Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801003956/na6059sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801003956/na6059Isup2.hkl |
CCDC reference: 162809
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.066
- wR factor = 0.191
- Data-to-parameter ratio = 14.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_731 Alert C Bond Calc 1.31(3), Rep 1.305(13) .... 2.31 s.u-Ratio C1B -C2B 1.555 1.555 PLAT_731 Alert C Bond Calc 1.33(3), Rep 1.332(13) .... 2.31 s.u-Ratio C1B -C3B 1.555 5.665 PLAT_731 Alert C Bond Calc 1.30(4), Rep 1.303(13) .... 3.08 s.u-Ratio C2B -C3B 1.555 1.555 PLAT_731 Alert C Bond Calc 1.33(3), Rep 1.332(13) .... 2.31 s.u-Ratio C3B -C1B 1.555 5.665
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check
Colourless single crystals were obtained as transparent needles by slow evaporation of a benzene solution at room temperature.
All the H atoms were located from a difference Fourier map and were allowed to ride on the heavier atoms to which they are attached using default values for bond lengths and displacement parameters.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
C36H36N2O5·C6H6 | F(000) = 1392 |
Mr = 654.78 | Dx = 1.224 Mg m−3 |
Orthorhombic, Pnma | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 25 reflections |
a = 16.6240 (5) Å | θ = 16–26° |
b = 26.0007 (16) Å | µ = 0.64 mm−1 |
c = 8.2207 (7) Å | T = 293 K |
V = 3553.3 (4) Å3 | Needles, colourless |
Z = 4 | 0.33 × 0.22 × 0.18 mm |
Enraf-Nonius CAD-4 diffractometer | 2226 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.010 |
Graphite monochromator | θmax = 70.0°, θmin = 3.4° |
/w–2/q scans | h = 0→20 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→31 |
Tmin = 0.864, Tmax = 0.892 | l = 0→10 |
3401 measured reflections | 2 standard reflections every 200 reflections |
3401 independent reflections | intensity decay: 0.1% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.066 | H-atom parameters constrained |
wR(F2) = 0.191 | w = 1/[σ2(Fo2) + (0.0399P)2 + 6.1627P] where P = (Fo2 + 2Fc2)/3 |
S = 1.13 | (Δ/σ)max < 0.001 |
3401 reflections | Δρmax = 0.29 e Å−3 |
230 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00090 (11) |
C36H36N2O5·C6H6 | V = 3553.3 (4) Å3 |
Mr = 654.78 | Z = 4 |
Orthorhombic, Pnma | Cu Kα radiation |
a = 16.6240 (5) Å | µ = 0.64 mm−1 |
b = 26.0007 (16) Å | T = 293 K |
c = 8.2207 (7) Å | 0.33 × 0.22 × 0.18 mm |
Enraf-Nonius CAD-4 diffractometer | 2226 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.010 |
Tmin = 0.864, Tmax = 0.892 | 2 standard reflections every 200 reflections |
3401 measured reflections | intensity decay: 0.1% |
3401 independent reflections |
R[F2 > 2σ(F2)] = 0.066 | 0 restraints |
wR(F2) = 0.191 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.29 e Å−3 |
3401 reflections | Δρmin = −0.20 e Å−3 |
230 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) | |
N1 | 0.3199 (2) | 0.2500 | −0.2382 (5) | 0.0376 (9) | |
C2 | 0.4080 (3) | 0.2500 | −0.2495 (6) | 0.0397 (11) | |
H2A | 0.4248 | 0.2801 | −0.3103 | 0.048* | 0.50 |
H2B | 0.4248 | 0.2199 | −0.3103 | 0.048* | 0.50 |
N3 | 0.4496 (2) | 0.2500 | −0.0909 (5) | 0.0386 (9) | |
C4 | 0.42588 (19) | 0.29796 (13) | −0.0049 (4) | 0.0378 (8) | |
H4 | 0.4367 | 0.3259 | −0.0817 | 0.045* | |
C5 | 0.33314 (19) | 0.29789 (13) | 0.0201 (4) | 0.0399 (8) | |
H5 | 0.3161 | 0.3286 | 0.0800 | 0.048* | |
C6 | 0.2918 (2) | 0.29584 (13) | −0.1496 (4) | 0.0395 (8) | |
H6 | 0.2341 | 0.2912 | −0.1302 | 0.047* | |
C10 | 0.3093 (3) | 0.2500 | 0.1103 (6) | 0.0402 (11) | |
O11 | 0.2731 (2) | 0.2500 | 0.2391 (4) | 0.0513 (9) | |
C41 | 0.4747 (2) | 0.31038 (12) | 0.1447 (4) | 0.0367 (8) | |
C42 | 0.5587 (2) | 0.31181 (14) | 0.1355 (5) | 0.0460 (9) | |
H42 | 0.5837 | 0.3029 | 0.0384 | 0.055* | |
C43 | 0.6051 (2) | 0.32602 (14) | 0.2657 (5) | 0.0474 (9) | |
H43 | 0.6609 | 0.3256 | 0.2569 | 0.057* | |
C44 | 0.5693 (2) | 0.34093 (13) | 0.4101 (4) | 0.0432 (8) | |
C45 | 0.4865 (2) | 0.34060 (14) | 0.4229 (4) | 0.0453 (9) | |
H45 | 0.4616 | 0.3509 | 0.5188 | 0.054* | |
C46 | 0.4408 (2) | 0.32464 (14) | 0.2903 (4) | 0.0450 (9) | |
H46 | 0.3851 | 0.3236 | 0.3007 | 0.054* | |
O47 | 0.62036 (15) | 0.35496 (11) | 0.5339 (3) | 0.0570 (7) | |
C48 | 0.5862 (3) | 0.3659 (2) | 0.6866 (5) | 0.0822 (16) | |
H48A | 0.6279 | 0.3751 | 0.7619 | 0.123* | |
H48B | 0.5583 | 0.3360 | 0.7260 | 0.123* | |
H48C | 0.5490 | 0.3939 | 0.6761 | 0.123* | |
C61 | 0.3010 (2) | 0.34442 (13) | −0.2511 (4) | 0.0412 (8) | |
C62 | 0.2767 (2) | 0.34370 (14) | −0.4137 (4) | 0.0462 (9) | |
H62 | 0.2599 | 0.3129 | −0.4602 | 0.055* | |
C63 | 0.2771 (2) | 0.38790 (15) | −0.5065 (5) | 0.0522 (10) | |
H63 | 0.2597 | 0.3868 | −0.6139 | 0.063* | |
C64 | 0.3032 (2) | 0.43397 (15) | −0.4404 (5) | 0.0560 (10) | |
C65 | 0.3290 (3) | 0.43554 (15) | −0.2823 (5) | 0.0632 (12) | |
H65 | 0.3477 | 0.4661 | −0.2377 | 0.076* | |
C66 | 0.3270 (3) | 0.39082 (15) | −0.1889 (5) | 0.0579 (11) | |
H66 | 0.3438 | 0.3923 | −0.0811 | 0.070* | |
O67 | 0.3004 (2) | 0.47552 (11) | −0.5421 (4) | 0.0791 (10) | |
C68 | 0.3254 (4) | 0.52372 (18) | −0.4764 (8) | 0.109 (2) | |
H68A | 0.3209 | 0.5498 | −0.5585 | 0.164* | |
H68B | 0.3802 | 0.5213 | −0.4410 | 0.164* | |
H68C | 0.2917 | 0.5325 | −0.3856 | 0.164* | |
C1B | 0.4342 (9) | 0.4969 (12) | 0.090 (2) | 0.162 (5) | |
H1B | 0.3884 | 0.4947 | 0.1547 | 0.195* | |
C2B | 0.4424 (14) | 0.5339 (7) | −0.016 (3) | 0.161 (5) | |
H2B1 | 0.4014 | 0.5578 | −0.0283 | 0.193* | |
C3B | 0.5072 (19) | 0.5378 (5) | −0.1042 (16) | 0.155 (5) | |
H3B | 0.5125 | 0.5649 | −0.1773 | 0.186* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.038 (2) | 0.038 (2) | 0.036 (2) | 0.000 | 0.0003 (18) | 0.000 |
C2 | 0.049 (3) | 0.034 (2) | 0.036 (3) | 0.000 | 0.006 (2) | 0.000 |
N3 | 0.037 (2) | 0.042 (2) | 0.036 (2) | 0.000 | 0.0059 (18) | 0.000 |
C4 | 0.0393 (18) | 0.0388 (18) | 0.0352 (18) | 0.0017 (15) | 0.0019 (15) | −0.0007 (15) |
C5 | 0.0375 (18) | 0.0435 (19) | 0.0388 (19) | 0.0024 (15) | 0.0008 (15) | −0.0006 (16) |
C6 | 0.0386 (18) | 0.0428 (19) | 0.0370 (18) | 0.0045 (15) | 0.0012 (15) | −0.0017 (16) |
C10 | 0.028 (2) | 0.051 (3) | 0.042 (3) | 0.000 | 0.002 (2) | 0.000 |
O11 | 0.044 (2) | 0.068 (2) | 0.042 (2) | 0.000 | 0.0075 (17) | 0.000 |
C41 | 0.0383 (17) | 0.0350 (17) | 0.0367 (18) | −0.0006 (14) | 0.0002 (15) | 0.0005 (14) |
C42 | 0.0423 (19) | 0.047 (2) | 0.048 (2) | 0.0005 (16) | 0.0041 (17) | −0.0048 (17) |
C43 | 0.0369 (18) | 0.052 (2) | 0.053 (2) | −0.0029 (16) | 0.0000 (17) | −0.0016 (19) |
C44 | 0.045 (2) | 0.0388 (19) | 0.046 (2) | −0.0040 (16) | −0.0088 (17) | 0.0047 (17) |
C45 | 0.045 (2) | 0.053 (2) | 0.0376 (19) | −0.0032 (17) | 0.0028 (16) | −0.0031 (17) |
C46 | 0.0379 (18) | 0.055 (2) | 0.042 (2) | −0.0020 (16) | 0.0024 (16) | −0.0022 (17) |
O47 | 0.0518 (15) | 0.0679 (18) | 0.0512 (16) | −0.0067 (13) | −0.0122 (13) | −0.0066 (14) |
C48 | 0.070 (3) | 0.120 (4) | 0.056 (3) | −0.012 (3) | −0.012 (2) | −0.015 (3) |
C61 | 0.0420 (18) | 0.0389 (18) | 0.0429 (19) | 0.0036 (15) | 0.0023 (17) | −0.0034 (17) |
C62 | 0.051 (2) | 0.044 (2) | 0.044 (2) | 0.0034 (17) | −0.0015 (18) | −0.0032 (17) |
C63 | 0.057 (2) | 0.056 (2) | 0.044 (2) | 0.0047 (19) | −0.0063 (19) | 0.0026 (19) |
C64 | 0.060 (2) | 0.049 (2) | 0.059 (3) | 0.0022 (19) | −0.003 (2) | 0.009 (2) |
C65 | 0.086 (3) | 0.038 (2) | 0.065 (3) | −0.002 (2) | −0.016 (2) | −0.002 (2) |
C66 | 0.076 (3) | 0.049 (2) | 0.048 (2) | 0.003 (2) | −0.013 (2) | −0.0018 (19) |
O67 | 0.111 (3) | 0.0510 (17) | 0.075 (2) | −0.0044 (17) | −0.015 (2) | 0.0179 (16) |
C68 | 0.159 (6) | 0.046 (3) | 0.123 (5) | −0.015 (3) | −0.031 (5) | 0.023 (3) |
C1B | 0.134 (9) | 0.240 (15) | 0.112 (9) | −0.055 (10) | 0.019 (7) | −0.069 (9) |
C2B | 0.188 (13) | 0.125 (9) | 0.170 (12) | 0.071 (9) | −0.088 (9) | −0.071 (8) |
C3B | 0.281 (16) | 0.082 (6) | 0.103 (7) | −0.064 (9) | −0.048 (10) | 0.021 (5) |
N1—C2 | 1.467 (6) | C44—O47 | 1.375 (4) |
N1—C6 | 1.473 (4) | C44—C45 | 1.381 (5) |
N1—C6i | 1.473 (4) | C45—C46 | 1.392 (5) |
C2—N3 | 1.476 (6) | O47—C48 | 1.407 (5) |
N3—C4 | 1.487 (4) | C61—C66 | 1.379 (5) |
N3—C4i | 1.487 (4) | C61—C62 | 1.397 (5) |
C4—C41 | 1.509 (4) | C62—C63 | 1.379 (5) |
C4—C5 | 1.555 (4) | C63—C64 | 1.385 (5) |
C5—C10 | 1.503 (4) | C64—O67 | 1.367 (5) |
C5—C6 | 1.556 (5) | C64—C65 | 1.370 (6) |
C6—C61 | 1.521 (5) | C65—C66 | 1.394 (5) |
C10—O11 | 1.217 (6) | O67—C68 | 1.426 (5) |
C10—C5i | 1.503 (4) | C1B—C2B | 1.305 (13) |
C41—C46 | 1.374 (5) | C1B—C3Bii | 1.332 (13) |
C41—C42 | 1.398 (5) | C2B—C3B | 1.303 (13) |
C42—C43 | 1.370 (5) | C3B—C1Bii | 1.332 (13) |
C43—C44 | 1.384 (5) | ||
C2—N1—C6 | 110.4 (2) | C43—C42—C41 | 121.8 (3) |
C2—N1—C6i | 110.4 (2) | C42—C43—C44 | 120.2 (3) |
C6—N1—C6i | 108.0 (4) | O47—C44—C45 | 124.1 (3) |
N1—C2—N3 | 114.3 (4) | O47—C44—C43 | 116.3 (3) |
C2—N3—C4 | 107.2 (2) | C45—C44—C43 | 119.6 (3) |
C2—N3—C4i | 107.2 (2) | C44—C45—C46 | 119.1 (3) |
C4—N3—C4i | 114.0 (4) | C41—C46—C45 | 122.5 (3) |
N3—C4—C41 | 115.1 (3) | C44—O47—C48 | 117.7 (3) |
N3—C4—C5 | 109.0 (3) | C66—C61—C62 | 117.2 (3) |
C41—C4—C5 | 115.2 (3) | C66—C61—C6 | 123.7 (3) |
C10—C5—C4 | 109.1 (3) | C62—C61—C6 | 119.0 (3) |
C10—C5—C6 | 107.3 (3) | C63—C62—C61 | 121.1 (4) |
C4—C5—C6 | 108.6 (3) | C62—C63—C64 | 120.4 (4) |
N1—C6—C61 | 111.6 (3) | O67—C64—C65 | 124.6 (4) |
N1—C6—C5 | 109.3 (3) | O67—C64—C63 | 115.7 (4) |
C61—C6—C5 | 114.7 (3) | C65—C64—C63 | 119.7 (4) |
O11—C10—C5i | 124.0 (2) | C64—C65—C66 | 119.4 (4) |
O11—C10—C5 | 124.0 (2) | C61—C66—C65 | 122.2 (4) |
C5i—C10—C5 | 111.9 (4) | C64—O67—C68 | 117.0 (4) |
C46—C41—C42 | 116.7 (3) | C2B—C1B—C3Bii | 118.7 (10) |
C46—C41—C4 | 123.1 (3) | C3B—C2B—C1B | 121.1 (10) |
C42—C41—C4 | 119.9 (3) | C2B—C3B—C1Bii | 120.2 (10) |
C6—N1—C2—N3 | 59.7 (2) | C4—C41—C42—C43 | 175.9 (3) |
C6i—N1—C2—N3 | −59.7 (2) | C41—C42—C43—C44 | −1.9 (6) |
N1—C2—N3—C4 | −61.4 (2) | C42—C43—C44—O47 | −179.5 (3) |
N1—C2—N3—C4i | 61.4 (2) | C42—C43—C44—C45 | 1.0 (6) |
C2—N3—C4—C41 | −168.3 (3) | O47—C44—C45—C46 | −178.7 (3) |
C4i—N3—C4—C41 | 73.3 (4) | C43—C44—C45—C46 | 0.7 (6) |
C2—N3—C4—C5 | 60.6 (4) | C42—C41—C46—C45 | 0.9 (5) |
C4i—N3—C4—C5 | −57.9 (4) | C4—C41—C46—C45 | −173.9 (3) |
N3—C4—C5—C10 | 56.2 (4) | C44—C45—C46—C41 | −1.8 (6) |
C41—C4—C5—C10 | −74.9 (4) | C45—C44—O47—C48 | 5.0 (6) |
N3—C4—C5—C6 | −60.5 (4) | C43—C44—O47—C48 | −174.4 (4) |
C41—C4—C5—C6 | 168.4 (3) | N1—C6—C61—C66 | −139.3 (4) |
C2—N1—C6—C61 | 72.4 (4) | C5—C6—C61—C66 | −14.3 (5) |
C6i—N1—C6—C61 | −166.9 (2) | N1—C6—C61—C62 | 45.5 (4) |
C2—N1—C6—C5 | −55.6 (4) | C5—C6—C61—C62 | 170.5 (3) |
C6i—N1—C6—C5 | 65.1 (4) | C66—C61—C62—C63 | −1.4 (5) |
C10—C5—C6—N1 | −60.7 (3) | C6—C61—C62—C63 | 174.1 (3) |
C4—C5—C6—N1 | 57.2 (4) | C61—C62—C63—C64 | 1.2 (6) |
C10—C5—C6—C61 | 173.0 (3) | C62—C63—C64—O67 | −179.4 (4) |
C4—C5—C6—C61 | −69.1 (4) | C62—C63—C64—C65 | 0.2 (6) |
C4—C5—C10—O11 | 122.5 (4) | O67—C64—C65—C66 | 178.2 (4) |
C6—C5—C10—O11 | −120.0 (5) | C63—C64—C65—C66 | −1.4 (7) |
C4—C5—C10—C5i | −59.2 (5) | C62—C61—C66—C65 | 0.3 (6) |
C6—C5—C10—C5i | 58.3 (4) | C6—C61—C66—C65 | −175.0 (4) |
N3—C4—C41—C46 | −133.1 (3) | C64—C65—C66—C61 | 1.1 (7) |
C5—C4—C41—C46 | −4.9 (5) | C65—C64—O67—C68 | −0.9 (7) |
N3—C4—C41—C42 | 52.3 (4) | C63—C64—O67—C68 | 178.7 (4) |
C5—C4—C41—C42 | −179.6 (3) | C3Bii—C1B—C2B—C3B | −1.5 (17) |
C46—C41—C42—C43 | 0.9 (5) | C1B—C2B—C3B—C1Bii | 1.5 (18) |
Symmetry codes: (i) x, −y+1/2, z; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C36H36N2O5·C6H6 |
Mr | 654.78 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 293 |
a, b, c (Å) | 16.6240 (5), 26.0007 (16), 8.2207 (7) |
V (Å3) | 3553.3 (4) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.64 |
Crystal size (mm) | 0.33 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.864, 0.892 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3401, 3401, 2226 |
Rint | 0.010 |
(sin θ/λ)max (Å−1) | 0.609 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.066, 0.191, 1.13 |
No. of reflections | 3401 |
No. of parameters | 230 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.20 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
Subscribe to Acta Crystallographica Section E: Crystallographic Communications
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Crystallographic studies on symmetrically shaped molecules, with a view to understand the nature and strength of intermolecular interactions, are expected to provide information regarding their role in effecting symmetry carry-over from the free state to the solid and obtain information about specific interactions. The symmetry of a molecule in the solid state is often found reduced than that observed in the free state as the molecules tend to pack as closely as possible upon crystallization (Kitaigorodskii, 1973), giving rise to a variety of intermolecular interactions. While inversion centre is often carried over into the crystal, the retention of mirror or twofold symmetry by molecules seems to depend on the presence, nature and strength of the intermolecular interactions. The present crystal structure (I) is a good example of the retention of mirror symmetry by a molecule in the crystal state.
Fig. 1 shows the crystallographic numbering scheme adopted. All four six-membered rings which constitute the diazaadamantanone cage adopt the chair conformation which is the most preferred conformation for adamantanes, irrespective of substitution. The molecule is bisected by a mirror plane passing through atoms C2, N1, N3, C10 and O11 of the diazaadamantanone cage. The solvent benzene molecule is trapped in the crystal lattice and held inside the channel running along the c axis by van der Waals interactions (Fig. 2). In the absence of C—H···X-type hydrogen bonds, the solvent molecule presumably plays a role in optimizing packing efficiency within the lattice. The absence of C—H···X-type interactions may be attributed to the deficiency of acceptors compared to donors (phenyl C—H) whose presence otherwise might have had a considerable influence on the molecular conformation.