles [161.7 (2) and 161.2 (2)°] alternate with larger and smaller values for Cu2—C1 and Cu3–C25 [2.031 (4) and 2.033 (4) Å], and Cu2—C1···C4 and Cu3—C25···C28 [124.8 (2) and 125.1 (2)°], respectively. Therefore, the bonding to the aryl Cipso atoms can be described as an alternating 2 e-2c Cipso—Cu and π-type Cipso—Cu interaction. This view is in agreement with the alternative formulation of (I) as contact ion pair [Cu2I]+[Cu2(Dmp)2(OtBu)]-. In contrast, a rather symmetric bridging interaction is observed to the iodo [Cu2—I 2.4457 (6) Å and Cu3—I 2.4499 (6) Å] and tert-butoxide [Cu1—O 1.856 (3) Å and Cu4—O 1.861 (3) Å] ligands. With values of 2.3761 (7) (Cu1···Cu2), 2.3765 (7) (Cu3···Cu4), 2.7226 (8) (Cu2···Cu3) and 2.8578 (8) Å (Cu1···Cu4), the non-bonding copper–copper separations are of the same magnitude as previously observed for other copper organyls. A unique feature in (I) is the presence of a Cu—I—Cu bridge in which all three atoms possess coordination number 2.