Bis([mu]₆-cis-2,4,6,8,10,12,14,16-octa­methyl­cyclo­octa­siloxane-2,4,6,8,10,12,14,16-octolato)octa­kis[(dimethyl­formamide)copper(II)] dimethyl­formamide solvate enclosing a pyrazine mol­ecule

The title compound, [Cu₈(C₈H₂₄O₂Si)₂(C₃H₇NO)₈]·C₄H₄N₂·C₃H₇NO, features a sandwich-like cage enclosing a pyrazine mol­ecule, both situated on a centre of inversion. In addition, the crystal structure contains one dimethyl­formamide mol­ecule which is disordered over a centre of inversion. The copper layer, containing eight atoms, is located between two siloxanolate fragments. The whole structure of Cu atoms and siloxanolate rings is distorted by the pyrazine mol­ecule, leading to an oval form. As a result, the angles between the Cu atoms differ at the copper layer. The difference in the angles could lead to some deviations in the Cu-Cu exchange inter­actions within the copper ring, which is of inter­est for mol­ecular magnetism.

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

H atoms were placed in calculated positions and refined with fixed individual displacement parameters [U_iso(H) = 1.2U_eq(C) or 1.5 U_eq(C_methyl)] using a riding model, with C—H = 0.95 or 0.98 Å, for C_aromatic or C_methyl, respectively. The methyl groups of the non disordered dimethylformamide molecules were allowed to rotate but not to tip.

Computing details

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).

Figures

Fig. 1. A perspective view of the title compound, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms and the disordered dimethylformamide molecule have been omitted for clarity. Atoms with the suffix a were generated by the symmetry operator (1 − x, 1 − y, 1 − z).

Bis(µ₆-cis-2,4,6,8,10,12,14,16-octamethylcyclooctasiloxane- 2,4,6,8,10,12,14,16-octolato)octakis[(dimethylformamide)copper(II)] dimethylformamide pyrazine solvate

Crystal data

[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) Å^3	0.22 × 0.20 × 0.18 mm
Z = 2

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H-atom parameters constrained
S = 0.74	w = 1/[σ^2(Fo^2) + (0.0111P)^2] where P = (Fo^2 + 2Fc^2)/3
9372 reflections	(Δ/σ)max = 0.004
573 parameters	Δρmax = 0.66 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Cu1—O11	1.951 (3)	Si7—C7	1.849 (5)
Cu1—O61^i	1.953 (3)	C7—H7A	0.9800
Cu1—O51^i	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—Cu2^i	1.955 (3)
Cu1—Cu4^i	2.9587 (7)	O71—Cu3^i	1.971 (3)
Cu2—O21	1.949 (3)	Si8—O81	1.611 (3)
Cu2—O71^i	1.955 (3)	Si8—O8	1.626 (3)
Cu2—O31	1.959 (3)	Si8—C8	1.861 (5)
Cu2—O61^i	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—O81^i	1.946 (4)	O81—Cu3^i	1.946 (4)
Cu3—O41	1.957 (3)	O81—Cu4^i	1.973 (3)
Cu3—O31	1.965 (3)	O101—C101	1.241 (6)
Cu3—O71^i	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—O11^i	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—O81^i	1.973 (3)	C102—H10C	0.9800
Cu4—O401	2.341 (4)	C103—H10D	0.9800
Cu4—Cu1^i	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—Cu4^i	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—C93^i	1.341 (6)
C5—H5C	0.9800	N91—C92	1.340 (7)
O5—Si6	1.625 (3)	C92—C93	1.333 (6)
O51—Cu1^i	1.956 (3)	C92—H92	0.9500
Si6—O61	1.601 (3)	C93—N91^i	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—C2L^ii	1.322 (19)
O6—Si7	1.631 (3)	N1L—C2L	1.322 (19)
O61—Cu1^i	1.953 (3)	N1L—C1L^ii	1.64 (4)
O61—Cu2^i	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—O61^i	163.57 (15)	Si5—C5—H5B	109.5
O11—Cu1—O51^i	79.65 (12)	H5A—C5—H5B	109.5
O61^i—Cu1—O51^i	96.87 (12)	Si5—C5—H5C	109.5
O11—Cu1—O21	98.15 (12)	H5A—C5—H5C	109.5
O61^i—Cu1—O21	81.28 (12)	H5B—C5—H5C	109.5
O51^i—Cu1—O21	165.86 (15)	Si6—O5—Si5	131.4 (2)
O11—Cu1—O101	96.26 (13)	Si5—O51—Cu4	130.22 (18)
O61^i—Cu1—O101	100.14 (13)	Si5—O51—Cu1^i	130.70 (17)
O51^i—Cu1—O101	98.10 (13)	Cu4—O51—Cu1^i	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)
O61^i—Cu1—Cu2	42.50 (8)	O5—Si6—O6	107.51 (19)
O51^i—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—Cu4^i	40.17 (9)	Si6—C6—H6A	109.5
O61^i—Cu1—Cu4^i	131.82 (10)	Si6—C6—H6B	109.5
O51^i—Cu1—Cu4^i	40.39 (8)	H6A—C6—H6B	109.5
O21—Cu1—Cu4^i	133.60 (9)	Si6—C6—H6C	109.5
O101—Cu1—Cu4^i	105.98 (8)	H6A—C6—H6C	109.5
Cu2—Cu1—Cu4^i	140.84 (3)	H6B—C6—H6C	109.5
O21—Cu2—O71^i	167.67 (14)	Si7—O6—Si6	134.8 (2)
O21—Cu2—O31	97.55 (13)	Si6—O61—Cu1^i	130.72 (17)
O71^i—Cu2—O31	81.85 (13)	Si6—O61—Cu2^i	132.21 (18)
O21—Cu2—O61^i	81.07 (12)	Cu1^i—O61—Cu2^i	95.45 (13)
O71^i—Cu2—O61^i	96.69 (13)	O71—Si7—O7	109.81 (18)
O31—Cu2—O61^i	166.85 (13)	O71—Si7—O6	110.41 (17)
O21—Cu2—O201	96.73 (14)	O7—Si7—O6	108.05 (19)
O71^i—Cu2—O201	95.51 (13)	O71—Si7—C7	111.4 (2)
O31—Cu2—O201	99.40 (13)	O7—Si7—C7	109.5 (2)
O61^i—Cu2—O201	93.75 (13)	O6—Si7—C7	107.6 (2)
O21—Cu2—Cu3	128.66 (10)	Si7—C7—H7A	109.5
O71^i—Cu2—Cu3	44.42 (9)	Si7—C7—H7B	109.5
O31—Cu2—Cu3	44.24 (10)	H7A—C7—H7B	109.5
O61^i—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
O71^i—Cu2—Cu1	131.03 (9)	Si7—O7—Si8	136.3 (2)
O31—Cu2—Cu1	131.40 (9)	Si7—O71—Cu2^i	131.33 (19)
O61^i—Cu2—Cu1	42.05 (8)	Si7—O71—Cu3^i	132.5 (2)
O201—Cu2—Cu1	109.37 (9)	Cu2^i—O71—Cu3^i	91.62 (12)
Cu3—Cu2—Cu1	131.93 (3)	O81—Si8—O8	110.27 (16)
O81^i—Cu3—O41	81.68 (14)	O81—Si8—O7	110.10 (19)
O81^i—Cu3—O31	168.45 (12)	O8—Si8—O7	108.18 (17)
O41—Cu3—O31	97.90 (14)	O81—Si8—C8	111.1 (2)
O81^i—Cu3—O71^i	96.86 (13)	O8—Si8—C8	108.5 (2)
O41—Cu3—O71^i	168.80 (12)	O7—Si8—C8	108.7 (2)
O31—Cu3—O71^i	81.30 (13)	Si8—C8—H8A	109.5
O81^i—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
O71^i—Cu3—O301	90.33 (13)	H8A—C8—H8C	109.5
O81^i—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—Cu3^i	132.3 (2)
O71^i—Cu3—Cu2	43.97 (9)	Si8—O81—Cu4^i	129.8 (2)
O301—Cu3—Cu2	109.34 (11)	Cu3^i—O81—Cu4^i	92.77 (14)
O81^i—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
O71^i—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)
O11^i—Cu4—O51	80.48 (12)	C102—N101—C103	116.9 (5)
O11^i—Cu4—O41	166.69 (14)	N101—C102—H10A	109.5
O51—Cu4—O41	98.44 (13)	N101—C102—H10B	109.5
O11^i—Cu4—O81^i	97.26 (13)	H10A—C102—H10B	109.5
O51—Cu4—O81^i	166.93 (14)	N101—C102—H10C	109.5
O41—Cu4—O81^i	80.78 (13)	H10A—C102—H10C	109.5
O11^i—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
O81^i—Cu4—O401	92.90 (13)	H10D—C103—H10E	109.5
O11^i—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
O81^i—Cu4—Cu3	43.23 (10)	C201—O201—Cu2	109.8 (3)
O401—Cu4—Cu3	112.84 (9)	O201—C201—N201	126.0 (5)
O11^i—Cu4—Cu1^i	40.62 (8)	O201—C201—H201	117.0
O51—Cu4—Cu1^i	40.78 (9)	N201—C201—H201	117.0
O41—Cu4—Cu1^i	134.63 (9)	C201—N201—C203	121.1 (5)
O81^i—Cu4—Cu1^i	133.53 (9)	C201—N201—C202	119.7 (5)
O401—Cu4—Cu1^i	108.55 (9)	C203—N201—C202	118.9 (5)
Cu3—Cu4—Cu1^i	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—Cu4^i	130.91 (17)	O301—C301—H301	117.4
Si1—O11—Cu1	129.78 (17)	N301—C301—H301	117.4
Cu4^i—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)	C93^i—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—N91^i	122.2 (5)
Si4—C4—H4A	109.5	C92—C93—H93	118.9
Si4—C4—H4B	109.5	N91^i—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	C2L^ii—N1L—C2L	179.998 (8)
Si5—O4—Si4	133.4 (2)	C2L^ii—N1L—C1L	92.3 (12)
Si4—O41—Cu3	131.1 (2)	C2L—N1L—C1L	87.7 (12)
Si4—O41—Cu4	130.11 (18)	C2L^ii—N1L—C1L^ii	87.7 (12)
Cu3—O41—Cu4	92.68 (13)	C2L—N1L—C1L^ii	92.3 (12)
O51—Si5—O4	109.32 (17)	C1L—N1L—C1L^ii	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)
O61^i—Cu1—Cu2—O21	−151.6 (2)	C3—Si3—O31—Cu2	106.2 (3)
O51^i—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)
Cu4^i—Cu1—Cu2—O21	105.48 (15)	C3—Si3—O31—Cu3	−108.2 (3)
O11—Cu1—Cu2—O71^i	−116.83 (18)	O21—Cu2—O31—Si3	14.9 (3)
O61^i—Cu1—Cu2—O71^i	42.8 (2)	O71^i—Cu2—O31—Si3	−177.5 (3)
O51^i—Cu1—Cu2—O71^i	−2.48 (18)	O61^i—Cu2—O31—Si3	98.0 (6)
O21—Cu1—Cu2—O71^i	−165.6 (2)	O201—Cu2—O31—Si3	−83.2 (2)
O101—Cu1—Cu2—O71^i	122.22 (16)	Cu3—Cu2—O31—Si3	155.0 (3)
Cu4^i—Cu1—Cu2—O71^i	−60.11 (13)	Cu1—Cu2—O31—Si3	43.2 (3)
O11—Cu1—Cu2—O31	4.29 (19)	O21—Cu2—O31—Cu3	−140.10 (12)
O61^i—Cu1—Cu2—O31	163.9 (2)	O71^i—Cu2—O31—Cu3	27.47 (12)
O51^i—Cu1—Cu2—O31	118.63 (18)	O61^i—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)
Cu4^i—Cu1—Cu2—O31	61.01 (14)	O81^i—Cu3—O31—Si3	−100.4 (7)
O11—Cu1—Cu2—O61^i	−159.6 (2)	O41—Cu3—O31—Si3	−13.3 (2)
O51^i—Cu1—Cu2—O61^i	−45.27 (19)	O71^i—Cu3—O31—Si3	178.0 (2)
O21—Cu1—Cu2—O61^i	151.6 (2)	O301—Cu3—O31—Si3	87.8 (2)
O101—Cu1—Cu2—O61^i	79.44 (18)	Cu2—Cu3—O31—Si3	−154.7 (3)
Cu4^i—Cu1—Cu2—O61^i	−102.89 (16)	Cu4—Cu3—O31—Si3	−46.8 (3)
O11—Cu1—Cu2—O201	127.02 (17)	O81^i—Cu3—O31—Cu2	54.4 (7)
O61^i—Cu1—Cu2—O201	−73.36 (19)	O41—Cu3—O31—Cu2	141.43 (11)
O51^i—Cu1—Cu2—O201	−118.63 (16)	O71^i—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)
Cu4^i—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)
O61^i—Cu1—Cu2—Cu3	103.37 (15)	Si3—O3—Si4—C4	−117.2 (3)
O51^i—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)
Cu4^i—Cu1—Cu2—Cu3	0.48 (6)	O3—Si4—O41—Cu3	−8.8 (3)
O21—Cu2—Cu3—O81^i	−113.47 (15)	O4—Si4—O41—Cu3	−127.2 (2)
O71^i—Cu2—Cu3—O81^i	52.73 (16)	C4—Si4—O41—Cu3	112.0 (3)
O31—Cu2—Cu3—O81^i	−168.00 (17)	O3—Si4—O41—Cu4	135.8 (2)
O61^i—Cu2—Cu3—O81^i	−1.96 (15)	O4—Si4—O41—Cu4	17.4 (3)
O201—Cu2—Cu3—O81^i	119.09 (16)	C4—Si4—O41—Cu4	−103.4 (3)
Cu1—Cu2—Cu3—O81^i	−57.39 (12)	O81^i—Cu3—O41—Si4	179.8 (2)
O21—Cu2—Cu3—O41	1.26 (17)	O31—Cu3—O41—Si4	11.4 (2)
O71^i—Cu2—Cu3—O41	167.47 (17)	O71^i—Cu3—O41—Si4	96.5 (8)
O31—Cu2—Cu3—O41	−53.26 (17)	O301—Cu3—O41—Si4	−81.0 (2)
O61^i—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)	O81^i—Cu3—O41—Cu4	26.08 (12)
O21—Cu2—Cu3—O31	54.52 (16)	O31—Cu3—O41—Cu4	−142.26 (12)
O71^i—Cu2—Cu3—O31	−139.27 (17)	O71^i—Cu3—O41—Cu4	−57.2 (8)
O61^i—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)	O11^i—Cu4—O41—Si4	−97.3 (6)
O21—Cu2—Cu3—O71^i	−166.21 (17)	O51—Cu4—O41—Si4	−13.0 (3)
O31—Cu2—Cu3—O71^i	139.27 (17)	O81^i—Cu4—O41—Si4	−179.8 (3)
O61^i—Cu2—Cu3—O71^i	−54.69 (16)	O401—Cu4—O41—Si4	88.1 (3)
O201—Cu2—Cu3—O71^i	66.36 (17)	Cu3—Cu4—O41—Si4	−154.1 (3)
Cu1—Cu2—Cu3—O71^i	−110.13 (13)	Cu1^i—Cu4—O41—Si4	−34.7 (3)
O21—Cu2—Cu3—O301	124.60 (16)	O11^i—Cu4—O41—Cu3	56.7 (6)
O71^i—Cu2—Cu3—O301	−69.20 (17)	O51—Cu4—O41—Cu3	141.04 (13)
O31—Cu2—Cu3—O301	70.08 (16)	O81^i—Cu4—O41—Cu3	−25.76 (13)
O61^i—Cu2—Cu3—O301	−123.88 (16)	O401—Cu4—O41—Cu3	−117.83 (13)
O201—Cu2—Cu3—O301	−2.83 (17)	Cu1^i—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)
O71^i—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)
O61^i—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)
O81^i—Cu3—Cu4—O11^i	52.96 (17)	O5—Si5—O51—Cu4	−144.8 (2)
O41—Cu3—Cu4—O11^i	−165.82 (18)	C5—Si5—O51—Cu4	93.8 (3)
O31—Cu3—Cu4—O11^i	−113.63 (16)	O4—Si5—O51—Cu1^i	146.3 (2)
O71^i—Cu3—Cu4—O11^i	1.97 (17)	O5—Si5—O51—Cu1^i	28.2 (3)
O301—Cu3—Cu4—O11^i	123.45 (18)	C5—Si5—O51—Cu1^i	−93.2 (3)
Cu2—Cu3—Cu4—O11^i	−55.67 (12)	O11^i—Cu4—O51—Si5	−175.0 (3)
O81^i—Cu3—Cu4—O51	165.05 (17)	O41—Cu4—O51—Si5	18.4 (3)
O41—Cu3—Cu4—O51	−53.73 (17)	O81^i—Cu4—O51—Si5	103.9 (6)
O31—Cu3—Cu4—O51	−1.54 (16)	O401—Cu4—O51—Si5	−78.7 (3)
O71^i—Cu3—Cu4—O51	114.06 (16)	Cu3—Cu4—O51—Si5	52.5 (3)
O301—Cu3—Cu4—O51	−124.46 (17)	Cu1^i—Cu4—O51—Si5	174.6 (4)
Cu2—Cu3—Cu4—O51	56.42 (12)	O11^i—Cu4—O51—Cu1^i	10.32 (14)
O81^i—Cu3—Cu4—O41	−141.22 (18)	O41—Cu4—O51—Cu1^i	−156.25 (14)
O31—Cu3—Cu4—O41	52.18 (17)	O81^i—Cu4—O51—Cu1^i	−70.7 (7)
O71^i—Cu3—Cu4—O41	167.79 (18)	O401—Cu4—O51—Cu1^i	106.69 (15)
O301—Cu3—Cu4—O41	−70.73 (19)	Cu3—Cu4—O51—Cu1^i	−122.09 (10)
Cu2—Cu3—Cu4—O41	110.14 (14)	Si5—O5—Si6—O61	34.4 (3)
O41—Cu3—Cu4—O81^i	141.22 (18)	Si5—O5—Si6—O6	153.3 (3)
O31—Cu3—Cu4—O81^i	−166.59 (17)	Si5—O5—Si6—C6	−88.9 (3)
O71^i—Cu3—Cu4—O81^i	−50.99 (17)	O61—Si6—O6—Si7	−19.7 (4)
O301—Cu3—Cu4—O81^i	70.49 (18)	O5—Si6—O6—Si7	−139.0 (3)
Cu2—Cu3—Cu4—O81^i	−108.63 (13)	C6—Si6—O6—Si7	103.7 (3)
O81^i—Cu3—Cu4—O401	−68.41 (17)	O5—Si6—O61—Cu1^i	−25.6 (3)
O41—Cu3—Cu4—O401	72.81 (17)	O6—Si6—O61—Cu1^i	−143.4 (2)
O31—Cu3—Cu4—O401	125.00 (16)	C6—Si6—O61—Cu1^i	95.3 (3)
O71^i—Cu3—Cu4—O401	−119.40 (16)	O5—Si6—O61—Cu2^i	136.2 (2)
O301—Cu3—Cu4—O401	2.08 (17)	O6—Si6—O61—Cu2^i	18.4 (3)
Cu2—Cu3—Cu4—O401	−177.04 (11)	C6—Si6—O61—Cu2^i	−102.9 (3)
O81^i—Cu3—Cu4—Cu1^i	108.34 (13)	Si6—O6—Si7—O71	20.6 (4)
O41—Cu3—Cu4—Cu1^i	−110.43 (14)	Si6—O6—Si7—O7	140.7 (3)
O31—Cu3—Cu4—Cu1^i	−58.25 (12)	Si6—O6—Si7—C7	−101.1 (3)
O71^i—Cu3—Cu4—Cu1^i	57.36 (12)	O71—Si7—O7—Si8	5.4 (3)
O301—Cu3—Cu4—Cu1^i	178.83 (13)	O6—Si7—O7—Si8	−115.1 (3)
Cu2—Cu3—Cu4—Cu1^i	−0.29 (6)	C7—Si7—O7—Si8	128.0 (3)
O11—Si1—O1—Si2	−33.6 (4)	O7—Si7—O71—Cu2^i	−139.2 (2)
O8—Si1—O1—Si2	−151.8 (3)	O6—Si7—O71—Cu2^i	−20.2 (3)
C1—Si1—O1—Si2	88.6 (4)	C7—Si7—O71—Cu2^i	99.4 (3)
O1—Si1—O11—Cu4^i	−149.0 (2)	O7—Si7—O71—Cu3^i	9.6 (3)
O8—Si1—O11—Cu4^i	−30.7 (3)	O6—Si7—O71—Cu3^i	128.7 (2)
C1—Si1—O11—Cu4^i	89.0 (3)	C7—Si7—O71—Cu3^i	−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)
O61^i—Cu1—O11—Si1	−108.0 (5)	O81—Si8—O8—Si1	−37.9 (3)
O51^i—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)
Cu4^i—Cu1—O11—Si1	−176.8 (4)	C1—Si1—O8—Si8	−80.4 (3)
O61^i—Cu1—O11—Cu4^i	68.8 (5)	O8—Si8—O81—Cu3^i	−123.8 (2)
O51^i—Cu1—O11—Cu4^i	−10.30 (14)	O7—Si8—O81—Cu3^i	−4.5 (3)
O21—Cu1—O11—Cu4^i	155.55 (14)	C8—Si8—O81—Cu3^i	115.9 (3)
O101—Cu1—O11—Cu4^i	−107.43 (14)	O8—Si8—O81—Cu4^i	23.8 (3)
Cu2—Cu1—O11—Cu4^i	125.07 (9)	O7—Si8—O81—Cu4^i	143.1 (2)
Si1—O1—Si2—O21	33.1 (4)	C8—Si8—O81—Cu4^i	−96.5 (3)
Si1—O1—Si2—O2	152.0 (3)	O11—Cu1—O101—C101	50.6 (4)
Si1—O1—Si2—C2	−89.5 (4)	O61^i—Cu1—O101—C101	−128.3 (3)
O21—Si2—O2—Si3	−14.1 (4)	O51^i—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)	Cu4^i—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)	O71^i—Cu2—O201—C201	−136.8 (4)
O71^i—Cu2—O21—Si2	−102.6 (6)	O31—Cu2—O201—C201	140.6 (4)
O31—Cu2—O21—Si2	−16.2 (3)	O61^i—Cu2—O201—C201	−39.7 (4)
O61^i—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)
O71^i—Cu2—O21—Cu1	61.6 (6)	O201—C201—N201—C202	−4.4 (9)
O31—Cu2—O21—Cu1	147.99 (13)	O81^i—Cu3—O301—C301	−141.2 (4)
O61^i—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)	O71^i—Cu3—O301—C301	−44.2 (4)
O11—Cu1—O21—Si2	20.4 (3)	Cu2—Cu3—O301—C301	−3.7 (4)
O61^i—Cu1—O21—Si2	−176.2 (3)	Cu4—Cu3—O301—C301	177.0 (4)
O51^i—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)
Cu4^i—Cu1—O21—Si2	42.0 (3)	O11^i—Cu4—O401—C401	−134.2 (4)
O11—Cu1—O21—Cu2	−144.44 (14)	O51—Cu4—O401—C401	144.1 (4)
O61^i—Cu1—O21—Cu2	18.95 (14)	O41—Cu4—O401—C401	44.5 (4)
O51^i—Cu1—O21—Cu2	−64.5 (5)	O81^i—Cu4—O401—C401	−36.5 (4)
O101—Cu1—O21—Cu2	118.32 (14)	Cu3—Cu4—O401—C401	3.2 (4)
Cu4^i—Cu1—O21—Cu2	−122.81 (9)	Cu1^i—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)	C93^i—N91—C92—C93	0.8 (9)
O2—Si3—O3—Si4	−128.1 (3)	N91—C92—C93—N91^i	−0.9 (10)
C3—Si3—O3—Si4	115.2 (3)	O1L—C1L—N1L—C2L^ii	−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.