A tetranuclear copper compound containing three different types of anions: trans-(μ-tert-butoxy)­bis(μ-2,4,6,2′′,4′′,6′′-hexa­methyl-1,1′:3′,1′′-ter­phenyl-2′,2′-diyl)(μ-iodo)­tetracopper(I)

Niemeyer, M.

doi:10.1107/S1600536801013551

A tetranuclear copper compound containing three different types of anions: trans-(μ-tert-butoxy)bis(μ-2,4,6,2′′,4′′,6′′-hexamethyl-1,1′:3′,1′′-terphenyl-2′,2′-diyl)(μ-iodo)tetracopper(I)

The title compound [(CuDmp)₂(CuI)(CuO^tBu)] (Dmp = 2,6-Mes₂C₆H₃ with Mes = 2,4,6–Me₃C₆H₂), [Cu₄I(C₄H₉O)(C₂₄H₂₅)₂], was obtained as by-product of the synthesis of the copper aryl (CuDmp)₂. It contains an almost planar central Cu₄C₂IO ring with two-coordinate Cu atoms and two different sets of Cu—C distances (average Cu—C = 1.952 and 2.032 Å; average Cu—O = 1.859 Å; average Cu—I = 2.4478 Å).

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013551/ya6052sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013551/ya6052Isup2.hkl Contains datablock I

CCDC reference: 172197

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.007 Å
R factor = 0.035
wR factor = 0.059
Data-to-parameter ratio = 15.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



GOODF_01  Alert C The least squares goodness of fit parameter lies
          outside the range 0.80 <> 2.00
          Goodness of fit given =      0.720

PLAT_213  Alert C Atom  C38    has ADP max/min Ratio ...........       3.50


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

Comment top

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 C_ipso atoms can be described as an alternating 2 e-2c C_ipso—Cu and π-type C_ipso—Cu interaction. This view is in agreement with the alternative formulation of (I) as contact ion pair [Cu₂I]⁺[Cu₂(Dmp)₂(O^tBu)]^-. 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.

Experimental top

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, CuO^tBu (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 CuO^tBu. 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].

Computing details top

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.

Figures top

	Fig. 1. Displacement ellipsoid plot (at the 35% probability level) of (I). H atoms have been omitted for clarity.
	Fig. 2. View perpendicular to the central Cu₄C₂IO ring. Mes substituents and H atoms have been omitted for clarity.

trans-(µ²-tert-butoxy)bis(µ²-2,4,6,2'',4'',6''-hexamethyl-1,1':3';1''- terphenyl-2',2'-diyl)(µ²-iodo)tetracopper(I) top

Crystal data top

[Cu₄(C₂₄H₂₅)₂(C₄H₉O)I]	F(000) = 1096
M_r = 1081.05	D_x = 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

Data collection top

Siemens P4 diffractometer	5430 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.050
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
ω scans	h = −15→15
Absorption correction: ψ scan (North et al., 1968)	k = −14→15
T_min = 0.280, T_max = 0.888	l = −19→20
9829 measured reflections	2 standard reflections every 198 reflections
9372 independent reflections	intensity decay: none

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.059	Only H-atom displacement parameters refined
S = 0.72	w = 1/[σ²(F_o²) + (0.0129P)²] where P = (F_o² + 2F_c²)/3
9372 reflections	(Δ/σ)_max = 0.002
594 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Cu₄(C₂₄H₂₅)₂(C₄H₉O)I]	γ = 72.592 (9)°
M_r = 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)°

Data collection top

Siemens P4 diffractometer	5430 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.050
T_min = 0.280, T_max = 0.888	2 standard reflections every 198 reflections
9829 measured reflections	intensity decay: none
9372 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.059	Only H-atom displacement parameters refined
S = 0.72	Δρ_max = 0.63 e Å⁻³
9372 reflections	Δρ_min = −0.36 e Å⁻³
594 parameters

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	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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]
M_r	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)
T_min, T_max	0.280, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	9829, 9372, 5430
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.36

Computer programs: XSCANS (Siemens, 1994), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 1998), SHELXTL.

Selected geometric parameters (Å, º) top

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)

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A tetranuclear copper compound containing three different types of anions: trans-(μ-tert-butoxy)­bis(μ-2,4,6,2′′,4′′,6′′-hexa­methyl-1,1′:3′,1′′-ter­phenyl-2′,2′-diyl)(μ-iodo)­tetracopper(I)

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A tetranuclear copper compound containing three different types of anions: trans-(μ-tert-butoxy)bis(μ-2,4,6,2′′,4′′,6′′-hexamethyl-1,1′:3′,1′′-terphenyl-2′,2′-diyl)(μ-iodo)tetracopper(I)