Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041486/tk6297sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041486/tk6297Isup2.hkl |
CCDC reference: 296690
1D-3,4,5,6-Tetra-O-benzy-myo-inositol was treated with methanesulfonyl chloride in pyridine overnight at room temperature to give the 1,2-dimesylate, which was then subjected to a displacement reaction using sodium azide in dimethylformamide overnight at 383 K. [Please give brief details of quantities] Crystals of the title compound were isolated from diethyl ether.
All non-H atoms except C23 and C24 were refined with anisotropic displacement parameters. Friedel-related reflections were merged. The H atoms of the amino (N1) and hydroxyl (O1) atoms were positionally refined. All C-bound H atoms were constrained to their expected geometries, with C—H(methyl) = 0.98 Å and the remaining C—H = 1.0 Å. For all H atoms, Uiso(H) = 1.2Ueq(parent atom). The disordered diethyl ether was modelled with density at 11 atomic sites using C atoms only and a common Uiso; no extra O or H atoms were included for the ether solvate. Models of diethyl ether in two main orientations fit on these positions, but no rational model could be constructed. On the basis of the total electron density, about 0.62 of a diethyl ether molecule per asymmetric unit was found.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
C34H34N6O4·0.6C4H10O | F(000) = 1356 |
Mr = 655.53 | Dx = 1.241 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 895 reflections |
a = 9.006 (3) Å | θ = 2.6–14.6° |
b = 15.324 (6) Å | µ = 0.08 mm−1 |
c = 25.424 (11) Å | T = 88 K |
V = 3509 (2) Å3 | Needle, colourless |
Z = 4 | 0.50 × 0.22 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 4038 independent reflections |
Radiation source: fine-focus sealed tube | 908 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.328 |
Detector resolution: 8.192 pixels mm-1 | θmax = 26.4°, θmin = 2.1° |
ϕ and ω scans | h = −10→11 |
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 1996) | k = −19→19 |
Tmin = 0.597, Tmax = 0.986 | l = −31→28 |
19603 measured reflections |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.77 | w = 1/[σ2(Fo2) + (0.0367P)2] where P = (Fo2 + 2Fc2)/3 |
4038 reflections | (Δ/σ)max = 0.001 |
432 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
C34H34N6O4·0.6C4H10O | V = 3509 (2) Å3 |
Mr = 655.53 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 9.006 (3) Å | µ = 0.08 mm−1 |
b = 15.324 (6) Å | T = 88 K |
c = 25.424 (11) Å | 0.50 × 0.22 × 0.18 mm |
Bruker SMART CCD area-detector diffractometer | 4038 independent reflections |
Absorption correction: multi-scan (SADABS; Blessing, 1995; Sheldrick, 1996) | 908 reflections with I > 2σ(I) |
Tmin = 0.597, Tmax = 0.986 | Rint = 0.328 |
19603 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.77 | Δρmax = 0.16 e Å−3 |
4038 reflections | Δρmin = −0.20 e Å−3 |
432 parameters |
Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used. |
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) | |
O1 | 0.7436 (6) | 0.3110 (4) | 0.1485 (2) | 0.0547 (17) | |
O2 | 0.7278 (6) | 0.1551 (4) | 0.0859 (2) | 0.0522 (17) | |
O3 | 0.8286 (5) | 0.1748 (4) | −0.0209 (2) | 0.0477 (16) | |
O4 | 0.7249 (6) | 0.3301 (3) | −0.0704 (2) | 0.0451 (15) | |
N1 | 0.7476 (11) | 0.4853 (7) | −0.0070 (3) | 0.076 (3) | |
N2 | 0.6674 (12) | 0.5128 (6) | −0.0405 (4) | 0.080 (3) | |
N3 | 0.5965 (14) | 0.5481 (7) | −0.0733 (4) | 0.105 (4) | |
N4 | 0.8966 (10) | 0.4188 (6) | 0.0776 (3) | 0.067 (3) | |
N5 | 0.9346 (8) | 0.4555 (7) | 0.1199 (4) | 0.076 (3) | |
N6 | 0.9805 (10) | 0.4868 (7) | 0.1563 (4) | 0.095 (4) | |
C1 | 0.6971 (9) | 0.3995 (6) | 0.0131 (3) | 0.045 (2) | |
H1 | 0.5874 | 0.3930 | 0.0082 | 0.054* | |
C2 | 0.7362 (10) | 0.3986 (6) | 0.0714 (3) | 0.049 (2) | |
H2 | 0.6763 | 0.4441 | 0.0900 | 0.058* | |
C3 | 0.7012 (9) | 0.3103 (6) | 0.0944 (4) | 0.050 (3) | |
H3 | 0.5916 | 0.3008 | 0.0922 | 0.060* | |
C4 | 0.7785 (9) | 0.2368 (6) | 0.0649 (3) | 0.049 (2) | |
H4 | 0.8883 | 0.2417 | 0.0700 | 0.058* | |
C5 | 0.7432 (9) | 0.2396 (5) | 0.0064 (3) | 0.044 (2) | |
H5 | 0.6351 | 0.2272 | 0.0012 | 0.053* | |
C6 | 0.7795 (9) | 0.3291 (6) | −0.0171 (3) | 0.046 (2) | |
H6 | 0.8889 | 0.3401 | −0.0163 | 0.056* | |
C10 | 0.6367 (10) | 0.2744 (6) | 0.1831 (3) | 0.060 (3) | |
H10A | 0.6218 | 0.2118 | 0.1751 | 0.073* | |
H10B | 0.5404 | 0.3049 | 0.1793 | 0.073* | |
C11 | 0.6970 (10) | 0.2856 (8) | 0.2388 (4) | 0.057 (3) | |
C12 | 0.7496 (10) | 0.3635 (7) | 0.2570 (4) | 0.061 (3) | |
H12 | 0.7446 | 0.4136 | 0.2351 | 0.073* | |
C13 | 0.8094 (11) | 0.3703 (7) | 0.3062 (4) | 0.072 (3) | |
H13 | 0.8445 | 0.4251 | 0.3185 | 0.086* | |
C14 | 0.8187 (11) | 0.2975 (8) | 0.3382 (4) | 0.074 (3) | |
H14 | 0.8598 | 0.3023 | 0.3725 | 0.089* | |
C15 | 0.7697 (12) | 0.2198 (7) | 0.3208 (4) | 0.082 (3) | |
H15 | 0.7764 | 0.1700 | 0.3430 | 0.098* | |
C16 | 0.7088 (9) | 0.2114 (7) | 0.2702 (4) | 0.067 (3) | |
H16 | 0.6762 | 0.1562 | 0.2577 | 0.080* | |
C20 | 0.8410 (11) | 0.1078 (7) | 0.1139 (4) | 0.096 (4) | |
H20A | 0.8894 | 0.1462 | 0.1401 | 0.115* | |
H20B | 0.9177 | 0.0864 | 0.0892 | 0.115* | |
C21 | 0.7654 (16) | 0.0311 (8) | 0.1413 (5) | 0.088 (4) | |
C22 | 0.8293 (11) | 0.0112 (7) | 0.1900 (5) | 0.090 (4) | |
H22 | 0.9091 | 0.0457 | 0.2029 | 0.108* | |
C23 | 0.7766 (14) | −0.0590 (7) | 0.2197 (5) | 0.106 (4)* | |
H23 | 0.8199 | −0.0742 | 0.2526 | 0.127* | |
C24 | 0.6635 (15) | −0.1032 (7) | 0.1999 (5) | 0.107 (5)* | |
H24 | 0.6271 | −0.1507 | 0.2201 | 0.129* | |
C25 | 0.5942 (13) | −0.0871 (9) | 0.1531 (6) | 0.111 (4) | |
H25 | 0.5120 | −0.1208 | 0.1415 | 0.133* | |
C26 | 0.6519 (14) | −0.0166 (9) | 0.1225 (6) | 0.106 (5) | |
H26 | 0.6105 | −0.0035 | 0.0890 | 0.127* | |
C30 | 0.7428 (11) | 0.1059 (7) | −0.0402 (4) | 0.094 (4) | |
H30A | 0.6617 | 0.1298 | −0.0622 | 0.113* | |
H30B | 0.6969 | 0.0746 | −0.0102 | 0.113* | |
C31 | 0.8306 (11) | 0.0438 (8) | −0.0716 (6) | 0.068 (4) | |
C32 | 0.8859 (13) | −0.0288 (10) | −0.0474 (5) | 0.082 (4) | |
H32 | 0.8670 | −0.0383 | −0.0111 | 0.099* | |
C33 | 0.9672 (17) | −0.0869 (10) | −0.0747 (7) | 0.109 (5) | |
H33 | 1.0062 | −0.1359 | −0.0563 | 0.131* | |
C34 | 0.9964 (12) | −0.0800 (9) | −0.1260 (7) | 0.092 (4) | |
H34 | 1.0544 | −0.1229 | −0.1435 | 0.110* | |
C35 | 0.9387 (13) | −0.0068 (11) | −0.1541 (4) | 0.078 (3) | |
H35 | 0.9548 | −0.0002 | −0.1908 | 0.093* | |
C36 | 0.8576 (13) | 0.0548 (8) | −0.1254 (6) | 0.079 (4) | |
H36 | 0.8202 | 0.1051 | −0.1428 | 0.094* | |
C40 | 0.8304 (10) | 0.3439 (7) | −0.1094 (3) | 0.089 (4) | |
H40A | 0.9110 | 0.3004 | −0.1057 | 0.107* | |
H40B | 0.8743 | 0.4027 | −0.1051 | 0.107* | |
C41 | 0.7624 (11) | 0.3364 (7) | −0.1631 (3) | 0.050 (3) | |
C42 | 0.6582 (11) | 0.2761 (6) | −0.1741 (4) | 0.053 (3) | |
H42 | 0.6249 | 0.2376 | −0.1473 | 0.064* | |
C43 | 0.5992 (11) | 0.2697 (6) | −0.2243 (5) | 0.068 (3) | |
H43 | 0.5252 | 0.2272 | −0.2316 | 0.081* | |
C44 | 0.6467 (12) | 0.3238 (8) | −0.2628 (4) | 0.074 (3) | |
H44 | 0.6069 | 0.3188 | −0.2973 | 0.089* | |
C45 | 0.7535 (13) | 0.3865 (6) | −0.2520 (4) | 0.073 (3) | |
H45 | 0.7852 | 0.4255 | −0.2788 | 0.088* | |
C46 | 0.8135 (11) | 0.3919 (6) | −0.2021 (4) | 0.064 (3) | |
H46 | 0.8890 | 0.4333 | −0.1946 | 0.076* | |
C51 | 0.541 (5) | −0.171 (4) | −0.001 (2) | 0.205 (6)* | 0.65 (5) |
C52 | 0.387 (4) | −0.170 (2) | −0.0678 (14) | 0.205 (6)* | 0.73 (4) |
C53 | 0.389 (4) | −0.220 (3) | −0.036 (2) | 0.205 (6)* | 0.63 (4) |
C54 | 0.508 (4) | −0.1490 (19) | −0.0428 (19) | 0.205 (6)* | 0.71 (4) |
C55 | 0.305 (4) | −0.254 (2) | −0.0731 (15) | 0.205 (6)* | 0.63 (3) |
C56 | 0.657 (7) | −0.230 (3) | −0.009 (2) | 0.205 (6)* | 0.45 (3) |
C57 | 0.218 (5) | −0.285 (2) | −0.038 (2) | 0.205 (6)* | 0.50 (3) |
C58 | 0.304 (7) | −0.223 (3) | 0.0128 (17) | 0.205 (6)* | 0.44 (3) |
C59 | 0.438 (7) | −0.163 (4) | 0.042 (3) | 0.205 (6)* | 0.32 (3) |
C60 | 0.578 (9) | −0.102 (8) | 0.012 (3) | 0.205 (6)* | 0.22 (3) |
C61 | 0.081 (13) | −0.240 (8) | −0.101 (5) | 0.205 (6)* | 0.132 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.046 (4) | 0.083 (5) | 0.035 (4) | 0.002 (4) | 0.010 (3) | 0.009 (4) |
O2 | 0.036 (4) | 0.060 (5) | 0.061 (4) | −0.002 (3) | 0.001 (3) | 0.019 (4) |
O3 | 0.031 (4) | 0.057 (4) | 0.055 (4) | −0.011 (4) | −0.005 (3) | 0.000 (4) |
O4 | 0.035 (4) | 0.061 (4) | 0.040 (4) | 0.002 (3) | 0.003 (3) | −0.004 (4) |
N1 | 0.094 (8) | 0.083 (8) | 0.050 (7) | 0.011 (6) | −0.004 (6) | 0.002 (6) |
N2 | 0.097 (11) | 0.059 (9) | 0.084 (11) | −0.024 (7) | 0.039 (8) | −0.013 (8) |
N3 | 0.151 (11) | 0.084 (9) | 0.079 (10) | −0.024 (7) | 0.013 (7) | 0.002 (6) |
N4 | 0.069 (7) | 0.085 (7) | 0.046 (6) | 0.000 (5) | 0.013 (5) | 0.003 (5) |
N5 | 0.032 (6) | 0.134 (11) | 0.061 (8) | −0.002 (6) | 0.012 (6) | 0.000 (8) |
N6 | 0.064 (7) | 0.147 (10) | 0.073 (8) | −0.011 (6) | 0.012 (5) | −0.042 (7) |
C1 | 0.038 (6) | 0.037 (6) | 0.059 (7) | −0.003 (5) | 0.001 (5) | 0.008 (6) |
C2 | 0.022 (6) | 0.073 (8) | 0.051 (7) | 0.003 (5) | 0.006 (5) | −0.005 (6) |
C3 | 0.042 (7) | 0.056 (7) | 0.052 (7) | −0.007 (5) | 0.002 (5) | 0.020 (6) |
C4 | 0.029 (6) | 0.065 (8) | 0.053 (7) | −0.001 (5) | −0.007 (5) | 0.007 (6) |
C5 | 0.029 (6) | 0.054 (7) | 0.049 (7) | 0.010 (5) | −0.005 (5) | −0.009 (6) |
C6 | 0.039 (6) | 0.045 (6) | 0.055 (7) | −0.001 (5) | 0.011 (5) | −0.003 (6) |
C10 | 0.051 (7) | 0.079 (8) | 0.051 (7) | −0.001 (6) | 0.010 (6) | 0.002 (6) |
C11 | 0.053 (7) | 0.060 (8) | 0.058 (8) | −0.003 (6) | 0.006 (6) | 0.008 (7) |
C12 | 0.057 (8) | 0.074 (9) | 0.052 (8) | 0.012 (7) | 0.006 (6) | 0.008 (6) |
C13 | 0.084 (9) | 0.081 (10) | 0.050 (8) | 0.013 (7) | 0.019 (7) | −0.002 (7) |
C14 | 0.090 (9) | 0.082 (9) | 0.049 (7) | −0.024 (7) | −0.018 (6) | −0.005 (8) |
C15 | 0.110 (9) | 0.081 (9) | 0.054 (8) | −0.029 (8) | 0.008 (7) | 0.010 (6) |
C16 | 0.054 (7) | 0.093 (10) | 0.054 (7) | −0.019 (6) | −0.007 (5) | −0.019 (7) |
C20 | 0.054 (8) | 0.096 (9) | 0.138 (11) | 0.020 (7) | 0.012 (7) | 0.073 (8) |
C21 | 0.093 (12) | 0.083 (11) | 0.087 (10) | 0.057 (9) | 0.015 (9) | 0.030 (8) |
C22 | 0.085 (9) | 0.071 (9) | 0.113 (10) | −0.020 (8) | 0.034 (8) | −0.008 (8) |
C25 | 0.047 (9) | 0.120 (11) | 0.165 (15) | −0.003 (8) | 0.033 (9) | −0.009 (10) |
C26 | 0.048 (10) | 0.108 (12) | 0.162 (15) | 0.009 (8) | 0.017 (9) | −0.031 (11) |
C30 | 0.068 (9) | 0.072 (8) | 0.141 (11) | −0.006 (8) | 0.030 (8) | −0.019 (8) |
C31 | 0.048 (8) | 0.042 (9) | 0.114 (13) | −0.016 (7) | −0.017 (8) | 0.003 (9) |
C32 | 0.075 (10) | 0.081 (11) | 0.091 (11) | −0.032 (8) | 0.009 (8) | −0.026 (11) |
C33 | 0.145 (14) | 0.088 (12) | 0.094 (13) | −0.029 (11) | −0.026 (11) | 0.029 (11) |
C34 | 0.086 (10) | 0.068 (11) | 0.121 (14) | −0.014 (8) | −0.012 (10) | −0.024 (10) |
C35 | 0.066 (9) | 0.111 (12) | 0.057 (9) | −0.020 (8) | −0.003 (7) | 0.002 (10) |
C36 | 0.057 (9) | 0.092 (11) | 0.087 (11) | −0.012 (8) | −0.023 (7) | 0.004 (10) |
C40 | 0.058 (8) | 0.169 (11) | 0.039 (7) | −0.013 (8) | −0.001 (6) | 0.012 (7) |
C41 | 0.039 (7) | 0.075 (8) | 0.038 (6) | 0.003 (6) | 0.013 (5) | −0.001 (6) |
C42 | 0.042 (7) | 0.065 (8) | 0.053 (8) | 0.010 (6) | 0.000 (5) | 0.031 (6) |
C43 | 0.075 (8) | 0.042 (8) | 0.086 (9) | −0.015 (6) | 0.021 (7) | −0.006 (7) |
C44 | 0.086 (9) | 0.087 (10) | 0.049 (8) | −0.006 (8) | −0.011 (6) | −0.021 (8) |
C45 | 0.103 (10) | 0.067 (8) | 0.050 (8) | −0.004 (8) | 0.003 (7) | 0.013 (6) |
C46 | 0.070 (8) | 0.067 (8) | 0.053 (8) | −0.013 (6) | 0.002 (6) | −0.015 (6) |
O1—C10 | 1.418 (8) | C23—H23 | 0.9500 |
O1—C3 | 1.429 (8) | C24—C25 | 1.367 (14) |
O2—C4 | 1.435 (8) | C24—H24 | 0.9500 |
O2—C20 | 1.440 (9) | C25—C26 | 1.430 (14) |
O3—C30 | 1.397 (9) | C25—H25 | 0.9500 |
O3—C5 | 1.435 (8) | C26—H26 | 0.9500 |
O4—C40 | 1.389 (8) | C30—C31 | 1.474 (13) |
O4—C6 | 1.442 (8) | C30—H30A | 0.9900 |
N1—N2 | 1.194 (11) | C30—H30B | 0.9900 |
N1—C1 | 1.482 (10) | C31—C32 | 1.365 (13) |
N2—N3 | 1.180 (11) | C31—C36 | 1.400 (12) |
N4—N5 | 1.261 (10) | C32—C33 | 1.345 (14) |
N4—C2 | 1.486 (10) | C32—H32 | 0.9500 |
N5—N6 | 1.122 (10) | C33—C34 | 1.335 (13) |
C1—C6 | 1.518 (9) | C33—H33 | 0.9500 |
C1—C2 | 1.522 (9) | C34—C35 | 1.427 (12) |
C1—H1 | 1.0000 | C34—H34 | 0.9500 |
C2—C3 | 1.507 (10) | C35—C36 | 1.399 (13) |
C2—H2 | 1.0000 | C35—H35 | 0.9500 |
C3—C4 | 1.522 (10) | C36—H36 | 0.9500 |
C3—H3 | 1.0000 | C40—C41 | 1.500 (10) |
C4—C5 | 1.520 (9) | C40—H40A | 0.9900 |
C4—H4 | 1.0000 | C40—H40B | 0.9900 |
C5—C6 | 1.532 (9) | C41—C42 | 1.347 (11) |
C5—H5 | 1.0000 | C41—C46 | 1.386 (10) |
C6—H6 | 1.0000 | C42—C43 | 1.385 (11) |
C10—C11 | 1.526 (11) | C42—H42 | 0.9500 |
C10—H10A | 0.9900 | C43—C44 | 1.353 (11) |
C10—H10B | 0.9900 | C43—H43 | 0.9500 |
C11—C12 | 1.364 (10) | C44—C45 | 1.387 (11) |
C11—C16 | 1.394 (10) | C44—H44 | 0.9500 |
C12—C13 | 1.367 (11) | C45—C46 | 1.381 (11) |
C12—H12 | 0.9500 | C45—H45 | 0.9500 |
C13—C14 | 1.383 (10) | C46—H46 | 0.9500 |
C13—H13 | 0.9500 | C51—C56 | 1.40 (6) |
C14—C15 | 1.344 (10) | C51—C59 | 1.44 (6) |
C14—H14 | 0.9500 | C52—C54 | 1.31 (4) |
C15—C16 | 1.404 (10) | C52—C55 | 1.49 (5) |
C15—H15 | 0.9500 | C53—C55 | 1.31 (4) |
C16—H16 | 0.9500 | C53—C58 | 1.47 (5) |
C20—C21 | 1.528 (13) | C53—C54 | 1.54 (5) |
C20—H20A | 0.9900 | C54—C60 | 1.69 (11) |
C20—H20B | 0.9900 | C55—C57 | 1.27 (5) |
C21—C26 | 1.344 (14) | C56—C57i | 1.35 (5) |
C21—C22 | 1.397 (13) | C56—C58i | 1.50 (6) |
C22—C23 | 1.399 (12) | C57—C56ii | 1.35 (5) |
C22—H22 | 0.9500 | C58—C56ii | 1.50 (6) |
C23—C24 | 1.323 (13) | ||
C10—O1—C3 | 114.4 (6) | C21—C20—H20A | 110.2 |
C4—O2—C20 | 113.5 (7) | O2—C20—H20B | 110.2 |
C30—O3—C5 | 113.3 (7) | C21—C20—H20B | 110.2 |
C40—O4—C6 | 116.1 (6) | H20A—C20—H20B | 108.5 |
N2—N1—C1 | 111.9 (10) | C26—C21—C22 | 120.8 (13) |
N3—N2—N1 | 172.9 (13) | C26—C21—C20 | 126.4 (14) |
N5—N4—C2 | 116.6 (8) | C22—C21—C20 | 112.8 (14) |
N6—N5—N4 | 174.1 (11) | C21—C22—C23 | 120.4 (12) |
N1—C1—C6 | 107.7 (7) | C21—C22—H22 | 119.8 |
N1—C1—C2 | 105.8 (8) | C23—C22—H22 | 119.8 |
C6—C1—C2 | 111.9 (7) | C24—C23—C22 | 116.7 (12) |
N1—C1—H1 | 110.4 | C24—C23—H23 | 121.7 |
C6—C1—H1 | 110.4 | C22—C23—H23 | 121.7 |
C2—C1—H1 | 110.4 | C23—C24—C25 | 126.2 (13) |
N4—C2—C3 | 110.4 (7) | C23—C24—H24 | 116.9 |
N4—C2—C1 | 109.1 (7) | C25—C24—H24 | 116.9 |
C3—C2—C1 | 109.7 (8) | C24—C25—C26 | 116.4 (13) |
N4—C2—H2 | 109.2 | C24—C25—H25 | 121.8 |
C3—C2—H2 | 109.2 | C26—C25—H25 | 121.8 |
C1—C2—H2 | 109.2 | C21—C26—C25 | 119.5 (14) |
O1—C3—C2 | 108.2 (7) | C21—C26—H26 | 120.3 |
O1—C3—C4 | 111.0 (7) | C25—C26—H26 | 120.3 |
C2—C3—C4 | 112.2 (7) | O3—C30—C31 | 112.5 (8) |
O1—C3—H3 | 108.5 | O3—C30—H30A | 109.1 |
C2—C3—H3 | 108.5 | C31—C30—H30A | 109.1 |
C4—C3—H3 | 108.5 | O3—C30—H30B | 109.1 |
O2—C4—C5 | 108.8 (7) | C31—C30—H30B | 109.1 |
O2—C4—C3 | 108.5 (7) | H30A—C30—H30B | 107.8 |
C5—C4—C3 | 111.4 (8) | C32—C31—C36 | 118.3 (12) |
O2—C4—H4 | 109.4 | C32—C31—C30 | 118.6 (15) |
C5—C4—H4 | 109.4 | C36—C31—C30 | 123.0 (14) |
C3—C4—H4 | 109.4 | C33—C32—C31 | 120.4 (14) |
O3—C5—C4 | 110.0 (7) | C33—C32—H32 | 119.8 |
O3—C5—C6 | 108.4 (7) | C31—C32—H32 | 119.8 |
C4—C5—C6 | 111.2 (7) | C34—C33—C32 | 123.9 (16) |
O3—C5—H5 | 109.1 | C34—C33—H33 | 118.1 |
C4—C5—H5 | 109.1 | C32—C33—H33 | 118.1 |
C6—C5—H5 | 109.1 | C33—C34—C35 | 118.7 (14) |
O4—C6—C1 | 107.6 (7) | C33—C34—H34 | 120.7 |
O4—C6—C5 | 107.6 (7) | C35—C34—H34 | 120.7 |
C1—C6—C5 | 109.5 (7) | C36—C35—C34 | 117.4 (11) |
O4—C6—H6 | 110.7 | C36—C35—H35 | 121.3 |
C1—C6—H6 | 110.7 | C34—C35—H35 | 121.3 |
C5—C6—H6 | 110.7 | C35—C36—C31 | 121.2 (12) |
O1—C10—C11 | 106.8 (7) | C35—C36—H36 | 119.4 |
O1—C10—H10A | 110.4 | C31—C36—H36 | 119.4 |
C11—C10—H10A | 110.4 | O4—C40—C41 | 111.0 (7) |
O1—C10—H10B | 110.4 | O4—C40—H40A | 109.4 |
C11—C10—H10B | 110.4 | C41—C40—H40A | 109.4 |
H10A—C10—H10B | 108.6 | O4—C40—H40B | 109.4 |
C12—C11—C16 | 119.5 (9) | C41—C40—H40B | 109.4 |
C12—C11—C10 | 122.4 (10) | H40A—C40—H40B | 108.0 |
C16—C11—C10 | 117.8 (10) | C42—C41—C46 | 120.2 (9) |
C11—C12—C13 | 120.9 (10) | C42—C41—C40 | 121.8 (10) |
C11—C12—H12 | 119.5 | C46—C41—C40 | 118.0 (10) |
C13—C12—H12 | 119.5 | C41—C42—C43 | 120.5 (9) |
C12—C13—C14 | 120.0 (10) | C41—C42—H42 | 119.8 |
C12—C13—H13 | 120.0 | C43—C42—H42 | 119.8 |
C14—C13—H13 | 120.0 | C44—C43—C42 | 120.2 (9) |
C15—C14—C13 | 120.1 (10) | C44—C43—H43 | 119.9 |
C15—C14—H14 | 120.0 | C42—C43—H43 | 119.9 |
C13—C14—H14 | 120.0 | C43—C44—C45 | 120.0 (9) |
C14—C15—C16 | 120.7 (10) | C43—C44—H44 | 120.0 |
C14—C15—H15 | 119.6 | C45—C44—H44 | 120.0 |
C16—C15—H15 | 119.6 | C46—C45—C44 | 119.7 (9) |
C11—C16—C15 | 118.7 (9) | C46—C45—H45 | 120.2 |
C11—C16—H16 | 120.7 | C44—C45—H45 | 120.2 |
C15—C16—H16 | 120.7 | C45—C46—C41 | 119.4 (9) |
O2—C20—C21 | 107.3 (9) | C45—C46—H46 | 120.3 |
O2—C20—H20A | 110.2 | C41—C46—H46 | 120.3 |
N2—N1—C1—C6 | 94.6 (10) | C10—C11—C12—C13 | −176.9 (8) |
N2—N1—C1—C2 | −145.5 (9) | C11—C12—C13—C14 | 0.7 (14) |
N5—N4—C2—C3 | −88.0 (10) | C12—C13—C14—C15 | 0.3 (15) |
N5—N4—C2—C1 | 151.4 (8) | C13—C14—C15—C16 | 0.1 (16) |
N1—C1—C2—N4 | −53.9 (9) | C12—C11—C16—C15 | 2.4 (13) |
C6—C1—C2—N4 | 63.2 (9) | C10—C11—C16—C15 | 177.4 (8) |
N1—C1—C2—C3 | −175.0 (7) | C14—C15—C16—C11 | −1.4 (14) |
C6—C1—C2—C3 | −57.9 (9) | C4—O2—C20—C21 | 170.8 (8) |
C10—O1—C3—C2 | 134.6 (7) | O2—C20—C21—C26 | 36.3 (15) |
C10—O1—C3—C4 | −101.9 (8) | O2—C20—C21—C22 | −145.3 (9) |
N4—C2—C3—O1 | 58.0 (9) | C26—C21—C22—C23 | 0.4 (17) |
C1—C2—C3—O1 | 178.2 (6) | C20—C21—C22—C23 | −178.1 (9) |
N4—C2—C3—C4 | −64.8 (10) | C21—C22—C23—C24 | −1.3 (15) |
C1—C2—C3—C4 | 55.5 (9) | C22—C23—C24—C25 | 0.4 (17) |
C20—O2—C4—C5 | 126.6 (8) | C23—C24—C25—C26 | 1.3 (18) |
C20—O2—C4—C3 | −112.0 (8) | C22—C21—C26—C25 | 1.4 (18) |
O1—C3—C4—O2 | 64.5 (8) | C20—C21—C26—C25 | 179.6 (9) |
C2—C3—C4—O2 | −174.4 (7) | C24—C25—C26—C21 | −2.1 (17) |
O1—C3—C4—C5 | −175.8 (7) | C5—O3—C30—C31 | 175.5 (9) |
C2—C3—C4—C5 | −54.7 (10) | O3—C30—C31—C32 | 95.1 (11) |
C30—O3—C5—C4 | 110.5 (8) | O3—C30—C31—C36 | −86.1 (12) |
C30—O3—C5—C6 | −127.7 (8) | C36—C31—C32—C33 | 1.5 (15) |
O2—C4—C5—O3 | −66.0 (8) | C30—C31—C32—C33 | −179.7 (10) |
C3—C4—C5—O3 | 174.5 (7) | C31—C32—C33—C34 | −1.7 (19) |
O2—C4—C5—C6 | 173.9 (7) | C32—C33—C34—C35 | 0.0 (19) |
C3—C4—C5—C6 | 54.4 (9) | C33—C34—C35—C36 | 1.7 (16) |
C40—O4—C6—C1 | 122.1 (8) | C34—C35—C36—C31 | −1.8 (16) |
C40—O4—C6—C5 | −119.9 (8) | C32—C31—C36—C35 | 0.3 (15) |
N1—C1—C6—O4 | −69.3 (8) | C30—C31—C36—C35 | −178.5 (10) |
C2—C1—C6—O4 | 174.8 (7) | C6—O4—C40—C41 | 175.5 (7) |
N1—C1—C6—C5 | 174.0 (7) | O4—C40—C41—C42 | −38.5 (13) |
C2—C1—C6—C5 | 58.1 (9) | O4—C40—C41—C46 | 143.5 (9) |
O3—C5—C6—O4 | 66.5 (8) | C46—C41—C42—C43 | −1.0 (13) |
C4—C5—C6—O4 | −172.5 (6) | C40—C41—C42—C43 | −178.9 (9) |
O3—C5—C6—C1 | −176.9 (7) | C41—C42—C43—C44 | 0.5 (14) |
C4—C5—C6—C1 | −55.8 (9) | C42—C43—C44—C45 | −0.7 (15) |
C3—O1—C10—C11 | −176.8 (7) | C43—C44—C45—C46 | 1.6 (15) |
O1—C10—C11—C12 | 49.4 (11) | C44—C45—C46—C41 | −2.1 (14) |
O1—C10—C11—C16 | −125.5 (8) | C42—C41—C46—C45 | 1.8 (14) |
C16—C11—C12—C13 | −2.1 (14) | C40—C41—C46—C45 | 179.8 (9) |
Symmetry codes: (i) x+1/2, −y−1/2, −z; (ii) x−1/2, −y−1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg1iii | 1.0 | 2.64 | 3.510 (10) | 146 |
C43—H43···Cg2iii | 0.95 | 2.82 | 3.597 (11) | 140 |
C1—H1···O3iii | 1.00 | 2.57 | 3.514 (10) | 157 |
C30—H30A···N4iii | 0.99 | 2.53 | 3.282 (13) | 132 |
C14—H14···N3iv | 0.95 | 2.70 | 3.353 (16) | 126 |
C20—H20B···N3v | 0.99 | 2.65 | 3.474 (16) | 141 |
Symmetry codes: (iii) x−1/2, −y+1/2, −z; (iv) −x+3/2, −y+1, z+1/2; (v) x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C34H34N6O4·0.6C4H10O |
Mr | 655.53 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 88 |
a, b, c (Å) | 9.006 (3), 15.324 (6), 25.424 (11) |
V (Å3) | 3509 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Blessing, 1995; Sheldrick, 1996) |
Tmin, Tmax | 0.597, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19603, 4038, 908 |
Rint | 0.328 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.127, 0.77 |
No. of reflections | 4038 |
No. of parameters | 432 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.20 |
Computer programs: SMART (Siemens, 1996), SMART, SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).
O1—C3 | 1.429 (8) | N1—C1 | 1.482 (10) |
N1—N2 | 1.194 (11) | N2—N3 | 1.180 (11) |
C10—O1—C3 | 114.4 (6) | N3—N2—N1 | 172.9 (13) |
N2—N1—C1 | 111.9 (10) | N1—C1—C2 | 105.8 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···Cg1i | 1.0 | 2.64 | 3.510 (10) | 146 |
C43—H43···Cg2i | 0.95 | 2.82 | 3.597 (11) | 140 |
C1—H1···O3i | 1.00 | 2.57 | 3.514 (10) | 157 |
C30—H30A···N4i | 0.99 | 2.53 | 3.282 (13) | 132 |
C14—H14···N3ii | 0.95 | 2.70 | 3.353 (16) | 126 |
C20—H20B···N3iii | 0.99 | 2.65 | 3.474 (16) | 141 |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x+3/2, −y+1, z+1/2; (iii) x+1/2, −y+1/2, −z. |
The title compound, (I), was prepared as part of a programme aimed at generating new hydrogenation catalyst ligands from inositol molecules (Gainsford et al., 2000; Falshaw et al., 1999).
The asymmetric unit of (I) contains one independent molecule, as shown in Fig. 1. The absolute configuration shown is that determined from the chemical synthesis route. There are few cyclohexane structures in the Cambridge Structural Database (CSD, Version?; Allen, 2002) with adjacent azide and O substituents, namely CSD refcodes QAPSAB and QAPSEF (Akai, Nakamura et al., 1999; Akai, Sugita et al., 1999), AZUZAW (Busscher et al., 2004) and IXEVAI (Carballido et al., 2004). The azide angular geometries C1—N1—N2 and N1—N2—N3 in (I) fall within the previously observed ranges of 114–119° and 170–174°, respectively. The cyclohexane ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.573 (9) Å, θ = 2.6 (9)° and ϕ = 347 (20)°.
Normally, inositol derivatives are strongly hydrogen-bonded, utilizing all available bound groups, e.g. O—H···O (GEGWIY; Dietrich et al., 1999) and C—H···O═C (HADKIG; Steiner et al., 1993). Although the crystals of (I) were weakly diffracting, the crystal packing stability has again been assisted by definite, though weak, non-classical hydrogen bonding involving C—H···X (where X is O or Nazide) and C—H···π interactions, as detailed in Table 2. These forces are sufficient to stabilize a partial molecule of the crystallizing solvent diethyl ether in the lattice (estimated as 0.6 of a molecule).
There are two types of C—H···Nazide interactions in the structure of (I). One was unexpected, being to the inositol ring-bound atom N4, while the other two were to the terminal azide atom N3. The former have rarely been observed, according to a CSD search, with only one occurrence noted in SUMRAT (Goulaouic et al., 1993), with H···N = 2.67 Å and C—H···N = 131°. There are currently five instances of C—H···Nterminal interactions. Three examples are ZDGPLN (Schmidt et al., 1980), MIYKIO (Barnes et al., 2002) and YASBAW (Humphreys et al., 2005) with H···N values of 2.62, 2.59 and 2.47 Å, respectively, and C—H···N angles of 127, 146 and 161°, respectively. In the last of these structures, the interaction was apparently insufficient to reduce the disorder found in the azide group.
The C—H···π interactions listed in Table 2 fit within the normal applied H···Cg limit of 3 Å. From the interaction distances, it seems highly likely that there is also a C—H···O hydrogen bond to the disordered diethyl ether solvent, with C26—H26···O(C60) = 2.49 Å, C26···O = 3.17 (9) Å and C—H···O = 138°.
The combined weak interactions give three-dimensional stability to the crystal structure, although it is difficult to show this meaningfully in a packing diagram. Instead, Fig. 2 (Mercury; Bruno et al., 2002), shows the full interaction commitments of all the bound groups to the inositol as dotted bonds, with the disordered solvent molecules represented by one atom, O(C60) (see Experimental).