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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 61| Part 4| April 2005| Pages o918-o919
https://doi.org/10.1107/S1600536805006689

Iso­propyl 2,5-an­hydro-4-(2,5-an­hydro-4-azido-3-O-tert-butyl­di­phenyl­silyl-4-de­oxy-L-ribonylamino)-3-O-tert-butyl­di­phenyl­silyl-4-de­oxy-L-ribonate

CROSSMARK_Color_square_no_text.svg
Steven Humphreys,a David J. Watkin,a* Gangadharar J. Sanjayan,b George E. Tranter,c Alison A. Edwardsc and George W. J. Fleetb

aDepartment of Chemical Crystallography, Chemical Research Laboratory, Mansfield Road, Oxford OX1 3TA, England, bDepartment of Organic Chemistry, Chemical Research Laboratory, Mansfield Road, Oxford OX1 3TA, England, and cBiological Chemistry, Division of Biomedical Sciences, Imperial College, London SW7 2AZ, England
*Correspondence e-mail: david.watkin@chem.ox.ac.uk

(Received 24 February 2005; accepted 3 March 2005; online 11 March 2005)

The crystal structure of the title compound, C45H56N4O7Si2, shows a γ-turn conformation which is stabilized by an intramolecular hydrogen bond.

Comment

Tetra­hydro­furan (THF)-derived sugar amino acids (SAA) have been extensively investigated as dipeptide isosteres (Chakraborty et al., 2004[Chakraborty, T. K., Srinivasi, P., Tapadar, S. & Mohan, B. K. (2004). J. Chem. Sci. 116, 187-207.]; Grotenberg et al., 2004[Grotenberg, G. M., Timmerj, M. S. M., Llamas-Saiz, A. L., Verdoes, M., van der Marel, G. A., van Raaij, M. J., Overkleeft, H. S. & Overhand, M. (2004). J. Am. Chem. Soc. 126, 3444-3446.]). A multitude of peptidomimetics, including a number of δ-THF SAA scaffolds, induce β-turn-like structures (Smith et al., 2003[Smith, M. D., Claridge, T. D. W., Sansom, M. P. & Fleet, G. W. J. (2003). Org. Biomol. Chem. 1, 3647-3655.]). However, there are relatively few examples of γ-turn conformations (Etzkorn et al., 1999[Etzkorn, F. A., Travins, J. M. & Hart, S. A. (1999). Adv. Amino Acid Mimetics Peptidomimetics, 2, 125-163.]; Lindvall et al., 1999[Lindvall, M. K., Rissanen, K., Hakala, J. M. L. & Koskinen, A. M. P. (1999). Tetrahedron Lett. 40, 7427-7430.]; Belvisi et al., 1999[Belvisi, L., Gennari, C., Mieglo, A., Potenza, D. & Scolastico, C. (1999). Eur. J. Org. Chem. pp. 389-400.]). In contrast to the extensive studies on β-peptides built from residues containing five- or six-membered rings (Wang et al., 2000[Wang, X., Espinosa, J. F. & Gellman, S. H. (2000). J. Am. Chem. Soc. 122, 4821-4822.]), there are only limited reports of γ-peptides based on cyclic templates (Curran et al., 1996[Curran, T. P., Chandler, N. M., Kennedy, R. J. & Keaney, M. T. (1996). Tetrahedron Lett. 37, 1933-1936.]; Crisma et al., 2001[Crisma, M., Moretto, A., Toniolo, C., Kaczmarek, K. & Zabrocki, J. (2001). Macromol­ecules, 34, 5048-5052.]; Goswami & Moloney, 1999[Goswami, R. & Moloney, M. G. (1999). Chem. Commun. pp. 2333-2334.]). [link]

[Scheme 1]

This paper reports the structure of the γ-THF SAA compound, (1[link]). The γ-turn conformation (Fig. 1[link]) is stabilized by bifurcated intramolecular N14—H14⋯O39 and N14—H14⋯O5 hydrogen bonds. There is no intermolecular hydrogen bonding, thus leading to an open structure (calculated density = 1.219 Mg m−3) with a substantial opportunity for disorder and large atomic displacements (Fig. 2[link]).

[Figure 1]
Figure 1
The central section of the mol­ecule, showing the γ-turn stabilized by the bifurcated internal hydrogen bond (dashed lines.
[Figure 2]
Figure 2
The complete mol­ecule with displacement ellipsoids drawn at the 50% probability level. The cavity containing the disordered azide is evident, as are the large displacements of the atoms in the periphery. Some labels have been omitted for clarity.

Experimental

Compound (1[link]) was prepared by conventional peptide coupling procedures from the dipeptidomimetic compound (2[link]) (Sanjayan et al., 2003[Sanjayan, G. J., Stewart, A. J., Hachisu, S., Gonzalez, R., Watterson, M. P. & Fleet, G. W. J. (2003). Tetrahedron Lett. 44, 5847-5852.]), and was crystallized from methanol.

Crystal data

  • C45H56N4O7Si2

  • Mr = 821.13

  • Monoclinic, P21

  • a = 15.4548 (4) Å

  • b = 9.0111 (2) Å

  • c = 16.4767 (5) Å

  • β = 102.7868 (10)°

  • V = 2237.72 (10) Å3

  • Z = 2

  • Dx = 1.219 Mg m−3

  • Mo Kα radiation

  • Cell parameters from 4658 reflections

  • θ = 5–30°

  • μ = 0.13 mm−1

  • T = 190 K

  • Prism, colourless

  • 0.80 × 0.30 × 0.20 mm
Data collection

  • Nonius KappaCCD diffractometer

  • ω scans

  • Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307-326. New York: Academic Press.]) Tmin = 0.96, Tmax = 0.97

  • 23431 measured reflections

  • 6788 independent reflections

  • 6788 reflections with I > −3σ(I)

  • Rint = 0.057

  • θmax = 30.0°

  • h = −21 → 21

  • k = −12 → 8

  • l = −23 → 23
Refinement

  • Refinement on F2

  • R[F2 > 2σ(F2)] = 0.085

  • wR(F2) = 0.119

  • S = 0.99

  • 6788 reflections

  • 550 parameters

  • H-atom parameters constrained

  • w = 1/[σ2(F2) + 0.03 + 1.13P] where P = [max(Fo2,0) + 2Fc2]/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.57 e Å−3

  • Δρmin = −0.48 e Å−3

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N14—H14⋯O39 0.84 2.39 3.057 (5) 137
N14—H14⋯O5 0.84 2.21 2.624 (5) 110

The disordered azide group could only be refined satisfactorily with distance and anisotropic displacement parameter (adp) similarity restraints. The small angle C3—C7—N801 [93.1 (4)°] and the large angle C3—C7—N901 [123.7 (5)°] suggests that the disorder probably extends into the ring system, but is accommodated by the adps. Atom H71 should also be represented by two partial atoms, but they could not be resolved. The other H atoms were all located in a difference map. Those attached to C atoms were repositioned geometrically. All H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H = 0.93–0.98, O—N = 0.86–0.89 and O—H = 0.82 Å) and Uiso values (in the range 1.2–1.5 times Ueq of the parent atom), after which they were refined with riding constraints. The large adps in the phenyl groups are consistent with rigid-body librations (RTLS in the range 2.5–5.0%). The large adps in the tert-butyl groups are not amenable to TLS analysis, but look consistent with simple libration. Both the large displacement parameters and the disorder in the azide are not unexpected, because there are no intermolecular hydrogen bonds to consolidate the crystal packing.

Data collection: COLLECT (Nonius, 2001[Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr and R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994[Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.]); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003[Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487.]); molecular graphics: CAMERON (Watkin et al., 1996[Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England.]); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, 1. DOI: https://doi.org/10.1107/S1600536805006689/cf6411sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S1600536805006689/cf64111sup2.hkl


Computing details top

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

(1) top
Crystal data top
C45H56N4O7Si2F(000) = 876
Mr = 821.13Dx = 1.219 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 15.4548 (4) ÅCell parameters from 4658 reflections
b = 9.0111 (2) Åθ = 5–30°
c = 16.4767 (5) ŵ = 0.13 mm−1
β = 102.7868 (10)°T = 190 K
V = 2237.72 (10) Å3Prism, colourless
Z = 20.80 × 0.30 × 0.20 mm
Data collection top
Nonius KappaCCD
diffractometer		6788 reflections with I > −3σ(I)
Graphite monochromatorRint = 0.057
ω scansθmax = 30.0°, θmin = 5.1°
Absorption correction: multi-scan
(DENZO/SCALEPACK; Otwinowski & Minor, 1997)		h = −21→21
Tmin = 0.96, Tmax = 0.97k = −12→8
23431 measured reflectionsl = −23→23
6788 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.085H-atom parameters constrained
wR(F2) = 0.119 w = 1/[σ2(F2) + 0.03 + 1.13P]
where P = [max(Fo2,0) + 2Fc2]/3
S = 0.99(Δ/σ)max = 0.001
6788 reflectionsΔρmax = 0.57 e Å−3
550 parametersΔρmin = −0.48 e Å−3
44 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Si10.14482 (6)0.36845 (13)0.25970 (5)0.0362
Si180.28747 (5)0.47285 (12)0.84360 (5)0.0307
C30.2651 (2)0.4364 (5)0.40455 (19)0.0467
C40.3032 (2)0.5867 (5)0.4362 (2)0.0430
C60.4197 (3)0.4315 (8)0.4285 (3)0.0948
C70.3418 (4)0.3372 (7)0.4321 (3)0.0865
C130.2785 (2)0.6316 (5)0.5169 (2)0.0446
C150.3333 (2)0.7119 (4)0.66015 (18)0.0336
C160.36860 (18)0.5938 (3)0.72532 (17)0.0289
C190.1894 (2)0.5551 (4)0.87813 (19)0.0349
C200.1216 (2)0.6032 (5)0.7992 (2)0.0490
C210.1462 (2)0.4374 (5)0.9232 (2)0.0478
C220.2133 (2)0.6925 (4)0.9332 (2)0.0457
C230.2496 (2)0.3135 (4)0.7724 (2)0.0365
C240.2086 (2)0.3349 (4)0.6880 (2)0.0454
C250.1747 (3)0.2164 (5)0.6373 (3)0.0627
C260.1804 (3)0.0739 (6)0.6688 (4)0.0761
C270.2187 (3)0.0508 (5)0.7508 (4)0.0759
C280.2530 (3)0.1678 (4)0.8019 (3)0.0576
C290.3823 (2)0.4158 (4)0.9299 (2)0.0415
C300.3861 (3)0.4411 (5)1.0152 (2)0.0595
C310.4627 (3)0.4083 (6)1.0747 (3)0.0714
C320.5356 (3)0.3520 (6)1.0510 (3)0.0677
C330.5317 (3)0.3236 (8)0.9700 (3)0.0955
C340.4561 (3)0.3576 (7)0.9103 (3)0.0764
C350.4674 (2)0.6379 (4)0.7527 (2)0.0349
C370.3888 (2)0.8455 (4)0.6941 (2)0.0433
C380.5238 (2)0.5435 (4)0.7081 (2)0.0391
C410.6082 (3)0.3190 (5)0.7176 (3)0.0688
C420.7008 (3)0.3848 (7)0.7285 (3)0.0835
C430.6078 (5)0.1813 (7)0.7669 (5)0.1347
C450.0883 (2)0.2542 (4)0.3279 (2)0.0371
C460.0226 (2)0.3088 (4)0.3664 (2)0.0442
C47−0.0166 (2)0.2214 (5)0.4169 (2)0.0461
C480.0097 (3)0.0756 (5)0.4313 (2)0.0504
C490.0742 (3)0.0193 (5)0.3963 (3)0.0606
C500.1126 (3)0.1068 (5)0.3437 (2)0.0526
C510.1797 (2)0.2446 (4)0.18129 (19)0.0401
C520.2645 (2)0.2492 (5)0.1659 (2)0.0462
C530.2874 (3)0.1602 (5)0.1050 (2)0.0587
C540.2272 (3)0.0654 (5)0.0587 (2)0.0628
C550.1428 (3)0.0575 (6)0.0725 (2)0.0629
C560.1200 (3)0.1459 (5)0.1330 (2)0.0562
C570.0774 (2)0.5299 (4)0.2059 (2)0.0433
C58−0.0142 (3)0.4788 (5)0.1571 (3)0.0600
C590.0653 (3)0.6531 (5)0.2669 (2)0.0562
C600.1279 (3)0.5981 (5)0.1436 (3)0.0672
O20.23825 (14)0.4387 (3)0.31647 (13)0.0472
O50.39594 (17)0.5793 (4)0.44477 (16)0.0661
O170.32402 (13)0.6086 (2)0.79167 (12)0.0306
O360.47512 (16)0.7875 (3)0.72919 (16)0.0468
O390.53825 (16)0.5705 (3)0.64113 (15)0.0547
O400.55231 (18)0.4244 (3)0.75264 (17)0.0572
O440.20056 (16)0.6364 (5)0.52043 (17)0.0807
N140.34587 (18)0.6699 (3)0.57860 (15)0.0389
N8010.3204 (6)0.3119 (13)0.5206 (5)0.08600.4308
N8020.3745 (7)0.2480 (12)0.5756 (6)0.08460.4321
N8030.4213 (7)0.2048 (14)0.6321 (7)0.10220.4321
N9010.3658 (5)0.2755 (9)0.5127 (4)0.08710.5692
N9020.3353 (5)0.1546 (9)0.5120 (5)0.08710.5679
N9030.3137 (10)0.0369 (10)0.5186 (7)0.14840.5679
H140.39790.66620.57050.0567*
H310.21560.40730.42880.0666*
H410.28050.66380.39450.0610*
H610.47130.40170.46970.1317*
H620.43230.42290.37360.1319*
H710.33730.25100.39540.1191*
H1510.27100.73340.65690.0473*
H1610.36170.49430.70210.0408*
H2010.07040.64790.81530.0851*
H2020.14780.67480.76720.0853*
H2030.10160.51660.76500.0859*
H2110.09440.47980.93810.0897*
H2120.18770.40610.97430.0894*
H2130.12840.35270.88840.0898*
H2210.16070.73170.94770.0816*
H2220.25550.66850.98350.0818*
H2230.23760.77010.90290.0812*
H2410.20470.43060.66590.0643*
H2510.14840.23310.58150.0886*
H2610.1583−0.00700.63450.1158*
H2710.2207−0.04600.77150.1167*
H2810.27840.15160.85740.0871*
H3010.33500.47981.03270.0857*
H3110.46380.42381.13320.0998*
H3210.58820.33241.09000.0947*
H3310.58170.28130.95350.1379*
H3410.45510.33960.85230.1103*
H3510.48780.62420.81240.0492*
H3710.36430.89640.73680.0617*
H3720.39170.91520.64890.0621*
H4110.58200.30070.65810.1025*
H4210.73870.31250.70810.1486*
H4220.72370.40340.78820.1490*
H4230.69900.47800.69730.1492*
H4310.64910.11080.75230.2648*
H4320.62340.20510.82620.2649*
H4330.54730.14150.75230.2648*
H4610.00480.40840.35610.0645*
H471−0.06000.26050.44140.0677*
H481−0.01760.01620.46470.0749*
H4910.0917−0.07960.40550.0899*
H5010.15620.06550.31960.0781*
H5210.30680.31670.19610.0669*
H5310.34510.16730.09610.0887*
H5410.24350.00300.01760.0914*
H5510.1011−0.00760.04230.0898*
H5610.06280.13690.14290.0810*
H581−0.04360.56290.12660.1018*
H582−0.04920.44260.19530.1016*
H583−0.00640.40240.11720.1012*
H5910.03740.73920.23820.1018*
H5920.12150.68310.30180.1015*
H5930.02900.61550.30200.1015*
H6010.09620.68440.11760.1247*
H6020.18620.62690.17260.1244*
H6030.13210.52400.10250.1246*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Si10.0301 (4)0.0519 (5)0.0278 (4)−0.0106 (4)0.0094 (3)−0.0050 (4)
Si180.0261 (4)0.0375 (4)0.0287 (4)0.0061 (4)0.0064 (3)0.0041 (4)
C30.0413 (18)0.074 (3)0.0255 (16)−0.0136 (18)0.0085 (14)−0.0082 (17)
C40.0309 (16)0.072 (2)0.0262 (16)−0.0068 (18)0.0072 (13)−0.0059 (17)
C60.047 (3)0.154 (6)0.077 (3)0.026 (3)−0.001 (2)−0.034 (4)
C70.086 (3)0.088 (3)0.071 (2)0.021 (2)−0.013 (2)0.005 (2)
C130.0343 (17)0.068 (2)0.0309 (17)0.0036 (18)0.0071 (14)−0.0052 (17)
C150.0327 (16)0.0425 (17)0.0262 (15)0.0021 (14)0.0077 (12)−0.0025 (13)
C160.0273 (14)0.0320 (15)0.0273 (14)0.0003 (13)0.0062 (11)−0.0046 (12)
C190.0257 (14)0.0460 (18)0.0335 (16)0.0061 (14)0.0076 (12)0.0022 (14)
C200.0342 (17)0.066 (2)0.0439 (19)0.0204 (18)0.0034 (15)0.0020 (19)
C210.0384 (18)0.060 (2)0.050 (2)−0.0010 (17)0.0196 (16)0.0018 (18)
C220.0429 (19)0.051 (2)0.046 (2)0.0071 (17)0.0144 (16)−0.0057 (17)
C230.0319 (16)0.0374 (16)0.0434 (19)0.0022 (14)0.0154 (14)−0.0011 (14)
C240.0378 (18)0.047 (2)0.052 (2)−0.0059 (16)0.0108 (16)−0.0085 (17)
C250.042 (2)0.071 (3)0.074 (3)−0.015 (2)0.010 (2)−0.028 (2)
C260.058 (3)0.056 (3)0.124 (5)−0.018 (2)0.041 (3)−0.036 (3)
C270.076 (3)0.034 (2)0.133 (5)−0.008 (2)0.056 (3)−0.007 (3)
C280.061 (3)0.042 (2)0.080 (3)0.0063 (19)0.038 (2)0.008 (2)
C290.0333 (17)0.054 (2)0.0372 (18)0.0125 (15)0.0083 (13)0.0156 (16)
C300.049 (2)0.081 (3)0.046 (2)0.019 (2)0.0052 (17)0.005 (2)
C310.066 (3)0.100 (4)0.041 (2)0.025 (3)−0.0049 (19)0.007 (2)
C320.042 (2)0.108 (4)0.047 (2)0.021 (3)−0.0032 (17)0.023 (3)
C330.060 (3)0.161 (6)0.062 (3)0.062 (4)0.005 (2)0.021 (3)
C340.054 (2)0.123 (4)0.051 (2)0.043 (3)0.010 (2)0.017 (3)
C350.0313 (16)0.0374 (17)0.0359 (17)0.0029 (14)0.0072 (13)−0.0033 (14)
C370.052 (2)0.0348 (18)0.0410 (19)0.0035 (17)0.0068 (16)−0.0013 (15)
C380.0259 (15)0.0484 (19)0.044 (2)−0.0010 (15)0.0091 (14)−0.0041 (16)
C410.078 (3)0.059 (3)0.080 (3)0.031 (2)0.041 (3)0.002 (2)
C420.060 (3)0.098 (4)0.094 (4)0.030 (3)0.020 (2)−0.023 (3)
C430.183 (7)0.078 (4)0.180 (7)0.063 (5)0.118 (6)0.047 (5)
C450.0295 (16)0.050 (2)0.0320 (17)−0.0049 (15)0.0076 (13)−0.0029 (15)
C460.0388 (18)0.052 (2)0.0434 (19)−0.0007 (16)0.0131 (15)0.0021 (16)
C470.0363 (18)0.064 (2)0.042 (2)−0.0079 (18)0.0167 (15)−0.0026 (18)
C480.056 (2)0.059 (2)0.0397 (19)−0.017 (2)0.0175 (17)0.0032 (18)
C490.079 (3)0.047 (2)0.061 (3)0.005 (2)0.029 (2)0.0083 (19)
C500.052 (2)0.056 (2)0.055 (2)0.009 (2)0.0238 (18)0.0039 (19)
C510.0392 (18)0.056 (2)0.0262 (16)−0.0044 (17)0.0105 (13)−0.0029 (15)
C520.0410 (19)0.062 (2)0.0381 (19)−0.0062 (18)0.0140 (15)−0.0016 (17)
C530.056 (2)0.078 (3)0.051 (2)0.006 (2)0.0302 (19)0.001 (2)
C540.089 (3)0.063 (3)0.040 (2)0.009 (3)0.023 (2)−0.007 (2)
C550.070 (3)0.077 (3)0.041 (2)−0.006 (2)0.0107 (19)−0.020 (2)
C560.049 (2)0.077 (3)0.043 (2)−0.009 (2)0.0116 (17)−0.016 (2)
C570.0455 (19)0.050 (2)0.0340 (17)−0.0123 (17)0.0081 (15)−0.0013 (16)
C580.058 (2)0.053 (2)0.059 (2)−0.005 (2)−0.0074 (19)0.002 (2)
C590.062 (2)0.054 (2)0.055 (2)−0.004 (2)0.017 (2)−0.009 (2)
C600.086 (3)0.066 (3)0.056 (3)−0.019 (3)0.029 (2)0.007 (2)
O20.0366 (12)0.0813 (19)0.0247 (11)−0.0217 (13)0.0086 (9)−0.0097 (12)
O50.0412 (14)0.119 (3)0.0437 (15)−0.0256 (17)0.0210 (12)−0.0300 (17)
O170.0340 (11)0.0350 (11)0.0245 (10)0.0047 (9)0.0098 (8)0.0008 (9)
O360.0402 (13)0.0353 (12)0.0605 (16)−0.0061 (11)0.0018 (11)−0.0033 (11)
O390.0489 (14)0.0752 (19)0.0448 (14)0.0122 (15)0.0206 (12)0.0038 (14)
O400.0635 (17)0.0518 (15)0.0650 (17)0.0255 (14)0.0327 (14)0.0109 (13)
O440.0306 (13)0.160 (4)0.0494 (16)0.0069 (18)0.0052 (11)−0.038 (2)
N140.0339 (14)0.0620 (18)0.0219 (13)−0.0014 (13)0.0082 (11)−0.0049 (12)
N8010.085 (3)0.087 (3)0.071 (2)0.020 (2)−0.013 (2)0.007 (2)
N8020.084 (3)0.086 (3)0.070 (2)0.020 (3)−0.012 (2)0.008 (2)
N8030.085 (7)0.119 (10)0.106 (8)−0.027 (7)0.028 (6)0.016 (8)
N9010.087 (3)0.089 (3)0.071 (2)0.021 (2)−0.013 (2)0.006 (2)
N9020.087 (3)0.089 (3)0.071 (2)0.021 (2)−0.013 (2)0.006 (2)
N9030.245 (15)0.071 (6)0.118 (8)0.006 (8)0.018 (8)0.032 (6)
Geometric parameters (Å, º) top
Si1—C451.876 (3)C32—H3210.934
Si1—C511.874 (3)C33—C341.385 (6)
Si1—C571.892 (4)C33—H3310.953
Si1—O21.662 (2)C34—H3410.966
Si18—C191.884 (3)C35—C381.520 (4)
Si18—C231.865 (3)C35—O361.415 (4)
Si18—C291.874 (3)C35—H3510.972
Si18—O171.662 (2)C37—O361.430 (4)
C3—C41.522 (5)C37—H3710.984
C3—C71.473 (6)C37—H3720.983
C3—O21.419 (4)C38—O391.198 (4)
C3—H310.975C38—O401.320 (4)
C4—C131.517 (4)C41—C421.523 (7)
C4—O51.411 (4)C41—C431.484 (7)
C4—H410.986C41—O401.483 (4)
C6—C71.486 (8)C41—H4110.989
C6—O51.422 (7)C42—H4210.985
C6—H610.964C42—H4220.983
C6—H620.970C42—H4230.982
C7—N8011.582 (8)C43—H4310.968
C7—H710.978C43—H4320.976
C7—N9011.411 (7)C43—H4330.980
C7—H710.978C45—C461.402 (5)
C13—O441.220 (4)C45—C501.389 (5)
C13—N141.329 (4)C46—C471.380 (5)
C15—C161.524 (4)C46—H4610.943
C15—C371.512 (5)C47—C481.380 (6)
C15—N141.450 (4)C47—H4710.925
C15—H1510.973C48—C491.357 (6)
C16—C351.545 (4)C48—H4810.933
C16—O171.422 (3)C49—C501.397 (5)
C16—H1610.972C49—H4910.934
C19—C201.541 (4)C50—H5010.932
C19—C211.530 (5)C51—C521.390 (4)
C19—C221.531 (5)C51—C561.396 (5)
C20—H2010.976C52—C531.390 (5)
C20—H2020.975C52—H5210.949
C20—H2030.972C53—C541.364 (6)
C21—H2110.967C53—H5310.938
C21—H2120.980C54—C551.376 (6)
C21—H2130.957C54—H5410.956
C22—H2210.964C55—C561.381 (6)
C22—H2220.960C55—H5510.930
C22—H2230.981C56—H5610.938
C23—C241.407 (5)C57—C581.536 (5)
C23—C281.397 (5)C57—C591.537 (5)
C24—C251.386 (5)C57—C601.547 (5)
C24—H2410.933C58—H5810.965
C25—C261.380 (7)C58—H5820.973
C25—H2510.931C58—H5830.977
C26—C271.366 (7)C59—H5910.960
C26—H2610.939C59—H5920.968
C27—C281.380 (6)C59—H5930.953
C27—H2710.935C60—H6010.967
C28—H2810.923C60—H6020.957
C29—C301.412 (5)C60—H6030.964
C29—C341.357 (5)N14—H140.844
C30—C311.393 (5)N801—N8021.231 (8)
C30—H3010.965N802—N8031.116 (8)
C31—C321.369 (6)N901—N9021.186 (8)
C31—H3110.970N902—N9031.125 (8)
C32—C331.347 (6)
C45—Si1—C51109.19 (16)C32—C33—C34120.5 (4)
C45—Si1—C57114.94 (15)C32—C33—H331119.8
C51—Si1—C57110.32 (15)C34—C33—H331119.7
C45—Si1—O2109.50 (13)C33—C34—C29122.5 (4)
C51—Si1—O2105.56 (13)C33—C34—H341119.4
C57—Si1—O2106.89 (15)C29—C34—H341118.1
C19—Si18—C23109.35 (15)C16—C35—C38110.5 (3)
C19—Si18—C29115.16 (14)C16—C35—O36107.6 (3)
C23—Si18—C29110.50 (16)C38—C35—O36108.0 (3)
C19—Si18—O17104.69 (13)C16—C35—H351110.0
C23—Si18—O17109.76 (13)C38—C35—H351109.1
C29—Si18—O17107.13 (13)O36—C35—H351111.7
C4—C3—C7102.2 (3)C15—C37—O36105.1 (3)
C4—C3—O2109.9 (3)C15—C37—H371111.0
C7—C3—O2110.9 (3)O36—C37—H371110.7
C4—C3—H31112.2C15—C37—H372110.2
C7—C3—H31111.2O36—C37—H372110.3
O2—C3—H31110.1H371—C37—H372109.5
C3—C4—C13112.6 (3)C35—C38—O39125.1 (3)
C3—C4—O5107.4 (3)C35—C38—O40110.0 (3)
C13—C4—O5111.8 (3)O39—C38—O40124.8 (3)
C3—C4—H41109.7C42—C41—C43112.3 (5)
C13—C4—H41107.7C42—C41—O40108.5 (4)
O5—C4—H41107.4C43—C41—O40104.5 (3)
C7—C6—O5106.4 (4)C42—C41—H411110.4
C7—C6—H61111.4C43—C41—H411110.7
O5—C6—H61109.7O40—C41—H411110.3
C7—C6—H62108.8C41—C42—H421108.5
O5—C6—H62111.3C41—C42—H422107.8
H61—C6—H62109.2H421—C42—H422110.1
C6—C7—C3104.2 (5)C41—C42—H423110.8
C6—C7—N801117.1 (6)H421—C42—H423109.7
C3—C7—N80193.1 (4)H422—C42—H423109.9
C6—C7—H71112.2C41—C43—H431109.3
C3—C7—H71110.5C41—C43—H432109.5
N801—C7—H71117.0H431—C43—H432111.3
C6—C7—C3104.2 (5)C41—C43—H433106.9
C6—C7—N901102.5 (5)H431—C43—H433110.1
C3—C7—N901123.7 (5)H432—C43—H433109.8
C6—C7—H71112.2Si1—C45—C46124.0 (3)
C3—C7—H71110.5Si1—C45—C50119.7 (3)
N901—C7—H71103.6C46—C45—C50116.3 (3)
C4—C13—O44119.6 (3)C45—C46—C47122.1 (4)
C4—C13—N14115.7 (3)C45—C46—H461117.7
O44—C13—N14124.7 (3)C47—C46—H461120.1
C16—C15—C37102.1 (2)C46—C47—C48119.7 (3)
C16—C15—N14111.7 (3)C46—C47—H471120.1
C37—C15—N14111.7 (3)C48—C47—H471120.2
C16—C15—H151112.0C47—C48—C49120.0 (3)
C37—C15—H151109.6C47—C48—H481119.6
N14—C15—H151109.6C49—C48—H481120.5
C15—C16—C35101.7 (2)C48—C49—C50120.4 (4)
C15—C16—O17108.5 (2)C48—C49—H491120.0
C35—C16—O17111.5 (2)C50—C49—H491119.5
C15—C16—H161112.1C49—C50—C45121.5 (4)
C35—C16—H161111.6C49—C50—H501119.0
O17—C16—H161111.1C45—C50—H501119.5
Si18—C19—C20107.3 (2)Si1—C51—C52122.3 (3)
Si18—C19—C21109.9 (2)Si1—C51—C56121.2 (3)
C20—C19—C21108.4 (3)C52—C51—C56116.4 (3)
Si18—C19—C22113.1 (2)C51—C52—C53121.0 (4)
C20—C19—C22107.6 (3)C51—C52—H521119.3
C21—C19—C22110.3 (3)C53—C52—H521119.6
C19—C20—H201109.1C52—C53—C54121.0 (4)
C19—C20—H202110.9C52—C53—H531118.4
H201—C20—H202109.4C54—C53—H531120.7
C19—C20—H203109.5C53—C54—C55119.6 (4)
H201—C20—H203108.4C53—C54—H541120.8
H202—C20—H203109.7C55—C54—H541119.6
C19—C21—H211109.0C54—C55—C56119.5 (4)
C19—C21—H212110.1C54—C55—H551120.9
H211—C21—H212108.4C56—C55—H551119.6
C19—C21—H213111.2C51—C56—C55122.5 (4)
H211—C21—H213108.8C51—C56—H561119.0
H212—C21—H213109.3C55—C56—H561118.5
C19—C22—H221109.7Si1—C57—C58111.3 (3)
C19—C22—H222111.0Si1—C57—C59112.5 (2)
H221—C22—H222108.5C58—C57—C59109.2 (3)
C19—C22—H223110.1Si1—C57—C60108.0 (3)
H221—C22—H223107.8C58—C57—C60108.3 (3)
H222—C22—H223109.7C59—C57—C60107.4 (3)
Si18—C23—C24121.7 (3)C57—C58—H581108.1
Si18—C23—C28121.5 (3)C57—C58—H582109.9
C24—C23—C28116.6 (3)H581—C58—H582109.6
C23—C24—C25121.2 (4)C57—C58—H583109.1
C23—C24—H241119.2H581—C58—H583108.6
C25—C24—H241119.6H582—C58—H583111.6
C24—C25—C26120.4 (5)C57—C59—H591111.5
C24—C25—H251119.6C57—C59—H592111.6
C26—C25—H251120.0H591—C59—H592108.2
C25—C26—C27119.4 (4)C57—C59—H593108.2
C25—C26—H261120.8H591—C59—H593109.0
C27—C26—H261119.8H592—C59—H593108.2
C26—C27—C28120.8 (4)C57—C60—H601109.5
C26—C27—H271118.4C57—C60—H602109.6
C28—C27—H271120.9H601—C60—H602109.4
C23—C28—C27121.7 (4)C57—C60—H603108.2
C23—C28—H281118.0H601—C60—H603110.6
C27—C28—H281120.3H602—C60—H603109.5
Si18—C29—C30124.3 (3)C3—O2—Si1126.2 (2)
Si18—C29—C34118.9 (3)C6—O5—C4109.0 (3)
C30—C29—C34116.6 (3)C16—O17—Si18127.19 (19)
C29—C30—C31120.6 (4)C37—O36—C35109.4 (2)
C29—C30—H301120.0C41—O40—C38117.1 (3)
C31—C30—H301119.4C15—N14—C13122.2 (3)
C30—C31—C32120.1 (4)C15—N14—H14119.0
C30—C31—H311119.6C13—N14—H14118.7
C32—C31—H311120.2C7—N801—N802119.9 (7)
C31—C32—C33119.6 (4)N801—N802—N803170.7 (14)
C31—C32—H321121.2C7—N901—N902109.4 (6)
C33—C32—H321119.1N901—N902—N903172.5 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N14—H14···O390.842.393.057 (5)137
N14—H14···O50.842.212.624 (5)110
 

Acknowledgements

Financial support to AAE for a post-doctoral fellowship from EPSRC (grant No. GR/S44105/01) and to GJS from DST, New Delhi, for a BOYCAST Fellowship, is gratefully acknowledged.

References

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ISSN: 2056-9890
Volume 61| Part 4| April 2005| Pages o918-o919
https://doi.org/10.1107/S1600536805006689
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