Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110044549/sf3136sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270110044549/sf3136Isup2.hkl |
CCDC reference: 810032
N,N,N-Trimethyladamantylammonium hydroxide (TMAdaOH) was prepared by ion exchange from the iodide, which was obtained by reaction of 1-adamantylamine (Acros, 99%) with an excess of methyl iodide (Acros, 99%) according to the procedure of Zones (1985).
Silicate hydrate crystals were synthesized at room temperature from a clear solution, prepared by adding tetraethyl orthosilicate (TEOS; Acros, 98%) under vigorous stirring to a 0.7 M aqueous solution of TMAdaOH. The clear solution was then stirred continuously until crystals of (I) formed.
The 29Si MAS NMR spectrum was recorded on a Bruker AMX300 spectrometer. 4000 scans with a recycle delay of 60 s were accumulated.
The crystal structure displays a high degree of disorder of the template molecules. Of the three TMAda cations in the asymmetric unit, only one shows no disorder. A second molecule is present in two conformations [refined occupancy = 0.522 (6):0.478 (6) for adamantane and 0.559 (22):0.441 (22) for trimethylammonium], rotated approximately 60° around the N–adamantyl bond. The third cation shows threefold disorder, also around the N–adamantyl bond (occupancies were fixed at 0.333). The amandantane substructures of this threefold disordered TMAda cation were refined to target values provided by the undisordered one. Distance restraints were set-up with a standard deviation of 0.01 Å, the standard deviation on the angle restraints, expressed as 1,3-distances, were set at twice this value (0.02°). No distance or angle restraints were applied to the second cation showing twofold disorder. Rigid-bond restraints (standard deviation = 0.005 Å) were applied within every part of the threefold disordered amandantane substructure and simultaneous the same anisotropic displacement parameters were used for all corresponding atoms in the three disordered parts. Moreover, the individual thermal displacement components of the threefold disordered amandantane are refined to approximate to isotropic behavior (standard deviation = 0.01 Å2). The same anisotropic displacement parameters were used for the C atoms of the two parts of the trimethylamonium group attached to the threefold disordered amandantane substructure (the C atoms of one disordered part are refined without thermal displacement restraints, the other disordered part is pairwise given the same displacement parameters. The twofold disordered methyl groups of the trimethylammonium group attached to the threefold disordered amandantane were refined with site-occupation factors of 0.455 (6):0.545 (6).
The silanol H atom was located in a difference map, as were the majority of water H atoms. These H atoms were, after location in a difference map, fixed on their parent O atoms and the water molecules were refined as rigid groups, with the H atoms as dependent atoms able to rotate around and move with their O atoms, while retaining an idealized geometry. For the remaining water H atoms that could not be unequivocally located, the H-atom position was chosen to optimize the hydrogen-bond network, and again the water molecules were treated as above. For all H atoms, Uiso(H) = 1.2Ueq(parent atom) or 1.5Ueq(C) for methyl groups. The solvent water OH bonds were fixed at 0.84 Å, with a 108° angle between them. The reported hydrogen-bond H···A distances are in the range 1.78–2.12 Å and the hydrogen-bond D—H···A angle is in the range 129.2–177.2°. This is on average 1.92 Å and 165.2° for 39 observed hydrogen bonds.
Part of the solvent, 55 electrons (presumably water or ethanol molecules), in a cavity of 158 Å3 centred about an inversion centre, could not be modelled and was treated with the SQUEEZE procedure in PLATON (Spek, 2009). This solvent has not been included in the reported empirical formula, Mr, F(000), calculated density or linear absorption coefficient.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLUTON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
6C13H24N+·H2O20Si86−·44H2O | V = 3356.8 (3) Å3 |
Mr = 2505.44 | Z = 1 |
Triclinic, P1 | F(000) = 1368 |
Hall symbol: -P 1 | Dx = 1.239 Mg m−3 |
a = 15.5889 (8) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 15.9297 (8) Å | µ = 1.53 mm−1 |
c = 16.2269 (11) Å | T = 100 K |
α = 60.863 (2)° | Plate, colourless |
β = 72.511 (3)° | 0.24 × 0.24 × 0.10 mm |
γ = 82.119 (2)° |
Bruker SMART 6000 diffractometer | 12596 independent reflections |
Radiation source: fine-focus sealed tube | 10388 reflections with I > 2σ(I) |
Crossed Goebel mirrors monochromator | Rint = 0.041 |
ω and ϕ scans | θmax = 71.2°, θmin = 3.0° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −18→17 |
Tmin = 0.587, Tmax = 0.858 | k = −19→19 |
66631 measured reflections | l = −19→19 |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1073P)2 + 3.7976P] where P = (Fo2 + 2Fc2)/3 |
12596 reflections | (Δ/σ)max = 0.001 |
942 parameters | Δρmax = 0.90 e Å−3 |
399 restraints | Δρmin = −0.69 e Å−3 |
6C13H24N+·H2O20Si86−·44H2O | γ = 82.119 (2)° |
Mr = 2505.44 | V = 3356.8 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 15.5889 (8) Å | Cu Kα radiation |
b = 15.9297 (8) Å | µ = 1.53 mm−1 |
c = 16.2269 (11) Å | T = 100 K |
α = 60.863 (2)° | 0.24 × 0.24 × 0.10 mm |
β = 72.511 (3)° |
Bruker SMART 6000 diffractometer | 12596 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 10388 reflections with I > 2σ(I) |
Tmin = 0.587, Tmax = 0.858 | Rint = 0.041 |
66631 measured reflections |
R[F2 > 2σ(F2)] = 0.065 | 399 restraints |
wR(F2) = 0.186 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.90 e Å−3 |
12596 reflections | Δρmin = −0.69 e Å−3 |
942 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) | |
C1 | 0.6760 (2) | 0.9274 (2) | 0.1490 (2) | 0.0360 (7) | |
H1 | 0.6582 | 0.9791 | 0.0900 | 0.043* | |
C2 | 0.6078 (2) | 0.9221 (3) | 0.2411 (3) | 0.0448 (8) | |
H2A | 0.5470 | 0.9088 | 0.2425 | 0.054* | |
H2B | 0.6064 | 0.9843 | 0.2414 | 0.054* | |
C3 | 0.6348 (3) | 0.8415 (3) | 0.3314 (3) | 0.0463 (9) | |
H3 | 0.5900 | 0.8372 | 0.3922 | 0.056* | |
C4 | 0.6367 (3) | 0.7462 (3) | 0.3303 (3) | 0.0518 (10) | |
H4A | 0.6540 | 0.6940 | 0.3883 | 0.062* | |
H4B | 0.5761 | 0.7310 | 0.3329 | 0.062* | |
C5 | 0.7040 (2) | 0.7534 (2) | 0.2371 (3) | 0.0432 (8) | |
H5 | 0.7052 | 0.6908 | 0.2365 | 0.052* | |
C6 | 0.6787 (2) | 0.8313 (3) | 0.1486 (3) | 0.0436 (8) | |
H6A | 0.6190 | 0.8168 | 0.1486 | 0.052* | |
H6B | 0.7232 | 0.8350 | 0.0886 | 0.052* | |
C7 | 0.7695 (2) | 0.9506 (2) | 0.1457 (2) | 0.0288 (6) | |
H7A | 0.8137 | 0.9555 | 0.0852 | 0.035* | |
H7B | 0.7686 | 1.0130 | 0.1455 | 0.035* | |
C8 | 0.7275 (2) | 0.8652 (2) | 0.3289 (2) | 0.0407 (8) | |
H8A | 0.7451 | 0.8149 | 0.3877 | 0.049* | |
H8B | 0.7257 | 0.9275 | 0.3290 | 0.049* | |
C9 | 0.7983 (2) | 0.7745 (2) | 0.2361 (2) | 0.0342 (7) | |
H9A | 0.8152 | 0.7228 | 0.2947 | 0.041* | |
H9B | 0.8435 | 0.7769 | 0.1771 | 0.041* | |
C10 | 0.7967 (2) | 0.8707 (2) | 0.2357 (2) | 0.0266 (6) | |
N11 | 0.89302 (19) | 0.89321 (19) | 0.2337 (2) | 0.0350 (6) | |
C12 | 0.8899 (3) | 0.9768 (3) | 0.2518 (4) | 0.0563 (11) | |
H12A | 0.8572 | 0.9584 | 0.3202 | 0.084* | |
H12B | 0.8591 | 1.0302 | 0.2083 | 0.084* | |
H12C | 0.9513 | 0.9968 | 0.2390 | 0.084* | |
C13 | 0.9275 (3) | 0.8110 (3) | 0.3138 (4) | 0.0660 (13) | |
H13A | 0.9809 | 0.8321 | 0.3191 | 0.099* | |
H13B | 0.9434 | 0.7576 | 0.2984 | 0.099* | |
H13C | 0.8807 | 0.7898 | 0.3761 | 0.099* | |
C14 | 0.9594 (3) | 0.9145 (4) | 0.1385 (3) | 0.0546 (10) | |
H14A | 0.9411 | 0.9720 | 0.0861 | 0.082* | |
H14B | 0.9623 | 0.8599 | 0.1258 | 0.082* | |
H14C | 1.0188 | 0.9256 | 0.1408 | 0.082* | |
C21 | 0.5993 (7) | 0.4542 (8) | 0.2344 (8) | 0.039 (2) | 0.478 (6) |
H21 | 0.6100 | 0.4733 | 0.1636 | 0.047* | 0.478 (6) |
C22 | 0.5721 (9) | 0.5440 (9) | 0.2503 (9) | 0.043 (3) | 0.478 (6) |
H22A | 0.6208 | 0.5930 | 0.2106 | 0.052* | 0.478 (6) |
H22B | 0.5170 | 0.5723 | 0.2291 | 0.052* | 0.478 (6) |
C23 | 0.5556 (8) | 0.5153 (9) | 0.3557 (8) | 0.040 (3) | 0.478 (6) |
H23 | 0.5365 | 0.5724 | 0.3667 | 0.048* | 0.478 (6) |
C24 | 0.4816 (8) | 0.4369 (13) | 0.4176 (11) | 0.058 (4) | 0.478 (6) |
H24A | 0.4713 | 0.4174 | 0.4878 | 0.069* | 0.478 (6) |
H24B | 0.4247 | 0.4633 | 0.3997 | 0.069* | 0.478 (6) |
C25 | 0.5073 (10) | 0.3498 (14) | 0.4016 (14) | 0.051 (4) | 0.478 (6) |
H25 | 0.4575 | 0.3010 | 0.4413 | 0.061* | 0.478 (6) |
C26 | 0.5244 (8) | 0.3782 (9) | 0.2963 (9) | 0.048 (3) | 0.478 (6) |
H26A | 0.4687 | 0.4043 | 0.2755 | 0.058* | 0.478 (6) |
H26B | 0.5419 | 0.3211 | 0.2861 | 0.058* | 0.478 (6) |
C27 | 0.6849 (4) | 0.4095 (5) | 0.2665 (5) | 0.0317 (16) | 0.478 (6) |
H27A | 0.7012 | 0.3522 | 0.2564 | 0.038* | 0.478 (6) |
H27B | 0.7353 | 0.4564 | 0.2263 | 0.038* | 0.478 (6) |
C28 | 0.6432 (5) | 0.4732 (4) | 0.3876 (5) | 0.0313 (15) | 0.478 (6) |
H28A | 0.6334 | 0.4556 | 0.4573 | 0.038* | 0.478 (6) |
H28B | 0.6924 | 0.5217 | 0.3476 | 0.038* | 0.478 (6) |
C29 | 0.5914 (5) | 0.3088 (5) | 0.4385 (5) | 0.0400 (19) | 0.478 (6) |
H29A | 0.5791 | 0.2968 | 0.5069 | 0.048* | 0.478 (6) |
H29B | 0.6074 | 0.2471 | 0.4373 | 0.048* | 0.478 (6) |
C71 | 0.5983 (6) | 0.5163 (6) | 0.2487 (7) | 0.0269 (18) | 0.522 (6) |
H71 | 0.6095 | 0.5797 | 0.1879 | 0.032* | 0.522 (6) |
C72 | 0.5314 (7) | 0.5276 (7) | 0.3325 (9) | 0.039 (2) | 0.522 (6) |
H72A | 0.4742 | 0.5527 | 0.3150 | 0.047* | 0.522 (6) |
H72B | 0.5553 | 0.5745 | 0.3437 | 0.047* | 0.522 (6) |
C73 | 0.5140 (7) | 0.4318 (8) | 0.4256 (9) | 0.036 (2) | 0.522 (6) |
H73 | 0.4695 | 0.4403 | 0.4799 | 0.044* | 0.522 (6) |
C74 | 0.4777 (8) | 0.3601 (11) | 0.4088 (10) | 0.035 (2) | 0.522 (6) |
H74A | 0.4194 | 0.3829 | 0.3930 | 0.042* | 0.522 (6) |
H74B | 0.4669 | 0.2977 | 0.4694 | 0.042* | 0.522 (6) |
C75 | 0.5432 (6) | 0.3465 (6) | 0.3251 (7) | 0.0300 (18) | 0.522 (6) |
H75 | 0.5176 | 0.3002 | 0.3137 | 0.036* | 0.522 (6) |
C76 | 0.5630 (6) | 0.4443 (6) | 0.2310 (6) | 0.0320 (18) | 0.522 (6) |
H76A | 0.6081 | 0.4357 | 0.1778 | 0.038* | 0.522 (6) |
H76B | 0.5073 | 0.4689 | 0.2099 | 0.038* | 0.522 (6) |
C77 | 0.6876 (4) | 0.4773 (4) | 0.2784 (4) | 0.0264 (13) | 0.522 (6) |
H77A | 0.7323 | 0.4686 | 0.2251 | 0.032* | 0.522 (6) |
H77B | 0.7126 | 0.5240 | 0.2890 | 0.032* | 0.522 (6) |
C78 | 0.6019 (4) | 0.3898 (4) | 0.4554 (4) | 0.0285 (13) | 0.522 (6) |
H78A | 0.6259 | 0.4325 | 0.4719 | 0.034* | 0.522 (6) |
H78B | 0.5896 | 0.3258 | 0.5140 | 0.034* | 0.522 (6) |
C79 | 0.6331 (4) | 0.3090 (4) | 0.3509 (4) | 0.0251 (13) | 0.522 (6) |
H79A | 0.6772 | 0.3031 | 0.2956 | 0.030* | 0.522 (6) |
H79B | 0.6239 | 0.2446 | 0.4092 | 0.030* | 0.522 (6) |
C30 | 0.66948 (18) | 0.38107 (18) | 0.3724 (2) | 0.0220 (6) | |
N31 | 0.75959 (18) | 0.33984 (18) | 0.4026 (2) | 0.0314 (6) | |
C32 | 0.8093 (11) | 0.4132 (9) | 0.4011 (14) | 0.059 (4) | 0.56 (2) |
H32A | 0.7686 | 0.4432 | 0.4381 | 0.089* | 0.56 (2) |
H32B | 0.8336 | 0.4623 | 0.3332 | 0.089* | 0.56 (2) |
H32C | 0.8588 | 0.3827 | 0.4311 | 0.089* | 0.56 (2) |
C33 | 0.8254 (6) | 0.3119 (10) | 0.3265 (9) | 0.048 (2) | 0.56 (2) |
H33A | 0.8862 | 0.3056 | 0.3344 | 0.072* | 0.56 (2) |
H33B | 0.8253 | 0.3620 | 0.2601 | 0.072* | 0.56 (2) |
H33C | 0.8060 | 0.2506 | 0.3371 | 0.072* | 0.56 (2) |
C34 | 0.7458 (7) | 0.2551 (9) | 0.5004 (8) | 0.055 (3) | 0.56 (2) |
H34A | 0.8022 | 0.2401 | 0.5195 | 0.082* | 0.56 (2) |
H34B | 0.7269 | 0.2001 | 0.4985 | 0.082* | 0.56 (2) |
H34C | 0.6993 | 0.2689 | 0.5482 | 0.082* | 0.56 (2) |
C35 | 0.8302 (13) | 0.4179 (15) | 0.3560 (15) | 0.063 (5) | 0.44 (2) |
H35A | 0.8072 | 0.4674 | 0.3761 | 0.095* | 0.44 (2) |
H35B | 0.8444 | 0.4467 | 0.2845 | 0.095* | 0.44 (2) |
H35C | 0.8847 | 0.3901 | 0.3772 | 0.095* | 0.44 (2) |
C36 | 0.7961 (11) | 0.2632 (13) | 0.3763 (16) | 0.056 (5) | 0.44 (2) |
H36A | 0.8506 | 0.2376 | 0.3984 | 0.084* | 0.44 (2) |
H36B | 0.8109 | 0.2895 | 0.3051 | 0.084* | 0.44 (2) |
H36C | 0.7512 | 0.2116 | 0.4081 | 0.084* | 0.44 (2) |
C37 | 0.7427 (9) | 0.2967 (15) | 0.5138 (9) | 0.059 (4) | 0.44 (2) |
H37A | 0.7061 | 0.2380 | 0.5471 | 0.089* | 0.44 (2) |
H37B | 0.7109 | 0.3433 | 0.5350 | 0.089* | 0.44 (2) |
H37C | 0.8004 | 0.2812 | 0.5304 | 0.089* | 0.44 (2) |
C41 | 0.4525 (6) | 0.7055 (7) | 0.8792 (7) | 0.0484 (13) | 0.33 |
H41 | 0.4227 | 0.7003 | 0.8352 | 0.058* | 0.33 |
C42 | 0.4140 (7) | 0.7906 (7) | 0.8960 (7) | 0.0477 (12) | 0.33 |
H42A | 0.3477 | 0.7839 | 0.9220 | 0.057* | 0.33 |
H42B | 0.4282 | 0.8509 | 0.8332 | 0.057* | 0.33 |
C43 | 0.4547 (6) | 0.7949 (7) | 0.9698 (7) | 0.0465 (12) | 0.33 |
H43 | 0.4266 | 0.8481 | 0.9846 | 0.056* | 0.33 |
C44 | 0.4428 (8) | 0.7000 (6) | 1.0647 (6) | 0.0445 (11) | 0.33 |
H44A | 0.4740 | 0.7031 | 1.1080 | 0.053* | 0.33 |
H44B | 0.3781 | 0.6868 | 1.0997 | 0.053* | 0.33 |
C45 | 0.4820 (6) | 0.6220 (6) | 1.0385 (7) | 0.0409 (12) | 0.33 |
H45 | 0.4739 | 0.5598 | 1.1007 | 0.049* | 0.33 |
C46 | 0.4380 (7) | 0.6119 (7) | 0.9752 (7) | 0.0472 (11) | 0.33 |
H46A | 0.3729 | 0.5990 | 1.0075 | 0.057* | 0.33 |
H46B | 0.4644 | 0.5577 | 0.9626 | 0.057* | 0.33 |
C47 | 0.5541 (6) | 0.7235 (8) | 0.8288 (7) | 0.0471 (14) | 0.33 |
H47A | 0.5638 | 0.7814 | 0.7639 | 0.057* | 0.33 |
H47B | 0.5811 | 0.6680 | 0.8189 | 0.057* | 0.33 |
C48 | 0.5548 (6) | 0.8180 (6) | 0.9147 (7) | 0.0410 (12) | 0.33 |
H48A | 0.5599 | 0.8764 | 0.8507 | 0.049* | 0.33 |
H48B | 0.5843 | 0.8322 | 0.9529 | 0.049* | 0.33 |
C49 | 0.5830 (6) | 0.6407 (7) | 0.9909 (7) | 0.0375 (14) | 0.33 |
H49A | 0.6095 | 0.5893 | 0.9737 | 0.045* | 0.33 |
H49B | 0.6119 | 0.6387 | 1.0385 | 0.045* | 0.33 |
C81 | 0.4545 (8) | 0.8011 (7) | 0.8681 (8) | 0.0484 (13) | 0.33 |
H81 | 0.4229 | 0.8386 | 0.8157 | 0.058* | 0.33 |
C82 | 0.4454 (7) | 0.8517 (7) | 0.9285 (7) | 0.0477 (12) | 0.33 |
H82A | 0.3810 | 0.8619 | 0.9544 | 0.057* | 0.33 |
H82B | 0.4756 | 0.9154 | 0.8866 | 0.057* | 0.33 |
C83 | 0.4876 (6) | 0.7918 (6) | 1.0137 (7) | 0.0465 (12) | 0.33 |
H83 | 0.4772 | 0.8224 | 1.0569 | 0.056* | 0.33 |
C84 | 0.4529 (8) | 0.6881 (6) | 1.0731 (6) | 0.0445 (11) | 0.33 |
H84A | 0.4864 | 0.6504 | 1.1229 | 0.053* | 0.33 |
H84B | 0.3885 | 0.6868 | 1.1078 | 0.053* | 0.33 |
C85 | 0.4643 (6) | 0.6431 (7) | 1.0073 (7) | 0.0409 (12) | 0.33 |
H85 | 0.4392 | 0.5761 | 1.0477 | 0.049* | 0.33 |
C86 | 0.4173 (6) | 0.6985 (6) | 0.9300 (7) | 0.0472 (11) | 0.33 |
H86A | 0.3520 | 0.6994 | 0.9603 | 0.057* | 0.33 |
H86B | 0.4260 | 0.6676 | 0.8879 | 0.057* | 0.33 |
C87 | 0.5558 (7) | 0.7956 (8) | 0.8208 (7) | 0.0471 (14) | 0.33 |
H87A | 0.5638 | 0.7653 | 0.7784 | 0.057* | 0.33 |
H87B | 0.5820 | 0.8613 | 0.7796 | 0.057* | 0.33 |
C88 | 0.5894 (6) | 0.7882 (7) | 0.9664 (7) | 0.0410 (12) | 0.33 |
H88A | 0.6209 | 0.7508 | 1.0181 | 0.049* | 0.33 |
H88B | 0.6152 | 0.8541 | 0.9268 | 0.049* | 0.33 |
C89 | 0.5657 (6) | 0.6392 (6) | 0.9620 (7) | 0.0375 (14) | 0.33 |
H89A | 0.5965 | 0.6040 | 1.0147 | 0.045* | 0.33 |
H89B | 0.5763 | 0.6048 | 0.9230 | 0.045* | 0.33 |
C91 | 0.4656 (6) | 0.7295 (7) | 1.0286 (8) | 0.0484 (13) | 0.33 |
H91 | 0.4423 | 0.7256 | 1.0949 | 0.058* | 0.33 |
C92 | 0.4384 (7) | 0.6395 (7) | 1.0321 (6) | 0.0477 (12) | 0.33 |
H92A | 0.3720 | 0.6325 | 1.0556 | 0.057* | 0.33 |
H92B | 0.4642 | 0.5826 | 1.0794 | 0.057* | 0.33 |
C93 | 0.4708 (6) | 0.6431 (7) | 0.9310 (7) | 0.0465 (12) | 0.33 |
H93 | 0.4504 | 0.5842 | 0.9348 | 0.056* | 0.33 |
C94 | 0.4305 (7) | 0.7320 (6) | 0.8618 (7) | 0.0445 (11) | 0.33 |
H94A | 0.4504 | 0.7379 | 0.7952 | 0.053* | 0.33 |
H94B | 0.3641 | 0.7267 | 0.8841 | 0.053* | 0.33 |
C95 | 0.4599 (7) | 0.8194 (7) | 0.8590 (7) | 0.0409 (12) | 0.33 |
H95 | 0.4356 | 0.8774 | 0.8101 | 0.049* | 0.33 |
C96 | 0.4318 (8) | 0.8218 (7) | 0.9525 (7) | 0.0472 (11) | 0.33 |
H96A | 0.3654 | 0.8249 | 0.9739 | 0.057* | 0.33 |
H96B | 0.4578 | 0.8791 | 0.9453 | 0.057* | 0.33 |
C97 | 0.5695 (6) | 0.7326 (8) | 0.9977 (7) | 0.0471 (14) | 0.33 |
H97A | 0.5911 | 0.7891 | 0.9962 | 0.057* | 0.33 |
H97B | 0.5930 | 0.6739 | 1.0456 | 0.057* | 0.33 |
C98 | 0.5736 (6) | 0.6506 (7) | 0.8977 (8) | 0.0410 (12) | 0.33 |
H98A | 0.5959 | 0.6571 | 0.8309 | 0.049* | 0.33 |
H98B | 0.5994 | 0.5917 | 0.9425 | 0.049* | 0.33 |
C99 | 0.5638 (6) | 0.8253 (7) | 0.8236 (7) | 0.0375 (14) | 0.33 |
H99A | 0.5846 | 0.8263 | 0.7592 | 0.045* | 0.33 |
H99B | 0.5848 | 0.8853 | 0.8158 | 0.045* | 0.33 |
C50 | 0.6026 (2) | 0.7388 (2) | 0.8981 (2) | 0.0272 (6) | |
N51 | 0.7076 (2) | 0.7443 (2) | 0.8543 (2) | 0.0433 (7) | |
C52 | 0.7318 (8) | 0.8409 (8) | 0.7578 (9) | 0.075 (2) | 0.455 (6) |
H52A | 0.7966 | 0.8534 | 0.7381 | 0.112* | 0.455 (6) |
H52B | 0.6987 | 0.8932 | 0.7684 | 0.112* | 0.455 (6) |
H52C | 0.7154 | 0.8369 | 0.7060 | 0.112* | 0.455 (6) |
C53 | 0.739 (6) | 0.682 (5) | 0.808 (4) | 0.116 (9) | 0.455 (6) |
H53A | 0.6975 | 0.6867 | 0.7709 | 0.174* | 0.455 (6) |
H53B | 0.7409 | 0.6156 | 0.8585 | 0.174* | 0.455 (6) |
H53C | 0.7992 | 0.7030 | 0.7633 | 0.174* | 0.455 (6) |
C54 | 0.7569 (6) | 0.7487 (9) | 0.9125 (8) | 0.0607 (18) | 0.455 (6) |
H54A | 0.7588 | 0.6846 | 0.9675 | 0.091* | 0.455 (6) |
H54B | 0.7278 | 0.7933 | 0.9376 | 0.091* | 0.455 (6) |
H54C | 0.8184 | 0.7713 | 0.8726 | 0.091* | 0.455 (6) |
C55 | 0.7488 (6) | 0.8380 (7) | 0.8260 (7) | 0.075 (2) | 0.545 (6) |
H55A | 0.8143 | 0.8317 | 0.8130 | 0.112* | 0.545 (6) |
H55B | 0.7253 | 0.8542 | 0.8796 | 0.112* | 0.545 (6) |
H55C | 0.7336 | 0.8889 | 0.7669 | 0.112* | 0.545 (6) |
C56 | 0.740 (5) | 0.712 (4) | 0.779 (3) | 0.116 (9) | 0.545 (6) |
H56A | 0.8051 | 0.7039 | 0.7666 | 0.174* | 0.545 (6) |
H56B | 0.7250 | 0.7604 | 0.7190 | 0.174* | 0.545 (6) |
H56C | 0.7107 | 0.6509 | 0.8030 | 0.174* | 0.545 (6) |
C57 | 0.7550 (5) | 0.6742 (8) | 0.9353 (6) | 0.0607 (18) | 0.545 (6) |
H57A | 0.7380 | 0.6078 | 0.9586 | 0.091* | 0.545 (6) |
H57B | 0.7363 | 0.6889 | 0.9902 | 0.091* | 0.545 (6) |
H57C | 0.8204 | 0.6821 | 0.9080 | 0.091* | 0.545 (6) |
Si1 | 0.83438 (4) | 0.00022 (4) | 0.49345 (5) | 0.01540 (16) | |
Si2 | 0.98908 (4) | 0.12550 (4) | 0.31355 (5) | 0.01513 (16) | |
Si3 | 1.04679 (4) | 0.18139 (4) | 0.45071 (5) | 0.01549 (16) | |
Si4 | 0.88821 (4) | 0.05645 (4) | 0.63026 (5) | 0.01530 (16) | |
O1 | 0.82257 (12) | 0.09004 (13) | 0.70369 (13) | 0.0211 (4) | |
O2 | 0.83201 (13) | 0.02394 (14) | 0.57970 (14) | 0.0237 (4) | |
O3 | 0.87266 (13) | −0.10566 (12) | 0.51595 (14) | 0.0218 (4) | |
O4 | 0.73191 (12) | 0.00175 (14) | 0.48772 (14) | 0.0224 (4) | |
H4 | 0.6978 | 0.0243 | 0.5231 | 0.027* | |
O5 | 0.89129 (12) | 0.07994 (13) | 0.38886 (13) | 0.0218 (4) | |
O6 | 1.05351 (13) | 0.03611 (12) | 0.31381 (13) | 0.0210 (4) | |
O7 | 0.97992 (13) | 0.19821 (12) | 0.20719 (13) | 0.0210 (4) | |
O8 | 1.02992 (13) | 0.17834 (12) | 0.35807 (13) | 0.0209 (4) | |
O9 | 1.07315 (13) | 0.28655 (12) | 0.42231 (13) | 0.0212 (4) | |
O10 | 0.95671 (13) | 0.14254 (13) | 0.54122 (13) | 0.0228 (4) | |
O21 | 0.15723 (14) | 0.74214 (12) | 0.30518 (15) | 0.0299 (4) | |
H21D | 0.1618 | 0.7972 | 0.2985 | 0.036* | |
H21E | 0.1150 | 0.7128 | 0.3553 | 0.036* | |
O22 | 0.06433 (15) | 0.42982 (12) | 0.24943 (15) | 0.0315 (5) | |
H22D | 0.0638 | 0.3893 | 0.3073 | 0.038* | |
H22E | 0.0357 | 0.4781 | 0.2505 | 0.038* | |
O23 | 0.02431 (15) | 0.63275 (14) | 0.47239 (15) | 0.0294 (4) | |
H23D | −0.0059 | 0.6602 | 0.5046 | 0.035* | |
H23E | 0.0395 | 0.5788 | 0.5120 | 0.035* | |
O24 | 0.00855 (18) | 0.38233 (14) | 0.13337 (16) | 0.0370 (5) | |
H24D | 0.0040 | 0.3223 | 0.1589 | 0.044* | |
H24E | 0.0209 | 0.3952 | 0.1730 | 0.044* | |
O25 | 0.07021 (17) | 0.17180 (16) | 0.05214 (15) | 0.0357 (5) | |
H25D | 0.0436 | 0.1776 | 0.1024 | 0.043* | |
H25E | 0.1119 | 0.1322 | 0.0653 | 0.043* | |
O26 | 0.82267 (15) | 0.22182 (16) | 0.15971 (16) | 0.0341 (5) | |
H26D | 0.8633 | 0.2086 | 0.1883 | 0.041* | |
H26E | 0.8444 | 0.2171 | 0.1081 | 0.041* | |
O27 | 0.86336 (17) | 0.65388 (16) | 0.11203 (16) | 0.0385 (5) | |
H27D | 0.8653 | 0.6108 | 0.0959 | 0.046* | |
H27E | 0.8813 | 0.7056 | 0.0607 | 0.046* | |
O28 | 0.88650 (18) | 0.51510 (16) | 0.05309 (17) | 0.0421 (6) | |
H28D | 0.9152 | 0.5443 | −0.0062 | 0.050* | |
H28E | 0.9201 | 0.4728 | 0.0834 | 0.050* | |
O29 | 0.39883 (16) | 0.93926 (19) | 0.4037 (2) | 0.0441 (6) | |
H29D | 0.3948 | 0.9403 | 0.3528 | 0.053* | |
H29E | 0.4385 | 0.9794 | 0.3871 | 0.053* | |
O30 | 0.2052 (2) | 0.5585 (2) | 0.1336 (2) | 0.0524 (7) | |
H30D | 0.2172 | 0.5430 | 0.0889 | 0.063* | |
H30E | 0.1870 | 0.6154 | 0.1114 | 0.063* | |
O31 | 0.35432 (17) | 0.9228 (2) | 0.2638 (2) | 0.0499 (6) | |
H31D | 0.3573 | 0.8660 | 0.2727 | 0.060* | |
H31E | 0.2998 | 0.9377 | 0.2748 | 0.060* | |
O32 | 0.35441 (17) | 0.17892 (18) | 0.42222 (19) | 0.0433 (6) | |
H32D | 0.3197 | 0.2239 | 0.4232 | 0.052* | |
H32E | 0.3251 | 0.1271 | 0.4586 | 0.052* | |
O33 | 0.23910 (19) | 0.32786 (18) | 0.4150 (2) | 0.0552 (8) | |
H33D | 0.2111 | 0.3433 | 0.4586 | 0.066* | |
H33E | 0.2013 | 0.3082 | 0.4005 | 0.066* | |
O34 | 0.31854 (18) | 0.49364 (19) | 0.2500 (2) | 0.0556 (7) | |
H34D | 0.2820 | 0.5194 | 0.2157 | 0.067* | |
H34E | 0.2927 | 0.4461 | 0.3020 | 0.067* | |
O35 | 0.30247 (19) | 0.6179 (2) | 0.3288 (2) | 0.0527 (7) | |
H35D | 0.2595 | 0.6566 | 0.3230 | 0.063* | |
H35E | 0.3087 | 0.5976 | 0.2883 | 0.063* | |
O36 | 0.9736 (2) | 0.60024 (18) | 0.2322 (2) | 0.0564 (8) | |
H36D | 1.0249 | 0.6228 | 0.1954 | 0.068* | |
H36E | 0.9373 | 0.6210 | 0.1975 | 0.068* | |
O37 | 0.50648 (17) | 1.0682 (2) | 0.40103 (19) | 0.0477 (6) | |
H37D | 0.5090 | 1.0887 | 0.4392 | 0.057* | |
H37E | 0.5561 | 1.0803 | 0.3582 | 0.057* | |
O38 | 0.1842 (2) | 0.0105 (2) | 0.10472 (18) | 0.0600 (8) | |
H38D | 0.2207 | 0.0517 | 0.0930 | 0.072* | |
H38E | 0.1663 | −0.0235 | 0.1658 | 0.072* | |
O39 | 0.68527 (17) | 0.10889 (17) | 0.31493 (19) | 0.0557 (8) | |
H39D | 0.7037 | 0.0820 | 0.3655 | 0.067* | |
H39E | 0.7261 | 0.1461 | 0.2684 | 0.067* | |
O40 | 0.9194 (2) | 0.55104 (16) | 0.4210 (2) | 0.0628 (9) | |
H40D | 0.9500 | 0.5736 | 0.4406 | 0.075* | |
H40E | 0.9356 | 0.5793 | 0.3595 | 0.075* | |
O41 | 0.76331 (18) | 0.40699 (19) | 0.05717 (17) | 0.0501 (6) | |
H41D | 0.8004 | 0.4413 | 0.0561 | 0.060* | |
H41E | 0.7671 | 0.3505 | 0.1008 | 0.060* | |
O42 | 0.7486 (2) | 0.5623 (2) | 0.5015 (2) | 0.0617 (8) | |
H42D | 0.8034 | 0.5619 | 0.4730 | 0.074* | |
H42E | 0.7352 | 0.5079 | 0.5506 | 0.074* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0348 (18) | 0.0318 (16) | 0.0362 (16) | −0.0002 (13) | −0.0165 (14) | −0.0082 (13) |
C2 | 0.0323 (19) | 0.0378 (18) | 0.056 (2) | 0.0059 (14) | −0.0100 (16) | −0.0185 (17) |
C3 | 0.044 (2) | 0.0403 (19) | 0.0360 (18) | −0.0017 (15) | 0.0053 (15) | −0.0129 (15) |
C4 | 0.048 (2) | 0.0364 (19) | 0.046 (2) | −0.0110 (16) | 0.0015 (17) | −0.0064 (16) |
C5 | 0.043 (2) | 0.0280 (16) | 0.054 (2) | −0.0104 (14) | −0.0014 (16) | −0.0204 (15) |
C6 | 0.035 (2) | 0.052 (2) | 0.050 (2) | −0.0135 (15) | −0.0097 (15) | −0.0268 (17) |
C7 | 0.0339 (17) | 0.0225 (14) | 0.0258 (14) | −0.0030 (11) | −0.0115 (12) | −0.0055 (11) |
C8 | 0.059 (2) | 0.0323 (17) | 0.0253 (15) | 0.0110 (15) | −0.0124 (15) | −0.0118 (13) |
C9 | 0.0398 (18) | 0.0220 (14) | 0.0387 (17) | 0.0035 (12) | −0.0094 (14) | −0.0143 (13) |
C10 | 0.0334 (16) | 0.0201 (13) | 0.0268 (14) | 0.0051 (11) | −0.0121 (12) | −0.0104 (11) |
N11 | 0.0413 (16) | 0.0302 (13) | 0.0471 (16) | 0.0124 (11) | −0.0271 (13) | −0.0229 (12) |
C12 | 0.062 (3) | 0.047 (2) | 0.090 (3) | 0.0107 (18) | −0.043 (2) | −0.046 (2) |
C13 | 0.067 (3) | 0.061 (3) | 0.073 (3) | 0.023 (2) | −0.051 (3) | −0.021 (2) |
C14 | 0.033 (2) | 0.076 (3) | 0.062 (2) | −0.0116 (18) | −0.0085 (17) | −0.038 (2) |
C21 | 0.029 (6) | 0.050 (6) | 0.030 (4) | 0.001 (5) | −0.014 (4) | −0.009 (4) |
C22 | 0.050 (7) | 0.041 (7) | 0.038 (5) | 0.022 (4) | −0.018 (5) | −0.020 (5) |
C23 | 0.047 (7) | 0.039 (5) | 0.036 (5) | 0.028 (5) | −0.026 (4) | −0.017 (4) |
C24 | 0.021 (7) | 0.100 (9) | 0.033 (5) | −0.002 (6) | −0.003 (5) | −0.019 (5) |
C25 | 0.031 (8) | 0.051 (6) | 0.048 (6) | −0.007 (6) | −0.002 (6) | −0.008 (4) |
C26 | 0.043 (6) | 0.051 (8) | 0.050 (8) | −0.003 (5) | −0.024 (5) | −0.017 (6) |
C27 | 0.022 (3) | 0.034 (4) | 0.037 (3) | 0.000 (2) | −0.005 (3) | −0.017 (3) |
C28 | 0.033 (4) | 0.025 (3) | 0.039 (4) | 0.010 (2) | −0.018 (3) | −0.014 (3) |
C29 | 0.035 (4) | 0.029 (3) | 0.039 (4) | −0.014 (3) | −0.016 (3) | 0.004 (3) |
C71 | 0.023 (5) | 0.018 (4) | 0.032 (3) | 0.001 (3) | −0.006 (3) | −0.007 (3) |
C72 | 0.031 (5) | 0.030 (4) | 0.053 (7) | 0.015 (3) | −0.025 (4) | −0.012 (4) |
C73 | 0.026 (6) | 0.051 (5) | 0.039 (4) | 0.001 (4) | −0.010 (4) | −0.026 (4) |
C74 | 0.021 (6) | 0.044 (5) | 0.032 (4) | −0.003 (5) | 0.000 (4) | −0.014 (3) |
C75 | 0.031 (5) | 0.026 (4) | 0.029 (5) | −0.011 (3) | −0.010 (3) | −0.006 (3) |
C76 | 0.029 (5) | 0.031 (4) | 0.025 (3) | −0.003 (4) | −0.013 (4) | −0.001 (3) |
C77 | 0.018 (3) | 0.021 (3) | 0.033 (3) | −0.0038 (19) | −0.007 (2) | −0.006 (2) |
C78 | 0.031 (3) | 0.030 (3) | 0.025 (3) | 0.006 (2) | −0.011 (2) | −0.013 (2) |
C79 | 0.029 (3) | 0.019 (2) | 0.032 (3) | −0.001 (2) | −0.013 (2) | −0.013 (2) |
C30 | 0.0198 (14) | 0.0158 (12) | 0.0303 (14) | 0.0022 (10) | −0.0132 (11) | −0.0076 (11) |
N31 | 0.0281 (14) | 0.0247 (12) | 0.0514 (16) | 0.0093 (10) | −0.0250 (12) | −0.0196 (12) |
C32 | 0.051 (8) | 0.039 (5) | 0.100 (11) | 0.004 (4) | −0.051 (8) | −0.026 (7) |
C33 | 0.034 (4) | 0.042 (6) | 0.074 (6) | 0.014 (4) | −0.020 (4) | −0.032 (5) |
C34 | 0.051 (5) | 0.049 (6) | 0.055 (5) | 0.013 (4) | −0.037 (4) | −0.007 (4) |
C35 | 0.030 (8) | 0.076 (9) | 0.083 (11) | −0.010 (6) | −0.034 (8) | −0.024 (9) |
C36 | 0.052 (8) | 0.051 (8) | 0.110 (13) | 0.039 (7) | −0.058 (9) | −0.061 (9) |
C37 | 0.063 (7) | 0.068 (10) | 0.055 (6) | 0.034 (7) | −0.042 (5) | −0.028 (6) |
C41 | 0.040 (3) | 0.054 (3) | 0.046 (3) | −0.006 (2) | −0.017 (2) | −0.015 (2) |
C42 | 0.043 (3) | 0.044 (2) | 0.041 (2) | −0.004 (2) | −0.011 (2) | −0.007 (2) |
C43 | 0.046 (3) | 0.038 (2) | 0.053 (3) | 0.009 (2) | −0.020 (2) | −0.017 (2) |
C44 | 0.045 (2) | 0.038 (2) | 0.039 (2) | 0.0010 (18) | −0.0106 (18) | −0.0098 (17) |
C45 | 0.034 (3) | 0.036 (2) | 0.042 (3) | −0.001 (2) | −0.010 (2) | −0.010 (2) |
C46 | 0.038 (3) | 0.051 (2) | 0.051 (3) | 0.004 (2) | −0.015 (2) | −0.022 (2) |
C47 | 0.040 (2) | 0.065 (4) | 0.044 (3) | −0.005 (2) | −0.016 (2) | −0.027 (3) |
C48 | 0.044 (2) | 0.036 (3) | 0.052 (3) | −0.0015 (19) | −0.0196 (19) | −0.024 (2) |
C49 | 0.036 (2) | 0.032 (2) | 0.030 (3) | 0.0027 (19) | −0.0122 (19) | −0.002 (2) |
C81 | 0.040 (3) | 0.054 (3) | 0.046 (3) | −0.006 (2) | −0.017 (2) | −0.015 (2) |
C82 | 0.043 (3) | 0.044 (2) | 0.041 (2) | −0.004 (2) | −0.011 (2) | −0.007 (2) |
C83 | 0.046 (3) | 0.038 (2) | 0.053 (3) | 0.009 (2) | −0.020 (2) | −0.017 (2) |
C84 | 0.045 (2) | 0.038 (2) | 0.039 (2) | 0.0010 (18) | −0.0106 (18) | −0.0098 (17) |
C85 | 0.034 (3) | 0.036 (2) | 0.042 (3) | −0.001 (2) | −0.010 (2) | −0.010 (2) |
C86 | 0.038 (3) | 0.051 (2) | 0.051 (3) | 0.004 (2) | −0.015 (2) | −0.022 (2) |
C87 | 0.040 (2) | 0.065 (4) | 0.044 (3) | −0.005 (2) | −0.016 (2) | −0.027 (3) |
C88 | 0.044 (2) | 0.036 (3) | 0.052 (3) | −0.0015 (19) | −0.0196 (19) | −0.024 (2) |
C89 | 0.036 (2) | 0.032 (2) | 0.030 (3) | 0.0027 (19) | −0.0122 (19) | −0.002 (2) |
C91 | 0.040 (3) | 0.054 (3) | 0.046 (3) | −0.006 (2) | −0.017 (2) | −0.015 (2) |
C92 | 0.043 (3) | 0.044 (2) | 0.041 (2) | −0.004 (2) | −0.011 (2) | −0.007 (2) |
C93 | 0.046 (3) | 0.038 (2) | 0.053 (3) | 0.009 (2) | −0.020 (2) | −0.017 (2) |
C94 | 0.045 (2) | 0.038 (2) | 0.039 (2) | 0.0010 (18) | −0.0106 (18) | −0.0098 (17) |
C95 | 0.034 (3) | 0.036 (2) | 0.042 (3) | −0.001 (2) | −0.010 (2) | −0.010 (2) |
C96 | 0.038 (3) | 0.051 (2) | 0.051 (3) | 0.004 (2) | −0.015 (2) | −0.022 (2) |
C97 | 0.040 (2) | 0.065 (4) | 0.044 (3) | −0.005 (2) | −0.016 (2) | −0.027 (3) |
C98 | 0.044 (2) | 0.036 (3) | 0.052 (3) | −0.0015 (19) | −0.0196 (19) | −0.024 (2) |
C99 | 0.036 (2) | 0.032 (2) | 0.030 (3) | 0.0027 (19) | −0.0122 (19) | −0.002 (2) |
C50 | 0.0272 (16) | 0.0206 (13) | 0.0263 (14) | −0.0019 (11) | −0.0078 (11) | −0.0045 (11) |
N51 | 0.0278 (16) | 0.0516 (18) | 0.0387 (15) | −0.0125 (12) | −0.0027 (12) | −0.0127 (13) |
C52 | 0.056 (4) | 0.061 (4) | 0.074 (5) | −0.036 (3) | −0.002 (4) | −0.006 (4) |
C53 | 0.063 (4) | 0.21 (3) | 0.11 (2) | 0.041 (19) | −0.013 (18) | −0.118 (19) |
C54 | 0.035 (3) | 0.093 (5) | 0.055 (4) | 0.002 (4) | −0.024 (3) | −0.029 (4) |
C55 | 0.056 (4) | 0.061 (4) | 0.074 (5) | −0.036 (3) | −0.002 (4) | −0.006 (4) |
C56 | 0.063 (4) | 0.21 (3) | 0.11 (2) | 0.041 (19) | −0.013 (18) | −0.118 (19) |
C57 | 0.035 (3) | 0.093 (5) | 0.055 (4) | 0.002 (4) | −0.024 (3) | −0.029 (4) |
Si1 | 0.0135 (3) | 0.0129 (3) | 0.0186 (3) | −0.0009 (2) | −0.0067 (2) | −0.0050 (3) |
Si2 | 0.0170 (4) | 0.0101 (3) | 0.0164 (3) | −0.0008 (2) | −0.0077 (3) | −0.0029 (2) |
Si3 | 0.0182 (4) | 0.0089 (3) | 0.0178 (3) | −0.0023 (2) | −0.0071 (3) | −0.0032 (2) |
Si4 | 0.0151 (3) | 0.0125 (3) | 0.0175 (3) | −0.0001 (2) | −0.0056 (2) | −0.0057 (3) |
O1 | 0.0208 (10) | 0.0205 (9) | 0.0222 (9) | 0.0025 (7) | −0.0067 (7) | −0.0102 (7) |
O2 | 0.0200 (10) | 0.0274 (10) | 0.0288 (10) | 0.0000 (7) | −0.0096 (8) | −0.0153 (8) |
O3 | 0.0218 (10) | 0.0138 (8) | 0.0296 (10) | 0.0004 (7) | −0.0129 (8) | −0.0068 (7) |
O4 | 0.0161 (9) | 0.0267 (10) | 0.0261 (9) | −0.0008 (7) | −0.0086 (7) | −0.0118 (8) |
O5 | 0.0190 (10) | 0.0175 (9) | 0.0226 (9) | −0.0033 (7) | −0.0064 (7) | −0.0035 (7) |
O6 | 0.0238 (10) | 0.0147 (8) | 0.0243 (9) | 0.0036 (7) | −0.0110 (7) | −0.0075 (7) |
O7 | 0.0270 (10) | 0.0147 (8) | 0.0192 (9) | −0.0004 (7) | −0.0110 (7) | −0.0036 (7) |
O8 | 0.0258 (10) | 0.0156 (8) | 0.0214 (9) | −0.0033 (7) | −0.0094 (7) | −0.0063 (7) |
O9 | 0.0286 (10) | 0.0109 (8) | 0.0250 (9) | −0.0037 (7) | −0.0109 (8) | −0.0061 (7) |
O10 | 0.0252 (10) | 0.0156 (8) | 0.0232 (9) | −0.0034 (7) | −0.0033 (7) | −0.0068 (7) |
O21 | 0.0327 (12) | 0.0231 (10) | 0.0355 (11) | 0.0009 (8) | −0.0074 (9) | −0.0163 (9) |
O22 | 0.0427 (13) | 0.0149 (9) | 0.0315 (11) | −0.0020 (8) | −0.0184 (9) | −0.0016 (8) |
O23 | 0.0371 (12) | 0.0172 (9) | 0.0351 (11) | 0.0000 (8) | −0.0117 (9) | −0.0120 (8) |
O24 | 0.0686 (16) | 0.0134 (9) | 0.0278 (11) | −0.0035 (9) | −0.0201 (11) | −0.0039 (8) |
O25 | 0.0517 (15) | 0.0285 (11) | 0.0254 (10) | 0.0047 (9) | −0.0138 (10) | −0.0109 (9) |
O26 | 0.0323 (12) | 0.0369 (12) | 0.0324 (11) | 0.0007 (9) | −0.0176 (9) | −0.0108 (10) |
O27 | 0.0511 (15) | 0.0284 (11) | 0.0298 (11) | 0.0020 (10) | −0.0088 (10) | −0.0108 (9) |
O28 | 0.0603 (16) | 0.0232 (11) | 0.0328 (12) | 0.0004 (10) | −0.0111 (11) | −0.0067 (9) |
O29 | 0.0279 (13) | 0.0510 (15) | 0.0572 (15) | 0.0001 (10) | −0.0128 (11) | −0.0276 (13) |
O30 | 0.0531 (17) | 0.0415 (14) | 0.0577 (16) | −0.0053 (12) | −0.0209 (14) | −0.0148 (12) |
O31 | 0.0249 (13) | 0.0701 (18) | 0.0535 (15) | 0.0013 (11) | −0.0088 (11) | −0.0293 (15) |
O32 | 0.0348 (13) | 0.0381 (13) | 0.0508 (14) | −0.0139 (10) | −0.0054 (11) | −0.0163 (12) |
O33 | 0.0579 (18) | 0.0279 (12) | 0.077 (2) | −0.0122 (11) | −0.0455 (16) | −0.0045 (12) |
O34 | 0.0402 (15) | 0.0357 (14) | 0.0720 (19) | −0.0039 (11) | −0.0193 (13) | −0.0078 (13) |
O35 | 0.0388 (15) | 0.0450 (15) | 0.0634 (18) | 0.0138 (11) | −0.0154 (13) | −0.0199 (13) |
O36 | 0.0665 (19) | 0.0266 (12) | 0.088 (2) | 0.0100 (12) | −0.0523 (17) | −0.0205 (13) |
O37 | 0.0336 (14) | 0.0601 (17) | 0.0403 (13) | −0.0052 (11) | −0.0109 (10) | −0.0148 (12) |
O38 | 0.087 (2) | 0.0511 (17) | 0.0248 (12) | 0.0139 (15) | −0.0156 (13) | −0.0076 (11) |
O39 | 0.0342 (14) | 0.0729 (19) | 0.0391 (13) | −0.0136 (12) | −0.0154 (11) | −0.0042 (13) |
O40 | 0.090 (2) | 0.0280 (12) | 0.088 (2) | −0.0029 (13) | −0.067 (2) | −0.0154 (13) |
O41 | 0.0416 (15) | 0.0417 (14) | 0.0559 (16) | −0.0056 (11) | −0.0142 (12) | −0.0126 (12) |
O42 | 0.064 (2) | 0.0496 (16) | 0.0714 (19) | −0.0003 (14) | −0.0262 (16) | −0.0234 (15) |
C1—C2 | 1.522 (5) | C49—H49A | 0.9900 |
C1—C6 | 1.529 (5) | C49—H49B | 0.9900 |
C1—C7 | 1.532 (4) | C81—C82 | 1.511 (9) |
C1—H1 | 1.0000 | C81—C86 | 1.526 (9) |
C2—C3 | 1.537 (5) | C81—C87 | 1.545 (9) |
C2—H2A | 0.9900 | C81—H81 | 1.0000 |
C2—H2B | 0.9900 | C82—C83 | 1.531 (9) |
C3—C4 | 1.524 (5) | C82—H82A | 0.9900 |
C3—C8 | 1.527 (5) | C82—H82B | 0.9900 |
C3—H3 | 1.0000 | C83—C84 | 1.527 (8) |
C4—C5 | 1.520 (5) | C83—C88 | 1.548 (9) |
C4—H4A | 0.9900 | C83—H83 | 1.0000 |
C4—H4B | 0.9900 | C84—C85 | 1.511 (8) |
C5—C6 | 1.493 (5) | C84—H84A | 0.9900 |
C5—C9 | 1.546 (5) | C84—H84B | 0.9900 |
C5—H5 | 1.0000 | C85—C86 | 1.478 (9) |
C6—H6A | 0.9900 | C85—C89 | 1.538 (8) |
C6—H6B | 0.9900 | C85—H85 | 1.0000 |
C7—C10 | 1.532 (4) | C86—H86A | 0.9900 |
C7—H7A | 0.9900 | C86—H86B | 0.9900 |
C7—H7B | 0.9900 | C87—C50 | 1.480 (11) |
C8—C10 | 1.541 (4) | C87—H87A | 0.9900 |
C8—H8A | 0.9900 | C87—H87B | 0.9900 |
C8—H8B | 0.9900 | C88—C50 | 1.599 (9) |
C9—C10 | 1.525 (4) | C88—H88A | 0.9900 |
C9—H9A | 0.9900 | C88—H88B | 0.9900 |
C9—H9B | 0.9900 | C89—C50 | 1.487 (9) |
C10—N11 | 1.578 (4) | C89—H89A | 0.9900 |
N11—C14 | 1.482 (5) | C89—H89B | 0.9900 |
N11—C12 | 1.490 (4) | C91—C92 | 1.519 (9) |
N11—C13 | 1.504 (4) | C91—C96 | 1.541 (9) |
C12—H12A | 0.9800 | C91—C97 | 1.546 (9) |
C12—H12B | 0.9800 | C91—H91 | 1.0000 |
C12—H12C | 0.9800 | C92—C93 | 1.539 (9) |
C13—H13A | 0.9800 | C92—H92A | 0.9900 |
C13—H13B | 0.9800 | C92—H92B | 0.9900 |
C13—H13C | 0.9800 | C93—C94 | 1.515 (8) |
C14—H14A | 0.9800 | C93—C98 | 1.531 (9) |
C14—H14B | 0.9800 | C93—H93 | 1.0000 |
C14—H14C | 0.9800 | C94—C95 | 1.500 (8) |
C21—C26 | 1.529 (17) | C94—H94A | 0.9900 |
C21—C27 | 1.534 (11) | C94—H94B | 0.9900 |
C21—C22 | 1.555 (15) | C95—C96 | 1.465 (9) |
C21—H21 | 1.0000 | C95—C99 | 1.546 (8) |
C22—C23 | 1.484 (17) | C95—H95 | 1.0000 |
C22—H22A | 0.9900 | C96—H96A | 0.9900 |
C22—H22B | 0.9900 | C96—H96B | 0.9900 |
C23—C24 | 1.54 (2) | C97—C50 | 1.499 (10) |
C23—C28 | 1.556 (12) | C97—H97A | 0.9900 |
C23—H23 | 1.0000 | C97—H97B | 0.9900 |
C24—C25 | 1.51 (3) | C98—C50 | 1.537 (9) |
C24—H24A | 0.9900 | C98—H98A | 0.9900 |
C24—H24B | 0.9900 | C98—H98B | 0.9900 |
C25—C26 | 1.48 (2) | C99—C50 | 1.523 (9) |
C25—C29 | 1.535 (16) | C99—H99A | 0.9900 |
C25—H25 | 1.0000 | C99—H99B | 0.9900 |
C26—H26A | 0.9900 | C50—N51 | 1.572 (4) |
C26—H26B | 0.9900 | N51—C54 | 1.416 (10) |
C27—C30 | 1.497 (7) | N51—C53 | 1.47 (9) |
C27—H27A | 0.9900 | N51—C56 | 1.47 (7) |
C27—H27B | 0.9900 | N51—C55 | 1.506 (9) |
C28—C30 | 1.584 (7) | N51—C52 | 1.556 (10) |
C28—H28A | 0.9900 | N51—C57 | 1.566 (8) |
C28—H28B | 0.9900 | C52—H52A | 0.9800 |
C29—C30 | 1.535 (7) | C52—H52B | 0.9800 |
C29—H29A | 0.9900 | C52—H52C | 0.9800 |
C29—H29B | 0.9900 | C53—H53A | 0.9800 |
C71—C76 | 1.514 (12) | C53—H53B | 0.9800 |
C71—C72 | 1.517 (15) | C53—H53C | 0.9800 |
C71—C77 | 1.559 (10) | C54—H54A | 0.9800 |
C71—H71 | 1.0000 | C54—H54B | 0.9800 |
C72—C73 | 1.519 (17) | C54—H54C | 0.9800 |
C72—H72A | 0.9900 | C55—H55A | 0.9800 |
C72—H72B | 0.9900 | C55—H55B | 0.9800 |
C73—C74 | 1.507 (19) | C55—H55C | 0.9800 |
C73—C78 | 1.546 (10) | C56—H56A | 0.9800 |
C73—H73 | 1.0000 | C56—H56B | 0.9800 |
C74—C75 | 1.525 (16) | C56—H56C | 0.9800 |
C74—H74A | 0.9900 | C57—H57A | 0.9800 |
C74—H74B | 0.9900 | C57—H57B | 0.9800 |
C75—C79 | 1.541 (10) | C57—H57C | 0.9800 |
C75—C76 | 1.544 (11) | Si1—O2 | 1.607 (2) |
C75—H75 | 1.0000 | Si1—O5 | 1.6079 (18) |
C76—H76A | 0.9900 | Si1—O3 | 1.6092 (18) |
C76—H76B | 0.9900 | Si1—O4 | 1.6239 (18) |
C77—C30 | 1.529 (6) | Si2—O7 | 1.5801 (18) |
C77—H77A | 0.9900 | Si2—O6 | 1.6252 (18) |
C77—H77B | 0.9900 | Si2—O8 | 1.6284 (18) |
C78—C30 | 1.494 (6) | Si2—O5 | 1.6322 (19) |
C78—H78A | 0.9900 | Si3—O9 | 1.5845 (17) |
C78—H78B | 0.9900 | Si3—O10 | 1.6203 (19) |
C79—C30 | 1.566 (5) | Si3—O8 | 1.6258 (19) |
C79—H79A | 0.9900 | Si3—O3i | 1.6377 (18) |
C79—H79B | 0.9900 | Si4—O1 | 1.5783 (19) |
C30—N31 | 1.578 (3) | Si4—O6i | 1.6273 (18) |
N31—C36 | 1.471 (9) | Si4—O10 | 1.6290 (18) |
N31—C34 | 1.475 (9) | Si4—O2 | 1.6369 (19) |
N31—C32 | 1.476 (13) | O3—Si3i | 1.6377 (18) |
N31—C35 | 1.513 (18) | O4—H4 | 0.8400 |
N31—C37 | 1.535 (12) | O6—Si4i | 1.6274 (18) |
N31—C33 | 1.556 (9) | O21—H21D | 0.8401 |
C32—H32A | 0.9800 | O21—H21E | 0.8400 |
C32—H32B | 0.9800 | O22—H22D | 0.8400 |
C32—H32C | 0.9800 | O22—H22E | 0.8400 |
C33—H33A | 0.9800 | O23—H23D | 0.8400 |
C33—H33B | 0.9800 | O23—H23E | 0.8400 |
C33—H33C | 0.9800 | O24—H24D | 0.8400 |
C34—H34A | 0.9800 | O24—H24E | 0.8400 |
C34—H34B | 0.9800 | O25—H25D | 0.8400 |
C34—H34C | 0.9800 | O25—H25E | 0.8400 |
C35—H35A | 0.9800 | O26—H26D | 0.8400 |
C35—H35B | 0.9800 | O26—H26E | 0.8401 |
C35—H35C | 0.9800 | O27—H27D | 0.8399 |
C36—H36A | 0.9800 | O27—H27E | 0.8401 |
C36—H36B | 0.9800 | O28—H28D | 0.8400 |
C36—H36C | 0.9800 | O28—H28E | 0.8399 |
C37—H37A | 0.9800 | O29—H29D | 0.8400 |
C37—H37B | 0.9800 | O29—H29E | 0.8400 |
C37—H37C | 0.9800 | O30—H30D | 0.8399 |
C41—C42 | 1.521 (9) | O30—H30E | 0.8400 |
C41—C46 | 1.523 (9) | O31—H31D | 0.8400 |
C41—C47 | 1.542 (9) | O31—H31E | 0.8401 |
C41—H41 | 1.0000 | O32—H32D | 0.8400 |
C42—C43 | 1.546 (9) | O32—H32E | 0.8400 |
C42—H42A | 0.9900 | O33—H33D | 0.8400 |
C42—H42B | 0.9900 | O33—H33E | 0.8399 |
C43—C44 | 1.526 (8) | O34—H34D | 0.8400 |
C43—C48 | 1.540 (9) | O34—H34E | 0.8400 |
C43—H43 | 1.0000 | O35—H35D | 0.8400 |
C44—C45 | 1.500 (8) | O35—H35E | 0.8400 |
C44—H44A | 0.9900 | O36—H36D | 0.8399 |
C44—H44B | 0.9900 | O36—H36E | 0.8400 |
C45—C46 | 1.471 (9) | O37—H37D | 0.8399 |
C45—C49 | 1.529 (8) | O37—H37E | 0.8399 |
C45—H45 | 1.0000 | O38—H38D | 0.8400 |
C46—H46A | 0.9900 | O38—H38E | 0.8400 |
C46—H46B | 0.9900 | O39—H39D | 0.8400 |
C47—C50 | 1.650 (9) | O39—H39E | 0.8400 |
C47—H47A | 0.9900 | O40—H40D | 0.8400 |
C47—H47B | 0.9900 | O40—H40E | 0.8400 |
C48—C50 | 1.474 (9) | O41—H41D | 0.8400 |
C48—H48A | 0.9900 | O41—H41E | 0.8400 |
C48—H48B | 0.9900 | O42—H42D | 0.8400 |
C49—C50 | 1.538 (9) | O42—H42E | 0.8400 |
C2—C1—C6 | 110.0 (3) | C43—C44—H44B | 110.1 |
C2—C1—C7 | 109.7 (3) | H44A—C44—H44B | 108.4 |
C6—C1—C7 | 109.3 (3) | C46—C45—C44 | 113.3 (8) |
C2—C1—H1 | 109.3 | C46—C45—C49 | 111.2 (7) |
C6—C1—H1 | 109.3 | C44—C45—C49 | 108.8 (7) |
C7—C1—H1 | 109.3 | C46—C45—H45 | 107.8 |
C1—C2—C3 | 108.9 (3) | C44—C45—H45 | 107.8 |
C1—C2—H2A | 109.9 | C49—C45—H45 | 107.8 |
C3—C2—H2A | 109.9 | C45—C46—C41 | 107.9 (7) |
C1—C2—H2B | 109.9 | C45—C46—H46A | 110.1 |
C3—C2—H2B | 109.9 | C41—C46—H46A | 110.1 |
H2A—C2—H2B | 108.3 | C45—C46—H46B | 110.1 |
C4—C3—C8 | 110.4 (3) | C41—C46—H46B | 110.1 |
C4—C3—C2 | 109.5 (3) | H46A—C46—H46B | 108.4 |
C8—C3—C2 | 108.8 (3) | C41—C47—C50 | 109.3 (6) |
C4—C3—H3 | 109.4 | C41—C47—H47A | 109.8 |
C8—C3—H3 | 109.4 | C50—C47—H47A | 109.8 |
C2—C3—H3 | 109.4 | C41—C47—H47B | 109.8 |
C5—C4—C3 | 109.2 (3) | C50—C47—H47B | 109.8 |
C5—C4—H4A | 109.8 | H47A—C47—H47B | 108.3 |
C3—C4—H4A | 109.8 | C50—C48—C43 | 112.8 (6) |
C5—C4—H4B | 109.8 | C50—C48—H48A | 109.0 |
C3—C4—H4B | 109.8 | C43—C48—H48A | 109.0 |
H4A—C4—H4B | 108.3 | C50—C48—H48B | 109.0 |
C6—C5—C4 | 110.7 (3) | C43—C48—H48B | 109.0 |
C6—C5—C9 | 109.9 (3) | H48A—C48—H48B | 107.8 |
C4—C5—C9 | 108.8 (3) | C45—C49—C50 | 111.7 (6) |
C6—C5—H5 | 109.1 | C45—C49—H49A | 109.3 |
C4—C5—H5 | 109.1 | C50—C49—H49A | 109.3 |
C9—C5—H5 | 109.1 | C45—C49—H49B | 109.3 |
C5—C6—C1 | 109.6 (3) | C50—C49—H49B | 109.3 |
C5—C6—H6A | 109.7 | H49A—C49—H49B | 107.9 |
C1—C6—H6A | 109.7 | C82—C81—C86 | 112.5 (8) |
C5—C6—H6B | 109.7 | C82—C81—C87 | 107.8 (8) |
C1—C6—H6B | 109.7 | C86—C81—C87 | 107.6 (8) |
H6A—C6—H6B | 108.2 | C82—C81—H81 | 109.6 |
C10—C7—C1 | 109.0 (2) | C86—C81—H81 | 109.6 |
C10—C7—H7A | 109.9 | C87—C81—H81 | 109.6 |
C1—C7—H7A | 109.9 | C81—C82—C83 | 110.4 (7) |
C10—C7—H7B | 109.9 | C81—C82—H82A | 109.6 |
C1—C7—H7B | 109.9 | C83—C82—H82A | 109.6 |
H7A—C7—H7B | 108.3 | C81—C82—H82B | 109.6 |
C3—C8—C10 | 109.3 (3) | C83—C82—H82B | 109.6 |
C3—C8—H8A | 109.8 | H82A—C82—H82B | 108.1 |
C10—C8—H8A | 109.8 | C84—C83—C82 | 112.2 (7) |
C3—C8—H8B | 109.8 | C84—C83—C88 | 106.8 (7) |
C10—C8—H8B | 109.8 | C82—C83—C88 | 105.9 (7) |
H8A—C8—H8B | 108.3 | C84—C83—H83 | 110.6 |
C10—C9—C5 | 109.1 (3) | C82—C83—H83 | 110.6 |
C10—C9—H9A | 109.9 | C88—C83—H83 | 110.6 |
C5—C9—H9A | 109.9 | C85—C84—C83 | 110.8 (7) |
C10—C9—H9B | 109.9 | C85—C84—H84A | 109.5 |
C5—C9—H9B | 109.9 | C83—C84—H84A | 109.5 |
H9A—C9—H9B | 108.3 | C85—C84—H84B | 109.5 |
C9—C10—C7 | 109.9 (2) | C83—C84—H84B | 109.5 |
C9—C10—C8 | 109.3 (3) | H84A—C84—H84B | 108.1 |
C7—C10—C8 | 108.9 (2) | C86—C85—C84 | 111.5 (7) |
C9—C10—N11 | 109.4 (2) | C86—C85—C89 | 110.8 (7) |
C7—C10—N11 | 109.8 (2) | C84—C85—C89 | 107.4 (7) |
C8—C10—N11 | 109.6 (2) | C86—C85—H85 | 109.0 |
C14—N11—C12 | 108.6 (3) | C84—C85—H85 | 109.0 |
C14—N11—C13 | 108.4 (3) | C89—C85—H85 | 109.0 |
C12—N11—C13 | 105.4 (3) | C85—C86—C81 | 109.5 (7) |
C14—N11—C10 | 111.7 (2) | C85—C86—H86A | 109.8 |
C12—N11—C10 | 110.7 (3) | C81—C86—H86A | 109.8 |
C13—N11—C10 | 111.8 (3) | C85—C86—H86B | 109.8 |
N11—C12—H12A | 109.5 | C81—C86—H86B | 109.8 |
N11—C12—H12B | 109.5 | H86A—C86—H86B | 108.2 |
H12A—C12—H12B | 109.5 | C50—C87—C81 | 109.8 (7) |
N11—C12—H12C | 109.5 | C50—C87—H87A | 109.7 |
H12A—C12—H12C | 109.5 | C81—C87—H87A | 109.7 |
H12B—C12—H12C | 109.5 | C50—C87—H87B | 109.7 |
N11—C13—H13A | 109.5 | C81—C87—H87B | 109.7 |
N11—C13—H13B | 109.5 | H87A—C87—H87B | 108.2 |
H13A—C13—H13B | 109.5 | C83—C88—C50 | 108.8 (6) |
N11—C13—H13C | 109.5 | C83—C88—H88A | 109.9 |
H13A—C13—H13C | 109.5 | C50—C88—H88A | 109.9 |
H13B—C13—H13C | 109.5 | C83—C88—H88B | 109.9 |
N11—C14—H14A | 109.5 | C50—C88—H88B | 109.9 |
N11—C14—H14B | 109.5 | H88A—C88—H88B | 108.3 |
H14A—C14—H14B | 109.5 | C50—C89—C85 | 109.3 (6) |
N11—C14—H14C | 109.5 | C50—C89—H89A | 109.8 |
H14A—C14—H14C | 109.5 | C85—C89—H89A | 109.8 |
H14B—C14—H14C | 109.5 | C50—C89—H89B | 109.8 |
C26—C21—C27 | 107.8 (8) | C85—C89—H89B | 109.8 |
C26—C21—C22 | 109.8 (10) | H89A—C89—H89B | 108.3 |
C27—C21—C22 | 110.6 (9) | C92—C91—C96 | 112.2 (7) |
C26—C21—H21 | 109.5 | C92—C91—C97 | 106.5 (8) |
C27—C21—H21 | 109.5 | C96—C91—C97 | 108.4 (8) |
C22—C21—H21 | 109.5 | C92—C91—H91 | 109.9 |
C23—C22—C21 | 109.4 (9) | C96—C91—H91 | 109.9 |
C23—C22—H22A | 109.8 | C97—C91—H91 | 109.9 |
C21—C22—H22A | 109.8 | C91—C92—C93 | 111.9 (7) |
C23—C22—H22B | 109.8 | C91—C92—H92A | 109.2 |
C21—C22—H22B | 109.8 | C93—C92—H92A | 109.2 |
H22A—C22—H22B | 108.2 | C91—C92—H92B | 109.2 |
C22—C23—C24 | 109.6 (11) | C93—C92—H92B | 109.2 |
C22—C23—C28 | 109.4 (9) | H92A—C92—H92B | 107.9 |
C24—C23—C28 | 108.4 (9) | C94—C93—C98 | 110.3 (8) |
C22—C23—H23 | 109.8 | C94—C93—C92 | 106.8 (7) |
C24—C23—H23 | 109.8 | C98—C93—C92 | 108.3 (7) |
C28—C23—H23 | 109.8 | C94—C93—H93 | 110.4 |
C25—C24—C23 | 111.4 (12) | C98—C93—H93 | 110.4 |
C25—C24—H24A | 109.3 | C92—C93—H93 | 110.4 |
C23—C24—H24A | 109.3 | C95—C94—C93 | 109.7 (7) |
C25—C24—H24B | 109.3 | C95—C94—H94A | 109.7 |
C23—C24—H24B | 109.3 | C93—C94—H94A | 109.7 |
H24A—C24—H24B | 108.0 | C95—C94—H94B | 109.7 |
C26—C25—C24 | 109.9 (14) | C93—C94—H94B | 109.7 |
C26—C25—C29 | 112.3 (11) | H94A—C94—H94B | 108.2 |
C24—C25—C29 | 105.9 (14) | C96—C95—C94 | 115.5 (8) |
C26—C25—H25 | 109.5 | C96—C95—C99 | 108.1 (8) |
C24—C25—H25 | 109.5 | C94—C95—C99 | 108.1 (7) |
C29—C25—H25 | 109.5 | C96—C95—H95 | 108.3 |
C25—C26—C21 | 110.2 (12) | C94—C95—H95 | 108.3 |
C25—C26—H26A | 109.6 | C99—C95—H95 | 108.3 |
C21—C26—H26A | 109.6 | C95—C96—C91 | 107.8 (7) |
C25—C26—H26B | 109.6 | C95—C96—H96A | 110.1 |
C21—C26—H26B | 109.6 | C91—C96—H96A | 110.1 |
H26A—C26—H26B | 108.1 | C95—C96—H96B | 110.1 |
C30—C27—C21 | 109.8 (6) | C91—C96—H96B | 110.1 |
C30—C27—H27A | 109.7 | H96A—C96—H96B | 108.5 |
C21—C27—H27A | 109.7 | C50—C97—C91 | 108.8 (7) |
C30—C27—H27B | 109.7 | C50—C97—H97A | 109.9 |
C21—C27—H27B | 109.7 | C91—C97—H97A | 109.9 |
H27A—C27—H27B | 108.2 | C50—C97—H97B | 109.9 |
C23—C28—C30 | 108.3 (6) | C91—C97—H97B | 109.9 |
C23—C28—H28A | 110.0 | H97A—C97—H97B | 108.3 |
C30—C28—H28A | 110.0 | C93—C98—C50 | 109.0 (6) |
C23—C28—H28B | 110.0 | C93—C98—H98A | 109.9 |
C30—C28—H28B | 110.0 | C50—C98—H98A | 109.9 |
H28A—C28—H28B | 108.4 | C93—C98—H98B | 109.9 |
C30—C29—C25 | 109.2 (8) | C50—C98—H98B | 109.9 |
C30—C29—H29A | 109.8 | H98A—C98—H98B | 108.3 |
C25—C29—H29A | 109.8 | C50—C99—C95 | 109.4 (6) |
C30—C29—H29B | 109.8 | C50—C99—H99A | 109.8 |
C25—C29—H29B | 109.8 | C95—C99—H99A | 109.8 |
H29A—C29—H29B | 108.3 | C50—C99—H99B | 109.8 |
C76—C71—C72 | 110.2 (8) | C95—C99—H99B | 109.8 |
C76—C71—C77 | 108.4 (7) | H99A—C99—H99B | 108.2 |
C72—C71—C77 | 108.2 (7) | C48—C50—C87 | 71.3 (6) |
C76—C71—H71 | 110.0 | C48—C50—C89 | 119.6 (5) |
C72—C71—H71 | 110.0 | C87—C50—C89 | 111.8 (6) |
C77—C71—H71 | 110.0 | C48—C50—C97 | 57.3 (6) |
C71—C72—C73 | 110.6 (8) | C87—C50—C97 | 122.2 (6) |
C71—C72—H72A | 109.5 | C89—C50—C97 | 76.7 (6) |
C73—C72—H72A | 109.5 | C48—C50—C99 | 55.3 (6) |
C71—C72—H72B | 109.5 | C89—C50—C99 | 128.8 (5) |
C73—C72—H72B | 109.5 | C97—C50—C99 | 111.4 (6) |
H72A—C72—H72B | 108.1 | C48—C50—C98 | 134.8 (5) |
C74—C73—C72 | 109.7 (9) | C87—C50—C98 | 85.5 (6) |
C74—C73—C78 | 107.1 (8) | C89—C50—C98 | 36.1 (5) |
C72—C73—C78 | 111.2 (9) | C97—C50—C98 | 111.8 (6) |
C74—C73—H73 | 109.6 | C99—C50—C98 | 105.7 (5) |
C72—C73—H73 | 109.6 | C48—C50—C49 | 112.7 (6) |
C78—C73—H73 | 109.6 | C87—C50—C49 | 133.3 (6) |
C73—C74—C75 | 111.1 (10) | C97—C50—C49 | 59.3 (6) |
C73—C74—H74A | 109.4 | C99—C50—C49 | 146.4 (5) |
C75—C74—H74A | 109.4 | C98—C50—C49 | 58.1 (5) |
C73—C74—H74B | 109.4 | C48—C50—N51 | 120.0 (4) |
C75—C74—H74B | 109.4 | C87—C50—N51 | 111.6 (4) |
H74A—C74—H74B | 108.0 | C89—C50—N51 | 114.1 (4) |
C74—C75—C79 | 109.3 (8) | C97—C50—N51 | 115.7 (4) |
C74—C75—C76 | 109.8 (9) | C99—C50—N51 | 107.0 (4) |
C79—C75—C76 | 107.3 (6) | C98—C50—N51 | 104.4 (4) |
C74—C75—H75 | 110.1 | C49—C50—N51 | 105.6 (4) |
C79—C75—H75 | 110.1 | C87—C50—C88 | 109.4 (6) |
C76—C75—H75 | 110.1 | C89—C50—C88 | 107.4 (5) |
C71—C76—C75 | 110.6 (7) | C99—C50—C88 | 91.9 (6) |
C71—C76—H76A | 109.5 | C98—C50—C88 | 142.1 (5) |
C75—C76—H76A | 109.5 | C49—C50—C88 | 88.8 (6) |
C71—C76—H76B | 109.5 | N51—C50—C88 | 101.9 (4) |
C75—C76—H76B | 109.5 | C48—C50—C47 | 106.4 (5) |
H76A—C76—H76B | 108.1 | C89—C50—C47 | 77.2 (6) |
C30—C77—C71 | 109.7 (5) | C97—C50—C47 | 133.7 (5) |
C30—C77—H77A | 109.7 | C99—C50—C47 | 60.8 (5) |
C71—C77—H77A | 109.7 | C98—C50—C47 | 45.6 (5) |
C30—C77—H77B | 109.7 | C49—C50—C47 | 100.7 (5) |
C71—C77—H77B | 109.7 | N51—C50—C47 | 109.8 (4) |
H77A—C77—H77B | 108.2 | C88—C50—C47 | 142.8 (5) |
C30—C78—C73 | 109.4 (6) | C54—N51—C53 | 119 (3) |
C30—C78—H78A | 109.8 | C54—N51—C56 | 127 (3) |
C73—C78—H78A | 109.8 | C54—N51—C55 | 59.7 (6) |
C30—C78—H78B | 109.8 | C53—N51—C55 | 127 (3) |
C73—C78—H78B | 109.8 | C56—N51—C55 | 114 (2) |
H78A—C78—H78B | 108.3 | C54—N51—C52 | 103.5 (7) |
C75—C79—C30 | 108.8 (5) | C53—N51—C52 | 96 (2) |
C75—C79—H79A | 109.9 | C56—N51—C52 | 78 (2) |
C30—C79—H79A | 109.9 | C55—N51—C52 | 45.8 (6) |
C75—C79—H79B | 109.9 | C53—N51—C57 | 87 (3) |
C30—C79—H79B | 109.9 | C56—N51—C57 | 103 (2) |
H79A—C79—H79B | 108.3 | C55—N51—C57 | 99.4 (6) |
C78—C30—C27 | 141.2 (4) | C52—N51—C57 | 136.4 (6) |
C78—C30—C77 | 112.0 (4) | C54—N51—C50 | 114.8 (5) |
C27—C30—C77 | 46.5 (4) | C53—N51—C50 | 112 (3) |
C78—C30—C29 | 58.6 (4) | C56—N51—C50 | 114 (3) |
C27—C30—C29 | 112.1 (4) | C55—N51—C50 | 113.7 (5) |
C77—C30—C29 | 137.8 (4) | C52—N51—C50 | 108.3 (5) |
C78—C30—C79 | 109.3 (4) | C57—N51—C50 | 110.6 (4) |
C27—C30—C79 | 64.1 (3) | N51—C52—H52A | 109.5 |
C77—C30—C79 | 107.7 (3) | N51—C52—H52B | 109.5 |
C29—C30—C79 | 52.6 (4) | N51—C52—H52C | 109.5 |
C78—C30—N31 | 109.2 (3) | N51—C53—H53A | 109.5 |
C27—C30—N31 | 109.0 (3) | N51—C53—H53B | 109.5 |
C77—C30—N31 | 110.3 (3) | N51—C53—H53C | 109.5 |
C29—C30—N31 | 111.5 (3) | N51—C54—H54A | 109.5 |
C79—C30—N31 | 108.3 (3) | N51—C54—H54B | 109.5 |
C78—C30—C28 | 51.2 (4) | N51—C54—H54C | 109.5 |
C27—C30—C28 | 109.2 (4) | N51—C55—H55A | 109.5 |
C77—C30—C28 | 64.8 (3) | N51—C55—H55B | 109.5 |
C29—C30—C28 | 106.7 (5) | N51—C55—H55C | 109.5 |
C79—C30—C28 | 142.8 (4) | N51—C56—H56A | 109.5 |
N31—C30—C28 | 108.3 (3) | N51—C56—H56B | 109.5 |
C36—N31—C34 | 79.0 (7) | N51—C56—H56C | 109.5 |
C36—N31—C32 | 128.2 (8) | N51—C57—H57A | 109.5 |
C34—N31—C32 | 107.9 (7) | N51—C57—H57B | 109.5 |
C36—N31—C35 | 109.2 (10) | N51—C57—H57C | 109.5 |
C34—N31—C35 | 126.4 (8) | O2—Si1—O5 | 111.41 (10) |
C36—N31—C37 | 107.4 (7) | O2—Si1—O3 | 111.41 (10) |
C32—N31—C37 | 82.6 (8) | O5—Si1—O3 | 110.85 (10) |
C35—N31—C37 | 106.4 (9) | O2—Si1—O4 | 108.22 (10) |
C34—N31—C33 | 108.3 (6) | O5—Si1—O4 | 107.64 (10) |
C32—N31—C33 | 104.4 (7) | O3—Si1—O4 | 107.10 (10) |
C35—N31—C33 | 80.4 (8) | O7—Si2—O6 | 111.34 (10) |
C37—N31—C33 | 132.0 (6) | O7—Si2—O8 | 111.42 (10) |
C36—N31—C30 | 111.7 (4) | O6—Si2—O8 | 108.62 (10) |
C34—N31—C30 | 113.6 (4) | O7—Si2—O5 | 110.96 (10) |
C32—N31—C30 | 111.5 (6) | O6—Si2—O5 | 107.03 (10) |
C35—N31—C30 | 111.6 (8) | O8—Si2—O5 | 107.28 (10) |
C37—N31—C30 | 110.3 (5) | O9—Si3—O10 | 111.36 (10) |
C33—N31—C30 | 110.7 (4) | O9—Si3—O8 | 111.02 (10) |
N31—C32—H32A | 109.5 | O10—Si3—O8 | 108.60 (10) |
N31—C32—H32B | 109.5 | O9—Si3—O3i | 110.97 (10) |
N31—C32—H32C | 109.5 | O10—Si3—O3i | 107.47 (10) |
N31—C33—H33A | 109.5 | O8—Si3—O3i | 107.25 (10) |
N31—C33—H33B | 109.5 | O1—Si4—O6i | 111.38 (10) |
N31—C33—H33C | 109.5 | O1—Si4—O10 | 111.65 (10) |
N31—C34—H34A | 109.5 | O6i—Si4—O10 | 109.12 (10) |
N31—C34—H34B | 109.5 | O1—Si4—O2 | 111.00 (10) |
N31—C34—H34C | 109.5 | O6i—Si4—O2 | 106.74 (10) |
N31—C35—H35A | 109.5 | O10—Si4—O2 | 106.72 (10) |
N31—C35—H35B | 109.5 | Si1—O2—Si4 | 147.46 (13) |
N31—C35—H35C | 109.5 | Si1—O3—Si3i | 145.37 (12) |
N31—C36—H36A | 109.5 | Si1—O4—H4 | 109.5 |
N31—C36—H36B | 109.5 | Si1—O5—Si2 | 148.73 (13) |
N31—C36—H36C | 109.5 | Si2—O6—Si4i | 149.48 (13) |
N31—C37—H37A | 109.5 | Si3—O8—Si2 | 150.61 (12) |
N31—C37—H37B | 109.5 | Si3—O10—Si4 | 151.87 (13) |
N31—C37—H37C | 109.5 | H21D—O21—H21E | 108.0 |
C42—C41—C46 | 111.5 (7) | H22D—O22—H22E | 108.0 |
C42—C41—C47 | 108.4 (8) | H23D—O23—H23E | 108.0 |
C46—C41—C47 | 109.5 (8) | H24D—O24—H24E | 108.0 |
C42—C41—H41 | 109.2 | H25D—O25—H25E | 108.0 |
C46—C41—H41 | 109.2 | H26D—O26—H26E | 108.0 |
C47—C41—H41 | 109.2 | H27D—O27—H27E | 108.0 |
C41—C42—C43 | 109.6 (7) | H28D—O28—H28E | 108.0 |
C41—C42—H42A | 109.8 | H29D—O29—H29E | 108.0 |
C43—C42—H42A | 109.8 | H30D—O30—H30E | 108.0 |
C41—C42—H42B | 109.8 | H31D—O31—H31E | 108.0 |
C43—C42—H42B | 109.8 | H32D—O32—H32E | 108.0 |
H42A—C42—H42B | 108.2 | H33D—O33—H33E | 108.0 |
C44—C43—C48 | 111.2 (8) | H34D—O34—H34E | 108.0 |
C44—C43—C42 | 112.0 (7) | H35D—O35—H35E | 108.0 |
C48—C43—C42 | 103.8 (7) | H36D—O36—H36E | 108.0 |
C44—C43—H43 | 109.9 | H37D—O37—H37E | 108.0 |
C48—C43—H43 | 109.9 | H38D—O38—H38E | 108.0 |
C42—C43—H43 | 109.9 | H39D—O39—H39E | 108.0 |
C45—C44—C43 | 107.9 (7) | H40D—O40—H40E | 108.0 |
C45—C44—H44A | 110.1 | H41D—O41—H41E | 108.0 |
C43—C44—H44A | 110.1 | H42D—O42—H42E | 108.0 |
C45—C44—H44B | 110.1 |
Symmetry code: (i) −x+2, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O29ii | 0.84 | 1.84 | 2.659 (4) | 166 |
O21—H21D···O1ii | 0.84 | 1.83 | 2.664 (3) | 173 |
O21—H21E···O23 | 0.84 | 1.94 | 2.775 (3) | 174 |
O22—H22D···O9iii | 0.84 | 1.82 | 2.647 (3) | 169 |
O22—H22E···O36iii | 0.84 | 1.98 | 2.809 (3) | 172 |
O23—H23D···O9ii | 0.84 | 1.79 | 2.631 (3) | 177 |
O23—H23E···O40ii | 0.84 | 1.93 | 2.758 (3) | 167 |
O24—H24D···O7iii | 0.84 | 1.78 | 2.618 (3) | 172 |
O24—H24E···O22 | 0.84 | 1.89 | 2.725 (3) | 172 |
O25—H25D···O7iii | 0.84 | 1.85 | 2.689 (3) | 176 |
O25—H25E···O38 | 0.84 | 2.02 | 2.831 (3) | 163 |
O26—H26D···O7 | 0.84 | 1.91 | 2.710 (3) | 160 |
O26—H26E | 0.84 | |||
O27—H27D···O28 | 0.84 | 1.92 | 2.750 (3) | 173 |
O27—H27E···O25iv | 0.84 | 1.96 | 2.794 (3) | 174 |
O28—H28D···O24iv | 0.84 | 1.90 | 2.729 (3) | 171 |
O28—H28E···O24v | 0.84 | 1.90 | 2.737 (3) | 172 |
O29—H29D···O31 | 0.84 | 1.88 | 2.699 (3) | 163 |
O29—H29E···O37 | 0.84 | 2.01 | 2.802 (3) | 157 |
O30—H30D···O41iv | 0.84 | 2.03 | 2.763 (3) | 145 |
O30—H30E | 0.84 | |||
O31—H31D | 0.84 | |||
O31—H31E···O1ii | 0.84 | 1.91 | 2.665 (3) | 149 |
O32—H32D···O33 | 0.84 | 1.91 | 2.749 (3) | 175 |
O32—H32E···O4vi | 0.84 | 2.01 | 2.831 (4) | 164 |
O33—H33D···O42ii | 0.84 | 2.13 | 2.737 (3) | 129 |
O33—H33E···O9iii | 0.84 | 1.97 | 2.710 (4) | 147 |
O34—H34D···O30 | 0.84 | 1.88 | 2.712 (3) | 170 |
O34—H34E···O33 | 0.84 | 1.94 | 2.774 (3) | 174 |
O35—H35D···O21 | 0.84 | 1.94 | 2.783 (3) | 176 |
O35—H35E···O34 | 0.84 | 2.01 | 2.785 (3) | 154 |
O36—H36D | 0.84 | |||
O36—H36E···O27 | 0.84 | 1.90 | 2.734 (3) | 171 |
O37—H37D | 0.84 | |||
O37—H37E···O39vii | 0.84 | 1.96 | 2.723 (3) | 150 |
O38—H38D | 0.84 | |||
O38—H38E···O1vi | 0.84 | 1.90 | 2.691 (3) | 156 |
O39—H39D···O4 | 0.84 | 1.91 | 2.744 (3) | 170 |
O39—H39E···O26 | 0.84 | 1.91 | 2.751 (3) | 175 |
O40—H40D···O23v | 0.84 | 1.91 | 2.742 (3) | 175 |
O40—H40E···O36 | 0.84 | 1.84 | 2.647 (3) | 161 |
O41—H41D···O28 | 0.84 | 1.88 | 2.716 (3) | 178 |
O41—H41E···O26 | 0.84 | 1.99 | 2.779 (3) | 156 |
O42—H42D···O40 | 0.84 | 1.78 | 2.614 (3) | 175 |
O42—H42E···O35ii | 0.84 | 2.00 | 2.840 (3) | 177 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z; (v) x+1, y, z; (vi) −x+1, −y, −z+1; (vii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | 6C13H24N+·H2O20Si86−·44H2O |
Mr | 2505.44 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 15.5889 (8), 15.9297 (8), 16.2269 (11) |
α, β, γ (°) | 60.863 (2), 72.511 (3), 82.119 (2) |
V (Å3) | 3356.8 (3) |
Z | 1 |
Radiation type | Cu Kα |
µ (mm−1) | 1.53 |
Crystal size (mm) | 0.24 × 0.24 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 6000 diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.587, 0.858 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 66631, 12596, 10388 |
Rint | 0.041 |
(sin θ/λ)max (Å−1) | 0.614 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.186, 1.07 |
No. of reflections | 12596 |
No. of parameters | 942 |
No. of restraints | 399 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.90, −0.69 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLUTON (Spek, 2009), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O29i | 0.840 | 1.837 | 2.659 (4) | 165.67 |
O21—H21D···O1i | 0.840 | 1.828 | 2.664 (3) | 173.25 |
O21—H21E···O23 | 0.840 | 1.938 | 2.775 (3) | 173.97 |
O22—H22D···O9ii | 0.840 | 1.818 | 2.647 (3) | 168.86 |
O22—H22E···O36ii | 0.840 | 1.975 | 2.809 (3) | 171.76 |
O23—H23D···O9i | 0.840 | 1.792 | 2.631 (3) | 177.19 |
O23—H23E···O40i | 0.840 | 1.932 | 2.758 (3) | 167.40 |
O24—H24D···O7ii | 0.840 | 1.784 | 2.618 (3) | 171.68 |
O24—H24E···O22 | 0.840 | 1.891 | 2.725 (3) | 172.14 |
O25—H25D···O7ii | 0.840 | 1.850 | 2.689 (3) | 175.47 |
O25—H25E···O38 | 0.840 | 2.016 | 2.831 (3) | 163.19 |
O26—H26D···O7 | 0.840 | 1.905 | 2.710 (3) | 160.11 |
O27—H27D···O28 | 0.840 | 1.915 | 2.750 (3) | 172.45 |
O27—H27E···O25iii | 0.840 | 1.957 | 2.794 (3) | 174.41 |
O28—H28D···O24iii | 0.840 | 1.896 | 2.729 (3) | 171.11 |
O28—H28E···O24iv | 0.840 | 1.904 | 2.737 (3) | 171.51 |
O29—H29D···O31 | 0.840 | 1.884 | 2.699 (3) | 163.19 |
O29—H29E···O37 | 0.840 | 2.009 | 2.802 (3) | 156.94 |
O30—H30D···O41iii | 0.840 | 2.034 | 2.763 (3) | 144.76 |
O31—H31E···O1i | 0.840 | 1.907 | 2.665 (3) | 149.39 |
O32—H32D···O33 | 0.840 | 1.912 | 2.749 (3) | 174.92 |
O32—H32E···O4v | 0.840 | 2.013 | 2.831 (4) | 164.16 |
O33—H33D···O42i | 0.840 | 2.128 | 2.737 (3) | 129.20 |
O33—H33E···O9ii | 0.840 | 1.970 | 2.710 (4) | 146.45 |
O34—H34D···O30 | 0.840 | 1.882 | 2.712 (3) | 169.57 |
O34—H34E···O33 | 0.840 | 1.938 | 2.774 (3) | 173.62 |
O35—H35D···O21 | 0.840 | 1.944 | 2.783 (3) | 175.99 |
O35—H35E···O34 | 0.840 | 2.008 | 2.785 (3) | 153.53 |
O36—H36E···O27 | 0.840 | 1.901 | 2.734 (3) | 171.04 |
O37—H37E···O39vi | 0.840 | 1.961 | 2.723 (3) | 150.35 |
O38—H38E···O1v | 0.840 | 1.904 | 2.691 (3) | 155.50 |
O39—H39D···O4 | 0.840 | 1.913 | 2.744 (3) | 169.52 |
O39—H39E···O26 | 0.840 | 1.914 | 2.751 (3) | 174.91 |
O40—H40D···O23iv | 0.840 | 1.905 | 2.742 (3) | 174.61 |
O40—H40E···O36 | 0.840 | 1.838 | 2.647 (3) | 161.22 |
O41—H41D···O28 | 0.840 | 1.877 | 2.716 (3) | 177.99 |
O41—H41E···O26 | 0.840 | 1.991 | 2.779 (3) | 155.81 |
O42—H42D···O40 | 0.840 | 1.776 | 2.614 (3) | 175.08 |
O42—H42E···O35i | 0.840 | 2.001 | 2.840 (3) | 176.72 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x+1, −y+1, −z; (iv) x+1, y, z; (v) −x+1, −y, −z+1; (vi) x, y+1, z. |
Silicate hydrates are materials that structurally can be positioned between silicon dioxide-based zeolites, called zeosils, and silicate clathrate hydrates. In zeolites, (organic) template molecules are embedded in the pores of a four-connected silicon dioxide network. The template molecules reside in zero-, one-, two- or three-dimensional pores. In the crystal structure of clathrate hydrates, the template molecules are partially or entirely surrounded by water molecules. Silicate hydrates are crystalline materials consisting of water, individual silicate units and organic cations. The organic cations are embedded in cages or pores formed by a network of hydrogen-bonded water molecules and oligomeric silicate clusters (Wiebcke, 1991; Grube et al., 1993).
The templates used to synthesize silicate hydrate materials can be subdivided into different groups (Verlooy et al., 2010). The first group of organic templates consists of N-methyl quaternary amines (references 2–20 in Verlooy et al., 2010), the second group consists of the other quaternary amines (references 18 and 21–25 in Verlooy et al., 2010) and the third group comprises the metal–ethylenediamine complexes (references 26–30 in Verlooy et al., 2010). α-Cyclodextrine (Benner et al., 1997) and hexamethyleneimine (Verlooy et al., 2010) are the only reported templates that do not fit this classification.
In the group of silicate hydrate materials synthesized with N-methyl quaternary amines, which form the majority of reported silicate hydrate materials, silicate cubes are surrounded by a shell of 24 water molecules. This observation is generally referred to as the `24-water rule' (Wiebcke et al., 1994). Another generally observed property of silicate hydrate structures is the relationship between the environment and the C/N ratio of the organic template molecules. Among all reported silicate hydrates reported to date, organic template molecules with a low C/N ratio where found to reside in one-dimensional pores. Organic template molecules with a high C/N ratio are generally found in two- or three-dimensional pore architectures (Smolin, 1970; Bissert & Liebau, 1987; Emmer & Wiebcke, 1994; Wiebcke et al., 1995; Shantz & Lobo, 2001; Wiebcke & Felsche, 2001). So far no silicate hydrates with a C/N ratio higher then 10 have been synthesized (Wiebcke et al., 1995; Shantz & Lobo, 2001).
Here we report the title compound, (I), a silicate hydrate structure synthesized using an organic template with a C/N ratio of 13. In this new silicate hydrate structure the organic template cations, N,N,N-trimethyladamantylammonium (TMAda), reside in a two-dimensional pore structure enclosed by a hydrogen-bonded network formed by the silicate units and water molecules.
The crystals of (I) belong to the triclinic space group P1, with the silicate cage located on an inversion point (Fig. 1). The negative charges (6-) on the terminal O atoms are compensated by six TMAda cations (1+), pointing, with the trimethylammonium group, towards the faces of the silicate cage. Each template molecule is orientated in such a way that the distances between its N atom and the four Si atoms of one face of the cube are all in the range 4.8–5.1 Å.
Individual silicate cages are linked together by a hydrogen-bond network involving water molecules. The silicate units are separated by at least three water molecules. The hydrogen bonding gives rise to a pentagonal network (Fig. 2). The hydrophobic carbon-rich template molecules are grouped together, minimizing exposure to the hydrogen-bonded silicate–water network. This network surrounds the TMAda cations in two directions, where the template clusters are elongated along the c direction, basically forming hydrophobic columns embedded in a hydrophilic silicate–water matrix. When analysing the water network, most water molecules are located between the silicate cubes in the a and b directions. Along the c direction, the silicate cubes are less strongly connected through hydrogen bonding. Each terminal O atom (O- or OH) on the silicate cube is engaged in three hydrogen bonds with neighbouring water molecules, arranged in a tetragonal geometry. The hydrogen-bond distances and angles for (I) are reported in Table 1. Anisotropic displacement parameters are represented in Fig. 3. The water OH bonds were fixed at 0.84 Å, with an angle of 108° between them. The reported hydrogen-bond H···A distances are in the range 1.78–2.12 Å, and the hydrogen-bond angles D—H···A are in the range 129.2–177.2°.
Single-crystal X-ray diffraction revealed half a silicate cube in the asymmetric unit of (I). The 29Si MAS NMR spectrum of (I) shows three sharp signals at ca -98.7, -99.6 and -100.0 p.p.m. with respect to the reference trimethylsiloxane chemical shift, pointing to the presence of three types of silicate environments with a Q3 connectivity (Fig. 4). 29Si NMR resonances of silicate cubes are generally found around -99.5 p.p.m. The reduced symmetry of the silicate cube can give rise to different local environments, thereby generating different 29Si resonance signals (Harris et al., 1995; Harris & Naumov 1996; Wiebcke & Koller 1992; Wiebcke et al., 1993, 1994). Furthermore, a different charge on the terminal O atoms (O- versus OH) could also result in small differences in the NMR frequency of the Si atoms. Therefore, the 29Si MAS NMR spectrum of (I) can be explained by the presence of a single type of anionic silicate cube with a reduced symmetry, confirming the results obtained from single-crystal diffraction experiments.