In the crystals of bis(pyridine-
N)tetrakis(μ-trimethylsilylacetato-
O:
O′)dicopper(II), [Cu
2(C
5H
11O
2Si)
4(C
5H
5N)
2], (I), the dinuclear Cu
II complexes have cage structures with Cu
Cu distances of 2.632 (1) and 2.635 (1) Å. In the crystals of bis(2-methylpyridine-
N)tetrakis(μ-trimethylsilylacetato-
O:
O′)dicopper(II), [Cu
2(C
5H
11O
2Si)
4(C
6H
7N)
2], (II), bis(3-methylpyridine-
N)tetrakis(μ-trimethylsilylacetato-
O:
O′)dicopper(II), [Cu
2(C
5H
11O
2Si)
4(C
6H
7N)
2], (III), and bis(quinoline-
N)tetrakis(μ-trimethylsilylacetato-
O:
O′)dicopper(II), [Cu
2(C
5H
11O
2Si)
4(C
9H
7N)
2], (IV), the centrosymmetric dinuclear Cu
II complexes have a cage structure with Cu
Cu distances of 2.664 (1), 2.638 (3) and 2.665 (1) Å, respectively. In the crystals of
catena-poly[tetrakis(μ-trimethylsilylacetato-
O:
O′)dicopper(II)], [Cu
2(C
5H
11O
2Si)
4]
n, (V), the dinuclear Cu
II units of a cage structure are linked by the cyclic Cu—O bonds at the apical positions to form a linear chain by use of a glide translation.
Supporting information
CCDC references: 140916; 140917; 140918; 140919; 140920
Trimethylsilylacetic acid (132 mg, 1.0 mmol) and CuCO3·Cu(OH)2·H2O (60 mg, 0.25 mmol) were suspended in a mixture of water and methanol (3:1, 20 ml). After the solution was stirred for 1 h at room temperature, a green precipitate was collected and desolved in ethanol. When pyridine (40 mg, 0.50 mmol) was added to the solution, the colour changed from green to blue, and from the solution the green crystals of (I) were grown by slow evaporation. Crystals of (II), (III), and (IV) were prepared in a similar way using 2-methylpyridine, 3-methylpyridine, and quinoline as axial ligands. When these monodentate ligands were not introduced and the ethanol solution was kept in a desiccator, blue-green small crystals of polymer (V) were obtained together with pale green plate-like crystals of tetranuclear complex, [Cu2(Me3SiCH2COO)4(H2O)]2: monoclinic, P21/n, a = 12.697 (5), b = 12.085 (5), c = 22.609 (3) Å, β = 94.30 (2)°, V = 3459 (2) Å3, Z = 2.
During the data collection of (II), intensity decay of 10.1% was observed, and was corrected based on the standard reflections.
In (II), there is an orientational disorder of the 2-methylpyridine ligand. The site occupation factors of N1, C12 and C13 were assumed to be 100%, and the remaining four C atoms are either of two sets of positions, (C11, C14, C15, C16) or (C17, C18, C19, C20) with 50% probabilities. The max/min ratio of the atom displacement parameters are abnormally large for the methyl-C atoms of the trimethylsilyl groups, which may be due to the librational and rotational disorder. To avoid insufficient convergence in the refinement of (V), all the 12 terminal methyl-C atoms were refined isotropically.
The magnetic susceptibilities over the temperature range 80–300 K were determined by the Faraday method at Saga University. The procedure for determining the −2 J value from cryomagnetic data based on the Bleaney-Bowers equation is described elsewhere (Harada et al., 1997).
For all compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software. Data reduction: local programs for (I), (III); TEXSAN (Molecular Structure Corporation, 1998) for (II), (IV), (V). Program(s) used to solve structure: CRYSTAN-GM (Edwards et al., 1996) for (I), (III). Program(s) used to refine structure: CRYSTAN-GM for (I), (III); TEXSAN for (II), (IV), (V). Molecular graphics: CRYSTAN-GM for (I), (III). Software used to prepare material for publication: CRYSTAN-GM for (I), (III); TEXSAN for (II), (IV), (V).
(I) tetrakis(µ-trimethylsilylacetato-
O:
O')di(pyridine-N)dicopper(II)
top
Crystal data top
[Cu2(C5H11O2Si)4(C5H5N)2] | Z = 2 |
Mr = 810.20 | F(000) = 852 |
Triclinic, P1 | Dx = 1.239 Mg m−3 |
a = 11.392 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 18.508 (2) Å | Cell parameters from 25 reflections |
c = 10.851 (1) Å | θ = 10–15° |
α = 91.87 (1)° | µ = 1.13 mm−1 |
β = 102.79 (1)° | T = 299 K |
γ = 76.82 (1)° | Prism, green |
V = 2171.9 (5) Å3 | 0.4 × 0.3 × 0.3 mm |
Data collection top
Rigaku AFC-5 diffractometer | Rint = 0.017 |
θ–2θ scans | θmax = 27.5° |
Absorption correction: integration (Coppens et al., 1965) | h = 0→15 |
Tmin = 0.971, Tmax = 0.978 | k = −24→24 |
10462 measured reflections | l = −14→14 |
9960 independent reflections | 3 standard reflections every 100 reflections |
5122 reflections with |Fo| > 3σ(|Fo|) | intensity decay: none |
Refinement top
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.068 | w = 1/[σ2(F) + 0.000225F2] |
wR(F2) = 0.053 | (Δ/σ)max = 0.002 |
S = 1.34 | Δρmax = 0.80 e Å−3 |
5122 reflections | Δρmin = −0.57 e Å−3 |
415 parameters | |
Crystal data top
[Cu2(C5H11O2Si)4(C5H5N)2] | γ = 76.82 (1)° |
Mr = 810.20 | V = 2171.9 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 11.392 (1) Å | Mo Kα radiation |
b = 18.508 (2) Å | µ = 1.13 mm−1 |
c = 10.851 (1) Å | T = 299 K |
α = 91.87 (1)° | 0.4 × 0.3 × 0.3 mm |
β = 102.79 (1)° | |
Data collection top
Rigaku AFC-5 diffractometer | 5122 reflections with |Fo| > 3σ(|Fo|) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.017 |
Tmin = 0.971, Tmax = 0.978 | 3 standard reflections every 100 reflections |
10462 measured reflections | intensity decay: none |
9960 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.068 | 415 parameters |
wR(F2) = 0.053 | H-atom parameters constrained |
S = 1.34 | Δρmax = 0.80 e Å−3 |
5122 reflections | Δρmin = −0.57 e Å−3 |
Special details top
Refinement. The positions of all the H atoms were calculated geometrically, and a riding model was used in their refinement for (I) and (III) [C—H 0.96 Å, Uiso(H) = 0.2 Å2]. H atom parameters were not refined for (II), (IV), and (V) [Uiso(H)= 1.2 Ueq(parent atom)]. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.89306 (6) | 0.52455 (4) | 1.03174 (6) | 0.0543 (3) | |
Cu2 | 0.55785 (6) | 0.93449 (4) | 0.46790 (7) | 0.0641 (3) | |
Si3 | 0.7829 (2) | 0.4101 (1) | 0.5919 (2) | 0.0890 (9) | |
Si4 | 0.9800 (2) | 0.7410 (1) | 0.7950 (2) | 0.0776 (8) | |
Si5 | 0.8726 (2) | 1.0894 (1) | 0.7212 (2) | 0.100 (1) | |
Si6 | 0.4540 (2) | 0.8704 (1) | 0.8739 (2) | 0.097 (1) | |
O7 | 0.8604 (3) | 0.5976 (2) | 0.8942 (3) | 0.067 (2) | |
O8 | 1.0405 (3) | 0.5539 (2) | 0.8377 (3) | 0.068 (2) | |
O9 | 0.8426 (3) | 0.4498 (2) | 0.9086 (3) | 0.067 (2) | |
O10 | 1.0244 (3) | 0.4085 (2) | 0.8533 (3) | 0.070 (2) | |
O11 | 0.7055 (3) | 0.9757 (3) | 0.4954 (4) | 0.084 (2) | |
O12 | 0.6053 (4) | 1.0876 (2) | 0.5455 (4) | 0.085 (2) | |
O13 | 0.5953 (3) | 0.9096 (2) | 0.6486 (4) | 0.076 (2) | |
O14 | 0.4939 (4) | 1.0203 (2) | 0.7032 (4) | 0.077 (2) | |
N15 | 0.7091 (4) | 0.5554 (3) | 1.0750 (5) | 0.063 (2) | |
N16 | 0.6420 (4) | 0.8241 (3) | 0.4067 (5) | 0.070 (2) | |
C17 | 0.9366 (5) | 0.6000 (3) | 0.8266 (5) | 0.060 (3) | |
C18 | 0.9073 (5) | 0.6616 (3) | 0.7319 (5) | 0.068 (3) | |
C19 | 0.9492 (8) | 0.8083 (4) | 0.6621 (8) | 0.132 (5) | |
C20 | 0.9105 (8) | 0.7816 (4) | 0.9274 (8) | 0.154 (5) | |
C21 | 1.1496 (6) | 0.7071 (4) | 0.8566 (7) | 0.103 (4) | |
C22 | 0.9111 (5) | 0.4098 (3) | 0.8451 (5) | 0.057 (2) | |
C23 | 0.8540 (5) | 0.3606 (3) | 0.7481 (5) | 0.071 (3) | |
C24 | 0.701 (1) | 0.3489 (5) | 0.4854 (9) | 0.188 (6) | |
C25 | 0.6733 (7) | 0.4983 (5) | 0.6114 (7) | 0.125 (4) | |
C26 | 0.9057 (8) | 0.4331 (7) | 0.5272 (8) | 0.187 (7) | |
C27 | 0.6794 (6) | 0.5162 (4) | 1.1580 (6) | 0.086 (3) | |
C28 | 0.5609 (7) | 0.5275 (5) | 1.1775 (7) | 0.113 (4) | |
C29 | 0.4713 (6) | 0.5813 (5) | 1.1099 (9) | 0.113 (4) | |
C30 | 0.4995 (6) | 0.6234 (4) | 1.0254 (8) | 0.111 (4) | |
C31 | 0.6217 (6) | 0.6089 (4) | 1.0101 (7) | 0.083 (3) | |
C32 | 0.7013 (6) | 1.0416 (4) | 0.5279 (6) | 0.081 (3) | |
C33 | 0.8177 (5) | 1.0703 (4) | 0.5523 (6) | 0.100 (3) | |
C34 | 1.0263 (7) | 1.1124 (6) | 0.7358 (9) | 0.191 (6) | |
C35 | 0.7638 (8) | 1.1700 (5) | 0.7681 (9) | 0.188 (6) | |
C36 | 0.880 (1) | 1.0100 (6) | 0.8205 (9) | 0.193 (7) | |
C37 | 0.5532 (5) | 0.9545 (4) | 0.7286 (6) | 0.069 (3) | |
C38 | 0.5721 (6) | 0.9249 (3) | 0.8613 (6) | 0.079 (3) | |
C39 | 0.4908 (9) | 0.8355 (5) | 1.0390 (7) | 0.143 (5) | |
C40 | 0.2970 (7) | 0.9328 (5) | 0.8359 (8) | 0.148 (5) | |
C41 | 0.4633 (9) | 0.7920 (4) | 0.7629 (7) | 0.146 (5) | |
C42 | 0.6142 (7) | 0.7634 (4) | 0.4391 (7) | 0.109 (4) | |
C43 | 0.669 (1) | 0.6933 (4) | 0.4012 (9) | 0.139 (5) | |
C44 | 0.7518 (9) | 0.6885 (6) | 0.327 (1) | 0.137 (5) | |
C45 | 0.7792 (7) | 0.7502 (6) | 0.2917 (9) | 0.138 (5) | |
C46 | 0.7220 (6) | 0.8176 (4) | 0.3328 (7) | 0.103 (4) | |
H18A | 0.93677 | 0.64282 | 0.65824 | 0.20* | |
H18B | 0.81917 | 0.67952 | 0.70874 | 0.20* | |
H19A | 0.98688 | 0.84825 | 0.69528 | 0.20* | |
H19B | 0.86188 | 0.82615 | 0.63088 | 0.20* | |
H19C | 0.98508 | 0.78485 | 0.59448 | 0.20* | |
H20A | 0.94818 | 0.82158 | 0.96069 | 0.20* | |
H20B | 0.92398 | 0.74458 | 0.99219 | 0.20* | |
H20C | 0.82318 | 0.79978 | 0.89679 | 0.20* | |
H21A | 1.18727 | 0.74708 | 0.88986 | 0.20* | |
H21B | 1.18657 | 0.68438 | 0.78936 | 0.20* | |
H21C | 1.16317 | 0.67058 | 0.92226 | 0.20* | |
H23A | 0.91638 | 0.31794 | 0.73706 | 0.20* | |
H23B | 0.79068 | 0.34484 | 0.77826 | 0.20* | |
H24A | 0.66523 | 0.37465 | 0.40583 | 0.20* | |
H24B | 0.63673 | 0.33835 | 0.52193 | 0.20* | |
H24C | 0.75643 | 0.30295 | 0.47393 | 0.20* | |
H25A | 0.63787 | 0.52406 | 0.53181 | 0.20* | |
H25B | 0.71577 | 0.52926 | 0.66891 | 0.20* | |
H25C | 0.60857 | 0.48726 | 0.64601 | 0.20* | |
H26A | 0.87029 | 0.45895 | 0.44762 | 0.20* | |
H26B | 0.96299 | 0.38805 | 0.51502 | 0.20* | |
H26C | 0.94899 | 0.46385 | 0.58462 | 0.20* | |
H27 | 0.74287 | 0.47762 | 1.20528 | 0.20* | |
H28 | 0.54248 | 0.49780 | 1.23859 | 0.20* | |
H29 | 0.38807 | 0.58915 | 1.12107 | 0.20* | |
H30 | 0.43682 | 0.66241 | 0.97802 | 0.20* | |
H31 | 0.64343 | 0.63852 | 0.95145 | 0.20* | |
H33A | 0.88112 | 1.03414 | 0.52478 | 0.20* | |
H33B | 0.80192 | 1.11554 | 0.50418 | 0.20* | |
H34A | 1.05388 | 1.12187 | 0.82365 | 0.20* | |
H34B | 1.01638 | 1.15577 | 0.68505 | 0.20* | |
H34C | 1.08418 | 1.07237 | 0.70855 | 0.20* | |
H35A | 0.79143 | 1.17948 | 0.85615 | 0.20* | |
H35B | 0.68323 | 1.15938 | 0.75425 | 0.20* | |
H35C | 0.75923 | 1.21298 | 0.71865 | 0.20* | |
H36A | 0.90809 | 1.01954 | 0.90840 | 0.20* | |
H36B | 0.93629 | 0.96734 | 0.79710 | 0.20* | |
H36C | 0.79959 | 0.99994 | 0.80690 | 0.20* | |
H38A | 0.65318 | 0.89299 | 0.88480 | 0.20* | |
H38B | 0.56588 | 0.96549 | 0.91840 | 0.20* | |
H39A | 0.42985 | 0.80796 | 1.04372 | 0.20* | |
H39B | 0.48705 | 0.87576 | 1.09712 | 0.20* | |
H39C | 0.57225 | 0.80386 | 1.05852 | 0.20* | |
H40A | 0.23617 | 0.90531 | 0.84064 | 0.20* | |
H40B | 0.28157 | 0.95311 | 0.75204 | 0.20* | |
H40C | 0.29237 | 0.97271 | 0.89484 | 0.20* | |
H41A | 0.40240 | 0.76449 | 0.76760 | 0.20* | |
H41B | 0.54440 | 0.76019 | 0.78580 | 0.20* | |
H41C | 0.45020 | 0.81049 | 0.67810 | 0.20* | |
H42 | 0.55401 | 0.76799 | 0.49001 | 0.20* | |
H43 | 0.64964 | 0.64898 | 0.42666 | 0.20* | |
H44 | 0.79194 | 0.64132 | 0.29942 | 0.20* | |
H45 | 0.83811 | 0.74789 | 0.23969 | 0.20* | |
H46 | 0.73788 | 0.86270 | 0.30597 | 0.20* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0383 (4) | 0.0603 (5) | 0.0553 (5) | −0.0080 (3) | 0.0139 (3) | −0.0076 (4) |
Cu2 | 0.0526 (5) | 0.0575 (5) | 0.0681 (5) | −0.0087 (4) | 0.0161 (4) | −0.0148 (4) |
Si3 | 0.074 (1) | 0.122 (2) | 0.060 (1) | −0.028 (1) | 0.010 (1) | −0.017 (1) |
Si4 | 0.075 (1) | 0.066 (1) | 0.085 (1) | −0.008 (1) | 0.007 (1) | 0.011 (1) |
Si5 | 0.077 (1) | 0.105 (2) | 0.108 (2) | −0.046 (1) | 0.013 (1) | −0.031 (1) |
Si6 | 0.121 (2) | 0.100 (2) | 0.068 (1) | −0.036 (1) | 0.025 (1) | 0.000 (1) |
O7 | 0.049 (2) | 0.076 (3) | 0.072 (3) | −0.007 (2) | 0.012 (2) | 0.008 (2) |
O8 | 0.063 (3) | 0.069 (3) | 0.062 (3) | −0.006 (2) | 0.021 (2) | 0.001 (2) |
O9 | 0.053 (2) | 0.075 (3) | 0.064 (3) | −0.023 (2) | 0.021 (2) | −0.020 (2) |
O10 | 0.053 (2) | 0.067 (3) | 0.071 (3) | −0.011 (2) | 0.017 (2) | −0.022 (2) |
O11 | 0.051 (3) | 0.090 (3) | 0.094 (3) | −0.020 (2) | 0.021 (2) | −0.025 (3) |
O12 | 0.060 (3) | 0.080 (3) | 0.104 (3) | −0.027 (2) | 0.021 (2) | −0.018 (3) |
O13 | 0.071 (3) | 0.073 (3) | 0.072 (3) | −0.004 (2) | 0.021 (2) | −0.003 (2) |
O14 | 0.084 (3) | 0.066 (3) | 0.065 (3) | −0.012 (2) | 0.013 (2) | −0.013 (2) |
N15 | 0.043 (3) | 0.064 (3) | 0.069 (3) | −0.007 (3) | 0.021 (3) | −0.014 (3) |
N16 | 0.059 (3) | 0.062 (4) | 0.072 (4) | −0.007 (3) | 0.012 (3) | −0.019 (3) |
C17 | 0.057 (4) | 0.061 (4) | 0.053 (4) | −0.018 (3) | 0.000 (3) | −0.009 (3) |
C18 | 0.070 (4) | 0.071 (4) | 0.059 (4) | −0.009 (3) | 0.003 (3) | 0.016 (3) |
C19 | 0.166 (8) | 0.100 (6) | 0.142 (8) | −0.039 (6) | −0.018 (6) | 0.051 (6) |
C20 | 0.157 (8) | 0.105 (7) | 0.155 (8) | −0.002 (6) | 0.049 (6) | −0.041 (6) |
C21 | 0.074 (5) | 0.101 (6) | 0.141 (7) | −0.029 (4) | 0.001 (4) | 0.025 (5) |
C22 | 0.056 (4) | 0.056 (4) | 0.051 (4) | −0.012 (3) | 0.009 (3) | −0.005 (3) |
C23 | 0.066 (4) | 0.066 (4) | 0.067 (4) | −0.021 (3) | 0.007 (3) | −0.022 (3) |
C24 | 0.23 (1) | 0.17 (1) | 0.13 (1) | −0.07 (1) | −0.06 (1) | −0.04 (1) |
C25 | 0.111 (6) | 0.137 (7) | 0.110 (6) | 0.005 (5) | 0.007 (5) | 0.025 (5) |
C26 | 0.123 (7) | 0.341 (15) | 0.100 (7) | −0.049 (8) | 0.050 (6) | 0.030 (8) |
C27 | 0.066 (4) | 0.098 (5) | 0.085 (5) | −0.008 (4) | 0.039 (4) | 0.005 (4) |
C28 | 0.083 (5) | 0.132 (7) | 0.118 (7) | −0.022 (5) | 0.059 (5) | 0.001 (5) |
C29 | 0.056 (5) | 0.126 (7) | 0.140 (8) | −0.017 (5) | 0.049 (5) | −0.019 (6) |
C30 | 0.054 (4) | 0.099 (6) | 0.160 (8) | 0.009 (4) | 0.032 (5) | 0.000 (5) |
C31 | 0.053 (4) | 0.075 (5) | 0.114 (6) | −0.006 (4) | 0.018 (4) | 0.011 (4) |
C32 | 0.058 (4) | 0.107 (6) | 0.067 (5) | −0.024 (4) | 0.017 (3) | −0.014 (4) |
C33 | 0.064 (4) | 0.128 (6) | 0.102 (5) | −0.052 (4) | 0.032 (4) | −0.033 (5) |
C34 | 0.083 (6) | 0.244 (11) | 0.205 (10) | −0.082 (7) | 0.030 (6) | −0.103 (9) |
C35 | 0.128 (7) | 0.177 (9) | 0.207 (10) | −0.071 (7) | 0.073 (7) | −0.119 (8) |
C36 | 0.27 (1) | 0.19 (1) | 0.15 (1) | −0.11 (1) | −0.07 (1) | 0.05 (1) |
C37 | 0.051 (4) | 0.077 (5) | 0.071 (5) | −0.021 (4) | 0.005 (3) | −0.008 (4) |
C38 | 0.085 (5) | 0.087 (5) | 0.055 (4) | −0.013 (4) | 0.006 (3) | 0.003 (4) |
C39 | 0.211 (9) | 0.132 (7) | 0.079 (6) | −0.046 (7) | 0.040 (6) | 0.001 (5) |
C40 | 0.099 (6) | 0.199 (10) | 0.140 (8) | −0.037 (6) | 0.039 (6) | 0.005 (7) |
C41 | 0.23 (1) | 0.12 (1) | 0.10 (1) | −0.09 (1) | 0.06 (1) | −0.03 (1) |
C42 | 0.133 (7) | 0.067 (5) | 0.111 (6) | −0.025 (5) | 0.038 (5) | −0.015 (5) |
C43 | 0.18 (1) | 0.06 (1) | 0.15 (1) | −0.02 (1) | 0.03 (1) | −0.03 (1) |
C44 | 0.106 (7) | 0.110 (8) | 0.129 (9) | 0.025 (6) | −0.011 (6) | −0.063 (7) |
C45 | 0.085 (6) | 0.129 (8) | 0.146 (9) | −0.002 (6) | 0.032 (5) | −0.068 (8) |
C46 | 0.077 (5) | 0.098 (6) | 0.108 (6) | −0.015 (4) | 0.033 (4) | −0.034 (5) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.632 (1) | C18—H18B | 0.960 |
Cu1—O7 | 1.962 (4) | C19—H19A | 0.960 |
Cu1—O8i | 1.961 (4) | C19—H19B | 0.960 |
Cu1—O9 | 1.982 (4) | C19—H19C | 0.961 |
Cu1—O10i | 1.972 (4) | C20—H20A | 0.960 |
Cu1—N15 | 2.194 (5) | C20—H20B | 0.960 |
Cu2—Cu2ii | 2.635 (1) | C20—H20C | 0.960 |
Cu2—O11 | 1.961 (4) | C21—H21A | 0.960 |
Cu2—O12ii | 1.965 (4) | C21—H21B | 0.960 |
Cu2—O13 | 1.959 (4) | C21—H21C | 0.961 |
Cu2—O14ii | 1.972 (4) | C23—H23A | 0.959 |
Cu2—N16 | 2.198 (6) | C23—H23B | 0.959 |
Si3—C23 | 1.876 (6) | C24—H24A | 0.960 |
Si3—C24 | 1.848 (11) | C24—H24B | 0.960 |
Si3—C25 | 1.854 (9) | C24—H24C | 0.961 |
Si3—C26 | 1.832 (9) | C25—H25A | 0.960 |
Si4—C18 | 1.885 (7) | C25—H25B | 0.960 |
Si4—C19 | 1.856 (9) | C25—H25C | 0.960 |
Si4—C20 | 1.848 (9) | C26—H26A | 0.960 |
Si4—C21 | 1.864 (7) | C26—H26B | 0.961 |
Si5—C33 | 1.850 (7) | C26—H26C | 0.961 |
Si5—C34 | 1.867 (9) | C27—H27 | 0.960 |
Si5—C35 | 1.846 (10) | C28—H28 | 0.961 |
Si5—C36 | 1.824 (11) | C29—H29 | 0.960 |
Si6—C38 | 1.886 (7) | C30—H30 | 0.960 |
Si6—C39 | 1.850 (8) | C31—H31 | 0.959 |
Si6—C40 | 1.862 (9) | C33—H33A | 0.960 |
Si6—C41 | 1.854 (9) | C33—H33B | 0.961 |
O7—C17 | 1.263 (7) | C34—H34A | 0.960 |
O8—C17 | 1.276 (7) | C34—H34B | 0.960 |
O9—C22 | 1.255 (7) | C34—H34C | 0.959 |
O10—C22 | 1.268 (7) | C35—H35A | 0.961 |
O11—C32 | 1.252 (10) | C35—H35B | 0.961 |
O12—C32 | 1.271 (8) | C35—H35C | 0.960 |
O13—C37 | 1.276 (8) | C36—H36A | 0.960 |
O14—C37 | 1.258 (8) | C36—H36B | 0.961 |
N15—C27 | 1.319 (8) | C36—H36C | 0.959 |
N15—C31 | 1.324 (8) | C38—H38A | 0.961 |
N16—C42 | 1.314 (10) | C38—H38B | 0.958 |
N16—C46 | 1.325 (9) | C39—H39A | 0.960 |
C17—C18 | 1.490 (8) | C39—H39B | 0.960 |
C22—C23 | 1.505 (8) | C39—H39C | 0.960 |
C27—C28 | 1.380 (10) | C40—H40A | 0.959 |
C28—C29 | 1.350 (12) | C40—H40B | 0.960 |
C29—C30 | 1.358 (12) | C40—H40C | 0.961 |
C30—C31 | 1.403 (9) | C41—H41A | 0.960 |
C32—C33 | 1.506 (9) | C41—H41B | 0.960 |
C37—C38 | 1.511 (9) | C41—H41C | 0.961 |
C42—C43 | 1.397 (12) | C42—H42 | 0.959 |
C43—C44 | 1.359 (14) | C43—H43 | 0.960 |
C44—C45 | 1.337 (14) | C44—H44 | 0.959 |
C45—C46 | 1.379 (13) | C45—H45 | 0.961 |
C18—H18A | 0.960 | C46—H46 | 0.960 |
| | | |
O7—Cu1—O8i | 168.3 (2) | H20A—C20—H20B | 110.0 |
O7—Cu1—O9 | 90.4 (2) | H20A—C20—H20C | 110.2 |
O7—Cu1—O10i | 89.0 (2) | H20B—C20—H20C | 108.9 |
O7—Cu1—N15 | 96.5 (2) | Si4—C21—H21A | 111.1 |
O8i—Cu1—O9 | 89.5 (2) | Si4—C21—H21B | 109.2 |
O8i—Cu1—O10i | 88.8 (2) | Si4—C21—H21C | 108.9 |
O8i—Cu1—N15 | 95.1 (2) | H21A—C21—H21B | 109.3 |
O9—Cu1—O10i | 168.7 (2) | H21A—C21—H21C | 109.3 |
O9—Cu1—N15 | 91.9 (2) | H21B—C21—H21C | 108.9 |
O10i—Cu1—N15 | 99.4 (2) | Si3—C23—H23A | 109.4 |
O11—Cu2—O12ii | 168.3 (2) | Si3—C23—H23B | 108.6 |
O11—Cu2—O13 | 89.3 (2) | C22—C23—H23A | 109.0 |
O11—Cu2—O14ii | 88.8 (2) | C22—C23—H23B | 108.7 |
O11—Cu2—N16 | 97.2 (2) | H23A—C23—H23B | 109.1 |
O12ii—Cu2—O13 | 88.4 (2) | Si3—C24—H24A | 107.7 |
O12ii—Cu2—O14ii | 91.2 (2) | Si3—C24—H24B | 109.0 |
O12ii—Cu2—N16 | 94.5 (2) | Si3—C24—H24C | 110.7 |
O13—Cu2—O14ii | 168.5 (2) | H24A—C24—H24B | 110.2 |
O13—Cu2—N16 | 96.5 (2) | H24A—C24—H24C | 110.2 |
O14ii—Cu2—N16 | 95.0 (2) | H24B—C24—H24C | 109.0 |
C23—Si3—C24 | 108.6 (4) | Si3—C25—H25A | 111.0 |
C23—Si3—C25 | 110.8 (4) | Si3—C25—H25B | 109.5 |
C23—Si3—C26 | 108.7 (4) | Si3—C25—H25C | 108.7 |
C24—Si3—C25 | 109.7 (5) | H25A—C25—H25B | 109.4 |
C24—Si3—C26 | 111.4 (5) | H25A—C25—H25C | 109.3 |
C25—Si3—C26 | 107.6 (5) | H25B—C25—H25C | 109.0 |
C18—Si4—C19 | 107.1 (4) | Si3—C26—H26A | 109.5 |
C18—Si4—C20 | 108.0 (4) | Si3—C26—H26B | 108.9 |
C18—Si4—C21 | 110.5 (3) | Si3—C26—H26C | 110.4 |
C19—Si4—C20 | 112.4 (4) | H26A—C26—H26B | 109.5 |
C19—Si4—C21 | 110.5 (4) | H26A—C26—H26C | 109.5 |
C20—Si4—C21 | 108.3 (4) | H26B—C26—H26C | 109.0 |
C33—Si5—C34 | 106.4 (4) | N15—C27—H27 | 118.2 |
C33—Si5—C35 | 109.4 (4) | C28—C27—H27 | 119.0 |
C33—Si5—C36 | 110.9 (4) | C27—C28—H28 | 120.6 |
C34—Si5—C35 | 109.4 (5) | C29—C28—H28 | 120.5 |
C34—Si5—C36 | 112.5 (5) | C28—C29—H29 | 120.0 |
C35—Si5—C36 | 108.2 (5) | C30—C29—H29 | 120.4 |
C38—Si6—C39 | 107.0 (4) | C29—C30—H30 | 120.3 |
C38—Si6—C40 | 109.2 (4) | C31—C30—H30 | 121.2 |
C38—Si6—C41 | 109.7 (4) | N15—C31—H31 | 118.6 |
C39—Si6—C40 | 110.2 (4) | C30—C31—H31 | 119.6 |
C39—Si6—C41 | 110.5 (4) | Si5—C33—H33A | 109.0 |
C40—Si6—C41 | 110.2 (4) | Si5—C33—H33B | 108.6 |
Cu1—O7—C17 | 123.2 (4) | C32—C33—H33A | 108.7 |
Cu1i—O8—C17 | 124.6 (4) | C32—C33—H33B | 108.7 |
Cu1—O9—C22 | 125.0 (4) | H33A—C33—H33B | 109.1 |
Cu1i—O10—C22 | 120.7 (4) | Si5—C34—H34A | 105.6 |
Cu2—O11—C32 | 121.1 (4) | Si5—C34—H34B | 109.2 |
Cu2ii—O12—C32 | 125.5 (5) | Si5—C34—H34C | 111.7 |
Cu2—O13—C37 | 122.2 (4) | H34A—C34—H34B | 110.7 |
Cu2ii—O14—C37 | 124.4 (4) | H34A—C34—H34C | 110.7 |
Cu1—N15—C27 | 120.5 (4) | H34B—C34—H34C | 109.0 |
Cu1—N15—C31 | 120.9 (4) | Si5—C35—H35A | 109.6 |
C27—N15—C31 | 118.3 (5) | Si5—C35—H35B | 109.2 |
Cu2—N16—C42 | 122.2 (5) | Si5—C35—H35C | 110.1 |
Cu2—N16—C46 | 119.9 (5) | H35A—C35—H35B | 109.4 |
C42—N16—C46 | 117.9 (6) | H35A—C35—H35C | 109.5 |
O7—C17—O8 | 123.6 (6) | H35B—C35—H35C | 109.1 |
O7—C17—C18 | 118.9 (5) | Si5—C36—H36A | 111.5 |
O8—C17—C18 | 117.4 (5) | Si5—C36—H36B | 109.4 |
Si4—C18—C17 | 112.2 (4) | Si5—C36—H36C | 108.7 |
O9—C22—O10 | 125.5 (5) | H36A—C36—H36B | 109.1 |
O9—C22—C23 | 117.6 (5) | H36A—C36—H36C | 109.2 |
O10—C22—C23 | 116.8 (5) | H36B—C36—H36C | 108.9 |
Si3—C23—C22 | 112.0 (4) | Si6—C38—H38A | 108.8 |
N15—C27—C28 | 122.8 (7) | Si6—C38—H38B | 109.0 |
C27—C28—C29 | 119.0 (8) | C37—C38—H38A | 108.9 |
C28—C29—C30 | 119.6 (7) | C37—C38—H38B | 109.4 |
C29—C30—C31 | 118.6 (7) | H38A—C38—H38B | 109.0 |
N15—C31—C30 | 121.8 (7) | Si6—C39—H39A | 105.8 |
O11—C32—O12 | 125.0 (6) | Si6—C39—H39B | 111.0 |
O11—C32—C33 | 119.4 (6) | Si6—C39—H39C | 109.9 |
O12—C32—C33 | 115.6 (7) | H39A—C39—H39B | 110.6 |
Si5—C33—C32 | 112.7 (5) | H39A—C39—H39C | 110.6 |
O13—C37—O14 | 124.6 (6) | H39B—C39—H39C | 108.9 |
O13—C37—C38 | 117.2 (6) | Si6—C40—H40A | 109.7 |
O14—C37—C38 | 118.2 (6) | Si6—C40—H40B | 109.2 |
Si6—C38—C37 | 111.7 (5) | Si6—C40—H40C | 109.7 |
N16—C42—C43 | 122.0 (8) | H40A—C40—H40B | 109.6 |
C42—C43—C44 | 118.5 (9) | H40A—C40—H40C | 109.6 |
C43—C44—C45 | 119.9 (9) | H40B—C40—H40C | 109.0 |
C44—C45—C46 | 118.6 (9) | Si6—C41—H41A | 110.3 |
N16—C46—C45 | 123.1 (7) | Si6—C41—H41B | 108.4 |
Si4—C18—H18A | 109.1 | Si6—C41—H41C | 109.9 |
Si4—C18—H18B | 109.0 | H41A—C41—H41B | 109.7 |
C17—C18—H18A | 108.8 | H41A—C41—H41C | 109.6 |
C17—C18—H18B | 108.7 | H41B—C41—H41C | 109.0 |
H18A—C18—H18B | 109.0 | N16—C42—H42 | 118.3 |
Si4—C19—H19A | 106.2 | C43—C42—H42 | 119.7 |
Si4—C19—H19B | 110.6 | C42—C43—H43 | 121.7 |
Si4—C19—H19C | 110.0 | C44—C43—H43 | 119.8 |
H19A—C19—H19B | 110.6 | C43—C44—H44 | 120.9 |
H19A—C19—H19C | 110.5 | C45—C44—H44 | 119.2 |
H19B—C19—H19C | 109.0 | C44—C45—H45 | 121.0 |
Si4—C20—H20A | 108.3 | C46—C45—H45 | 120.3 |
Si4—C20—H20B | 110.2 | N16—C46—H46 | 117.0 |
Si4—C20—H20C | 109.2 | C45—C46—H46 | 119.9 |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+2, −z+1. |
(II) tetrakis(µ-trimethylsilylacetato-
O:
O')di(2-methylpyridine-N)dicopper(II)
top
Crystal data top
[Cu2(C5H11O2Si)4(C6H7N)2] | Z = 1 |
Mr = 838.26 | F(000) = 442 |
Triclinic, P1 | Dx = 1.199 Mg m−3 |
a = 10.874 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.508 (2) Å | Cell parameters from 25 reflections |
c = 10.330 (2) Å | θ = 10–15° |
α = 104.26 (2)° | µ = 1.06 mm−1 |
β = 109.10 (2)° | T = 298 K |
γ = 74.91 (2)° | Plate-like, green |
V = 1160.9 (4) Å3 | 0.5 × 0.5 × 0.2 mm |
Data collection top
Rigaku AFC7R diffractometer | 5169 reflections with I > 1.5σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.009 |
Graphite monochromator | θmax = 32.5°, θmin = 2.5° |
θ–2θ scans | h = −16→16 |
Absorption correction: ψ-scan (North et al., 1968) | k = −17→17 |
Tmin = 0.567, Tmax = 0.809 | l = −15→0 |
8822 measured reflections | 3 standard reflections every 150 reflections |
8412 independent reflections | intensity decay: 10.1% |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.051 | H-atom parameters not refined |
wR(F2) = 0.079 | w = 1/[σ2(Fo) + 0.00181|Fo|2] |
S = 1.39 | (Δ/σ)max = 0.03 |
5352 reflections | Δρmax = 0.45 e Å−3 |
253 parameters | Δρmin = −0.32 e Å−3 |
Crystal data top
[Cu2(C5H11O2Si)4(C6H7N)2] | γ = 74.91 (2)° |
Mr = 838.26 | V = 1160.9 (4) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.874 (2) Å | Mo Kα radiation |
b = 11.508 (2) Å | µ = 1.06 mm−1 |
c = 10.330 (2) Å | T = 298 K |
α = 104.26 (2)° | 0.5 × 0.5 × 0.2 mm |
β = 109.10 (2)° | |
Data collection top
Rigaku AFC7R diffractometer | 5169 reflections with I > 1.5σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.009 |
Tmin = 0.567, Tmax = 0.809 | 3 standard reflections every 150 reflections |
8822 measured reflections | intensity decay: 10.1% |
8412 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.079 | H-atom parameters not refined |
S = 1.39 | Δρmax = 0.45 e Å−3 |
5352 reflections | Δρmin = −0.32 e Å−3 |
253 parameters | |
Special details top
Refinement. Refinement based on F against all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F, conventional R-factors (R) are calculated on F, with F set to zero for negative F. The threshold expression of F2 > σ(F2) is used. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | −0.10007 (3) | −0.01009 (3) | −0.95868 (3) | 0.05532 (10) | |
Si1 | −0.2736 (1) | 0.3765 (1) | −1.1944 (2) | 0.1130 (5) | |
Si2 | 0.1577 (1) | 0.2429 (1) | −0.5267 (1) | 0.0919 (3) | |
O1 | −0.2106 (2) | 0.0936 (2) | −1.0981 (2) | 0.0778 (7) | |
O2 | −0.0416 (2) | 0.1116 (2) | −1.1633 (2) | 0.0725 (6) | |
O3 | −0.0549 (2) | 0.1365 (2) | −0.8262 (3) | 0.0806 (7) | |
O4 | 0.1172 (3) | 0.1517 (2) | −0.8893 (2) | 0.0824 (7) | |
N1 | −0.2633 (3) | −0.0253 (4) | −0.8793 (3) | 0.0884 (10) | |
C1 | −0.1631 (3) | 0.1307 (3) | −1.1711 (3) | 0.0637 (7) | |
C2 | −0.2580 (4) | 0.2098 (4) | −1.2728 (4) | 0.088 (1) | |
C3 | −0.320 (2) | 0.4042 (8) | −1.042 (1) | 0.319 (8) | |
C4 | −0.394 (1) | 0.4687 (8) | −1.317 (1) | 0.290 (6) | |
C5 | −0.1162 (9) | 0.4185 (7) | −1.150 (2) | 0.302 (6) | |
C6 | 0.0395 (4) | 0.1870 (3) | −0.8144 (3) | 0.0703 (8) | |
C7 | 0.0630 (5) | 0.2913 (3) | −0.6984 (4) | 0.092 (1) | |
C8 | 0.1841 (8) | 0.3815 (6) | −0.3964 (6) | 0.158 (2) | |
C9 | 0.3179 (8) | 0.1508 (9) | −0.5400 (8) | 0.186 (3) | |
C10 | 0.0712 (10) | 0.1400 (8) | −0.4901 (7) | 0.183 (3) | |
C11 | −0.348 (1) | 0.043 (2) | −0.831 (1) | 0.100 (4) | 0.50 |
C12 | −0.4753 (8) | 0.012 (1) | −0.8051 (9) | 0.165 (4) | |
C13 | −0.4568 (7) | −0.099 (1) | −0.8522 (8) | 0.150 (3) | |
C14 | −0.3740 (9) | −0.193 (2) | −0.898 (2) | 0.167 (6) | 0.50 |
C15 | −0.2696 (9) | −0.167 (1) | −0.925 (1) | 0.097 (4) | 0.50 |
C16 | −0.340 (2) | 0.170 (2) | −0.800 (2) | 0.168 (6) | 0.50 |
C17 | −0.3211 (10) | −0.111 (1) | −0.8913 (8) | 0.084 (3) | 0.50 |
C18 | −0.4311 (9) | 0.120 (1) | −0.769 (1) | 0.126 (4) | 0.50 |
C19 | −0.319 (1) | 0.098 (1) | −0.816 (2) | 0.096 (4) | 0.50 |
C20 | −0.271 (2) | −0.234 (1) | −0.958 (2) | 0.137 (5) | 0.50 |
H1 | −0.3438 | 0.1885 | −1.3007 | 0.1060* | |
H2 | −0.2262 | 0.1952 | −1.3530 | 0.1060* | |
H3 | −0.3242 | 0.4893 | −1.0012 | 0.3847* | |
H4 | −0.4031 | 0.3825 | −1.0616 | 0.3847* | |
H5 | −0.2530 | 0.3560 | −0.9773 | 0.3847* | |
H6 | −0.3982 | 0.5537 | −1.2770 | 0.3497* | |
H7 | −0.3680 | 0.4520 | −1.4011 | 0.3497* | |
H8 | −0.4798 | 0.4488 | −1.3381 | 0.3497* | |
H9 | −0.0527 | 0.3706 | −1.0833 | 0.3629* | |
H10 | −0.0875 | 0.4045 | −1.2308 | 0.3629* | |
H11 | −0.1239 | 0.5038 | −1.1077 | 0.3629* | |
H12 | −0.0213 | 0.3406 | −0.6910 | 0.1106* | |
H13 | 0.1124 | 0.3390 | −0.7191 | 0.1106* | |
H14 | 0.2365 | 0.3595 | −0.3082 | 0.1893* | |
H15 | 0.2296 | 0.4279 | −0.4250 | 0.1893* | |
H16 | 0.0998 | 0.4306 | −0.3882 | 0.1893* | |
H17 | 0.3663 | 0.1221 | −0.4541 | 0.2218* | |
H18 | 0.3056 | 0.0826 | −0.6145 | 0.2218* | |
H19 | 0.3680 | 0.2000 | −0.5582 | 0.2218* | |
H20 | −0.0151 | 0.1843 | −0.4823 | 0.2197* | |
H21 | 0.0613 | 0.0714 | −0.5647 | 0.2197* | |
H22 | 0.1220 | 0.1121 | −0.4045 | 0.2197* | |
H23 | −0.5434 | 0.0645 | −0.7652 | 0.1989* | 0.50 |
H24 | −0.5334 | −0.1282 | −0.8569 | 0.1811* | 0.50 |
H25 | −0.3858 | −0.2753 | −0.9123 | 0.1965* | 0.50 |
H26 | −0.2074 | −0.2277 | −0.9664 | 0.1167* | 0.50 |
H27 | −0.2576 | 0.1806 | −0.7323 | 0.1993* | 0.50 |
H28 | −0.3470 | 0.1963 | −0.8830 | 0.1993* | 0.50 |
H29 | −0.4124 | 0.2163 | −0.7626 | 0.1993* | 0.50 |
H30 | −0.5073 | −0.1595 | −0.8623 | 0.1811* | 0.50 |
H31 | −0.5590 | 0.0318 | −0.7842 | 0.1989* | 0.50 |
H32 | −0.4696 | 0.1971 | −0.7204 | 0.1500* | 0.50 |
H33 | −0.2774 | 0.1649 | −0.8075 | 0.1148* | 0.50 |
H34 | −0.3244 | −0.2889 | −0.9583 | 0.1633* | 0.50 |
H35 | −0.2743 | −0.2332 | −1.0512 | 0.1633* | 0.50 |
H36 | −0.1806 | −0.2614 | −0.9061 | 0.1633* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0511 (2) | 0.0635 (2) | 0.0555 (2) | −0.0114 (1) | 0.0156 (1) | 0.0158 (1) |
Si1 | 0.1011 (8) | 0.0738 (7) | 0.159 (1) | −0.0006 (6) | 0.0141 (8) | 0.0560 (8) |
Si2 | 0.1253 (9) | 0.0816 (6) | 0.0593 (5) | −0.0268 (6) | 0.0206 (5) | −0.0058 (4) |
O1 | 0.0556 (10) | 0.094 (2) | 0.089 (1) | −0.009 (1) | 0.0106 (10) | 0.042 (1) |
O2 | 0.066 (1) | 0.085 (1) | 0.071 (1) | −0.0027 (10) | 0.0187 (9) | 0.035 (1) |
O3 | 0.082 (1) | 0.075 (1) | 0.081 (1) | −0.014 (1) | 0.030 (1) | −0.004 (1) |
O4 | 0.109 (2) | 0.080 (1) | 0.070 (1) | −0.044 (1) | 0.028 (1) | 0.002 (1) |
N1 | 0.055 (1) | 0.144 (3) | 0.080 (2) | −0.024 (2) | 0.016 (1) | 0.044 (2) |
C1 | 0.064 (1) | 0.061 (1) | 0.063 (1) | −0.009 (1) | 0.008 (1) | 0.020 (1) |
C2 | 0.076 (2) | 0.092 (2) | 0.092 (2) | −0.011 (2) | −0.004 (2) | 0.048 (2) |
C3 | 0.57 (2) | 0.107 (6) | 0.32 (1) | −0.007 (10) | 0.25 (2) | −0.009 (7) |
C4 | 0.28 (1) | 0.159 (7) | 0.34 (1) | 0.023 (7) | −0.06 (1) | 0.162 (9) |
C5 | 0.181 (8) | 0.098 (5) | 0.57 (3) | −0.042 (5) | 0.01 (1) | 0.055 (9) |
C6 | 0.096 (2) | 0.054 (1) | 0.056 (1) | −0.018 (1) | 0.012 (1) | 0.009 (1) |
C7 | 0.135 (3) | 0.060 (2) | 0.075 (2) | −0.026 (2) | 0.023 (2) | −0.001 (2) |
C8 | 0.223 (7) | 0.126 (4) | 0.087 (3) | −0.057 (5) | 0.004 (4) | −0.022 (3) |
C9 | 0.156 (6) | 0.219 (8) | 0.120 (5) | 0.008 (6) | 0.012 (4) | −0.001 (5) |
C10 | 0.266 (9) | 0.210 (7) | 0.116 (4) | −0.113 (7) | 0.041 (5) | 0.047 (5) |
C11 | 0.066 (5) | 0.16 (1) | 0.083 (6) | −0.007 (6) | 0.032 (4) | 0.037 (7) |
C12 | 0.122 (5) | 0.28 (1) | 0.112 (5) | −0.054 (7) | 0.017 (4) | 0.070 (7) |
C13 | 0.090 (4) | 0.249 (10) | 0.123 (5) | −0.031 (6) | 0.029 (3) | 0.054 (6) |
C14 | 0.071 (5) | 0.26 (2) | 0.23 (1) | −0.068 (8) | 0.012 (7) | 0.16 (1) |
C15 | 0.066 (5) | 0.14 (1) | 0.116 (8) | −0.030 (6) | 0.033 (4) | 0.048 (8) |
C16 | 0.101 (8) | 0.19 (2) | 0.18 (1) | 0.03 (1) | 0.061 (8) | −0.01 (1) |
C17 | 0.082 (5) | 0.121 (8) | 0.066 (4) | −0.034 (5) | 0.017 (4) | 0.034 (4) |
C18 | 0.081 (5) | 0.18 (1) | 0.120 (7) | −0.003 (6) | 0.058 (5) | 0.015 (7) |
C19 | 0.068 (6) | 0.108 (10) | 0.119 (8) | −0.009 (6) | 0.041 (5) | 0.020 (7) |
C20 | 0.16 (1) | 0.094 (7) | 0.18 (1) | −0.061 (8) | 0.051 (9) | 0.032 (8) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.664 (1) | C7—H12 | 0.960 |
Cu1—O1 | 1.977 (2) | C7—H13 | 0.960 |
Cu1—O2i | 1.960 (2) | C8—H14 | 0.958 |
Cu1—O3 | 1.953 (2) | C8—H15 | 0.962 |
Cu1—O4i | 1.965 (2) | C8—H16 | 0.961 |
Cu1—N1 | 2.244 (3) | C9—H17 | 0.960 |
Si1—C2 | 1.876 (4) | C9—H18 | 0.957 |
Si1—C3 | 1.74 (1) | C9—H19 | 0.967 |
Si1—C4 | 1.816 (7) | C10—H20 | 0.963 |
Si1—C5 | 1.783 (10) | C10—H21 | 0.958 |
Si2—C7 | 1.873 (4) | C10—H22 | 0.958 |
Si2—C8 | 1.835 (5) | C11—C12 | 1.63 (1) |
Si2—C9 | 1.816 (8) | C11—C16 | 1.43 (2) |
Si2—C10 | 1.861 (7) | C12—C13 | 1.24 (1) |
O1—C1 | 1.243 (4) | C12—C18 | 1.37 (2) |
O2—C1 | 1.261 (4) | C12—H23 | 0.962 |
O3—C6 | 1.264 (4) | C12—H31 | 0.961 |
O4—C6 | 1.254 (4) | C13—C14 | 1.31 (2) |
N1—C11 | 1.20 (1) | C13—C17 | 1.62 (1) |
N1—C15 | 1.60 (2) | C13—H24 | 0.959 |
N1—C17 | 1.263 (10) | C13—H30 | 0.960 |
N1—C19 | 1.47 (2) | C14—C15 | 1.37 (1) |
C1—C2 | 1.507 (4) | C14—H25 | 0.962 |
C2—H1 | 0.960 | C15—H26 | 0.961 |
C2—H2 | 0.960 | C16—H27 | 0.958 |
C3—H3 | 0.961 | C16—H28 | 0.949 |
C3—H4 | 0.950 | C16—H29 | 0.961 |
C3—H5 | 0.967 | C17—C20 | 1.46 (2) |
C4—H6 | 0.958 | C18—C19 | 1.40 (1) |
C4—H7 | 0.961 | C18—H32 | 0.964 |
C4—H8 | 0.962 | C19—H33 | 0.962 |
C5—H9 | 0.965 | C20—H34 | 0.957 |
C5—H10 | 0.951 | C20—H35 | 0.960 |
C5—H11 | 0.964 | C20—H36 | 0.963 |
C6—C7 | 1.482 (4) | | |
| | | |
Cu1i—Cu1—O1 | 84.4 (1) | Si2—C7—C6 | 113.1 (2) |
Cu1i—Cu1—O2i | 82.8 (1) | Si2—C7—H12 | 108.5 (3) |
Cu1i—Cu1—O3 | 82.1 (1) | Si2—C7—H13 | 108.6 (3) |
Cu1i—Cu1—O4i | 85.2 (1) | C6—C7—H12 | 108.5 (4) |
Cu1i—Cu1—N1 | 177.5 (1) | C6—C7—H13 | 108.5 (3) |
O1—Cu1—O2i | 167.1 (1) | H12—C7—H13 | 109.5 (4) |
O1—Cu1—O3 | 89.4 (1) | Si2—C8—H14 | 109.7 (5) |
O1—Cu1—O4i | 87.5 (1) | Si2—C8—H15 | 109.5 (5) |
O1—Cu1—N1 | 97.4 (1) | Si2—C8—H16 | 109.5 (5) |
O2i—Cu1—O3 | 89.8 (1) | H14—C8—H15 | 109.4 (7) |
O2i—Cu1—O4i | 90.5 (1) | H14—C8—H16 | 109.5 (7) |
O2i—Cu1—N1 | 95.5 (1) | H15—C8—H16 | 109.2 (7) |
O3—Cu1—O4i | 167.2 (1) | Si2—C9—H17 | 109.7 (7) |
O3—Cu1—N1 | 96.1 (1) | Si2—C9—H18 | 109.9 (6) |
O4i—Cu1—N1 | 96.7 (1) | Si2—C9—H19 | 109.4 (7) |
C2—Si1—C3 | 110.1 (3) | H17—C9—H18 | 109.7 (9) |
C2—Si1—C4 | 110.5 (4) | H17—C9—H19 | 108.9 (8) |
C2—Si1—C5 | 109.2 (3) | H18—C9—H19 | 109.2 (9) |
C3—Si1—C4 | 110.3 (7) | Si2—C10—H20 | 109.3 (6) |
C3—Si1—C5 | 107.4 (8) | Si2—C10—H21 | 109.5 (5) |
C4—Si1—C5 | 109.2 (6) | Si2—C10—H22 | 109.5 (6) |
C7—Si2—C8 | 107.7 (2) | H20—C10—H21 | 109.4 (8) |
C7—Si2—C9 | 108.6 (3) | H20—C10—H22 | 109.4 (7) |
C7—Si2—C10 | 109.6 (3) | H21—C10—H22 | 109.8 (9) |
C8—Si2—C9 | 108.9 (3) | N1—C11—C12 | 128 (1) |
C8—Si2—C10 | 116.1 (4) | N1—C11—C16 | 115 (1) |
C9—Si2—C10 | 105.6 (5) | C12—C11—C16 | 115 (1) |
Cu1—O1—C1 | 122.5 (2) | C11—C12—C13 | 98.4 (10) |
Cu1i—O2—C1 | 124.8 (2) | C11—C12—H23 | 130 (1) |
Cu1—O3—C6 | 125.9 (2) | C13—C12—C18 | 148.7 (10) |
Cu1i—O4—C6 | 121.8 (2) | C13—C12—H23 | 131 (1) |
Cu1—N1—C11 | 137.0 (8) | C13—C12—H31 | 105 (1) |
Cu1—N1—C15 | 103.5 (4) | C18—C12—H31 | 105 (1) |
Cu1—N1—C17 | 133.8 (6) | C12—C13—C14 | 144.9 (10) |
Cu1—N1—C19 | 108.0 (5) | C12—C13—C17 | 98.3 (9) |
C11—N1—C15 | 118.7 (8) | C12—C13—H24 | 107.6 (9) |
C17—N1—C19 | 117.7 (7) | C12—C13—H30 | 130.9 (9) |
O1—C1—O2 | 125.4 (3) | C14—C13—H24 | 107.6 (10) |
O1—C1—C2 | 117.3 (3) | C17—C13—H30 | 130.8 (10) |
O2—C1—C2 | 117.3 (3) | C13—C14—C15 | 116 (1) |
Si1—C2—C1 | 111.7 (2) | C13—C14—H25 | 121.7 (10) |
Si1—C2—H1 | 108.9 (3) | C15—C14—H25 | 121 (1) |
Si1—C2—H2 | 108.9 (3) | N1—C15—C14 | 112 (1) |
C1—C2—H1 | 108.9 (3) | N1—C15—H26 | 123.9 (8) |
C1—C2—H2 | 108.9 (3) | C14—C15—H26 | 123 (1) |
H1—C2—H2 | 109.4 (4) | C11—C16—H27 | 108 (1) |
Si1—C3—H3 | 109 (1) | C11—C16—H28 | 109 (1) |
Si1—C3—H4 | 109 (1) | C11—C16—H29 | 108 (1) |
Si1—C3—H5 | 108 (1) | H27—C16—H28 | 110 (2) |
H3—C3—H4 | 110 (1) | H27—C16—H29 | 109 (1) |
H3—C3—H5 | 108 (1) | H28—C16—H29 | 110 (1) |
H4—C3—H5 | 109 (1) | N1—C17—C13 | 126.8 (9) |
Si1—C4—H6 | 109.6 (8) | N1—C17—C20 | 119.4 (9) |
Si1—C4—H7 | 109.5 (8) | C13—C17—C20 | 113.6 (8) |
Si1—C4—H8 | 109.5 (8) | C12—C18—C19 | 106 (1) |
H6—C4—H7 | 109 (1) | C12—C18—H32 | 127 (1) |
H6—C4—H8 | 109 (1) | C19—C18—H32 | 126 (1) |
H7—C4—H8 | 109 (1) | N1—C19—C18 | 121 (1) |
Si1—C5—H9 | 109.2 (10) | N1—C19—H33 | 118 (1) |
Si1—C5—H10 | 109.9 (9) | C18—C19—H33 | 119 (1) |
Si1—C5—H11 | 109.2 (9) | C17—C20—H34 | 109 (1) |
H9—C5—H10 | 109 (1) | C17—C20—H35 | 109 (1) |
H9—C5—H11 | 108 (1) | C17—C20—H36 | 109 (1) |
H10—C5—H11 | 109 (1) | H34—C20—H35 | 109 (1) |
O3—C6—O4 | 124.8 (3) | H34—C20—H36 | 109 (1) |
O3—C6—C7 | 116.8 (3) | H35—C20—H36 | 109 (1) |
O4—C6—C7 | 118.2 (3) | | |
Symmetry code: (i) −x, −y, −z−2. |
(III) tetrakis(µ-trimethylsilylacetato-
O:
O')di(3-methylpyridine-N)dicopper(II)
top
Crystal data top
[Cu2(C5H11O2Si)4(C6H7N)2] | Z = 1 |
Mr = 838.26 | F(000) = 442 |
Triclinic, P1 | Dx = 1.220 Mg m−3 |
a = 11.148 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.755 (1) Å | Cell parameters from 25 reflections |
c = 10.563 (3) Å | θ = 10–15° |
α = 110.91 (1)° | µ = 1.08 mm−1 |
β = 117.70 (2)° | T = 297 K |
γ = 84.23 (2)° | Plate-like, light green |
V = 1141.3 (5) Å3 | 0.4 × 0.3 × 0.1 mm |
Data collection top
Rigaku AFC-5 diffractometer | Rint = 0.017 |
θ–2θ scans | θmax = 27.5° |
Absorption correction: integration (Coppens et al., 1965) | h = 0→14 |
Tmin = 0.676, Tmax = 0.893 | k = −15→15 |
5532 measured reflections | l = −14→14 |
5261 independent reflections | 3 standard reflections every 100 reflections |
3377 reflections with |Fo| > 3σ(|Fo|) | intensity decay: none |
Refinement top
Refinement on F | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.064 | w = 1/[σ2(F) + 0.000225F2] |
wR(F2) = 0.054 | (Δ/σ)max = 0.001 |
S = 1.23 | Δρmax = 0.66 e Å−3 |
3377 reflections | Δρmin = −0.51 e Å−3 |
217 parameters | |
Crystal data top
[Cu2(C5H11O2Si)4(C6H7N)2] | γ = 84.23 (2)° |
Mr = 838.26 | V = 1141.3 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.148 (3) Å | Mo Kα radiation |
b = 11.755 (1) Å | µ = 1.08 mm−1 |
c = 10.563 (3) Å | T = 297 K |
α = 110.91 (1)° | 0.4 × 0.3 × 0.1 mm |
β = 117.70 (2)° | |
Data collection top
Rigaku AFC-5 diffractometer | 3377 reflections with |Fo| > 3σ(|Fo|) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.017 |
Tmin = 0.676, Tmax = 0.893 | 3 standard reflections every 100 reflections |
5532 measured reflections | intensity decay: none |
5261 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.064 | 217 parameters |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.66 e Å−3 |
3377 reflections | Δρmin = −0.51 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.89600 (4) | −0.03538 (4) | 0.50817 (5) | 0.0465 (2) | |
Si2 | 1.1805 (1) | 0.2993 (1) | 1.0221 (1) | 0.0742 (7) | |
Si3 | 0.7665 (1) | 0.3346 (1) | 0.3148 (2) | 0.0769 (8) | |
O4 | 1.0200 (3) | 0.0260 (2) | 0.7293 (3) | 0.061 (1) | |
O5 | 1.1962 (2) | 0.0846 (2) | 0.7147 (3) | 0.062 (1) | |
O6 | 0.8398 (2) | 0.1315 (2) | 0.5199 (3) | 0.057 (1) | |
O7 | 1.0195 (2) | 0.1923 (2) | 0.5127 (3) | 0.062 (2) | |
N8 | 0.7301 (3) | −0.0919 (3) | 0.5323 (4) | 0.058 (2) | |
C9 | 1.1389 (4) | 0.0758 (3) | 0.7875 (4) | 0.054 (2) | |
C10 | 1.2122 (4) | 0.1330 (4) | 0.9597 (4) | 0.067 (2) | |
C11 | 1.2646 (6) | 0.3610 (5) | 1.2363 (5) | 0.113 (3) | |
C12 | 1.2534 (6) | 0.3803 (5) | 0.9489 (6) | 0.117 (4) | |
C13 | 0.9930 (5) | 0.3121 (5) | 0.9406 (6) | 0.111 (3) | |
C14 | 0.9072 (4) | 0.2084 (3) | 0.5170 (4) | 0.052 (2) | |
C15 | 0.8504 (4) | 0.3295 (3) | 0.5129 (4) | 0.065 (2) | |
C16 | 0.6929 (6) | 0.4841 (5) | 0.3239 (7) | 0.135 (5) | |
C17 | 0.8923 (6) | 0.3155 (7) | 0.2437 (7) | 0.150 (6) | |
C18 | 0.6300 (5) | 0.2080 (6) | 0.1875 (6) | 0.120 (4) | |
C19 | 0.7183 (4) | −0.0375 (4) | 0.6602 (5) | 0.070 (3) | |
C20 | 0.6033 (5) | −0.0598 (5) | 0.6707 (6) | 0.086 (3) | |
C21 | 0.5015 (5) | −0.1402 (5) | 0.5471 (7) | 0.084 (4) | |
C22 | 0.5120 (4) | −0.1989 (4) | 0.4152 (7) | 0.084 (3) | |
C23 | 0.4011 (6) | −0.2842 (6) | 0.2733 (9) | 0.165 (5) | |
C24 | 0.6283 (4) | −0.1713 (4) | 0.4116 (5) | 0.074 (3) | |
H17A | 0.84963 | 0.31689 | 0.14167 | 0.20* | |
H17B | 0.93293 | 0.23959 | 0.24437 | 0.20* | |
H17C | 0.96183 | 0.38149 | 0.30997 | 0.20* | |
H16A | 0.65020 | 0.48552 | 0.22189 | 0.20* | |
H16B | 0.76380 | 0.54882 | 0.39089 | 0.20* | |
H16C | 0.62750 | 0.49352 | 0.36139 | 0.20* | |
H18A | 0.58723 | 0.20936 | 0.08552 | 0.20* | |
H18B | 0.56403 | 0.21846 | 0.22442 | 0.20* | |
H18C | 0.66803 | 0.13096 | 0.18782 | 0.20* | |
H19 | 0.79132 | 0.01876 | 0.74699 | 0.20* | |
H20 | 0.59516 | −0.01904 | 0.76263 | 0.20* | |
H21 | 0.42194 | −0.15717 | 0.55253 | 0.20* | |
H23A | 0.42569 | −0.31621 | 0.19196 | 0.20* | |
H23B | 0.32243 | −0.23838 | 0.24698 | 0.20* | |
H23C | 0.38463 | −0.34758 | 0.30198 | 0.20* | |
H24 | 0.63623 | −0.20994 | 0.31924 | 0.20* | |
H15A | 0.78502 | 0.34373 | 0.55102 | 0.20* | |
H15B | 0.92322 | 0.39283 | 0.57772 | 0.20* | |
H10A | 1.17960 | 0.09147 | 1.00265 | 0.20* | |
H10B | 1.30800 | 0.12497 | 0.99555 | 0.20* | |
H13A | 0.97627 | 0.39691 | 0.97090 | 0.20* | |
H13B | 0.95527 | 0.26971 | 0.97830 | 0.20* | |
H13C | 0.95117 | 0.27651 | 0.83120 | 0.20* | |
H11A | 1.24789 | 0.44579 | 1.26656 | 0.20* | |
H11B | 1.36049 | 0.35199 | 1.27586 | 0.20* | |
H11C | 1.22729 | 0.31769 | 1.27336 | 0.20* | |
H12A | 1.23666 | 0.46511 | 0.97917 | 0.20* | |
H12B | 1.21236 | 0.34501 | 0.83947 | 0.20* | |
H12C | 1.34946 | 0.37241 | 0.99007 | 0.20* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0337 (2) | 0.0498 (3) | 0.0536 (3) | −0.0002 (2) | 0.0204 (2) | 0.0158 (2) |
Si2 | 0.0781 (8) | 0.0670 (9) | 0.0558 (8) | 0.0053 (7) | 0.0289 (7) | 0.0085 (6) |
Si3 | 0.0752 (8) | 0.0875 (10) | 0.0921 (10) | 0.0196 (7) | 0.0424 (8) | 0.0521 (8) |
O4 | 0.056 (2) | 0.070 (2) | 0.050 (2) | −0.003 (1) | 0.019 (1) | 0.020 (1) |
O5 | 0.046 (1) | 0.076 (2) | 0.054 (2) | −0.004 (1) | 0.021 (1) | 0.013 (1) |
O6 | 0.049 (1) | 0.055 (2) | 0.073 (2) | 0.009 (1) | 0.035 (1) | 0.024 (1) |
O7 | 0.052 (2) | 0.051 (2) | 0.083 (2) | 0.001 (1) | 0.033 (1) | 0.023 (1) |
N8 | 0.044 (2) | 0.060 (2) | 0.074 (2) | 0.005 (2) | 0.030 (2) | 0.026 (2) |
C9 | 0.052 (2) | 0.047 (2) | 0.055 (3) | 0.010 (2) | 0.018 (2) | 0.019 (2) |
C10 | 0.065 (3) | 0.071 (3) | 0.044 (2) | 0.002 (2) | 0.012 (2) | 0.014 (2) |
C11 | 0.132 (4) | 0.098 (4) | 0.061 (3) | 0.005 (3) | 0.037 (3) | 0.000 (3) |
C12 | 0.142 (5) | 0.085 (4) | 0.114 (4) | −0.016 (3) | 0.065 (4) | 0.026 (3) |
C13 | 0.089 (4) | 0.117 (4) | 0.099 (4) | 0.030 (3) | 0.047 (3) | 0.019 (3) |
C14 | 0.046 (2) | 0.056 (3) | 0.041 (2) | 0.007 (2) | 0.016 (2) | 0.010 (2) |
C15 | 0.068 (3) | 0.049 (2) | 0.076 (3) | 0.015 (2) | 0.036 (2) | 0.024 (2) |
C16 | 0.164 (6) | 0.112 (5) | 0.158 (6) | 0.053 (4) | 0.068 (5) | 0.090 (4) |
C17 | 0.146 (6) | 0.224 (8) | 0.168 (6) | 0.035 (5) | 0.106 (5) | 0.119 (6) |
C18 | 0.098 (4) | 0.141 (5) | 0.102 (4) | −0.001 (4) | 0.008 (3) | 0.055 (4) |
C19 | 0.063 (3) | 0.089 (3) | 0.076 (3) | 0.009 (2) | 0.037 (2) | 0.041 (3) |
C20 | 0.073 (3) | 0.126 (5) | 0.110 (4) | 0.024 (3) | 0.052 (3) | 0.077 (4) |
C21 | 0.056 (3) | 0.103 (4) | 0.147 (5) | 0.025 (3) | 0.058 (3) | 0.082 (4) |
C22 | 0.046 (2) | 0.062 (3) | 0.135 (5) | −0.005 (2) | 0.038 (3) | 0.031 (3) |
C23 | 0.085 (4) | 0.111 (5) | 0.246 (8) | −0.026 (4) | 0.078 (5) | 0.017 (5) |
C24 | 0.051 (2) | 0.059 (3) | 0.102 (4) | 0.003 (2) | 0.037 (2) | 0.020 (3) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.638 (3) | C10—H10B | 0.960 |
Cu1—O4 | 1.971 (3) | C11—H11A | 0.960 |
Cu1—O5i | 1.958 (3) | C11—H11B | 0.960 |
Cu1—O6 | 1.976 (3) | C11—H11C | 0.960 |
Cu1—O7i | 1.973 (3) | C12—H12A | 0.960 |
Cu1—N8 | 2.176 (3) | C12—H12B | 0.960 |
Si2—C10 | 1.881 (5) | C12—H12C | 0.960 |
Si2—C11 | 1.875 (5) | C13—H13A | 0.960 |
Si2—C12 | 1.853 (5) | C13—H13B | 0.961 |
Si2—C13 | 1.868 (6) | C13—H13C | 0.960 |
Si3—C15 | 1.875 (5) | C15—H15A | 0.960 |
Si3—C16 | 1.853 (7) | C15—H15B | 0.960 |
Si3—C17 | 1.839 (7) | C16—H16A | 0.960 |
Si3—C18 | 1.861 (6) | C16—H16B | 0.960 |
O4—C9 | 1.273 (5) | C16—H16C | 0.960 |
O5—C9 | 1.240 (5) | C17—H17A | 0.960 |
O6—C14 | 1.249 (4) | C17—H17B | 0.960 |
O7—C14 | 1.267 (5) | C17—H17C | 0.960 |
N8—C19 | 1.334 (6) | C18—H18A | 0.960 |
N8—C24 | 1.343 (5) | C18—H18B | 0.960 |
C9—C10 | 1.512 (6) | C18—H18C | 0.960 |
C14—C15 | 1.505 (6) | C19—H19 | 0.960 |
C19—C20 | 1.396 (6) | C20—H20 | 0.960 |
C20—C21 | 1.357 (8) | C21—H21 | 0.960 |
C21—C22 | 1.371 (9) | C23—H23A | 0.960 |
C22—C23 | 1.495 (8) | C23—H23B | 0.960 |
C22—C24 | 1.388 (6) | C23—H23C | 0.960 |
C10—H10A | 0.960 | C24—H24 | 0.960 |
| | | |
O4—Cu1—O5i | 168.2 (2) | H11A—C11—H11B | 110.4 |
O4—Cu1—O6 | 90.0 (2) | H11A—C11—H11C | 110.5 |
O4—Cu1—O7i | 90.3 (2) | H11B—C11—H11C | 109.0 |
O4—Cu1—N8 | 94.5 (2) | Si2—C12—H12A | 109.5 |
O5i—Cu1—O6 | 88.5 (2) | Si2—C12—H12B | 109.7 |
O5i—Cu1—O7i | 88.8 (2) | Si2—C12—H12C | 109.3 |
O5i—Cu1—N8 | 97.4 (2) | H12A—C12—H12B | 109.7 |
O6—Cu1—O7i | 168.1 (1) | H12A—C12—H12C | 109.6 |
O6—Cu1—N8 | 95.4 (2) | H12B—C12—H12C | 109.0 |
O7i—Cu1—N8 | 96.4 (2) | Si2—C13—H13A | 108.8 |
C10—Si2—C11 | 107.7 (3) | Si2—C13—H13B | 109.6 |
C10—Si2—C12 | 108.9 (3) | Si2—C13—H13C | 109.9 |
C10—Si2—C13 | 108.5 (3) | H13A—C13—H13B | 109.8 |
C11—Si2—C12 | 110.8 (3) | H13A—C13—H13C | 109.7 |
C11—Si2—C13 | 111.1 (3) | H13B—C13—H13C | 109.0 |
C12—Si2—C13 | 109.7 (3) | Si3—C15—H15A | 109.1 |
C15—Si3—C16 | 107.7 (3) | Si3—C15—H15B | 108.9 |
C15—Si3—C17 | 109.7 (3) | C14—C15—H15A | 108.9 |
C15—Si3—C18 | 108.9 (3) | C14—C15—H15B | 108.8 |
C16—Si3—C17 | 111.0 (4) | H15A—C15—H15B | 109.0 |
C16—Si3—C18 | 110.3 (3) | Si3—C16—H16A | 106.9 |
C17—Si3—C18 | 109.2 (3) | Si3—C16—H16B | 109.7 |
Cu1—O4—C9 | 123.6 (3) | Si3—C16—H16C | 110.5 |
Cu1i—O5—C9 | 122.5 (3) | H16A—C16—H16B | 110.4 |
Cu1—O6—C14 | 122.4 (3) | H16A—C16—H16C | 110.4 |
Cu1i—O7—C14 | 123.9 (3) | H16B—C16—H16C | 109.0 |
Cu1—N8—C19 | 120.9 (3) | Si3—C17—H17A | 110.1 |
Cu1—N8—C24 | 120.1 (3) | Si3—C17—H17B | 110.2 |
C19—N8—C24 | 118.5 (4) | Si3—C17—H17C | 108.4 |
O4—C9—O5 | 125.5 (4) | H17A—C17—H17B | 109.6 |
O4—C9—C10 | 116.2 (4) | H17A—C17—H17C | 109.6 |
O5—C9—C10 | 118.2 (4) | H17B—C17—H17C | 109.0 |
Si2—C10—C9 | 110.2 (3) | Si3—C18—H18A | 109.4 |
O6—C14—O7 | 125.3 (4) | Si3—C18—H18B | 109.1 |
O6—C14—C15 | 118.6 (4) | Si3—C18—H18C | 109.9 |
O7—C14—C15 | 116.0 (4) | H18A—C18—H18B | 109.7 |
Si3—C15—C14 | 112.0 (3) | H18A—C18—H18C | 109.7 |
N8—C19—C20 | 121.9 (4) | H18B—C18—H18C | 109.0 |
C19—C20—C21 | 118.5 (5) | N8—C19—H19 | 118.7 |
C20—C21—C22 | 120.8 (5) | C20—C19—H19 | 119.4 |
C21—C22—C23 | 123.3 (5) | C19—C20—H20 | 121.2 |
C21—C22—C24 | 117.8 (5) | C21—C20—H20 | 120.3 |
C23—C22—C24 | 118.8 (5) | C20—C21—H21 | 119.7 |
N8—C24—C22 | 122.5 (5) | C22—C21—H21 | 119.5 |
Si2—C10—H10A | 109.3 | C22—C23—H23A | 111.8 |
Si2—C10—H10B | 109.6 | C22—C23—H23B | 106.2 |
C9—C10—H10A | 109.2 | C22—C23—H23C | 105.6 |
C9—C10—H10B | 109.5 | H23A—C23—H23B | 111.9 |
H10A—C10—H10B | 109.0 | H23A—C23—H23C | 111.9 |
Si2—C11—H11A | 106.9 | H23B—C23—H23C | 109.0 |
Si2—C11—H11B | 109.8 | N8—C24—H24 | 118.6 |
Si2—C11—H11C | 110.3 | C22—C24—H24 | 118.9 |
Symmetry code: (i) −x+2, −y, −z+1. |
(IV) tetrakis(µ-trimethylsilylacetato-
O:
O')di(quinoline-N)dicopper(II)
top
Crystal data top
[Cu2(C5H11O2Si)4(C9H7N)2] | Z = 1 |
Mr = 910.32 | F(000) = 478 |
Triclinic, P1 | Dx = 1.260 Mg m−3 |
a = 11.298 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.495 (3) Å | Cell parameters from 25 reflections |
c = 10.261 (3) Å | θ = 10–15° |
α = 104.03 (2)° | µ = 1.03 mm−1 |
β = 110.10 (2)° | T = 298 K |
γ = 76.99 (2)° | Plate-like, dark green |
V = 1199.4 (5) Å3 | 0.8 × 0.4 × 0.1 mm |
Data collection top
Rigaku AFC7R diffractometer | 6024 reflections with I > 1.5σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.040 |
Graphite monochromator | θmax = 32.5°, θmin = 2.5° |
θ–2θ scans | h = −17→17 |
Absorption correction: integration (Coppens et al., 1965) numerical | k = −17→17 |
Tmin = 0.659, Tmax = 0.902 | l = −16→0 |
9728 measured reflections | 3 standard reflections every 150 reflections |
8692 independent reflections | intensity decay: 2.2% |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters not refined |
wR(F2) = 0.069 | w = 1/[σ2(Fo) + 0.00181|Fo|2] |
S = 1.18 | (Δ/σ)max = 0.004 |
6191 reflections | Δρmax = 0.53 e Å−3 |
244 parameters | Δρmin = −0.26 e Å−3 |
Crystal data top
[Cu2(C5H11O2Si)4(C9H7N)2] | γ = 76.99 (2)° |
Mr = 910.32 | V = 1199.4 (5) Å3 |
Triclinic, P1 | Z = 1 |
a = 11.298 (2) Å | Mo Kα radiation |
b = 11.495 (3) Å | µ = 1.03 mm−1 |
c = 10.261 (3) Å | T = 298 K |
α = 104.03 (2)° | 0.8 × 0.4 × 0.1 mm |
β = 110.10 (2)° | |
Data collection top
Rigaku AFC7R diffractometer | 6024 reflections with I > 1.5σ(I) |
Absorption correction: integration (Coppens et al., 1965) numerical | Rint = 0.040 |
Tmin = 0.659, Tmax = 0.902 | 3 standard reflections every 150 reflections |
9728 measured reflections | intensity decay: 2.2% |
8692 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters not refined |
S = 1.18 | Δρmax = 0.53 e Å−3 |
6191 reflections | Δρmin = −0.26 e Å−3 |
244 parameters | |
Special details top
Refinement. Refinement based on F against all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F, conventional R-factors (R) are calculated on F, with F set to zero for negative F. The threshold expression of F2 > 1.5σ(F2) is used. The positions of all the H atoms were calculated geometrically, and a riding model was used in their refinement for (I) and (III) [C—H 0.96 Å, Uiso(H) = 0.2 Å2]. H atom parameters were not refined for (II), (IV), and (V) [Uiso(H)= 1.2 Ueq(parent atom)]. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.09339 (2) | 0.51565 (3) | 0.45752 (3) | 0.03655 (7) | |
Si1 | 0.2776 (1) | 0.12685 (8) | 0.6814 (1) | 0.0748 (3) | |
Si2 | 0.1308 (1) | 0.75034 (10) | 0.98828 (9) | 0.0695 (3) | |
O1 | 0.2044 (2) | 0.4123 (2) | 0.5940 (2) | 0.0529 (5) | |
O2 | 0.0466 (2) | 0.3836 (2) | 0.6612 (2) | 0.0554 (5) | |
O3 | 0.1126 (2) | 0.6567 (2) | 0.6133 (2) | 0.0561 (6) | |
O4 | −0.0456 (2) | 0.6306 (2) | 0.6796 (2) | 0.0564 (5) | |
N1 | 0.2502 (2) | 0.5550 (2) | 0.3903 (2) | 0.0462 (5) | |
C1 | 0.1617 (2) | 0.3695 (2) | 0.6678 (2) | 0.0426 (5) | |
C2 | 0.2556 (3) | 0.2907 (3) | 0.7664 (3) | 0.0556 (7) | |
C3 | 0.1304 (9) | 0.0698 (6) | 0.634 (1) | 0.238 (5) | |
C4 | 0.397 (1) | 0.0418 (7) | 0.809 (1) | 0.314 (5) | |
C5 | 0.3127 (10) | 0.1084 (5) | 0.5167 (8) | 0.179 (3) | |
C6 | 0.0417 (2) | 0.6865 (2) | 0.6912 (3) | 0.0451 (6) | |
C7 | 0.0633 (3) | 0.7939 (3) | 0.8083 (3) | 0.0630 (8) | |
C8 | 0.2585 (7) | 0.6221 (5) | 0.9873 (5) | 0.141 (2) | |
C9 | 0.0030 (8) | 0.702 (1) | 1.0292 (8) | 0.273 (5) | |
C10 | 0.1905 (8) | 0.8831 (6) | 1.1173 (6) | 0.198 (3) | |
C11 | 0.2761 (3) | 0.6658 (3) | 0.4399 (3) | 0.0576 (8) | |
C12 | 0.3834 (3) | 0.7056 (3) | 0.4351 (4) | 0.0650 (9) | |
C13 | 0.4672 (3) | 0.6256 (3) | 0.3774 (3) | 0.0627 (9) | |
C14 | 0.4431 (2) | 0.5072 (3) | 0.3190 (3) | 0.0517 (7) | |
C15 | 0.5241 (3) | 0.4197 (4) | 0.2524 (4) | 0.071 (1) | |
C16 | 0.4962 (4) | 0.3077 (4) | 0.1952 (5) | 0.084 (1) | |
C17 | 0.3864 (4) | 0.2737 (3) | 0.2020 (5) | 0.082 (1) | |
C18 | 0.3071 (3) | 0.3549 (3) | 0.2686 (4) | 0.0613 (8) | |
C19 | 0.3326 (2) | 0.4736 (2) | 0.3270 (3) | 0.0460 (6) | |
H1 | 0.2258 | 0.2976 | 0.8454 | 0.0667* | |
H2 | 0.3365 | 0.3188 | 0.7989 | 0.0667* | |
H3 | 0.1064 | 0.0768 | 0.7166 | 0.2851* | |
H4 | 0.0648 | 0.1160 | 0.5692 | 0.2851* | |
H5 | 0.1407 | −0.0139 | 0.5889 | 0.2851* | |
H6 | 0.3711 | 0.0525 | 0.8911 | 0.3772* | |
H7 | 0.4080 | −0.0427 | 0.7678 | 0.3772* | |
H8 | 0.4775 | 0.0711 | 0.8357 | 0.3772* | |
H9 | 0.3213 | 0.0240 | 0.4744 | 0.2143* | |
H10 | 0.2444 | 0.1534 | 0.4535 | 0.2143* | |
H11 | 0.3909 | 0.1381 | 0.5352 | 0.2143* | |
H12 | −0.0167 | 0.8465 | 0.8029 | 0.0756* | |
H13 | 0.1220 | 0.8363 | 0.7963 | 0.0756* | |
H14 | 0.2261 | 0.5552 | 0.9172 | 0.1696* | |
H15 | 0.3257 | 0.6446 | 0.9659 | 0.1696* | |
H16 | 0.2913 | 0.5988 | 1.0784 | 0.1696* | |
H17 | −0.0658 | 0.7687 | 1.0299 | 0.3278* | |
H18 | −0.0277 | 0.6349 | 0.9588 | 0.3278* | |
H19 | 0.0367 | 0.6787 | 1.1202 | 0.3278* | |
H20 | 0.2248 | 0.8629 | 1.2100 | 0.2380* | |
H21 | 0.2560 | 0.9057 | 1.0932 | 0.2380* | |
H22 | 0.1216 | 0.9497 | 1.1159 | 0.2380* | |
H23 | 0.2181 | 0.7237 | 0.4824 | 0.0692* | |
H24 | 0.3967 | 0.7883 | 0.4722 | 0.0780* | |
H25 | 0.5428 | 0.6500 | 0.3766 | 0.0753* | |
H26 | 0.5999 | 0.4410 | 0.2481 | 0.0850* | |
H27 | 0.5516 | 0.2498 | 0.1490 | 0.1008* | |
H28 | 0.3672 | 0.1933 | 0.1599 | 0.0985* | |
H29 | 0.2338 | 0.3305 | 0.2753 | 0.0736* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0316 (1) | 0.0420 (2) | 0.0384 (1) | −0.00332 (9) | 0.01314 (10) | 0.0092 (1) |
Si1 | 0.0872 (7) | 0.0467 (5) | 0.0874 (7) | 0.0051 (4) | 0.0227 (5) | 0.0244 (4) |
Si2 | 0.0777 (6) | 0.0803 (6) | 0.0411 (4) | −0.0118 (5) | 0.0188 (4) | −0.0073 (4) |
O1 | 0.0382 (8) | 0.061 (1) | 0.064 (1) | 0.0004 (7) | 0.0141 (8) | 0.0284 (9) |
O2 | 0.0421 (8) | 0.072 (1) | 0.060 (1) | 0.0034 (8) | 0.0173 (8) | 0.0333 (10) |
O3 | 0.065 (1) | 0.054 (1) | 0.059 (1) | −0.0202 (9) | 0.0312 (9) | −0.0010 (9) |
O4 | 0.0519 (10) | 0.062 (1) | 0.057 (1) | −0.0136 (8) | 0.0262 (9) | −0.0053 (9) |
N1 | 0.0392 (9) | 0.051 (1) | 0.054 (1) | −0.0035 (8) | 0.0203 (8) | 0.0140 (9) |
C1 | 0.042 (1) | 0.040 (1) | 0.042 (1) | −0.0006 (8) | 0.0098 (9) | 0.0084 (9) |
C2 | 0.051 (1) | 0.060 (2) | 0.050 (1) | 0.004 (1) | 0.008 (1) | 0.023 (1) |
C3 | 0.220 (9) | 0.102 (5) | 0.42 (2) | −0.090 (5) | 0.155 (10) | −0.048 (7) |
C4 | 0.43 (2) | 0.133 (6) | 0.214 (9) | 0.158 (8) | −0.01 (1) | 0.063 (6) |
C5 | 0.32 (1) | 0.081 (3) | 0.158 (6) | −0.022 (5) | 0.140 (7) | −0.024 (4) |
C6 | 0.050 (1) | 0.041 (1) | 0.040 (1) | −0.0038 (9) | 0.0113 (9) | 0.0069 (9) |
C7 | 0.083 (2) | 0.047 (1) | 0.052 (1) | −0.013 (1) | 0.018 (1) | −0.005 (1) |
C8 | 0.191 (6) | 0.129 (4) | 0.071 (3) | 0.059 (4) | 0.042 (3) | 0.031 (3) |
C9 | 0.142 (6) | 0.63 (2) | 0.117 (5) | −0.104 (9) | 0.029 (4) | 0.168 (9) |
C10 | 0.29 (1) | 0.108 (4) | 0.086 (4) | −0.023 (5) | −0.043 (5) | −0.028 (3) |
C11 | 0.058 (1) | 0.054 (1) | 0.072 (2) | −0.008 (1) | 0.031 (1) | 0.014 (1) |
C12 | 0.067 (2) | 0.059 (2) | 0.083 (2) | −0.021 (1) | 0.029 (2) | 0.016 (2) |
C13 | 0.049 (1) | 0.083 (2) | 0.071 (2) | −0.018 (1) | 0.021 (1) | 0.026 (2) |
C14 | 0.039 (1) | 0.070 (2) | 0.052 (1) | −0.003 (1) | 0.0156 (10) | 0.023 (1) |
C15 | 0.052 (1) | 0.090 (2) | 0.083 (2) | 0.001 (1) | 0.038 (2) | 0.022 (2) |
C16 | 0.065 (2) | 0.089 (3) | 0.102 (3) | 0.005 (2) | 0.049 (2) | 0.004 (2) |
C17 | 0.077 (2) | 0.066 (2) | 0.108 (3) | −0.004 (2) | 0.050 (2) | −0.004 (2) |
C18 | 0.048 (1) | 0.064 (2) | 0.074 (2) | −0.008 (1) | 0.027 (1) | 0.004 (1) |
C19 | 0.038 (1) | 0.057 (1) | 0.044 (1) | −0.0018 (9) | 0.0126 (9) | 0.015 (1) |
Geometric parameters (Å, º) top
Cu1—Cu1i | 2.665 (1) | C5—H10 | 0.960 |
Cu1—O1 | 1.969 (2) | C5—H11 | 0.960 |
Cu1—O2i | 1.965 (2) | C6—C7 | 1.497 (4) |
Cu1—O3 | 1.973 (2) | C7—H12 | 0.960 |
Cu1—O4i | 1.959 (2) | C7—H13 | 0.960 |
Cu1—N1 | 2.274 (2) | C8—H14 | 0.960 |
Si1—C2 | 1.874 (3) | C8—H15 | 0.960 |
Si1—C3 | 1.792 (8) | C8—H16 | 0.960 |
Si1—C4 | 1.820 (7) | C9—H17 | 0.960 |
Si1—C5 | 1.818 (7) | C9—H18 | 0.959 |
Si2—C7 | 1.885 (3) | C9—H19 | 0.960 |
Si2—C8 | 1.816 (5) | C10—H20 | 0.960 |
Si2—C9 | 1.858 (7) | C10—H21 | 0.960 |
Si2—C10 | 1.846 (5) | C10—H22 | 0.960 |
O1—C1 | 1.259 (3) | C11—C12 | 1.408 (4) |
O2—C1 | 1.254 (3) | C11—H23 | 0.960 |
O3—C6 | 1.258 (3) | C12—C13 | 1.349 (4) |
O4—C6 | 1.251 (3) | C12—H24 | 0.960 |
N1—C11 | 1.311 (4) | C13—C14 | 1.395 (4) |
N1—C19 | 1.376 (3) | C13—H25 | 0.960 |
C1—C2 | 1.498 (3) | C14—C15 | 1.414 (4) |
C2—H1 | 0.960 | C14—C19 | 1.420 (3) |
C2—H2 | 0.960 | C15—C16 | 1.339 (6) |
C3—H3 | 0.960 | C15—H26 | 0.960 |
C3—H4 | 0.961 | C16—C17 | 1.410 (5) |
C3—H5 | 0.960 | C16—H27 | 0.960 |
C4—H6 | 0.958 | C17—C18 | 1.370 (4) |
C4—H7 | 0.959 | C17—H28 | 0.960 |
C4—H8 | 0.964 | C18—C19 | 1.402 (4) |
C5—H9 | 0.960 | C18—H29 | 0.960 |
| | | |
Cu1i—Cu1—O1 | 84.8 (1) | H9—C5—H10 | 109.5 (8) |
Cu1i—Cu1—O2i | 82.6 (1) | H9—C5—H11 | 109.4 (8) |
Cu1i—Cu1—O3 | 85.1 (1) | H10—C5—H11 | 109.5 (7) |
Cu1i—Cu1—O4i | 81.9 (1) | O3—C6—O4 | 124.3 (2) |
Cu1i—Cu1—N1 | 176.4 (1) | O3—C6—C7 | 118.8 (2) |
O1—Cu1—O2i | 167.3 (1) | O4—C6—C7 | 116.9 (2) |
O1—Cu1—O3 | 88.5 (1) | Si2—C7—C6 | 112.8 (2) |
O1—Cu1—O4i | 89.2 (1) | Si2—C7—H12 | 108.6 (2) |
O1—Cu1—N1 | 96.9 (1) | Si2—C7—H13 | 108.6 (2) |
O2i—Cu1—O3 | 89.2 (1) | C6—C7—H12 | 108.6 (3) |
O2i—Cu1—O4i | 90.2 (1) | C6—C7—H13 | 108.6 (3) |
O2i—Cu1—N1 | 95.7 (1) | H12—C7—H13 | 109.5 (3) |
O3—Cu1—O4i | 166.9 (1) | Si2—C8—H14 | 109.5 (5) |
O3—Cu1—N1 | 91.8 (1) | Si2—C8—H15 | 109.5 (5) |
O4i—Cu1—N1 | 101.3 (1) | Si2—C8—H16 | 109.5 (4) |
C2—Si1—C3 | 109.1 (3) | H14—C8—H15 | 109.5 (5) |
C2—Si1—C4 | 108.6 (3) | H14—C8—H16 | 109.5 (6) |
C2—Si1—C5 | 111.3 (2) | H15—C8—H16 | 109.5 (7) |
C3—Si1—C4 | 108.2 (5) | Si2—C9—H17 | 109.4 (9) |
C3—Si1—C5 | 105.3 (5) | Si2—C9—H18 | 109.5 (6) |
C4—Si1—C5 | 114.0 (5) | Si2—C9—H19 | 109.4 (6) |
C7—Si2—C8 | 109.6 (2) | H17—C9—H18 | 109.5 (7) |
C7—Si2—C9 | 108.7 (2) | H17—C9—H19 | 109.4 (9) |
C7—Si2—C10 | 108.2 (3) | H18—C9—H19 | 109 (1) |
C8—Si2—C9 | 107.9 (5) | Si2—C10—H20 | 109.5 (5) |
C8—Si2—C10 | 110.9 (3) | Si2—C10—H21 | 109.5 (5) |
C9—Si2—C10 | 111.5 (5) | Si2—C10—H22 | 109.4 (5) |
Cu1—O1—C1 | 122.2 (1) | H20—C10—H21 | 109.5 (7) |
Cu1i—O2—C1 | 125.1 (2) | H20—C10—H22 | 109.4 (8) |
Cu1—O3—C6 | 122.0 (2) | H21—C10—H22 | 109.5 (7) |
Cu1i—O4—C6 | 126.7 (2) | N1—C11—C12 | 124.4 (3) |
Cu1—N1—C11 | 113.7 (2) | N1—C11—H23 | 117.8 (3) |
Cu1—N1—C19 | 128.0 (2) | C12—C11—H23 | 117.8 (3) |
C11—N1—C19 | 117.2 (2) | C11—C12—C13 | 119.0 (3) |
O1—C1—O2 | 125.3 (2) | C11—C12—H24 | 120.5 (3) |
O1—C1—C2 | 117.1 (2) | C13—C12—H24 | 120.5 (3) |
O2—C1—C2 | 117.6 (2) | C12—C13—C14 | 119.4 (3) |
Si1—C2—C1 | 112.8 (2) | C12—C13—H25 | 120.3 (3) |
Si1—C2—H1 | 108.6 (2) | C14—C13—H25 | 120.3 (3) |
Si1—C2—H2 | 108.6 (2) | C13—C14—C15 | 122.7 (3) |
C1—C2—H1 | 108.6 (2) | C13—C14—C19 | 118.5 (2) |
C1—C2—H2 | 108.6 (2) | C15—C14—C19 | 118.9 (3) |
H1—C2—H2 | 109.5 (3) | C14—C15—C16 | 120.8 (3) |
Si1—C3—H3 | 109.5 (8) | C14—C15—H26 | 119.6 (4) |
Si1—C3—H4 | 109.4 (6) | C16—C15—H26 | 119.6 (3) |
Si1—C3—H5 | 109.5 (7) | C15—C16—C17 | 120.7 (3) |
H3—C3—H4 | 109.4 (9) | C15—C16—H27 | 119.7 (4) |
H3—C3—H5 | 109.5 (9) | C17—C16—H27 | 119.7 (4) |
H4—C3—H5 | 109 (1) | C16—C17—C18 | 120.3 (3) |
Si1—C4—H6 | 109.6 (7) | C16—C17—H28 | 119.8 (3) |
Si1—C4—H7 | 109.6 (8) | C18—C17—H28 | 119.8 (4) |
Si1—C4—H8 | 109.3 (7) | C17—C18—C19 | 120.2 (3) |
H6—C4—H7 | 109 (1) | C17—C18—H29 | 119.9 (3) |
H6—C4—H8 | 109 (1) | C19—C18—H29 | 119.9 (3) |
H7—C4—H8 | 109.2 (10) | N1—C19—C14 | 121.5 (2) |
Si1—C5—H9 | 109.5 (6) | N1—C19—C18 | 119.4 (2) |
Si1—C5—H10 | 109.5 (6) | C14—C19—C18 | 119.1 (2) |
Si1—C5—H11 | 109.5 (6) | | |
Symmetry code: (i) −x, −y+1, −z+1. |
(V)
catena-poly[tetrakis(µ-trimethylsilylacetato-O:
O')dicopper(II)]
top
Crystal data top
[Cu2(C5H11O2Si)4] | F(000) = 1368 |
Mr = 652.00 | Dx = 1.312 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
a = 10.288 (6) Å | Cell parameters from 25 reflections |
b = 24.692 (5) Å | θ = 10–15° |
c = 13.116 (5) Å | µ = 1.47 mm−1 |
β = 97.71 (4)° | T = 298 K |
V = 3302 (2) Å3 | Plate-like, blue-green |
Z = 4 | 0.3 × 0.1 × 0.05 mm |
Data collection top
Rigaku AFC7R diffractometer | 3260 reflections with I > 1.5σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.042 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω scans | h = −13→0 |
Absorption correction: Ψ-scan (North et al., 1968) | k = 0→32 |
Tmin = 0.852, Tmax = 0.929 | l = −17→17 |
7986 measured reflections | 3 standard reflections every 150 reflections |
7574 independent reflections | intensity decay: 1.4% |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.068 | H-atom parameters not refined |
wR(F2) = 0.100 | w = 1/[σ2(Fo) + 0.00212|Fo|2] |
S = 1.48 | (Δ/σ)max = 0.003 |
3309 reflections | Δρmax = 0.78 e Å−3 |
247 parameters | Δρmin = −0.60 e Å−3 |
Crystal data top
[Cu2(C5H11O2Si)4] | V = 3302 (2) Å3 |
Mr = 652.00 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 10.288 (6) Å | µ = 1.47 mm−1 |
b = 24.692 (5) Å | T = 298 K |
c = 13.116 (5) Å | 0.3 × 0.1 × 0.05 mm |
β = 97.71 (4)° | |
Data collection top
Rigaku AFC7R diffractometer | 3260 reflections with I > 1.5σ(I) |
Absorption correction: Ψ-scan (North et al., 1968) | Rint = 0.042 |
Tmin = 0.852, Tmax = 0.929 | 3 standard reflections every 150 reflections |
7986 measured reflections | intensity decay: 1.4% |
7574 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.068 | 0 restraints |
wR(F2) = 0.100 | H-atom parameters not refined |
S = 1.48 | Δρmax = 0.78 e Å−3 |
3309 reflections | Δρmin = −0.60 e Å−3 |
247 parameters | |
Special details top
Refinement. Refinement based on F against all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F, conventional R-factors (R) are calculated on F, with F set to zero for negative F. The threshold expression of F2 > 1.5σ(F2) is used. The positions of all the H atoms were calculated geometrically, and a riding model was used in their refinement for (I) and (III) [C—H 0.96 Å, Uiso(H) = 0.2 Å2]. H atom parameters were not refined for (II), (IV), and (V) [Uiso(H)= 1.2 Ueq(parent atom)]. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.17891 (9) | 0.28330 (5) | 0.74109 (8) | 0.0320 (3) | |
Cu2 | 0.43030 (9) | 0.28346 (5) | 0.80830 (8) | 0.0329 (3) | |
Si1 | 0.2659 (3) | 0.3594 (2) | 1.1210 (2) | 0.066 (1) | |
Si2 | 0.2816 (4) | 0.4689 (1) | 0.6079 (3) | 0.072 (1) | |
Si3 | 0.3737 (6) | 0.1901 (2) | 0.4418 (3) | 0.103 (2) | |
Si4 | 0.2556 (3) | 0.0964 (1) | 0.9330 (3) | 0.068 (1) | |
O1 | 0.1835 (6) | 0.3393 (3) | 0.8505 (5) | 0.043 (2) | |
O2 | 0.3986 (6) | 0.3364 (3) | 0.9063 (5) | 0.050 (2) | |
O3 | 0.2122 (7) | 0.3367 (3) | 0.6419 (5) | 0.054 (2) | |
O4 | 0.4233 (7) | 0.3408 (3) | 0.7034 (6) | 0.050 (2) | |
O5 | 0.2431 (6) | 0.2259 (3) | 0.6528 (5) | 0.043 (2) | |
O6 | 0.4564 (6) | 0.2286 (2) | 0.7076 (5) | 0.037 (2) | |
O7 | 0.1497 (6) | 0.2284 (2) | 0.8425 (5) | 0.037 (2) | |
O8 | 0.3636 (6) | 0.2263 (3) | 0.8965 (5) | 0.043 (2) | |
C1 | 0.2827 (10) | 0.3540 (4) | 0.9102 (8) | 0.042 (3) | |
C2 | 0.266 (1) | 0.3932 (4) | 0.9934 (8) | 0.054 (3) | |
C3 | 0.232 (2) | 0.4130 (7) | 1.212 (1) | 0.099 (5)* | |
C4 | 0.424 (2) | 0.3275 (8) | 1.158 (2) | 0.138 (7)* | |
C5 | 0.136 (1) | 0.3077 (6) | 1.112 (1) | 0.090 (4)* | |
C6 | 0.326 (1) | 0.3558 (4) | 0.6429 (8) | 0.046 (3) | |
C7 | 0.340 (1) | 0.4014 (5) | 0.5690 (9) | 0.068 (4) | |
C8 | 0.276 (2) | 0.5136 (9) | 0.496 (2) | 0.152 (8)* | |
C9 | 0.117 (2) | 0.4643 (9) | 0.645 (2) | 0.152 (8)* | |
C10 | 0.390 (2) | 0.4941 (9) | 0.721 (2) | 0.155 (8)* | |
C11 | 0.3566 (8) | 0.2095 (4) | 0.6507 (7) | 0.039 (3) | |
C12 | 0.378 (1) | 0.1657 (4) | 0.5734 (8) | 0.056 (3) | |
C13 | 0.391 (3) | 0.264 (1) | 0.438 (2) | 0.189 (10)* | |
C14 | 0.215 (4) | 0.172 (2) | 0.375 (3) | 0.31 (1)* | |
C15 | 0.482 (4) | 0.150 (2) | 0.376 (3) | 0.29 (1)* | |
C16 | 0.2493 (9) | 0.2106 (4) | 0.9012 (7) | 0.037 (2) | |
C17 | 0.2285 (9) | 0.1681 (4) | 0.9774 (8) | 0.049 (3) | |
C18 | 0.255 (3) | 0.095 (1) | 0.791 (2) | 0.24 (1)* | |
C19 | 0.125 (2) | 0.0540 (9) | 0.962 (2) | 0.156 (8)* | |
C20 | 0.389 (4) | 0.067 (1) | 1.022 (3) | 0.26 (1)* | |
H1 | 0.1847 | 0.4120 | 0.9759 | 0.0648* | |
H2 | 0.3373 | 0.4188 | 0.9987 | 0.0648* | |
H3 | 0.2988 | 0.4402 | 1.2151 | 0.1191* | |
H4 | 0.1480 | 0.4291 | 1.1884 | 0.1191* | |
H5 | 0.2303 | 0.3976 | 1.2787 | 0.1191* | |
H6 | 0.4247 | 0.3101 | 1.2232 | 0.1654* | |
H7 | 0.4387 | 0.3011 | 1.1068 | 0.1654* | |
H8 | 0.4915 | 0.3545 | 1.1624 | 0.1654* | |
H9 | 0.0524 | 0.3246 | 1.0921 | 0.1078* | |
H10 | 0.1513 | 0.2811 | 1.0617 | 0.1078* | |
H11 | 0.1364 | 0.2905 | 1.1777 | 0.1078* | |
H12 | 0.2917 | 0.3920 | 0.5038 | 0.0818* | |
H13 | 0.4317 | 0.4046 | 0.5618 | 0.0818* | |
H14 | 0.3618 | 0.5163 | 0.4760 | 0.1819* | |
H15 | 0.2159 | 0.4991 | 0.4407 | 0.1819* | |
H16 | 0.2468 | 0.5489 | 0.5142 | 0.1819* | |
H17 | 0.0891 | 0.4995 | 0.6648 | 0.1829* | |
H18 | 0.0568 | 0.4513 | 0.5877 | 0.1829* | |
H19 | 0.1174 | 0.4397 | 0.7017 | 0.1829* | |
H20 | 0.3882 | 0.4695 | 0.7775 | 0.1861* | |
H21 | 0.4783 | 0.4968 | 0.7048 | 0.1861* | |
H22 | 0.3608 | 0.5292 | 0.7397 | 0.1861* | |
H23 | 0.3101 | 0.1389 | 0.5743 | 0.0673* | |
H24 | 0.4618 | 0.1493 | 0.5942 | 0.0673* | |
H25 | 0.4751 | 0.2748 | 0.4725 | 0.2272* | |
H26 | 0.3824 | 0.2763 | 0.3674 | 0.2272* | |
H27 | 0.3232 | 0.2810 | 0.4711 | 0.2272* | |
H28 | 0.1480 | 0.1914 | 0.4042 | 0.3762* | |
H29 | 0.2109 | 0.1805 | 0.3037 | 0.3762* | |
H30 | 0.2012 | 0.1336 | 0.3828 | 0.3762* | |
H31 | 0.4619 | 0.1120 | 0.3830 | 0.3533* | |
H32 | 0.4705 | 0.1591 | 0.3040 | 0.3533* | |
H33 | 0.5712 | 0.1563 | 0.4048 | 0.3533* | |
H34 | 0.1399 | 0.1710 | 0.9924 | 0.0593* | |
H35 | 0.2881 | 0.1747 | 1.0390 | 0.0593* | |
H36 | 0.1725 | 0.1075 | 0.7575 | 0.2836* | |
H37 | 0.3245 | 0.1170 | 0.7729 | 0.2836* | |
H38 | 0.2685 | 0.0580 | 0.7698 | 0.2836* | |
H39 | 0.1147 | 0.0579 | 1.0329 | 0.1872* | |
H40 | 0.0454 | 0.0643 | 0.9196 | 0.1872* | |
H41 | 0.1453 | 0.0170 | 0.9478 | 0.1872* | |
H42 | 0.3685 | 0.0703 | 1.0910 | 0.3126* | |
H43 | 0.3995 | 0.0298 | 1.0054 | 0.3126* | |
H44 | 0.4687 | 0.0865 | 1.0162 | 0.3126* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0254 (6) | 0.0347 (6) | 0.0360 (6) | −0.0009 (5) | 0.0040 (4) | 0.0048 (5) |
Cu2 | 0.0251 (6) | 0.0326 (6) | 0.0410 (6) | 0.0001 (5) | 0.0041 (4) | −0.0036 (6) |
Si1 | 0.061 (2) | 0.091 (3) | 0.046 (2) | −0.006 (2) | 0.010 (2) | −0.014 (2) |
Si2 | 0.074 (2) | 0.048 (2) | 0.093 (3) | 0.001 (2) | 0.004 (2) | 0.023 (2) |
Si3 | 0.142 (4) | 0.112 (4) | 0.051 (2) | 0.032 (3) | 0.005 (2) | −0.017 (2) |
Si4 | 0.051 (2) | 0.038 (2) | 0.118 (3) | 0.005 (1) | 0.023 (2) | 0.023 (2) |
O1 | 0.039 (4) | 0.045 (4) | 0.045 (4) | −0.003 (3) | 0.005 (3) | −0.010 (3) |
O2 | 0.040 (4) | 0.050 (4) | 0.060 (5) | 0.002 (3) | 0.010 (3) | −0.016 (3) |
O3 | 0.049 (4) | 0.060 (5) | 0.053 (4) | −0.004 (4) | 0.007 (3) | 0.019 (4) |
O4 | 0.043 (4) | 0.039 (4) | 0.071 (5) | 0.002 (3) | 0.015 (4) | 0.010 (4) |
O5 | 0.032 (3) | 0.048 (4) | 0.047 (4) | −0.001 (3) | 0.000 (3) | −0.010 (3) |
O6 | 0.028 (3) | 0.040 (4) | 0.045 (4) | −0.002 (3) | 0.004 (3) | −0.009 (3) |
O7 | 0.029 (3) | 0.042 (4) | 0.039 (4) | −0.002 (3) | 0.001 (3) | 0.007 (3) |
O8 | 0.031 (3) | 0.045 (4) | 0.052 (4) | −0.007 (3) | 0.006 (3) | 0.006 (3) |
C1 | 0.044 (6) | 0.031 (5) | 0.051 (6) | 0.000 (4) | 0.008 (5) | −0.003 (4) |
C2 | 0.060 (7) | 0.039 (6) | 0.065 (7) | 0.001 (5) | 0.018 (5) | −0.017 (5) |
C6 | 0.055 (7) | 0.036 (6) | 0.051 (6) | −0.002 (5) | 0.019 (5) | 0.004 (5) |
C7 | 0.070 (8) | 0.066 (8) | 0.070 (8) | −0.001 (7) | 0.017 (6) | 0.022 (7) |
C11 | 0.032 (5) | 0.039 (6) | 0.045 (5) | 0.003 (4) | 0.005 (4) | 0.001 (4) |
C12 | 0.060 (7) | 0.054 (7) | 0.055 (7) | −0.003 (6) | 0.008 (5) | −0.022 (6) |
C16 | 0.034 (5) | 0.035 (5) | 0.041 (5) | 0.003 (4) | 0.000 (4) | 0.001 (4) |
C17 | 0.034 (5) | 0.055 (6) | 0.062 (7) | 0.002 (5) | 0.014 (5) | 0.019 (5) |
Geometric parameters (Å, º) top
Cu1—Cu2 | 2.618 (2) | C4—H7 | 0.960 |
Cu1—O1 | 1.988 (6) | C4—H8 | 0.960 |
Cu1—O3 | 1.916 (7) | C5—H9 | 0.960 |
Cu1—O5 | 1.997 (6) | C5—H10 | 0.960 |
Cu1—O6i | 2.291 (6) | C5—H11 | 0.960 |
Cu1—O7 | 1.950 (6) | C6—C7 | 1.50 (1) |
Cu2—O2 | 1.892 (6) | C7—H12 | 0.960 |
Cu2—O4 | 1.970 (7) | C7—H13 | 0.960 |
Cu2—O6 | 1.935 (6) | C8—H14 | 0.960 |
Cu2—O7ii | 2.261 (6) | C8—H15 | 0.960 |
Cu2—O8 | 2.003 (6) | C8—H16 | 0.960 |
Si1—C2 | 1.87 (1) | C9—H17 | 0.960 |
Si1—C3 | 1.85 (2) | C9—H18 | 0.960 |
Si1—C4 | 1.81 (2) | C9—H19 | 0.960 |
Si1—C5 | 1.84 (2) | C10—H20 | 0.960 |
Si2—C7 | 1.87 (1) | C10—H21 | 0.960 |
Si2—C8 | 1.83 (2) | C10—H22 | 0.960 |
Si2—C9 | 1.83 (2) | C11—C12 | 1.52 (1) |
Si2—C10 | 1.84 (2) | C12—H23 | 0.960 |
Si3—C12 | 1.82 (1) | C12—H24 | 0.960 |
Si3—C13 | 1.85 (3) | C13—H25 | 0.960 |
Si3—C14 | 1.80 (4) | C13—H26 | 0.960 |
Si3—C15 | 1.80 (4) | C13—H27 | 0.960 |
Si4—C17 | 1.90 (1) | C14—H28 | 0.958 |
Si4—C18 | 1.86 (3) | C14—H29 | 0.961 |
Si4—C19 | 1.78 (2) | C14—H30 | 0.961 |
Si4—C20 | 1.82 (4) | C15—H31 | 0.960 |
O1—C1 | 1.25 (1) | C15—H32 | 0.961 |
O2—C1 | 1.28 (1) | C15—H33 | 0.959 |
O3—C6 | 1.26 (1) | C16—C17 | 1.48 (1) |
O4—C6 | 1.25 (1) | C17—H34 | 0.960 |
O5—C11 | 1.24 (1) | C17—H35 | 0.960 |
O6—C11 | 1.28 (1) | C18—H36 | 0.960 |
O7—C16 | 1.27 (1) | C18—H37 | 0.960 |
O8—C16 | 1.25 (1) | C18—H38 | 0.960 |
C1—C2 | 1.49 (1) | C19—H39 | 0.960 |
C2—H1 | 0.960 | C19—H40 | 0.960 |
C2—H2 | 0.960 | C19—H41 | 0.960 |
C3—H3 | 0.960 | C20—H42 | 0.959 |
C3—H4 | 0.960 | C20—H43 | 0.960 |
C3—H5 | 0.960 | C20—H44 | 0.961 |
C4—H6 | 0.960 | | |
| | | |
Cu2—Cu1—O1 | 80.2 (2) | H9—C5—H10 | 109 (1) |
Cu2—Cu1—O3 | 88.2 (2) | H9—C5—H11 | 109 (1) |
Cu2—Cu1—O5 | 78.9 (2) | H10—C5—H11 | 109 (1) |
Cu2—Cu1—O7 | 90.4 (2) | O3—C6—O4 | 124.1 (9) |
O1—Cu1—O3 | 91.2 (3) | O3—C6—C7 | 116.4 (10) |
O1—Cu1—O5 | 159.0 (3) | O4—C6—C7 | 119.4 (9) |
O1—Cu1—O7 | 89.0 (3) | Si2—C7—C6 | 115.3 (8) |
O3—Cu1—O5 | 89.5 (3) | Si2—C7—H12 | 108.0 (9) |
O3—Cu1—O7 | 178.5 (3) | Si2—C7—H13 | 108.0 (9) |
O5—Cu1—O7 | 89.8 (3) | C6—C7—H12 | 107 (1) |
Cu1—Cu2—O2 | 88.7 (2) | C6—C7—H13 | 107 (1) |
Cu1—Cu2—O4 | 79.9 (2) | H12—C7—H13 | 109 (1) |
Cu1—Cu2—O6 | 89.5 (2) | Si2—C8—H14 | 109 (1) |
Cu1—Cu2—O7ii | 169.0 (2) | Si2—C8—H15 | 109 (1) |
Cu1—Cu2—O8 | 78.1 (2) | Si2—C8—H16 | 109 (1) |
O2—Cu2—O4 | 89.1 (3) | H14—C8—H15 | 109 (2) |
O2—Cu2—O6 | 178.0 (3) | H14—C8—H16 | 109 (2) |
O2—Cu2—O7ii | 102.3 (2) | H15—C8—H16 | 109 (2) |
O2—Cu2—O8 | 89.5 (3) | Si2—C9—H17 | 109 (1) |
O4—Cu2—O6 | 91.2 (3) | Si2—C9—H18 | 109 (1) |
O4—Cu2—O7ii | 100.0 (3) | Si2—C9—H19 | 109 (1) |
O4—Cu2—O8 | 158.0 (3) | H17—C9—H18 | 109 (2) |
O6—Cu2—O7ii | 79.5 (2) | H17—C9—H19 | 109 (2) |
O6—Cu2—O8 | 89.5 (3) | H18—C9—H19 | 109 (2) |
O7ii—Cu2—O8 | 101.8 (2) | Si2—C10—H20 | 109 (1) |
C2—Si1—C3 | 106.2 (6) | Si2—C10—H21 | 109 (1) |
C2—Si1—C4 | 108.8 (7) | Si2—C10—H22 | 109 (1) |
C2—Si1—C5 | 109.9 (6) | H20—C10—H21 | 109 (2) |
C3—Si1—C4 | 112.5 (8) | H20—C10—H22 | 109 (2) |
C3—Si1—C5 | 109.8 (7) | H21—C10—H22 | 109 (2) |
C4—Si1—C5 | 109.5 (8) | O5—C11—O6 | 123.5 (9) |
C7—Si2—C8 | 107.3 (8) | O5—C11—C12 | 117.9 (8) |
C7—Si2—C9 | 111.3 (8) | O6—C11—C12 | 118.6 (8) |
C7—Si2—C10 | 109.8 (8) | Si3—C12—C11 | 114.1 (8) |
C8—Si2—C9 | 108 (1) | Si3—C12—H23 | 108.3 (8) |
C8—Si2—C10 | 113 (1) | Si3—C12—H24 | 108.3 (8) |
C9—Si2—C10 | 106.9 (10) | C11—C12—H23 | 108.3 (9) |
C12—Si3—C13 | 111.5 (9) | C11—C12—H24 | 108.3 (9) |
C12—Si3—C14 | 106 (1) | H23—C12—H24 | 109 (1) |
C12—Si3—C15 | 109 (1) | Si3—C13—H25 | 109 (2) |
C13—Si3—C14 | 108 (1) | Si3—C13—H26 | 109 (2) |
C13—Si3—C15 | 118 (1) | Si3—C13—H27 | 109 (2) |
C14—Si3—C15 | 101 (1) | H25—C13—H26 | 109 (2) |
C17—Si4—C18 | 110 (1) | H25—C13—H27 | 109 (2) |
C17—Si4—C19 | 109.7 (8) | H26—C13—H27 | 109 (2) |
C17—Si4—C20 | 107 (1) | Si3—C14—H28 | 109 (3) |
C18—Si4—C19 | 107 (1) | Si3—C14—H29 | 109 (3) |
C18—Si4—C20 | 122 (1) | Si3—C14—H30 | 109 (3) |
C19—Si4—C20 | 99 (1) | H28—C14—H29 | 109 (4) |
Cu1—O1—C1 | 126.2 (6) | H28—C14—H30 | 109 (4) |
Cu2—O2—C1 | 120.6 (6) | H29—C14—H30 | 109 (4) |
Cu1—O3—C6 | 120.1 (7) | Si3—C15—H31 | 109 (3) |
Cu2—O4—C6 | 127.5 (6) | Si3—C15—H32 | 109 (3) |
Cu1—O5—C11 | 129.1 (6) | Si3—C15—H33 | 109 (3) |
Cu1—O6i—Cu2i | 100.7 (2) | H31—C15—H32 | 109 (3) |
Cu2—O6—C11 | 118.9 (6) | H31—C15—H33 | 109 (3) |
Cu1—O7—Cu2i | 101.3 (2) | H32—C15—H33 | 109 (3) |
Cu1—O7—C16 | 117.8 (5) | O7—C16—O8 | 123.4 (8) |
Cu2i—O7—C16 | 140.9 (6) | O7—C16—C17 | 118.3 (8) |
Cu2—O8—C16 | 130.2 (6) | O8—C16—C17 | 118.4 (8) |
O1—C1—O2 | 124.2 (9) | Si4—C17—C16 | 114.4 (7) |
O1—C1—C2 | 119.0 (9) | Si4—C17—H34 | 108.2 (8) |
O2—C1—C2 | 116.8 (9) | Si4—C17—H35 | 108.2 (7) |
Si1—C2—C1 | 112.3 (7) | C16—C17—H34 | 108.2 (9) |
Si1—C2—H1 | 108.8 (8) | C16—C17—H35 | 108.2 (9) |
Si1—C2—H2 | 108.8 (9) | H34—C17—H35 | 109 (1) |
C1—C2—H1 | 108.8 (9) | Si4—C18—H36 | 109 (2) |
C1—C2—H2 | 108.8 (9) | Si4—C18—H37 | 109 (2) |
H1—C2—H2 | 109 (1) | Si4—C18—H38 | 109 (2) |
Si1—C3—H3 | 109 (1) | H36—C18—H37 | 109 (3) |
Si1—C3—H4 | 109 (1) | H36—C18—H38 | 109 (3) |
Si1—C3—H5 | 109 (1) | H37—C18—H38 | 109 (3) |
H3—C3—H4 | 109 (1) | Si4—C19—H39 | 109 (1) |
H3—C3—H5 | 109 (1) | Si4—C19—H40 | 109 (1) |
H4—C3—H5 | 109 (1) | Si4—C19—H41 | 109 (1) |
Si1—C4—H6 | 109 (1) | H39—C19—H40 | 109 (2) |
Si1—C4—H7 | 109 (1) | H39—C19—H41 | 109 (2) |
Si1—C4—H8 | 109 (1) | H40—C19—H41 | 109 (2) |
H6—C4—H7 | 109 (1) | Si4—C20—H42 | 109 (2) |
H6—C4—H8 | 109 (2) | Si4—C20—H43 | 109 (2) |
H7—C4—H8 | 109 (1) | Si4—C20—H44 | 109 (2) |
Si1—C5—H9 | 109 (1) | H42—C20—H43 | 109 (3) |
Si1—C5—H10 | 109 (1) | H42—C20—H44 | 109 (3) |
Si1—C5—H11 | 109 (1) | H43—C20—H44 | 109 (3) |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | [Cu2(C5H11O2Si)4(C5H5N)2] | [Cu2(C5H11O2Si)4(C6H7N)2] | [Cu2(C5H11O2Si)4(C6H7N)2] | [Cu2(C5H11O2Si)4(C9H7N)2] |
Mr | 810.20 | 838.26 | 838.26 | 910.32 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 299 | 298 | 297 | 298 |
a, b, c (Å) | 11.392 (1), 18.508 (2), 10.851 (1) | 10.874 (2), 11.508 (2), 10.330 (2) | 11.148 (3), 11.755 (1), 10.563 (3) | 11.298 (2), 11.495 (3), 10.261 (3) |
α, β, γ (°) | 91.87 (1), 102.79 (1), 76.82 (1) | 104.26 (2), 109.10 (2), 74.91 (2) | 110.91 (1), 117.70 (2), 84.23 (2) | 104.03 (2), 110.10 (2), 76.99 (2) |
V (Å3) | 2171.9 (5) | 1160.9 (4) | 1141.3 (5) | 1199.4 (5) |
Z | 2 | 1 | 1 | 1 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.13 | 1.06 | 1.08 | 1.03 |
Crystal size (mm) | 0.4 × 0.3 × 0.3 | 0.5 × 0.5 × 0.2 | 0.4 × 0.3 × 0.1 | 0.8 × 0.4 × 0.1 |
|
Data collection |
Diffractometer | Rigaku AFC-5 diffractometer | Rigaku AFC7R diffractometer | Rigaku AFC-5 diffractometer | Rigaku AFC7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) | ψ-scan (North et al., 1968) | Integration (Coppens et al., 1965) | Integration (Coppens et al., 1965) numerical |
Tmin, Tmax | 0.971, 0.978 | 0.567, 0.809 | 0.676, 0.893 | 0.659, 0.902 |
No. of measured, independent and observed reflections | 10462, 9960, 5122 [|Fo| > 3σ(|Fo|)] | 8822, 8412, 5169 [I > 1.5σ(I)] | 5532, 5261, 3377 [|Fo| > 3σ(|Fo|)] | 9728, 8692, 6024 [I > 1.5σ(I)] |
Rint | 0.017 | 0.009 | 0.017 | 0.040 |
(sin θ/λ)max (Å−1) | 0.650 | 0.756 | 0.650 | 0.756 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.053, 1.34 | 0.051, 0.079, 1.39 | 0.064, 0.054, 1.23 | 0.048, 0.069, 1.18 |
No. of reflections | 5122 | 5352 | 3377 | 6191 |
No. of parameters | 415 | 253 | 217 | 244 |
No. of restraints | ? | 0 | ? | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters not refined | H-atom parameters constrained | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.80, −0.57 | 0.45, −0.32 | 0.66, −0.51 | 0.53, −0.26 |
| (V) |
Crystal data |
Chemical formula | [Cu2(C5H11O2Si)4] |
Mr | 652.00 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 298 |
a, b, c (Å) | 10.288 (6), 24.692 (5), 13.116 (5) |
α, β, γ (°) | 90, 97.71 (4), 90 |
V (Å3) | 3302 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.3 × 0.1 × 0.05 |
|
Data collection |
Diffractometer | Rigaku AFC7R diffractometer |
Absorption correction | Ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.852, 0.929 |
No. of measured, independent and observed reflections | 7986, 7574, 3260 [I > 1.5σ(I)] |
Rint | 0.042 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.068, 0.100, 1.48 |
No. of reflections | 3309 |
No. of parameters | 247 |
No. of restraints | 0 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.78, −0.60 |
Selected geometric parameters (Å, º) for (I) topCu1—Cu1i | 2.632 (1) | Cu2—O14ii | 1.972 (4) |
Cu1—O7 | 1.962 (4) | Cu2—N16 | 2.198 (6) |
Cu1—O8i | 1.961 (4) | O7—C17 | 1.263 (7) |
Cu1—O9 | 1.982 (4) | O8—C17 | 1.276 (7) |
Cu1—O10i | 1.972 (4) | O9—C22 | 1.255 (7) |
Cu1—N15 | 2.194 (5) | O10—C22 | 1.268 (7) |
Cu2—Cu2ii | 2.635 (1) | O11—C32 | 1.252 (10) |
Cu2—O11 | 1.961 (4) | O12—C32 | 1.271 (8) |
Cu2—O12ii | 1.965 (4) | O13—C37 | 1.276 (8) |
Cu2—O13 | 1.959 (4) | O14—C37 | 1.258 (8) |
| | | |
O7—Cu1—O8i | 168.3 (2) | O7—C17—O8 | 123.6 (6) |
O9—Cu1—O10i | 168.7 (2) | O9—C22—O10 | 125.5 (5) |
O11—Cu2—O12ii | 168.3 (2) | O11—C32—O12 | 125.0 (6) |
O13—Cu2—O14ii | 168.5 (2) | O13—C37—O14 | 124.6 (6) |
Symmetry codes: (i) −x+2, −y+1, −z+2; (ii) −x+1, −y+2, −z+1. |
Selected geometric parameters (Å, º) for (II) topCu1—Cu1i | 2.664 (1) | Cu1—N1 | 2.244 (3) |
Cu1—O1 | 1.977 (2) | O1—C1 | 1.243 (4) |
Cu1—O2i | 1.960 (2) | O2—C1 | 1.261 (4) |
Cu1—O3 | 1.953 (2) | O3—C6 | 1.264 (4) |
Cu1—O4i | 1.965 (2) | O4—C6 | 1.254 (4) |
| | | |
O1—Cu1—O2i | 167.1 (1) | O1—C1—O2 | 125.4 (3) |
O3—Cu1—O4i | 167.2 (1) | O3—C6—O4 | 124.8 (3) |
Symmetry code: (i) −x, −y, −z−2. |
Selected geometric parameters (Å, º) for (III) topCu1—Cu1i | 2.638 (3) | Cu1—N8 | 2.176 (3) |
Cu1—O4 | 1.971 (3) | O4—C9 | 1.273 (5) |
Cu1—O5i | 1.958 (3) | O5—C9 | 1.240 (5) |
Cu1—O6 | 1.976 (3) | O6—C14 | 1.249 (4) |
Cu1—O7i | 1.973 (3) | O7—C14 | 1.267 (5) |
| | | |
O4—Cu1—O5i | 168.2 (2) | O4—C9—O5 | 125.5 (4) |
O6—Cu1—O7i | 168.1 (1) | O6—C14—O7 | 125.3 (4) |
Symmetry code: (i) −x+2, −y, −z+1. |
Selected geometric parameters (Å, º) for (IV) topCu1—Cu1i | 2.665 (1) | Cu1—N1 | 2.274 (2) |
Cu1—O1 | 1.969 (2) | O1—C1 | 1.259 (3) |
Cu1—O2i | 1.965 (2) | O2—C1 | 1.254 (3) |
Cu1—O3 | 1.973 (2) | O3—C6 | 1.258 (3) |
Cu1—O4i | 1.959 (2) | O4—C6 | 1.251 (3) |
| | | |
O1—Cu1—O2i | 167.3 (1) | O1—C1—O2 | 125.3 (2) |
O3—Cu1—O4i | 166.9 (1) | O3—C6—O4 | 124.3 (2) |
Symmetry code: (i) −x, −y+1, −z+1. |
Selected geometric parameters (Å, º) for (V) topCu1—Cu2 | 2.618 (2) | Cu2—O8 | 2.003 (6) |
Cu1—O1 | 1.988 (6) | O1—C1 | 1.25 (1) |
Cu1—O3 | 1.916 (7) | O2—C1 | 1.28 (1) |
Cu1—O5 | 1.997 (6) | O3—C6 | 1.26 (1) |
Cu1—O6i | 2.291 (6) | O4—C6 | 1.25 (1) |
Cu1—O7 | 1.950 (6) | O5—C11 | 1.24 (1) |
Cu2—O2 | 1.892 (6) | O6—C11 | 1.28 (1) |
Cu2—O4 | 1.970 (7) | O7—C16 | 1.27 (1) |
Cu2—O6 | 1.935 (6) | O8—C16 | 1.25 (1) |
Cu2—O7ii | 2.261 (6) | | |
| | | |
O1—Cu1—O5 | 159.0 (3) | Cu1—O7—Cu2i | 101.3 (2) |
O3—Cu1—O7 | 178.5 (3) | O1—C1—O2 | 124.2 (9) |
O2—Cu2—O6 | 178.0 (3) | O3—C6—O4 | 124.1 (9) |
O4—Cu2—O8 | 158.0 (3) | O5—C11—O6 | 123.5 (9) |
Cu1—O6i—Cu2i | 100.7 (2) | O7—C16—O8 | 123.4 (8) |
Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x+1/2, −y+1/2, z. |
The −2 J values of copper(II) carboxylates, i.e. the singlet-triplet energy separation, greatly depend on the kind of atom directly bonded to the COO bridge (Kato & Muto, 1988). There is a correlation between the electron density at the central C atom of the COO bridge and the antiferromagnetic spin-exchange interaction (Yamanaka et al., 1991; Harada et al., 1997). Silanecarboxylatocopper complexes show very large −2 J values due to the σ-electron donating character of the Si atom; for [Cu2(PhMe2SiCOO)4(H2O)2], −2 J = 1000±150 cm−1 (Steward et al., 1986). In (I)-(IV), a Si atom is bonded to the α-carbon of the carboxylate ions. Their −2 J values were determined to be (I) 323, (II) 334, (III) 322, and (IV) 333 cm−1 (H = −2JS1·S2). These −2 J values are slightly smaller than those of trimethylacetatocopper complexes (−2 J ~356 cm−1; Goto et al., 1999). In conclusion, the electronic influence of the Si atom on the spin-exchange interaction is very small if the Si atom is not bonded directly to the carboxylate ion.
The complexes (I)-(V) have a centre of symmetry. The trimethylsilyl groups are arranged to have approximately fourfold rotational symmetry along the Cu···Cu axis. Displacement ellipsoids of the terminal methyl-C atoms are large, indicating librational and rotational disorder. In (I)-(IV), the geometry around the Cu atoms is a typical square-pyramidal coordination, and the O—Cu—O bond angle between the bridges opposite each other is in the narrow range 166.9 (1) to 168.7 (2)°.
On the other hand, the Cu atoms in (V) have a distorted trigonal bipyramidal coordination geometry with O—Cu—O bond angles of 178.0 (3)–178.5 (3)° and 158.0 (3)–159.0 (3)°. The Cu—O—Cu bond angle in the polymer chain of (V) is 101.3 (2)°. In the April 1999 release of the CSD (Cambridge Structural Database, 1999) the number of entries of the polymeric copper carboxylates was fourteen, and the Cu—O—Cu angles range from 98.2 to 109.3°.
Polymeric copper carboxylates are essentially antiferromagnetic, although the spin-spin interaction through the Cu—O—Cu bonds is ferromagnetic. The −2 J values are generally much less than those of dimeric complexes (Muto et al., 1985). This may be due to a trigonal bipyramidal deformation of the cage structure, in accord with the magneto-structure correlations established in the study on the dimeric copper(II) trichloroacetates (Uekusa et al., 1992).