Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106008924/sk3009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106008924/sk3009Isup2.hkl |
CCDC reference: 609403
A three-necked flask was charged with EtOH (25 ml). NaOH (0.4 g, 0.01 mol) and MeSi(OEt)3 (2.0 ml, 1.79 g, 0.01 mol) were added with vigorous stirring and the mixture was stirred for 1 h at room temperature. A solution of CuCl2 (0.45 g, 0.003 mol) in EtOH (25 ml) was added dropwise, and then a mixture of water (1.08 g, 0.06 mol) and EtOH (5 ml) was quickly added. The reaction was heated for 20 min at temperature slightly below the boiling point and then filtered hot through the twice-folded filter paper. The resulting blue solution was evaporated using a rotory evaporator and dried in vacuum (1 mm H g, 353 K). A bright-blue crystalline product was obtained (yield 1.68 g, 76.5%). This product was dissolved in dimethylformamide (15 ml) and the solution was then added to a mixture of pyrazine (0.16 g) in dimethylformamide (15 ml). In a few months, some greenish crystals of (I) were obtained which were suitable for X-ray diffraction analysis.
H atoms were placed in calculated positions and refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C) or 1.5 Ueq(Cmethyl)] using a riding model, with C—H = 0.95 or 0.98 Å, for Caromatic or Cmethyl, respectively. The methyl groups of the non disordered dimethylformamide molecules were allowed to rotate but not to tip.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
[Cu8(C8H24O2Si)2(C3H7NO)8]·C4H4N2·C3H7NO | F(000) = 2516 |
Mr = 2448.26 | Dx = 1.594 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 20012 reflections |
a = 16.9402 (16) Å | θ = 3.5–25.8° |
b = 18.6388 (18) Å | µ = 1.90 mm−1 |
c = 17.2684 (16) Å | T = 173 K |
β = 110.679 (7)° | Block, light green |
V = 5101.1 (9) Å3 | 0.22 × 0.20 × 0.18 mm |
Z = 2 |
Stoe IPDS-II two-circle diffractometer | 9372 independent reflections |
Radiation source: fine-focus sealed tube | 5221 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
ω scans | θmax = 25.8°, θmin = 3.6° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −20→20 |
Tmin = 0.679, Tmax = 0.726 | k = −22→22 |
39433 measured reflections | l = −21→21 |
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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 0.74 | w = 1/[σ2(Fo2) + (0.0111P)2] where P = (Fo2 + 2Fc2)/3 |
9372 reflections | (Δ/σ)max = 0.004 |
573 parameters | Δρmax = 0.66 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
[Cu8(C8H24O2Si)2(C3H7NO)8]·C4H4N2·C3H7NO | V = 5101.1 (9) Å3 |
Mr = 2448.26 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 16.9402 (16) Å | µ = 1.90 mm−1 |
b = 18.6388 (18) Å | T = 173 K |
c = 17.2684 (16) Å | 0.22 × 0.20 × 0.18 mm |
β = 110.679 (7)° |
Stoe IPDS-II two-circle diffractometer | 9372 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 5221 reflections with I > 2σ(I) |
Tmin = 0.679, Tmax = 0.726 | Rint = 0.084 |
39433 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.069 | H-atom parameters constrained |
S = 0.74 | Δρmax = 0.66 e Å−3 |
9372 reflections | Δρmin = −0.45 e Å−3 |
573 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.61832 (3) | 0.58601 (3) | 0.68719 (4) | 0.02475 (13) | |
Cu2 | 0.45876 (4) | 0.54479 (3) | 0.70145 (4) | 0.02500 (14) | |
Cu3 | 0.31675 (4) | 0.47343 (3) | 0.59180 (4) | 0.02674 (14) | |
Cu4 | 0.29044 (4) | 0.42052 (3) | 0.43051 (4) | 0.02570 (14) | |
Si1 | 0.74894 (8) | 0.45479 (7) | 0.70793 (9) | 0.0270 (3) | |
C1 | 0.8515 (3) | 0.4746 (3) | 0.7893 (3) | 0.0382 (13) | |
H1A | 0.8781 | 0.4298 | 0.8152 | 0.057* | |
H1B | 0.8427 | 0.5058 | 0.8312 | 0.057* | |
H1C | 0.8882 | 0.4990 | 0.7646 | 0.057* | |
O1 | 0.6873 (2) | 0.41277 (17) | 0.7468 (2) | 0.0312 (8) | |
O11 | 0.70293 (19) | 0.52759 (15) | 0.6640 (2) | 0.0268 (7) | |
Si2 | 0.61954 (8) | 0.43980 (7) | 0.78820 (9) | 0.0279 (3) | |
C2 | 0.6729 (4) | 0.4518 (3) | 0.8994 (4) | 0.0420 (13) | |
H2A | 0.6988 | 0.4063 | 0.9242 | 0.063* | |
H2B | 0.6319 | 0.4669 | 0.9243 | 0.063* | |
H2C | 0.7168 | 0.4885 | 0.9093 | 0.063* | |
O2 | 0.5479 (2) | 0.37751 (17) | 0.7724 (2) | 0.0347 (9) | |
O21 | 0.57591 (19) | 0.51298 (15) | 0.7441 (2) | 0.0267 (8) | |
Si3 | 0.44505 (9) | 0.37552 (7) | 0.73938 (9) | 0.0273 (3) | |
C3 | 0.4120 (4) | 0.3537 (3) | 0.8286 (4) | 0.0420 (14) | |
H3A | 0.4368 | 0.3077 | 0.8527 | 0.063* | |
H3B | 0.3504 | 0.3504 | 0.8096 | 0.063* | |
H3C | 0.4315 | 0.3915 | 0.8705 | 0.063* | |
O3 | 0.4139 (2) | 0.31078 (16) | 0.6723 (2) | 0.0347 (8) | |
O31 | 0.40607 (19) | 0.45069 (16) | 0.6977 (2) | 0.0281 (7) | |
Si4 | 0.34807 (9) | 0.30198 (7) | 0.57851 (9) | 0.0285 (3) | |
C4 | 0.2652 (4) | 0.2386 (3) | 0.5796 (5) | 0.0536 (17) | |
H4A | 0.2911 | 0.1928 | 0.6032 | 0.080* | |
H4B | 0.2260 | 0.2309 | 0.5230 | 0.080* | |
H4C | 0.2345 | 0.2583 | 0.6134 | 0.080* | |
O4 | 0.4000 (2) | 0.26760 (17) | 0.5242 (2) | 0.0341 (9) | |
O41 | 0.3087 (2) | 0.37897 (16) | 0.5401 (2) | 0.0293 (8) | |
Si5 | 0.39066 (9) | 0.27406 (6) | 0.42748 (9) | 0.0267 (3) | |
C5 | 0.3174 (3) | 0.2040 (3) | 0.3677 (4) | 0.0426 (14) | |
H5A | 0.3393 | 0.1566 | 0.3896 | 0.064* | |
H5B | 0.3119 | 0.2071 | 0.3094 | 0.064* | |
H5C | 0.2619 | 0.2111 | 0.3725 | 0.064* | |
O5 | 0.4841 (2) | 0.26220 (16) | 0.4209 (2) | 0.0303 (8) | |
O51 | 0.35746 (19) | 0.35323 (15) | 0.3940 (2) | 0.0269 (8) | |
Si6 | 0.52381 (9) | 0.28975 (7) | 0.35316 (9) | 0.0282 (3) | |
C6 | 0.5001 (4) | 0.2226 (3) | 0.2700 (4) | 0.0409 (14) | |
H6A | 0.5236 | 0.1761 | 0.2935 | 0.061* | |
H6B | 0.5252 | 0.2376 | 0.2294 | 0.061* | |
H6C | 0.4388 | 0.2182 | 0.2427 | 0.061* | |
O6 | 0.6260 (2) | 0.29511 (16) | 0.3997 (2) | 0.0311 (8) | |
O61 | 0.4872 (2) | 0.36741 (15) | 0.3195 (2) | 0.0273 (7) | |
Si7 | 0.69851 (8) | 0.35213 (7) | 0.39817 (9) | 0.0275 (3) | |
C7 | 0.7528 (4) | 0.3141 (3) | 0.3316 (4) | 0.0438 (14) | |
H7A | 0.7775 | 0.2676 | 0.3538 | 0.066* | |
H7B | 0.7976 | 0.3469 | 0.3304 | 0.066* | |
H7C | 0.7122 | 0.3077 | 0.2753 | 0.066* | |
O7 | 0.7651 (2) | 0.36052 (17) | 0.4918 (2) | 0.0312 (8) | |
O71 | 0.65712 (19) | 0.42832 (16) | 0.3644 (2) | 0.0277 (7) | |
Si8 | 0.79477 (8) | 0.42484 (7) | 0.56099 (9) | 0.0283 (3) | |
C8 | 0.9120 (3) | 0.4305 (3) | 0.6004 (4) | 0.0394 (13) | |
H8A | 0.9359 | 0.3843 | 0.6246 | 0.059* | |
H8B | 0.9306 | 0.4680 | 0.6428 | 0.059* | |
H8C | 0.9312 | 0.4421 | 0.5547 | 0.059* | |
O8 | 0.7646 (2) | 0.40367 (16) | 0.6376 (2) | 0.0300 (8) | |
O81 | 0.7529 (2) | 0.49986 (16) | 0.5205 (2) | 0.0307 (8) | |
O101 | 0.7082 (2) | 0.63818 (18) | 0.8033 (2) | 0.0407 (9) | |
C101 | 0.7708 (3) | 0.6642 (3) | 0.7925 (4) | 0.0366 (13) | |
H101 | 0.7772 | 0.6553 | 0.7408 | 0.044* | |
N101 | 0.8289 (3) | 0.7029 (2) | 0.8466 (3) | 0.0371 (11) | |
C102 | 0.8231 (4) | 0.7203 (4) | 0.9262 (5) | 0.075 (2) | |
H10A | 0.7856 | 0.7616 | 0.9202 | 0.112* | |
H10B | 0.8793 | 0.7321 | 0.9656 | 0.112* | |
H10C | 0.8004 | 0.6790 | 0.9468 | 0.112* | |
C103 | 0.8955 (4) | 0.7381 (3) | 0.8256 (5) | 0.0575 (18) | |
H10D | 0.8946 | 0.7207 | 0.7717 | 0.086* | |
H10E | 0.9504 | 0.7272 | 0.8680 | 0.086* | |
H10F | 0.8863 | 0.7901 | 0.8229 | 0.086* | |
O201 | 0.4537 (2) | 0.5863 (2) | 0.8260 (2) | 0.0455 (9) | |
C201 | 0.5187 (4) | 0.6185 (3) | 0.8639 (3) | 0.0377 (13) | |
H201 | 0.5675 | 0.6065 | 0.8514 | 0.045* | |
N201 | 0.5276 (3) | 0.6690 (2) | 0.9209 (3) | 0.0411 (11) | |
C202 | 0.4545 (4) | 0.6934 (4) | 0.9384 (5) | 0.068 (2) | |
H20A | 0.4058 | 0.6635 | 0.9084 | 0.101* | |
H20B | 0.4425 | 0.7434 | 0.9208 | 0.101* | |
H20C | 0.4659 | 0.6899 | 0.9980 | 0.101* | |
C203 | 0.6070 (4) | 0.7041 (4) | 0.9607 (4) | 0.0582 (18) | |
H20D | 0.6250 | 0.6971 | 1.0206 | 0.087* | |
H20E | 0.6009 | 0.7556 | 0.9482 | 0.087* | |
H20F | 0.6493 | 0.6838 | 0.9403 | 0.087* | |
O301 | 0.2101 (3) | 0.4628 (2) | 0.6551 (3) | 0.0566 (11) | |
C301 | 0.2419 (4) | 0.4876 (3) | 0.7256 (4) | 0.0475 (16) | |
H301 | 0.2887 | 0.5190 | 0.7359 | 0.057* | |
N301 | 0.2161 (3) | 0.4739 (3) | 0.7882 (3) | 0.0540 (14) | |
C302 | 0.1487 (5) | 0.4250 (5) | 0.7797 (6) | 0.092 (3) | |
H30A | 0.1172 | 0.4164 | 0.7208 | 0.138* | |
H30B | 0.1108 | 0.4454 | 0.8056 | 0.138* | |
H30C | 0.1717 | 0.3795 | 0.8067 | 0.138* | |
C303 | 0.2584 (5) | 0.5034 (4) | 0.8683 (5) | 0.076 (2) | |
H30D | 0.3125 | 0.5237 | 0.8708 | 0.114* | |
H30E | 0.2682 | 0.4655 | 0.9101 | 0.114* | |
H30F | 0.2234 | 0.5411 | 0.8793 | 0.114* | |
O401 | 0.1560 (2) | 0.3710 (2) | 0.3667 (3) | 0.0464 (10) | |
C401 | 0.1138 (3) | 0.3777 (3) | 0.4103 (4) | 0.0448 (15) | |
H401 | 0.1427 | 0.3847 | 0.4679 | 0.054* | |
N401 | 0.0290 (3) | 0.3760 (3) | 0.3827 (3) | 0.0493 (13) | |
C402 | −0.0181 (4) | 0.3672 (5) | 0.2946 (5) | 0.075 (2) | |
H40A | 0.0213 | 0.3637 | 0.2647 | 0.112* | |
H40B | −0.0553 | 0.4086 | 0.2741 | 0.112* | |
H40C | −0.0521 | 0.3234 | 0.2856 | 0.112* | |
C403 | −0.0165 (4) | 0.3885 (4) | 0.4370 (5) | 0.066 (2) | |
H40D | 0.0233 | 0.3930 | 0.4939 | 0.100* | |
H40E | −0.0547 | 0.3482 | 0.4334 | 0.100* | |
H40F | −0.0492 | 0.4328 | 0.4208 | 0.100* | |
N91 | 0.4476 (3) | 0.4976 (2) | 0.5457 (3) | 0.0432 (12) | |
C92 | 0.4465 (3) | 0.5524 (3) | 0.4952 (3) | 0.0339 (12) | |
H92 | 0.4087 | 0.5911 | 0.4910 | 0.041* | |
C93 | 0.4967 (3) | 0.5546 (3) | 0.4507 (3) | 0.0311 (12) | |
H93 | 0.4929 | 0.5944 | 0.4153 | 0.037* | |
O1L | 0.0819 (13) | 0.5343 (18) | 0.9088 (15) | 0.229 (12) | 0.50 |
C1L | 0.0413 (18) | 0.5546 (19) | 0.9504 (19) | 0.155 (13) | 0.50 |
H1L | 0.0332 | 0.6048 | 0.9543 | 0.186* | 0.50 |
N1L | 0.0000 | 0.5000 | 1.0000 | 0.218 (15) | |
C2L | 0.0427 (10) | 0.4476 (9) | 0.9813 (11) | 0.209 (9) | |
H2LA | 0.0306 | 0.4027 | 1.0045 | 0.313* | |
H2LB | 0.0254 | 0.4430 | 0.9211 | 0.313* | |
H2LC | 0.1034 | 0.4576 | 1.0049 | 0.313* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0241 (3) | 0.0223 (3) | 0.0263 (4) | 0.0001 (2) | 0.0070 (3) | 0.0001 (2) |
Cu2 | 0.0230 (3) | 0.0235 (3) | 0.0261 (4) | −0.0002 (2) | 0.0057 (3) | 0.0007 (2) |
Cu3 | 0.0272 (3) | 0.0252 (3) | 0.0253 (4) | −0.0005 (2) | 0.0061 (3) | −0.0013 (2) |
Cu4 | 0.0258 (3) | 0.0246 (3) | 0.0251 (4) | 0.0002 (2) | 0.0069 (3) | −0.0012 (3) |
Si1 | 0.0257 (7) | 0.0270 (6) | 0.0261 (8) | 0.0027 (5) | 0.0064 (7) | 0.0017 (6) |
C1 | 0.032 (3) | 0.045 (3) | 0.034 (4) | 0.001 (2) | 0.007 (3) | 0.004 (3) |
O1 | 0.0291 (17) | 0.0300 (17) | 0.033 (2) | 0.0040 (15) | 0.0087 (17) | 0.0032 (16) |
O11 | 0.0282 (17) | 0.0255 (16) | 0.026 (2) | 0.0036 (14) | 0.0081 (17) | 0.0021 (14) |
Si2 | 0.0271 (7) | 0.0270 (7) | 0.0276 (9) | 0.0009 (5) | 0.0072 (7) | 0.0034 (6) |
C2 | 0.046 (3) | 0.042 (3) | 0.036 (4) | 0.005 (3) | 0.011 (3) | −0.001 (3) |
O2 | 0.031 (2) | 0.0279 (17) | 0.044 (3) | −0.0012 (14) | 0.012 (2) | 0.0098 (16) |
O21 | 0.0232 (17) | 0.0239 (16) | 0.031 (2) | 0.0023 (13) | 0.0065 (17) | 0.0043 (14) |
Si3 | 0.0305 (8) | 0.0259 (7) | 0.0237 (8) | −0.0029 (5) | 0.0073 (7) | 0.0022 (6) |
C3 | 0.051 (4) | 0.041 (3) | 0.036 (4) | −0.003 (3) | 0.019 (3) | 0.007 (3) |
O3 | 0.046 (2) | 0.0283 (18) | 0.024 (2) | 0.0005 (15) | 0.005 (2) | 0.0034 (15) |
O31 | 0.0274 (17) | 0.0256 (16) | 0.029 (2) | −0.0001 (14) | 0.0066 (17) | 0.0038 (15) |
Si4 | 0.0331 (8) | 0.0249 (7) | 0.0270 (9) | −0.0028 (6) | 0.0101 (7) | 0.0002 (6) |
C4 | 0.051 (4) | 0.041 (3) | 0.073 (5) | −0.016 (3) | 0.028 (4) | −0.001 (3) |
O4 | 0.041 (2) | 0.0288 (18) | 0.036 (2) | 0.0024 (15) | 0.017 (2) | 0.0064 (15) |
O41 | 0.0317 (19) | 0.0270 (16) | 0.030 (2) | −0.0039 (14) | 0.0113 (18) | −0.0051 (15) |
Si5 | 0.0293 (7) | 0.0206 (6) | 0.0293 (9) | −0.0012 (5) | 0.0092 (7) | −0.0015 (5) |
C5 | 0.032 (3) | 0.034 (3) | 0.054 (4) | −0.008 (2) | 0.006 (3) | −0.005 (3) |
O5 | 0.0305 (19) | 0.0272 (17) | 0.034 (2) | 0.0022 (14) | 0.0121 (19) | −0.0012 (15) |
O51 | 0.0295 (19) | 0.0240 (16) | 0.025 (2) | 0.0019 (13) | 0.0075 (18) | 0.0013 (14) |
Si6 | 0.0280 (7) | 0.0234 (6) | 0.0318 (9) | 0.0030 (5) | 0.0086 (7) | −0.0004 (6) |
C6 | 0.050 (3) | 0.027 (3) | 0.046 (4) | 0.002 (2) | 0.018 (3) | −0.003 (2) |
O6 | 0.0246 (18) | 0.0270 (17) | 0.039 (2) | 0.0026 (14) | 0.0075 (18) | 0.0060 (15) |
O61 | 0.0264 (18) | 0.0236 (16) | 0.031 (2) | 0.0009 (13) | 0.0085 (17) | 0.0034 (14) |
Si7 | 0.0258 (7) | 0.0258 (7) | 0.0294 (9) | 0.0032 (5) | 0.0077 (7) | −0.0015 (6) |
C7 | 0.034 (3) | 0.056 (4) | 0.044 (4) | 0.001 (3) | 0.017 (3) | −0.005 (3) |
O7 | 0.0294 (19) | 0.0327 (18) | 0.026 (2) | 0.0090 (14) | 0.0023 (18) | −0.0004 (15) |
O71 | 0.0259 (17) | 0.0283 (17) | 0.027 (2) | 0.0020 (13) | 0.0070 (17) | 0.0030 (14) |
Si8 | 0.0262 (7) | 0.0296 (7) | 0.0246 (8) | 0.0047 (6) | 0.0033 (7) | −0.0008 (6) |
C8 | 0.032 (3) | 0.040 (3) | 0.039 (4) | 0.004 (2) | 0.003 (3) | −0.003 (2) |
O8 | 0.0311 (18) | 0.0285 (18) | 0.030 (2) | 0.0035 (14) | 0.0102 (18) | −0.0023 (14) |
O81 | 0.0320 (19) | 0.0303 (17) | 0.030 (2) | 0.0038 (14) | 0.0108 (19) | 0.0015 (15) |
O101 | 0.038 (2) | 0.046 (2) | 0.038 (3) | −0.0120 (17) | 0.014 (2) | −0.0118 (18) |
C101 | 0.039 (3) | 0.038 (3) | 0.029 (4) | −0.003 (2) | 0.008 (3) | −0.003 (2) |
N101 | 0.030 (2) | 0.040 (2) | 0.036 (3) | −0.006 (2) | 0.007 (3) | −0.006 (2) |
C102 | 0.049 (4) | 0.112 (6) | 0.059 (5) | −0.018 (4) | 0.012 (4) | −0.050 (5) |
C103 | 0.046 (4) | 0.050 (4) | 0.071 (5) | −0.026 (3) | 0.014 (4) | −0.010 (3) |
O201 | 0.040 (2) | 0.056 (2) | 0.038 (3) | −0.011 (2) | 0.010 (2) | −0.018 (2) |
C201 | 0.039 (3) | 0.045 (3) | 0.026 (3) | 0.002 (3) | 0.008 (3) | −0.004 (2) |
N201 | 0.035 (3) | 0.047 (3) | 0.039 (3) | −0.002 (2) | 0.010 (3) | −0.009 (2) |
C202 | 0.064 (5) | 0.078 (5) | 0.066 (5) | 0.000 (4) | 0.030 (5) | −0.027 (4) |
C203 | 0.055 (4) | 0.069 (4) | 0.045 (5) | −0.022 (3) | 0.011 (4) | −0.020 (3) |
O301 | 0.054 (3) | 0.072 (3) | 0.047 (3) | −0.016 (2) | 0.022 (3) | −0.007 (2) |
C301 | 0.043 (4) | 0.058 (4) | 0.047 (5) | −0.007 (3) | 0.024 (4) | −0.009 (3) |
N301 | 0.054 (3) | 0.064 (3) | 0.051 (4) | −0.015 (3) | 0.027 (3) | −0.006 (3) |
C302 | 0.098 (6) | 0.105 (6) | 0.093 (7) | −0.043 (5) | 0.058 (6) | −0.012 (5) |
C303 | 0.089 (6) | 0.093 (6) | 0.054 (5) | −0.022 (4) | 0.035 (5) | −0.017 (4) |
O401 | 0.031 (2) | 0.067 (3) | 0.043 (3) | −0.0159 (18) | 0.015 (2) | −0.015 (2) |
C401 | 0.031 (3) | 0.054 (3) | 0.045 (4) | −0.005 (3) | 0.007 (3) | −0.005 (3) |
N401 | 0.035 (3) | 0.057 (3) | 0.056 (4) | −0.004 (2) | 0.016 (3) | −0.005 (3) |
C402 | 0.039 (4) | 0.115 (6) | 0.064 (6) | −0.013 (4) | 0.010 (4) | −0.014 (5) |
C403 | 0.043 (4) | 0.092 (5) | 0.077 (6) | 0.001 (3) | 0.036 (4) | 0.005 (4) |
N91 | 0.044 (3) | 0.042 (3) | 0.050 (4) | 0.004 (2) | 0.026 (3) | 0.010 (2) |
C92 | 0.032 (3) | 0.029 (2) | 0.040 (3) | 0.008 (2) | 0.011 (3) | 0.000 (2) |
C93 | 0.029 (3) | 0.030 (3) | 0.031 (3) | 0.003 (2) | 0.007 (3) | 0.007 (2) |
O1L | 0.148 (18) | 0.39 (4) | 0.17 (2) | 0.02 (2) | 0.082 (17) | −0.04 (2) |
C1L | 0.10 (2) | 0.24 (4) | 0.10 (2) | 0.04 (2) | −0.003 (16) | −0.07 (2) |
N1L | 0.087 (12) | 0.44 (4) | 0.074 (13) | 0.114 (19) | −0.038 (10) | −0.119 (19) |
C2L | 0.157 (14) | 0.184 (16) | 0.160 (18) | 0.027 (12) | −0.100 (13) | −0.036 (13) |
Cu1—O11 | 1.951 (3) | Si7—C7 | 1.849 (5) |
Cu1—O61i | 1.953 (3) | C7—H7A | 0.9800 |
Cu1—O51i | 1.956 (3) | C7—H7B | 0.9800 |
Cu1—O21 | 1.958 (3) | C7—H7C | 0.9800 |
Cu1—O101 | 2.265 (4) | O7—Si8 | 1.641 (4) |
Cu1—Cu2 | 2.9030 (8) | O71—Cu2i | 1.955 (3) |
Cu1—Cu4i | 2.9587 (7) | O71—Cu3i | 1.971 (3) |
Cu2—O21 | 1.949 (3) | Si8—O81 | 1.611 (3) |
Cu2—O71i | 1.955 (3) | Si8—O8 | 1.626 (3) |
Cu2—O31 | 1.959 (3) | Si8—C8 | 1.861 (5) |
Cu2—O61i | 1.970 (3) | C8—H8A | 0.9800 |
Cu2—O201 | 2.316 (4) | C8—H8B | 0.9800 |
Cu2—Cu3 | 2.8150 (9) | C8—H8C | 0.9800 |
Cu3—O81i | 1.946 (4) | O81—Cu3i | 1.946 (4) |
Cu3—O41 | 1.957 (3) | O81—Cu4i | 1.973 (3) |
Cu3—O31 | 1.965 (3) | O101—C101 | 1.241 (6) |
Cu3—O71i | 1.971 (3) | C101—N101 | 1.308 (7) |
Cu3—O301 | 2.428 (4) | C101—H101 | 0.9500 |
Cu3—Cu4 | 2.8377 (9) | N101—C102 | 1.449 (8) |
Cu4—O11i | 1.934 (3) | N101—C103 | 1.459 (6) |
Cu4—O51 | 1.940 (3) | C102—H10A | 0.9800 |
Cu4—O41 | 1.966 (3) | C102—H10B | 0.9800 |
Cu4—O81i | 1.973 (3) | C102—H10C | 0.9800 |
Cu4—O401 | 2.341 (4) | C103—H10D | 0.9800 |
Cu4—Cu1i | 2.9586 (7) | C103—H10E | 0.9800 |
Si1—O11 | 1.615 (3) | C103—H10F | 0.9800 |
Si1—O1 | 1.629 (3) | O201—C201 | 1.223 (6) |
Si1—O8 | 1.637 (3) | C201—N201 | 1.333 (7) |
Si1—C1 | 1.846 (6) | C201—H201 | 0.9500 |
C1—H1A | 0.9800 | N201—C203 | 1.434 (7) |
C1—H1B | 0.9800 | N201—C202 | 1.447 (7) |
C1—H1C | 0.9800 | C202—H20A | 0.9800 |
O1—Si2 | 1.631 (3) | C202—H20B | 0.9800 |
O11—Cu4i | 1.934 (3) | C202—H20C | 0.9800 |
Si2—O21 | 1.609 (3) | C203—H20D | 0.9800 |
Si2—O2 | 1.631 (3) | C203—H20E | 0.9800 |
Si2—C2 | 1.824 (6) | C203—H20F | 0.9800 |
C2—H2A | 0.9800 | O301—C301 | 1.235 (7) |
C2—H2B | 0.9800 | C301—N301 | 1.326 (7) |
C2—H2C | 0.9800 | C301—H301 | 0.9500 |
O2—Si3 | 1.632 (4) | N301—C303 | 1.425 (9) |
Si3—O31 | 1.607 (3) | N301—C302 | 1.427 (8) |
Si3—O3 | 1.627 (4) | C302—H30A | 0.9800 |
Si3—C3 | 1.860 (5) | C302—H30B | 0.9800 |
C3—H3A | 0.9800 | C302—H30C | 0.9800 |
C3—H3B | 0.9800 | C303—H30D | 0.9800 |
C3—H3C | 0.9800 | C303—H30E | 0.9800 |
O3—Si4 | 1.617 (4) | C303—H30F | 0.9800 |
Si4—O41 | 1.622 (3) | O401—C401 | 1.213 (6) |
Si4—O4 | 1.627 (3) | C401—N401 | 1.345 (7) |
Si4—C4 | 1.840 (5) | C401—H401 | 0.9500 |
C4—H4A | 0.9800 | N401—C403 | 1.425 (7) |
C4—H4B | 0.9800 | N401—C402 | 1.458 (9) |
C4—H4C | 0.9800 | C402—H40A | 0.9800 |
O4—Si5 | 1.625 (4) | C402—H40B | 0.9800 |
Si5—O51 | 1.612 (3) | C402—H40C | 0.9800 |
Si5—O5 | 1.641 (3) | C403—H40D | 0.9800 |
Si5—C5 | 1.846 (5) | C403—H40E | 0.9800 |
C5—H5A | 0.9800 | C403—H40F | 0.9800 |
C5—H5B | 0.9800 | N91—C93i | 1.341 (6) |
C5—H5C | 0.9800 | N91—C92 | 1.340 (7) |
O5—Si6 | 1.625 (3) | C92—C93 | 1.333 (6) |
O51—Cu1i | 1.956 (3) | C92—H92 | 0.9500 |
Si6—O61 | 1.601 (3) | C93—N91i | 1.341 (6) |
Si6—O6 | 1.635 (4) | C93—H93 | 0.9500 |
Si6—C6 | 1.840 (5) | O1L—C1L | 1.22 (3) |
C6—H6A | 0.9800 | C1L—N1L | 1.64 (4) |
C6—H6B | 0.9800 | C1L—H1L | 0.9500 |
C6—H6C | 0.9800 | N1L—C2Lii | 1.322 (19) |
O6—Si7 | 1.631 (3) | N1L—C2L | 1.322 (19) |
O61—Cu1i | 1.953 (3) | N1L—C1Lii | 1.64 (4) |
O61—Cu2i | 1.970 (3) | C2L—H2LA | 0.9800 |
Si7—O71 | 1.600 (3) | C2L—H2LB | 0.9800 |
Si7—O7 | 1.619 (4) | C2L—H2LC | 0.9800 |
O11—Cu1—O61i | 163.57 (15) | Si5—C5—H5B | 109.5 |
O11—Cu1—O51i | 79.65 (12) | H5A—C5—H5B | 109.5 |
O61i—Cu1—O51i | 96.87 (12) | Si5—C5—H5C | 109.5 |
O11—Cu1—O21 | 98.15 (12) | H5A—C5—H5C | 109.5 |
O61i—Cu1—O21 | 81.28 (12) | H5B—C5—H5C | 109.5 |
O51i—Cu1—O21 | 165.86 (15) | Si6—O5—Si5 | 131.4 (2) |
O11—Cu1—O101 | 96.26 (13) | Si5—O51—Cu4 | 130.22 (18) |
O61i—Cu1—O101 | 100.14 (13) | Si5—O51—Cu1i | 130.70 (17) |
O51i—Cu1—O101 | 98.10 (13) | Cu4—O51—Cu1i | 98.83 (13) |
O21—Cu1—O101 | 96.02 (13) | O61—Si6—O5 | 109.96 (16) |
O11—Cu1—Cu2 | 130.04 (9) | O61—Si6—O6 | 109.32 (17) |
O61i—Cu1—Cu2 | 42.50 (8) | O5—Si6—O6 | 107.51 (19) |
O51i—Cu1—Cu2 | 130.65 (10) | O61—Si6—C6 | 112.5 (2) |
O21—Cu1—Cu2 | 41.91 (9) | O5—Si6—C6 | 108.4 (2) |
O101—Cu1—Cu2 | 113.15 (8) | O6—Si6—C6 | 109.1 (2) |
O11—Cu1—Cu4i | 40.17 (9) | Si6—C6—H6A | 109.5 |
O61i—Cu1—Cu4i | 131.82 (10) | Si6—C6—H6B | 109.5 |
O51i—Cu1—Cu4i | 40.39 (8) | H6A—C6—H6B | 109.5 |
O21—Cu1—Cu4i | 133.60 (9) | Si6—C6—H6C | 109.5 |
O101—Cu1—Cu4i | 105.98 (8) | H6A—C6—H6C | 109.5 |
Cu2—Cu1—Cu4i | 140.84 (3) | H6B—C6—H6C | 109.5 |
O21—Cu2—O71i | 167.67 (14) | Si7—O6—Si6 | 134.8 (2) |
O21—Cu2—O31 | 97.55 (13) | Si6—O61—Cu1i | 130.72 (17) |
O71i—Cu2—O31 | 81.85 (13) | Si6—O61—Cu2i | 132.21 (18) |
O21—Cu2—O61i | 81.07 (12) | Cu1i—O61—Cu2i | 95.45 (13) |
O71i—Cu2—O61i | 96.69 (13) | O71—Si7—O7 | 109.81 (18) |
O31—Cu2—O61i | 166.85 (13) | O71—Si7—O6 | 110.41 (17) |
O21—Cu2—O201 | 96.73 (14) | O7—Si7—O6 | 108.05 (19) |
O71i—Cu2—O201 | 95.51 (13) | O71—Si7—C7 | 111.4 (2) |
O31—Cu2—O201 | 99.40 (13) | O7—Si7—C7 | 109.5 (2) |
O61i—Cu2—O201 | 93.75 (13) | O6—Si7—C7 | 107.6 (2) |
O21—Cu2—Cu3 | 128.66 (10) | Si7—C7—H7A | 109.5 |
O71i—Cu2—Cu3 | 44.42 (9) | Si7—C7—H7B | 109.5 |
O31—Cu2—Cu3 | 44.24 (10) | H7A—C7—H7B | 109.5 |
O61i—Cu2—Cu3 | 127.69 (11) | Si7—C7—H7C | 109.5 |
O201—Cu2—Cu3 | 118.63 (9) | H7A—C7—H7C | 109.5 |
O21—Cu2—Cu1 | 42.13 (8) | H7B—C7—H7C | 109.5 |
O71i—Cu2—Cu1 | 131.03 (9) | Si7—O7—Si8 | 136.3 (2) |
O31—Cu2—Cu1 | 131.40 (9) | Si7—O71—Cu2i | 131.33 (19) |
O61i—Cu2—Cu1 | 42.05 (8) | Si7—O71—Cu3i | 132.5 (2) |
O201—Cu2—Cu1 | 109.37 (9) | Cu2i—O71—Cu3i | 91.62 (12) |
Cu3—Cu2—Cu1 | 131.93 (3) | O81—Si8—O8 | 110.27 (16) |
O81i—Cu3—O41 | 81.68 (14) | O81—Si8—O7 | 110.10 (19) |
O81i—Cu3—O31 | 168.45 (12) | O8—Si8—O7 | 108.18 (17) |
O41—Cu3—O31 | 97.90 (14) | O81—Si8—C8 | 111.1 (2) |
O81i—Cu3—O71i | 96.86 (13) | O8—Si8—C8 | 108.5 (2) |
O41—Cu3—O71i | 168.80 (12) | O7—Si8—C8 | 108.7 (2) |
O31—Cu3—O71i | 81.30 (13) | Si8—C8—H8A | 109.5 |
O81i—Cu3—O301 | 100.61 (14) | Si8—C8—H8B | 109.5 |
O41—Cu3—O301 | 100.87 (13) | H8A—C8—H8B | 109.5 |
O31—Cu3—O301 | 90.82 (14) | Si8—C8—H8C | 109.5 |
O71i—Cu3—O301 | 90.33 (13) | H8A—C8—H8C | 109.5 |
O81i—Cu3—Cu2 | 128.53 (10) | H8B—C8—H8C | 109.5 |
O41—Cu3—Cu2 | 129.59 (10) | Si8—O8—Si1 | 129.9 (2) |
O31—Cu3—Cu2 | 44.06 (9) | Si8—O81—Cu3i | 132.3 (2) |
O71i—Cu3—Cu2 | 43.97 (9) | Si8—O81—Cu4i | 129.8 (2) |
O301—Cu3—Cu2 | 109.34 (11) | Cu3i—O81—Cu4i | 92.77 (14) |
O81i—Cu3—Cu4 | 43.99 (9) | C101—O101—Cu1 | 112.2 (3) |
O41—Cu3—Cu4 | 43.78 (10) | O101—C101—N101 | 125.0 (5) |
O31—Cu3—Cu4 | 129.88 (9) | O101—C101—H101 | 117.5 |
O71i—Cu3—Cu4 | 129.45 (9) | N101—C101—H101 | 117.5 |
O301—Cu3—Cu4 | 121.96 (11) | C101—N101—C102 | 121.1 (5) |
Cu2—Cu3—Cu4 | 128.69 (2) | C101—N101—C103 | 121.5 (5) |
O11i—Cu4—O51 | 80.48 (12) | C102—N101—C103 | 116.9 (5) |
O11i—Cu4—O41 | 166.69 (14) | N101—C102—H10A | 109.5 |
O51—Cu4—O41 | 98.44 (13) | N101—C102—H10B | 109.5 |
O11i—Cu4—O81i | 97.26 (13) | H10A—C102—H10B | 109.5 |
O51—Cu4—O81i | 166.93 (14) | N101—C102—H10C | 109.5 |
O41—Cu4—O81i | 80.78 (13) | H10A—C102—H10C | 109.5 |
O11i—Cu4—O401 | 97.87 (14) | H10B—C102—H10C | 109.5 |
O51—Cu4—O401 | 100.15 (13) | N101—C103—H10D | 109.5 |
O41—Cu4—O401 | 95.38 (14) | N101—C103—H10E | 109.5 |
O81i—Cu4—O401 | 92.90 (13) | H10D—C103—H10E | 109.5 |
O11i—Cu4—Cu3 | 128.20 (9) | N101—C103—H10F | 109.5 |
O51—Cu4—Cu3 | 129.51 (10) | H10D—C103—H10F | 109.5 |
O41—Cu4—Cu3 | 43.54 (9) | H10E—C103—H10F | 109.5 |
O81i—Cu4—Cu3 | 43.23 (10) | C201—O201—Cu2 | 109.8 (3) |
O401—Cu4—Cu3 | 112.84 (9) | O201—C201—N201 | 126.0 (5) |
O11i—Cu4—Cu1i | 40.62 (8) | O201—C201—H201 | 117.0 |
O51—Cu4—Cu1i | 40.78 (9) | N201—C201—H201 | 117.0 |
O41—Cu4—Cu1i | 134.63 (9) | C201—N201—C203 | 121.1 (5) |
O81i—Cu4—Cu1i | 133.53 (9) | C201—N201—C202 | 119.7 (5) |
O401—Cu4—Cu1i | 108.55 (9) | C203—N201—C202 | 118.9 (5) |
Cu3—Cu4—Cu1i | 138.55 (3) | N201—C202—H20A | 109.5 |
O11—Si1—O1 | 108.95 (16) | N201—C202—H20B | 109.5 |
O11—Si1—O8 | 108.54 (18) | H20A—C202—H20B | 109.5 |
O1—Si1—O8 | 108.77 (17) | N201—C202—H20C | 109.5 |
O11—Si1—C1 | 111.0 (2) | H20A—C202—H20C | 109.5 |
O1—Si1—C1 | 110.6 (2) | H20B—C202—H20C | 109.5 |
O8—Si1—C1 | 109.0 (2) | N201—C203—H20D | 109.5 |
Si1—C1—H1A | 109.5 | N201—C203—H20E | 109.5 |
Si1—C1—H1B | 109.5 | H20D—C203—H20E | 109.5 |
H1A—C1—H1B | 109.5 | N201—C203—H20F | 109.5 |
Si1—C1—H1C | 109.5 | H20D—C203—H20F | 109.5 |
H1A—C1—H1C | 109.5 | H20E—C203—H20F | 109.5 |
H1B—C1—H1C | 109.5 | C301—O301—Cu3 | 106.1 (3) |
Si1—O1—Si2 | 133.3 (2) | O301—C301—N301 | 125.2 (6) |
Si1—O11—Cu4i | 130.91 (17) | O301—C301—H301 | 117.4 |
Si1—O11—Cu1 | 129.78 (17) | N301—C301—H301 | 117.4 |
Cu4i—O11—Cu1 | 99.21 (14) | C301—N301—C303 | 121.3 (5) |
O21—Si2—O2 | 109.52 (18) | C301—N301—C302 | 121.4 (6) |
O21—Si2—O1 | 109.36 (16) | C303—N301—C302 | 117.2 (5) |
O2—Si2—O1 | 107.65 (18) | N301—C302—H30A | 109.5 |
O21—Si2—C2 | 111.6 (2) | N301—C302—H30B | 109.5 |
O2—Si2—C2 | 109.1 (2) | H30A—C302—H30B | 109.5 |
O1—Si2—C2 | 109.5 (2) | N301—C302—H30C | 109.5 |
Si2—C2—H2A | 109.5 | H30A—C302—H30C | 109.5 |
Si2—C2—H2B | 109.5 | H30B—C302—H30C | 109.5 |
H2A—C2—H2B | 109.5 | N301—C303—H30D | 109.5 |
Si2—C2—H2C | 109.5 | N301—C303—H30E | 109.5 |
H2A—C2—H2C | 109.5 | H30D—C303—H30E | 109.5 |
H2B—C2—H2C | 109.5 | N301—C303—H30F | 109.5 |
Si2—O2—Si3 | 135.6 (2) | H30D—C303—H30F | 109.5 |
Si2—O21—Cu2 | 132.29 (17) | H30E—C303—H30F | 109.5 |
Si2—O21—Cu1 | 129.66 (17) | C401—O401—Cu4 | 110.8 (4) |
Cu2—O21—Cu1 | 95.96 (14) | O401—C401—N401 | 124.6 (6) |
O31—Si3—O3 | 110.43 (19) | O401—C401—H401 | 117.7 |
O31—Si3—O2 | 110.85 (17) | N401—C401—H401 | 117.7 |
O3—Si3—O2 | 107.67 (18) | C401—N401—C403 | 121.4 (6) |
O31—Si3—C3 | 111.4 (2) | C401—N401—C402 | 119.7 (5) |
O3—Si3—C3 | 108.1 (2) | C403—N401—C402 | 118.8 (5) |
O2—Si3—C3 | 108.2 (2) | N401—C402—H40A | 109.5 |
Si3—C3—H3A | 109.5 | N401—C402—H40B | 109.5 |
Si3—C3—H3B | 109.5 | H40A—C402—H40B | 109.5 |
H3A—C3—H3B | 109.5 | N401—C402—H40C | 109.5 |
Si3—C3—H3C | 109.5 | H40A—C402—H40C | 109.5 |
H3A—C3—H3C | 109.5 | H40B—C402—H40C | 109.5 |
H3B—C3—H3C | 109.5 | N401—C403—H40D | 109.5 |
Si4—O3—Si3 | 136.4 (2) | N401—C403—H40E | 109.5 |
Si3—O31—Cu2 | 131.0 (2) | H40D—C403—H40E | 109.5 |
Si3—O31—Cu3 | 131.7 (2) | N401—C403—H40F | 109.5 |
Cu2—O31—Cu3 | 91.70 (13) | H40D—C403—H40F | 109.5 |
O3—Si4—O41 | 110.98 (18) | H40E—C403—H40F | 109.5 |
O3—Si4—O4 | 107.20 (19) | C93i—N91—C92 | 115.5 (4) |
O41—Si4—O4 | 109.91 (17) | C93—C92—N91 | 122.2 (4) |
O3—Si4—C4 | 108.2 (3) | C93—C92—H92 | 118.9 |
O41—Si4—C4 | 111.6 (3) | N91—C92—H92 | 118.9 |
O4—Si4—C4 | 108.8 (2) | C92—C93—N91i | 122.2 (5) |
Si4—C4—H4A | 109.5 | C92—C93—H93 | 118.9 |
Si4—C4—H4B | 109.5 | N91i—C93—H93 | 118.9 |
H4A—C4—H4B | 109.5 | O1L—C1L—N1L | 123 (3) |
Si4—C4—H4C | 109.5 | O1L—C1L—H1L | 118.3 |
H4A—C4—H4C | 109.5 | N1L—C1L—H1L | 118.3 |
H4B—C4—H4C | 109.5 | C2Lii—N1L—C2L | 179.998 (8) |
Si5—O4—Si4 | 133.4 (2) | C2Lii—N1L—C1L | 92.3 (12) |
Si4—O41—Cu3 | 131.1 (2) | C2L—N1L—C1L | 87.7 (12) |
Si4—O41—Cu4 | 130.11 (18) | C2Lii—N1L—C1Lii | 87.7 (12) |
Cu3—O41—Cu4 | 92.68 (13) | C2L—N1L—C1Lii | 92.3 (12) |
O51—Si5—O4 | 109.32 (17) | C1L—N1L—C1Lii | 180.0 (16) |
O51—Si5—O5 | 108.77 (16) | N1L—C2L—H2LA | 108.6 |
O4—Si5—O5 | 108.34 (19) | N1L—C2L—H2LB | 109.8 |
O51—Si5—C5 | 111.5 (2) | H2LA—C2L—H2LB | 109.5 |
O4—Si5—C5 | 108.9 (2) | N1L—C2L—H2LC | 110.0 |
O5—Si5—C5 | 109.9 (2) | H2LA—C2L—H2LC | 109.5 |
Si5—C5—H5A | 109.5 | H2LB—C2L—H2LC | 109.5 |
O11—Cu1—Cu2—O21 | 48.76 (19) | O2—Si3—O31—Cu2 | −14.4 (3) |
O61i—Cu1—Cu2—O21 | −151.6 (2) | C3—Si3—O31—Cu2 | 106.2 (3) |
O51i—Cu1—Cu2—O21 | 163.10 (19) | O3—Si3—O31—Cu3 | 12.0 (3) |
O101—Cu1—Cu2—O21 | −72.20 (18) | O2—Si3—O31—Cu3 | 131.2 (2) |
Cu4i—Cu1—Cu2—O21 | 105.48 (15) | C3—Si3—O31—Cu3 | −108.2 (3) |
O11—Cu1—Cu2—O71i | −116.83 (18) | O21—Cu2—O31—Si3 | 14.9 (3) |
O61i—Cu1—Cu2—O71i | 42.8 (2) | O71i—Cu2—O31—Si3 | −177.5 (3) |
O51i—Cu1—Cu2—O71i | −2.48 (18) | O61i—Cu2—O31—Si3 | 98.0 (6) |
O21—Cu1—Cu2—O71i | −165.6 (2) | O201—Cu2—O31—Si3 | −83.2 (2) |
O101—Cu1—Cu2—O71i | 122.22 (16) | Cu3—Cu2—O31—Si3 | 155.0 (3) |
Cu4i—Cu1—Cu2—O71i | −60.11 (13) | Cu1—Cu2—O31—Si3 | 43.2 (3) |
O11—Cu1—Cu2—O31 | 4.29 (19) | O21—Cu2—O31—Cu3 | −140.10 (12) |
O61i—Cu1—Cu2—O31 | 163.9 (2) | O71i—Cu2—O31—Cu3 | 27.47 (12) |
O51i—Cu1—Cu2—O31 | 118.63 (18) | O61i—Cu2—O31—Cu3 | −57.1 (6) |
O21—Cu1—Cu2—O31 | −44.5 (2) | O201—Cu2—O31—Cu3 | 121.75 (13) |
O101—Cu1—Cu2—O31 | −116.67 (17) | Cu1—Cu2—O31—Cu3 | −111.80 (10) |
Cu4i—Cu1—Cu2—O31 | 61.01 (14) | O81i—Cu3—O31—Si3 | −100.4 (7) |
O11—Cu1—Cu2—O61i | −159.6 (2) | O41—Cu3—O31—Si3 | −13.3 (2) |
O51i—Cu1—Cu2—O61i | −45.27 (19) | O71i—Cu3—O31—Si3 | 178.0 (2) |
O21—Cu1—Cu2—O61i | 151.6 (2) | O301—Cu3—O31—Si3 | 87.8 (2) |
O101—Cu1—Cu2—O61i | 79.44 (18) | Cu2—Cu3—O31—Si3 | −154.7 (3) |
Cu4i—Cu1—Cu2—O61i | −102.89 (16) | Cu4—Cu3—O31—Si3 | −46.8 (3) |
O11—Cu1—Cu2—O201 | 127.02 (17) | O81i—Cu3—O31—Cu2 | 54.4 (7) |
O61i—Cu1—Cu2—O201 | −73.36 (19) | O41—Cu3—O31—Cu2 | 141.43 (11) |
O51i—Cu1—Cu2—O201 | −118.63 (16) | O71i—Cu3—O31—Cu2 | −27.27 (11) |
O21—Cu1—Cu2—O201 | 78.27 (18) | O301—Cu3—O31—Cu2 | −117.48 (13) |
O101—Cu1—Cu2—O201 | 6.07 (15) | Cu4—Cu3—O31—Cu2 | 107.94 (10) |
Cu4i—Cu1—Cu2—O201 | −176.25 (11) | Si3—O3—Si4—O41 | 5.6 (4) |
O11—Cu1—Cu2—Cu3 | −56.24 (14) | Si3—O3—Si4—O4 | 125.6 (3) |
O61i—Cu1—Cu2—Cu3 | 103.37 (15) | Si3—O3—Si4—C4 | −117.2 (3) |
O51i—Cu1—Cu2—Cu3 | 58.10 (13) | O3—Si4—O4—Si5 | −149.9 (3) |
O21—Cu1—Cu2—Cu3 | −105.00 (14) | O41—Si4—O4—Si5 | −29.2 (4) |
O101—Cu1—Cu2—Cu3 | −177.20 (11) | C4—Si4—O4—Si5 | 93.3 (4) |
Cu4i—Cu1—Cu2—Cu3 | 0.48 (6) | O3—Si4—O41—Cu3 | −8.8 (3) |
O21—Cu2—Cu3—O81i | −113.47 (15) | O4—Si4—O41—Cu3 | −127.2 (2) |
O71i—Cu2—Cu3—O81i | 52.73 (16) | C4—Si4—O41—Cu3 | 112.0 (3) |
O31—Cu2—Cu3—O81i | −168.00 (17) | O3—Si4—O41—Cu4 | 135.8 (2) |
O61i—Cu2—Cu3—O81i | −1.96 (15) | O4—Si4—O41—Cu4 | 17.4 (3) |
O201—Cu2—Cu3—O81i | 119.09 (16) | C4—Si4—O41—Cu4 | −103.4 (3) |
Cu1—Cu2—Cu3—O81i | −57.39 (12) | O81i—Cu3—O41—Si4 | 179.8 (2) |
O21—Cu2—Cu3—O41 | 1.26 (17) | O31—Cu3—O41—Si4 | 11.4 (2) |
O71i—Cu2—Cu3—O41 | 167.47 (17) | O71i—Cu3—O41—Si4 | 96.5 (8) |
O31—Cu2—Cu3—O41 | −53.26 (17) | O301—Cu3—O41—Si4 | −81.0 (2) |
O61i—Cu2—Cu3—O41 | 112.78 (16) | Cu2—Cu3—O41—Si4 | 45.6 (3) |
O201—Cu2—Cu3—O41 | −126.17 (17) | Cu4—Cu3—O41—Si4 | 153.7 (3) |
Cu1—Cu2—Cu3—O41 | 57.35 (12) | O81i—Cu3—O41—Cu4 | 26.08 (12) |
O21—Cu2—Cu3—O31 | 54.52 (16) | O31—Cu3—O41—Cu4 | −142.26 (12) |
O71i—Cu2—Cu3—O31 | −139.27 (17) | O71i—Cu3—O41—Cu4 | −57.2 (8) |
O61i—Cu2—Cu3—O31 | 166.04 (16) | O301—Cu3—O41—Cu4 | 125.37 (14) |
O201—Cu2—Cu3—O31 | −72.91 (17) | Cu2—Cu3—O41—Cu4 | −108.03 (12) |
Cu1—Cu2—Cu3—O31 | 110.60 (12) | O11i—Cu4—O41—Si4 | −97.3 (6) |
O21—Cu2—Cu3—O71i | −166.21 (17) | O51—Cu4—O41—Si4 | −13.0 (3) |
O31—Cu2—Cu3—O71i | 139.27 (17) | O81i—Cu4—O41—Si4 | −179.8 (3) |
O61i—Cu2—Cu3—O71i | −54.69 (16) | O401—Cu4—O41—Si4 | 88.1 (3) |
O201—Cu2—Cu3—O71i | 66.36 (17) | Cu3—Cu4—O41—Si4 | −154.1 (3) |
Cu1—Cu2—Cu3—O71i | −110.13 (13) | Cu1i—Cu4—O41—Si4 | −34.7 (3) |
O21—Cu2—Cu3—O301 | 124.60 (16) | O11i—Cu4—O41—Cu3 | 56.7 (6) |
O71i—Cu2—Cu3—O301 | −69.20 (17) | O51—Cu4—O41—Cu3 | 141.04 (13) |
O31—Cu2—Cu3—O301 | 70.08 (16) | O81i—Cu4—O41—Cu3 | −25.76 (13) |
O61i—Cu2—Cu3—O301 | −123.88 (16) | O401—Cu4—O41—Cu3 | −117.83 (13) |
O201—Cu2—Cu3—O301 | −2.83 (17) | Cu1i—Cu4—O41—Cu3 | 119.34 (10) |
Cu1—Cu2—Cu3—O301 | −179.32 (12) | Si4—O4—Si5—O51 | 33.3 (3) |
O21—Cu2—Cu3—Cu4 | −56.19 (12) | Si4—O4—Si5—O5 | 151.7 (3) |
O71i—Cu2—Cu3—Cu4 | 110.02 (13) | Si4—O4—Si5—C5 | −88.7 (3) |
O31—Cu2—Cu3—Cu4 | −110.71 (12) | O51—Si5—O5—Si6 | −35.4 (3) |
O61i—Cu2—Cu3—Cu4 | 55.33 (11) | O4—Si5—O5—Si6 | −154.1 (3) |
O201—Cu2—Cu3—Cu4 | 176.38 (12) | C5—Si5—O5—Si6 | 87.0 (3) |
Cu1—Cu2—Cu3—Cu4 | −0.11 (5) | O4—Si5—O51—Cu4 | −26.7 (3) |
O81i—Cu3—Cu4—O11i | 52.96 (17) | O5—Si5—O51—Cu4 | −144.8 (2) |
O41—Cu3—Cu4—O11i | −165.82 (18) | C5—Si5—O51—Cu4 | 93.8 (3) |
O31—Cu3—Cu4—O11i | −113.63 (16) | O4—Si5—O51—Cu1i | 146.3 (2) |
O71i—Cu3—Cu4—O11i | 1.97 (17) | O5—Si5—O51—Cu1i | 28.2 (3) |
O301—Cu3—Cu4—O11i | 123.45 (18) | C5—Si5—O51—Cu1i | −93.2 (3) |
Cu2—Cu3—Cu4—O11i | −55.67 (12) | O11i—Cu4—O51—Si5 | −175.0 (3) |
O81i—Cu3—Cu4—O51 | 165.05 (17) | O41—Cu4—O51—Si5 | 18.4 (3) |
O41—Cu3—Cu4—O51 | −53.73 (17) | O81i—Cu4—O51—Si5 | 103.9 (6) |
O31—Cu3—Cu4—O51 | −1.54 (16) | O401—Cu4—O51—Si5 | −78.7 (3) |
O71i—Cu3—Cu4—O51 | 114.06 (16) | Cu3—Cu4—O51—Si5 | 52.5 (3) |
O301—Cu3—Cu4—O51 | −124.46 (17) | Cu1i—Cu4—O51—Si5 | 174.6 (4) |
Cu2—Cu3—Cu4—O51 | 56.42 (12) | O11i—Cu4—O51—Cu1i | 10.32 (14) |
O81i—Cu3—Cu4—O41 | −141.22 (18) | O41—Cu4—O51—Cu1i | −156.25 (14) |
O31—Cu3—Cu4—O41 | 52.18 (17) | O81i—Cu4—O51—Cu1i | −70.7 (7) |
O71i—Cu3—Cu4—O41 | 167.79 (18) | O401—Cu4—O51—Cu1i | 106.69 (15) |
O301—Cu3—Cu4—O41 | −70.73 (19) | Cu3—Cu4—O51—Cu1i | −122.09 (10) |
Cu2—Cu3—Cu4—O41 | 110.14 (14) | Si5—O5—Si6—O61 | 34.4 (3) |
O41—Cu3—Cu4—O81i | 141.22 (18) | Si5—O5—Si6—O6 | 153.3 (3) |
O31—Cu3—Cu4—O81i | −166.59 (17) | Si5—O5—Si6—C6 | −88.9 (3) |
O71i—Cu3—Cu4—O81i | −50.99 (17) | O61—Si6—O6—Si7 | −19.7 (4) |
O301—Cu3—Cu4—O81i | 70.49 (18) | O5—Si6—O6—Si7 | −139.0 (3) |
Cu2—Cu3—Cu4—O81i | −108.63 (13) | C6—Si6—O6—Si7 | 103.7 (3) |
O81i—Cu3—Cu4—O401 | −68.41 (17) | O5—Si6—O61—Cu1i | −25.6 (3) |
O41—Cu3—Cu4—O401 | 72.81 (17) | O6—Si6—O61—Cu1i | −143.4 (2) |
O31—Cu3—Cu4—O401 | 125.00 (16) | C6—Si6—O61—Cu1i | 95.3 (3) |
O71i—Cu3—Cu4—O401 | −119.40 (16) | O5—Si6—O61—Cu2i | 136.2 (2) |
O301—Cu3—Cu4—O401 | 2.08 (17) | O6—Si6—O61—Cu2i | 18.4 (3) |
Cu2—Cu3—Cu4—O401 | −177.04 (11) | C6—Si6—O61—Cu2i | −102.9 (3) |
O81i—Cu3—Cu4—Cu1i | 108.34 (13) | Si6—O6—Si7—O71 | 20.6 (4) |
O41—Cu3—Cu4—Cu1i | −110.43 (14) | Si6—O6—Si7—O7 | 140.7 (3) |
O31—Cu3—Cu4—Cu1i | −58.25 (12) | Si6—O6—Si7—C7 | −101.1 (3) |
O71i—Cu3—Cu4—Cu1i | 57.36 (12) | O71—Si7—O7—Si8 | 5.4 (3) |
O301—Cu3—Cu4—Cu1i | 178.83 (13) | O6—Si7—O7—Si8 | −115.1 (3) |
Cu2—Cu3—Cu4—Cu1i | −0.29 (6) | C7—Si7—O7—Si8 | 128.0 (3) |
O11—Si1—O1—Si2 | −33.6 (4) | O7—Si7—O71—Cu2i | −139.2 (2) |
O8—Si1—O1—Si2 | −151.8 (3) | O6—Si7—O71—Cu2i | −20.2 (3) |
C1—Si1—O1—Si2 | 88.6 (4) | C7—Si7—O71—Cu2i | 99.4 (3) |
O1—Si1—O11—Cu4i | −149.0 (2) | O7—Si7—O71—Cu3i | 9.6 (3) |
O8—Si1—O11—Cu4i | −30.7 (3) | O6—Si7—O71—Cu3i | 128.7 (2) |
C1—Si1—O11—Cu4i | 89.0 (3) | C7—Si7—O71—Cu3i | −111.8 (3) |
O1—Si1—O11—Cu1 | 26.7 (3) | Si7—O7—Si8—O81 | −7.7 (3) |
O8—Si1—O11—Cu1 | 145.0 (2) | Si7—O7—Si8—O8 | 112.8 (3) |
C1—Si1—O11—Cu1 | −95.2 (3) | Si7—O7—Si8—C8 | −129.6 (3) |
O61i—Cu1—O11—Si1 | −108.0 (5) | O81—Si8—O8—Si1 | −37.9 (3) |
O51i—Cu1—O11—Si1 | 172.9 (3) | O7—Si8—O8—Si1 | −158.3 (3) |
O21—Cu1—O11—Si1 | −21.2 (3) | C8—Si8—O8—Si1 | 83.9 (3) |
O101—Cu1—O11—Si1 | 75.8 (3) | O11—Si1—O8—Si8 | 40.6 (3) |
Cu2—Cu1—O11—Si1 | −51.7 (3) | O1—Si1—O8—Si8 | 159.0 (3) |
Cu4i—Cu1—O11—Si1 | −176.8 (4) | C1—Si1—O8—Si8 | −80.4 (3) |
O61i—Cu1—O11—Cu4i | 68.8 (5) | O8—Si8—O81—Cu3i | −123.8 (2) |
O51i—Cu1—O11—Cu4i | −10.30 (14) | O7—Si8—O81—Cu3i | −4.5 (3) |
O21—Cu1—O11—Cu4i | 155.55 (14) | C8—Si8—O81—Cu3i | 115.9 (3) |
O101—Cu1—O11—Cu4i | −107.43 (14) | O8—Si8—O81—Cu4i | 23.8 (3) |
Cu2—Cu1—O11—Cu4i | 125.07 (9) | O7—Si8—O81—Cu4i | 143.1 (2) |
Si1—O1—Si2—O21 | 33.1 (4) | C8—Si8—O81—Cu4i | −96.5 (3) |
Si1—O1—Si2—O2 | 152.0 (3) | O11—Cu1—O101—C101 | 50.6 (4) |
Si1—O1—Si2—C2 | −89.5 (4) | O61i—Cu1—O101—C101 | −128.3 (3) |
O21—Si2—O2—Si3 | −14.1 (4) | O51i—Cu1—O101—C101 | −29.8 (3) |
O1—Si2—O2—Si3 | −132.9 (3) | O21—Cu1—O101—C101 | 149.5 (3) |
C2—Si2—O2—Si3 | 108.4 (4) | Cu2—Cu1—O101—C101 | −170.7 (3) |
O2—Si2—O21—Cu2 | 16.3 (3) | Cu4i—Cu1—O101—C101 | 10.8 (3) |
O1—Si2—O21—Cu2 | 134.1 (2) | Cu1—O101—C101—N101 | 173.6 (4) |
C2—Si2—O21—Cu2 | −104.6 (3) | O101—C101—N101—C102 | −1.4 (9) |
O2—Si2—O21—Cu1 | −143.1 (2) | O101—C101—N101—C103 | −173.0 (5) |
O1—Si2—O21—Cu1 | −25.4 (3) | O21—Cu2—O201—C201 | 41.7 (4) |
C2—Si2—O21—Cu1 | 96.0 (3) | O71i—Cu2—O201—C201 | −136.8 (4) |
O71i—Cu2—O21—Si2 | −102.6 (6) | O31—Cu2—O201—C201 | 140.6 (4) |
O31—Cu2—O21—Si2 | −16.2 (3) | O61i—Cu2—O201—C201 | −39.7 (4) |
O61i—Cu2—O21—Si2 | 177.0 (3) | Cu3—Cu2—O201—C201 | −176.9 (3) |
O201—Cu2—O21—Si2 | 84.2 (3) | Cu1—Cu2—O201—C201 | 0.3 (4) |
Cu3—Cu2—O21—Si2 | −51.2 (3) | Cu2—O201—C201—N201 | 155.5 (5) |
Cu1—Cu2—O21—Si2 | −164.2 (3) | O201—C201—N201—C203 | −179.1 (6) |
O71i—Cu2—O21—Cu1 | 61.6 (6) | O201—C201—N201—C202 | −4.4 (9) |
O31—Cu2—O21—Cu1 | 147.99 (13) | O81i—Cu3—O301—C301 | −141.2 (4) |
O61i—Cu2—O21—Cu1 | −18.79 (13) | O41—Cu3—O301—C301 | 135.3 (4) |
O201—Cu2—O21—Cu1 | −111.55 (14) | O31—Cu3—O301—C301 | 37.1 (4) |
Cu3—Cu2—O21—Cu1 | 113.03 (10) | O71i—Cu3—O301—C301 | −44.2 (4) |
O11—Cu1—O21—Si2 | 20.4 (3) | Cu2—Cu3—O301—C301 | −3.7 (4) |
O61i—Cu1—O21—Si2 | −176.2 (3) | Cu4—Cu3—O301—C301 | 177.0 (4) |
O51i—Cu1—O21—Si2 | 100.3 (5) | Cu3—O301—C301—N301 | −159.4 (5) |
O101—Cu1—O21—Si2 | −76.8 (3) | O301—C301—N301—C303 | 178.1 (7) |
Cu2—Cu1—O21—Si2 | 164.9 (3) | O301—C301—N301—C302 | 2.7 (11) |
Cu4i—Cu1—O21—Si2 | 42.0 (3) | O11i—Cu4—O401—C401 | −134.2 (4) |
O11—Cu1—O21—Cu2 | −144.44 (14) | O51—Cu4—O401—C401 | 144.1 (4) |
O61i—Cu1—O21—Cu2 | 18.95 (14) | O41—Cu4—O401—C401 | 44.5 (4) |
O51i—Cu1—O21—Cu2 | −64.5 (5) | O81i—Cu4—O401—C401 | −36.5 (4) |
O101—Cu1—O21—Cu2 | 118.32 (14) | Cu3—Cu4—O401—C401 | 3.2 (4) |
Cu4i—Cu1—O21—Cu2 | −122.81 (9) | Cu1i—Cu4—O401—C401 | −174.6 (4) |
Si2—O2—Si3—O31 | 13.4 (4) | Cu4—O401—C401—N401 | 158.2 (5) |
Si2—O2—Si3—O3 | 134.3 (3) | O401—C401—N401—C403 | −176.3 (6) |
Si2—O2—Si3—C3 | −109.0 (3) | O401—C401—N401—C402 | −1.5 (9) |
O31—Si3—O3—Si4 | −6.9 (4) | C93i—N91—C92—C93 | 0.8 (9) |
O2—Si3—O3—Si4 | −128.1 (3) | N91—C92—C93—N91i | −0.9 (10) |
C3—Si3—O3—Si4 | 115.2 (3) | O1L—C1L—N1L—C2Lii | −171 (2) |
O3—Si3—O31—Cu2 | −133.6 (2) | O1L—C1L—N1L—C2L | 9 (2) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu8(C8H24O2Si)2(C3H7NO)8]·C4H4N2·C3H7NO |
Mr | 2448.26 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 16.9402 (16), 18.6388 (18), 17.2684 (16) |
β (°) | 110.679 (7) |
V (Å3) | 5101.1 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.90 |
Crystal size (mm) | 0.22 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Stoe IPDS-II two-circle diffractometer |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.679, 0.726 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 39433, 9372, 5221 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.613 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.069, 0.74 |
No. of reflections | 9372 |
No. of parameters | 573 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −0.45 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97 and PLATON (Spek, 2003).
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In recent years, the synthesis of metallaorganosiloxane compounds has attracted much attention due to the molecular magnetism of these compounds. A series of new crystalline copper-containing organosiloxanes has been synthesized and structurally characterized (Lindeman et al., 1997; Zucchi et al., 2000; Molodtsova et al., 1998; Abbati et al., 2003; Zucchi et al., 1998). We report here the structure of the title novel polyhedral methylsiloxane complex, (I), containing eight Cu atoms, with an encapsulated molecule of pyrazine.
A perspective view of (I) is shown in Fig. 1. The compound features a cage enclosing a pyrazine molecule, both located on a centre of inversion. The cage is composed of two [SiCH3O2]88− rings which are connected by eight Cu atoms. The coordination of the Cu atoms by the O atoms can be described as quadratically pyramidal, where the plane is composed of O atoms of the [SiCH3O2]88− rings. The Cu atoms deviate only slightly from this plane, by 0.2594 (18) Å for Cu1, 0.2170 (17) Å for Cu2, 0.1940 (15) Å for Cu3 and 0.2241 (17) Å for Cu4. The Cu—O distances in the quadratic plane range from 1.934 (3) to 1.973 (3) Å. In addition, each Cu atom is further bonded to the O atom of one dimethylformamide molecule, with Cu—O distances ranging from 2.265 (4) to 2.428 (4) Å. All dimethylformamide molecules are oriented in the same way around the cage. The longest diagonal in the plane of the eight Cu atoms is the distance from Cu3 to its symmetry equivalent [7.9677 (12) Å]. The shortest diagonal (between Cu1 and the symmetry equivalent of Cu4) is 6.5288 (10) Å.
In the centre of the cage, there is a pyrazine molecule oriented almost in the direction of the longest diagonal. The N atoms of the pyrazine molecule show two short contacts to two Cu atoms [N91···Cu3 2.644 (4) Å and N91···Cu2 2.772 (5) Å]. The bonds of the O atoms connecting two Si atoms are significantly longer [1.630 (7) Å] than the Si—O bonds of the O atoms connecting an Si and a Cu atom [1.610 (7) Å]. The only exceptions to this are the bonds Si4—O3 [1.617 (4) Å] and Si4—O41 [1.622 (3) Å].
The eight-membered ring of Cu atoms shows Cu—Cu distances ranging from 2.8150 (9) Å (Cu2—Cu3) to 2.9587 (7) Å [Cu1—Cu4i; symmetry code: (i) 1 − x, 1 − y, 1 − z]. The Cu—Cu—Cu angles at the Cu atoms which are bonded to the pyrazine molecule [131.93 (3)° for Cu2 and 128.69 (2)° for Cu3] are smaller than the remaining two [140.84 (3)° for Cu1 and 138.55 (3)° for Cu4].
In conclusion, it can be said that the title compound constitutes an ideal cage that has been designed to encapsulate a pyrazine guest molecule. The guest fits perfectly into the space offered by the host. Furthermore, attractive Cu···N interactions hold the guest tightly fixed in the cage.