Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101008940/gg1060sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101008940/gg1060Isup2.hkl |
CCDC reference: 170191
For related literature, see: Allen et al. (1987); Batten & Robson (1998); Castellari & Ottani (1997); DuBois, Zhi, Roy, Stevens & Yalpani (1992); Eilerman & Rudman (1973, 1979a, 1979b, 1980); Flack (1983); Flack & Bernardinelli (2000); Grami (1998); Gregson et al. (2000); Hope & Nichols (1981); Katrusiak (1995); Ladd (1979); Ross et al. (1996a, 1996b); Semmingsen (1988); With & Harkema (1977).
A sample of (I) was prepared according to the published procedure (DuBois et al., 1992). Crystals suitable for single-crystal X-ray diffraction were obtained from a solution in ethanol.
Compound (I) is orthorhombic. The systematic absences permitted Pna21 and Pnam as possible space groups; since the unit-cell volume indicated Z = 4, Pna21 was selected, and confirmed by the subsequent structure analysis: no additional symmetry could be detected in the refined structure. H atoms were treated as riding with C—H 0.99 Å, N—H 0.88 Å, O—H 0.84 Å. The quality of the diffraction data was poor, even at 150 (2) K, with R(int) of 0.101. It was apparent from the residual electron densities that the diffraction data could not be completely satisfied by just one molecular orientation, and it became clear that there was a small contribution from a second orientation of the molecule, whose occupancy derived from various refinements ranged from 0.058 (3) to 0.066 (3), and whose coordinates were approximately related to those of the major form by reflection across the plane y = 0.75. Free refinement of this component led to highly unrealistic interatomic distances and so it was handled via an extensive series of DFIX commands constraining all of the distances and some of the angles. O21B lay at the centre of a rather broad region of residual electron density, and attempts to refine its coordinates were unsuccessful: accordingly, its coordinates were fixed. To ensure the stability of the final refinements, the minor component was assigned a common isotropic displacement parameter and the occupancy was fixed at 0.06. In the absence of any significant anomalous scatterers, the refined Flack parameter (Flack, 1983) of -1.3 (18) was inconclusive (Flack & Bernardinelli, 2000); hence the Friedel equivalents were merged before the final refinements.
Data collection: Kappa-CCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
C10H20N2O8 | Dx = 1.484 Mg m−3 |
Mr = 296.28 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 9375 reflections |
a = 21.4097 (3) Å | θ = 2.9–27.5° |
b = 6.1559 (6) Å | µ = 0.13 mm−1 |
c = 10.0605 (13) Å | T = 150 K |
V = 1325.9 (2) Å3 | Needle, colourless |
Z = 4 | 0.30 × 0.10 × 0.10 mm |
F(000) = 632 |
Kappa-CCD diffractometer | 1573 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 1282 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.101 |
ϕ scans, and ω scans with κ offsets | θmax = 27.5°, θmin = 3.4° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −25→27 |
Tmin = 0.962, Tmax = 0.987 | k = −6→7 |
7853 measured reflections | l = −9→12 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.080P)2] where P = (Fo2 + 2Fc2)/3 |
1573 reflections | (Δ/σ)max = 0.001 |
235 parameters | Δρmax = 0.26 e Å−3 |
36 restraints | Δρmin = −0.28 e Å−3 |
C10H20N2O8 | V = 1325.9 (2) Å3 |
Mr = 296.28 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 21.4097 (3) Å | µ = 0.13 mm−1 |
b = 6.1559 (6) Å | T = 150 K |
c = 10.0605 (13) Å | 0.30 × 0.10 × 0.10 mm |
Kappa-CCD diffractometer | 1573 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 1282 reflections with I > 2σ(I) |
Tmin = 0.962, Tmax = 0.987 | Rint = 0.101 |
7853 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 36 restraints |
wR(F2) = 0.120 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.26 e Å−3 |
1573 reflections | Δρmin = −0.28 e Å−3 |
235 parameters |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G·C. & Holmes, K·C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C11 | 0.35599 (14) | 0.3989 (5) | 0.2429 (4) | 0.0200 (7) | 0.94 |
O11 | 0.37908 (11) | 0.2156 (3) | 0.2587 (4) | 0.0296 (7) | 0.94 |
N11 | 0.29955 (12) | 0.4639 (4) | 0.2785 (3) | 0.0207 (6) | 0.94 |
C12 | 0.24894 (13) | 0.3321 (4) | 0.3355 (4) | 0.0180 (6) | 0.94 |
C13 | 0.22009 (14) | 0.1975 (5) | 0.2239 (4) | 0.0215 (8) | 0.94 |
O13 | 0.16741 (10) | 0.0787 (3) | 0.2706 (3) | 0.0265 (6) | 0.94 |
C14 | 0.20187 (15) | 0.4947 (5) | 0.3908 (4) | 0.0228 (7) | 0.94 |
O14 | 0.18617 (9) | 0.6547 (3) | 0.2946 (3) | 0.0255 (6) | 0.94 |
C15 | 0.27109 (15) | 0.1848 (5) | 0.4504 (4) | 0.0247 (8) | 0.94 |
O15 | 0.29531 (11) | −0.0194 (4) | 0.4106 (3) | 0.0287 (6) | 0.94 |
C21 | 0.39443 (13) | 0.5817 (4) | 0.1789 (4) | 0.0202 (7) | 0.94 |
O21 | 0.37160 (10) | 0.7631 (3) | 0.1637 (4) | 0.0262 (6) | 0.94 |
N21 | 0.45178 (12) | 0.5185 (4) | 0.1451 (3) | 0.0202 (6) | 0.94 |
C22 | 0.50150 (13) | 0.6557 (4) | 0.0900 (4) | 0.0195 (7) | 0.94 |
C23 | 0.53100 (15) | 0.7838 (5) | 0.2040 (4) | 0.0211 (8) | 0.94 |
O23 | 0.58211 (9) | 0.9099 (3) | 0.1575 (3) | 0.0257 (5) | 0.94 |
C24 | 0.54960 (15) | 0.4980 (5) | 0.0314 (4) | 0.0224 (7) | 0.94 |
O24 | 0.56664 (9) | 0.3349 (3) | 0.1241 (3) | 0.0252 (6) | 0.94 |
C25 | 0.47878 (15) | 0.8090 (5) | −0.0215 (4) | 0.0236 (7) | 0.94 |
O25 | 0.45581 (11) | 1.0118 (3) | 0.0231 (3) | 0.0268 (6) | 0.94 |
C11B | 0.3544 (10) | 1.0900 (4) | 0.247 (2) | 0.040* | 0.06 |
O11B | 0.3772 (12) | 1.2689 (9) | 0.2611 (15) | 0.040* | 0.06 |
N11B | 0.2994 (9) | 1.0298 (4) | 0.279 (2) | 0.040* | 0.06 |
C12B | 0.2505 (12) | 1.165 (4) | 0.338 (4) | 0.040* | 0.06 |
C13B | 0.221 (2) | 1.300 (8) | 0.227 (4) | 0.040* | 0.06 |
O13B | 0.1675 (16) | 1.413 (6) | 0.272 (7) | 0.040* | 0.06 |
C14B | 0.204 (3) | 0.997 (7) | 0.392 (5) | 0.040* | 0.06 |
O14B | 0.1869 (18) | 0.844 (6) | 0.294 (6) | 0.040* | 0.06 |
C15B | 0.273 (3) | 1.312 (6) | 0.451 (5) | 0.040* | 0.06 |
O15B | 0.294 (2) | 1.516 (5) | 0.405 (5) | 0.040* | 0.06 |
C21B | 0.3933 (19) | 0.910 (6) | 0.182 (6) | 0.040* | 0.06 |
O21B | 0.3710 | 0.7295 | 0.1602 | 0.040* | 0.06 |
N21B | 0.4517 (19) | 0.963 (7) | 0.153 (6) | 0.040* | 0.06 |
C22B | 0.5022 (15) | 0.841 (4) | 0.090 (5) | 0.040* | 0.06 |
C23B | 0.530 (2) | 0.709 (8) | 0.203 (5) | 0.040* | 0.06 |
O23B | 0.5832 (17) | 0.589 (6) | 0.161 (7) | 0.040* | 0.06 |
C24B | 0.549 (3) | 1.002 (7) | 0.032 (5) | 0.040* | 0.06 |
O24B | 0.5676 (17) | 1.165 (6) | 0.123 (6) | 0.040* | 0.06 |
C25B | 0.478 (3) | 0.698 (7) | −0.021 (5) | 0.040* | 0.06 |
O25B | 0.453 (2) | 0.498 (5) | 0.022 (6) | 0.040* | 0.06 |
H11 | 0.2913 | 0.6026 | 0.2667 | 0.025* | 0.94 |
H13A | 0.2071 | 0.2949 | 0.1506 | 0.026* | 0.94 |
H13B | 0.2517 | 0.0953 | 0.1885 | 0.026* | 0.94 |
H13 | 0.1789 | −0.0454 | 0.2953 | 0.040* | 0.94 |
H14A | 0.1636 | 0.4168 | 0.4186 | 0.027* | 0.94 |
H14B | 0.2198 | 0.5665 | 0.4702 | 0.027* | 0.94 |
H14 | 0.1546 | 0.6139 | 0.2517 | 0.038* | 0.94 |
H15A | 0.3037 | 0.2628 | 0.5011 | 0.030* | 0.94 |
H15B | 0.2355 | 0.1596 | 0.5112 | 0.030* | 0.94 |
H15 | 0.3272 | −0.0003 | 0.3632 | 0.043* | 0.94 |
H21 | 0.4608 | 0.3804 | 0.1570 | 0.024* | 0.94 |
H23A | 0.4993 | 0.8807 | 0.2442 | 0.025* | 0.94 |
H23B | 0.5457 | 0.6820 | 0.2735 | 0.025* | 0.94 |
H23 | 0.5700 | 1.0373 | 0.1421 | 0.039* | 0.94 |
H24A | 0.5319 | 0.4286 | −0.0490 | 0.027* | 0.94 |
H24B | 0.5873 | 0.5799 | 0.0045 | 0.027* | 0.94 |
H24 | 0.5980 | 0.3761 | 0.1673 | 0.038* | 0.94 |
H25A | 0.5139 | 0.8354 | −0.0835 | 0.028* | 0.94 |
H25B | 0.4453 | 0.7347 | −0.0720 | 0.028* | 0.94 |
H25 | 0.4246 | 0.9918 | 0.0722 | 0.040* | 0.94 |
H11B | 0.2898 | 0.8932 | 0.2631 | 0.048* | 0.06 |
H13C | 0.2523 | 1.4052 | 0.1931 | 0.060* | 0.06 |
H13D | 0.2093 | 1.2026 | 0.1528 | 0.060* | 0.06 |
H13E | 0.1521 | 1.4847 | 0.2094 | 0.060* | 0.06 |
H14C | 0.2234 | 0.9203 | 0.4683 | 0.060* | 0.06 |
H14D | 0.1664 | 1.0729 | 0.4249 | 0.060* | 0.06 |
H14E | 0.1860 | 0.7197 | 0.3279 | 0.060* | 0.06 |
H15C | 0.2387 | 1.3353 | 0.5152 | 0.060* | 0.06 |
H15D | 0.3077 | 1.2387 | 0.4992 | 0.060* | 0.06 |
H15E | 0.2653 | 1.5791 | 0.3644 | 0.060* | 0.06 |
H21B | 0.4619 | 1.0961 | 0.1752 | 0.048* | 0.06 |
H23C | 0.5427 | 0.8086 | 0.2757 | 0.060* | 0.06 |
H23D | 0.4985 | 0.6082 | 0.2381 | 0.060* | 0.06 |
H23E | 0.5972 | 0.5166 | 0.2253 | 0.060* | 0.06 |
H24C | 0.5864 | 0.9208 | 0.0025 | 0.048* | 0.06 |
H24D | 0.5302 | 1.0715 | −0.0470 | 0.048* | 0.06 |
H24E | 0.5637 | 1.2878 | 0.0867 | 0.060* | 0.06 |
H25C | 0.4451 | 0.7782 | −0.0704 | 0.060* | 0.06 |
H25D | 0.5124 | 0.6688 | −0.0843 | 0.060* | 0.06 |
H25E | 0.4357 | 0.5146 | 0.0965 | 0.060* | 0.06 |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.0166 (14) | 0.0219 (15) | 0.0216 (16) | −0.0028 (11) | −0.0007 (13) | −0.0012 (14) |
O11 | 0.0239 (13) | 0.0199 (10) | 0.0449 (19) | 0.0008 (9) | 0.0048 (15) | 0.0029 (13) |
N11 | 0.0150 (12) | 0.0206 (12) | 0.0265 (16) | −0.0015 (9) | 0.0011 (11) | 0.0038 (13) |
C12 | 0.0141 (14) | 0.0206 (15) | 0.0193 (17) | −0.0016 (11) | −0.0001 (12) | 0.0009 (14) |
C13 | 0.0216 (17) | 0.0214 (14) | 0.0213 (19) | −0.0010 (14) | −0.0009 (15) | 0.0023 (15) |
O13 | 0.0191 (10) | 0.0193 (10) | 0.0412 (15) | −0.0028 (8) | −0.0055 (11) | 0.0029 (12) |
C14 | 0.0190 (15) | 0.0237 (16) | 0.0256 (19) | −0.0022 (12) | 0.0030 (14) | 0.0029 (14) |
O14 | 0.0190 (11) | 0.0195 (10) | 0.0380 (16) | −0.0002 (8) | −0.0058 (11) | 0.0016 (11) |
C15 | 0.0229 (17) | 0.0286 (18) | 0.023 (2) | −0.0012 (14) | −0.0033 (15) | 0.0051 (17) |
O15 | 0.0241 (12) | 0.0253 (12) | 0.0367 (16) | 0.0020 (9) | 0.0025 (12) | 0.0091 (12) |
C21 | 0.0172 (14) | 0.0218 (15) | 0.0216 (17) | −0.0019 (11) | −0.0032 (13) | −0.0015 (13) |
O21 | 0.0203 (12) | 0.0226 (10) | 0.0356 (17) | 0.0014 (8) | 0.0106 (14) | 0.0050 (11) |
N21 | 0.0169 (11) | 0.0204 (11) | 0.0233 (15) | −0.0013 (9) | 0.0032 (12) | 0.0019 (12) |
C22 | 0.0142 (14) | 0.0207 (15) | 0.024 (2) | −0.0010 (12) | 0.0026 (13) | 0.0030 (15) |
C23 | 0.0180 (16) | 0.0197 (15) | 0.026 (2) | −0.0012 (14) | −0.0006 (15) | −0.0008 (15) |
O23 | 0.0200 (10) | 0.0183 (9) | 0.0389 (15) | −0.0044 (8) | −0.0052 (11) | 0.0052 (12) |
C24 | 0.0200 (15) | 0.0239 (15) | 0.0232 (19) | 0.0010 (12) | 0.0007 (14) | −0.0004 (14) |
O24 | 0.0186 (11) | 0.0188 (10) | 0.0381 (15) | −0.0003 (8) | −0.0053 (10) | 0.0012 (11) |
C25 | 0.0208 (16) | 0.0262 (16) | 0.0239 (19) | 0.0000 (14) | 0.0009 (15) | 0.0025 (17) |
O25 | 0.0212 (12) | 0.0235 (11) | 0.0356 (16) | 0.0002 (8) | 0.0015 (11) | 0.0066 (11) |
C11—O11 | 1.242 (4) | C11B—O11B | 1.213 (4) |
C11—N11 | 1.323 (4) | C11B—N11B | 1.275 (5) |
N11—C12 | 1.470 (4) | C11B—C21B | 1.53 (2) |
C11—C21 | 1.535 (4) | N11B—C12B | 1.468 (19) |
N11—H11 | 0.8800 | N11B—H11B | 0.8800 |
C12—C13 | 1.526 (5) | C12B—C13B | 1.528 (19) |
C12—C14 | 1.526 (4) | C12B—C14B | 1.530 (19) |
C12—C15 | 1.544 (4) | C12B—C15B | 1.530 (19) |
C13—O13 | 1.424 (4) | C13B—O13B | 1.42 (2) |
C13—H13A | 0.9900 | C13B—H13C | 0.9900 |
C13—H13B | 0.9900 | C13B—H13D | 0.9900 |
O13—H13 | 0.8400 | O13B—H13E | 0.8400 |
C14—O14 | 1.421 (4) | C14B—O14B | 1.41 (2) |
C14—H14A | 0.9900 | C14B—H14C | 0.9900 |
C14—H14B | 0.9900 | C14B—H14D | 0.9900 |
O14—H14 | 0.8400 | O14B—H14E | 0.8400 |
C15—O15 | 1.417 (4) | C15B—O15B | 1.41 (2) |
C15—H15A | 0.9900 | C15B—H15C | 0.9900 |
C15—H15B | 0.9900 | C15B—H15D | 0.9900 |
O15—H15 | 0.8400 | O15B—H15E | 0.8400 |
C21—O21 | 1.229 (3) | C21B—O21B | 1.23 (4) |
C21—N21 | 1.332 (4) | C21B—N21B | 1.33 (2) |
N21—C22 | 1.467 (4) | N21B—C22B | 1.46 (2) |
N21—H21 | 0.8800 | N21B—H21B | 0.8800 |
C22—C23 | 1.529 (5) | C22B—C25B | 1.52 (2) |
C22—C24 | 1.533 (4) | C22B—C24B | 1.52 (2) |
C22—C25 | 1.544 (5) | C22B—C23B | 1.524 (19) |
C23—O23 | 1.421 (4) | C23B—O23B | 1.42 (2) |
C23—H23A | 0.9900 | C23B—H23C | 0.9900 |
C23—H23B | 0.9900 | C23B—H23D | 0.9900 |
O23—H23 | 0.8400 | O23B—H23E | 0.8400 |
C24—O24 | 1.418 (4) | C24B—O24B | 1.42 (2) |
C24—H24A | 0.9900 | C24B—H24C | 0.9900 |
C24—H24B | 0.9900 | C24B—H24D | 0.9900 |
O24—H24 | 0.8400 | O24B—H24E | 0.8400 |
C25—O25 | 1.415 (4) | C25B—O25B | 1.41 (2) |
C25—H25A | 0.9900 | C25B—H25C | 0.9900 |
C25—H25B | 0.9900 | C25B—H25D | 0.9900 |
O25—H25 | 0.8400 | O25B—H25E | 0.8400 |
O11—C11—N11 | 127.1 (3) | C11B—N11B—C12B | 126.6 (11) |
O11—C11—C21 | 120.4 (3) | C11B—N11B—H11B | 116.7 |
N11—C11—C21 | 112.5 (2) | C12B—N11B—H11B | 116.7 |
C11—N11—C12 | 127.8 (3) | N11B—C12B—C13B | 107 (3) |
C11—N11—H11 | 116.1 | N11B—C12B—C14B | 103 (3) |
C12—N11—H11 | 116.1 | C13B—C12B—C14B | 111.1 (17) |
N11—C12—C13 | 108.1 (3) | N11B—C12B—C15B | 114 (3) |
N11—C12—C14 | 105.5 (2) | C13B—C12B—C15B | 110.9 (17) |
C13—C12—C14 | 110.9 (3) | C14B—C12B—C15B | 110.1 (17) |
N11—C12—C15 | 112.9 (2) | O13B—C13B—C12B | 111.2 (19) |
C13—C12—C15 | 110.9 (2) | O13B—C13B—H13C | 109.4 |
C14—C12—C15 | 108.4 (3) | C12B—C13B—H13C | 109.4 |
O13—C13—C12 | 110.9 (3) | O13B—C13B—H13D | 109.4 |
O13—C13—H13A | 109.5 | C12B—C13B—H13D | 109.4 |
C12—C13—H13A | 109.5 | H13C—C13B—H13D | 108.0 |
O13—C13—H13B | 109.5 | C13B—O13B—H13E | 109.5 |
C12—C13—H13B | 109.5 | O14B—C14B—C12B | 112 (2) |
H13A—C13—H13B | 108.0 | O14B—C14B—H14C | 109.2 |
O14—C14—C12 | 111.2 (3) | C12B—C14B—H14C | 109.2 |
O14—C14—H14A | 109.4 | O14B—C14B—H14D | 109.2 |
C12—C14—H14A | 109.4 | C12B—C14B—H14D | 109.2 |
O14—C14—H14B | 109.4 | H14C—C14B—H14D | 107.9 |
C12—C14—H14B | 109.4 | C14B—O14B—H14E | 109.5 |
H14A—C14—H14B | 108.0 | O15B—C15B—C12B | 112 (2) |
O15—C15—C12 | 114.9 (3) | O15B—C15B—H15C | 109.2 |
O15—C15—H15A | 108.5 | C12B—C15B—H15C | 109.2 |
C12—C15—H15A | 108.5 | O15B—C15B—H15D | 109.2 |
O15—C15—H15B | 108.5 | C12B—C15B—H15D | 109.2 |
C12—C15—H15B | 108.5 | H15C—C15B—H15D | 107.9 |
H15A—C15—H15B | 107.5 | C15B—O15B—H15E | 109.5 |
O21—C21—N21 | 126.9 (3) | O21B—C21B—N21B | 123 (3) |
O21—C21—C11 | 120.3 (3) | O21B—C21B—C11B | 121 (3) |
N21—C21—C11 | 112.8 (2) | N21B—C21B—C11B | 116 (3) |
C21—N21—C22 | 126.7 (2) | C21B—N21B—C22B | 132 (4) |
C21—N21—H21 | 116.7 | C21B—N21B—H21B | 113.9 |
C22—N21—H21 | 116.7 | C22B—N21B—H21B | 113.9 |
N21—C22—C23 | 108.3 (3) | N21B—C22B—C25B | 111 (4) |
N21—C22—C24 | 105.6 (2) | N21B—C22B—C24B | 109 (3) |
C23—C22—C24 | 109.7 (3) | C25B—C22B—C24B | 109 (3) |
N21—C22—C25 | 113.4 (2) | N21B—C22B—C23B | 104 (4) |
C23—C22—C25 | 111.1 (2) | C25B—C22B—C23B | 112.1 (16) |
C24—C22—C25 | 108.6 (3) | C24B—C22B—C23B | 111.7 (18) |
O23—C23—C22 | 110.7 (3) | O23B—C23B—C22B | 112 (2) |
O23—C23—H23A | 109.5 | O23B—C23B—H23C | 109.2 |
C22—C23—H23A | 109.5 | C22B—C23B—H23C | 109.2 |
O23—C23—H23B | 109.5 | O23B—C23B—H23D | 109.2 |
C22—C23—H23B | 109.5 | C22B—C23B—H23D | 109.2 |
H23A—C23—H23B | 108.1 | H23C—C23B—H23D | 107.9 |
O24—C24—C22 | 111.6 (3) | C23B—O23B—H23E | 109.5 |
O24—C24—H24A | 109.3 | O24B—C24B—C22B | 114 (2) |
C22—C24—H24A | 109.3 | O24B—C24B—H24C | 108.8 |
O24—C24—H24B | 109.3 | C22B—C24B—H24C | 108.8 |
C22—C24—H24B | 109.3 | O24B—C24B—H24D | 108.8 |
H24A—C24—H24B | 108.0 | C22B—C24B—H24D | 108.8 |
O25—C25—C22 | 114.8 (3) | H24C—C24B—H24D | 107.7 |
O25—C25—H25A | 108.6 | C24B—O24B—H24E | 109.5 |
C22—C25—H25A | 108.6 | O25B—C25B—C22B | 114 (2) |
O25—C25—H25B | 108.6 | O25B—C25B—H25C | 108.7 |
C22—C25—H25B | 108.6 | C22B—C25B—H25C | 108.7 |
H25A—C25—H25B | 107.6 | O25B—C25B—H25D | 108.7 |
O11B—C11B—N11B | 127.2 (2) | C22B—C25B—H25D | 108.7 |
O11B—C11B—C21B | 119.3 (17) | H25C—C25B—H25D | 107.6 |
N11B—C11B—C21B | 113.5 (17) | C25B—O25B—H25E | 109.5 |
C12—N11—C11—C21 | 176.3 (3) | O11B—C11B—N11B—C12B | 1 (2) |
C12—N11—C11—O11 | −5.3 (6) | C21B—C11B—N11B—C12B | −178 (3) |
O11—C11—C21—O21 | −179.8 (5) | C11B—N11B—C12B—C13B | 79 (3) |
C11—N11—C12—C13 | −75.8 (4) | C11B—N11B—C12B—C14B | −163.4 (18) |
C11—N11—C12—C14 | 165.4 (3) | C11B—N11B—C12B—C15B | −44 (3) |
C11—N11—C12—C15 | 47.3 (5) | N11B—C12B—C13B—O13B | 172 (4) |
N11—C12—C13—O13 | −175.4 (2) | C14B—C12B—C13B—O13B | 60 (5) |
C14—C12—C13—O13 | −60.2 (3) | C15B—C12B—C13B—O13B | −63 (5) |
C15—C12—C13—O13 | 60.3 (3) | N11B—C12B—C14B—O14B | −52 (5) |
N11—C12—C14—O14 | 50.6 (4) | C13B—C12B—C14B—O14B | 63 (5) |
C13—C12—C14—O14 | −66.3 (3) | C15B—C12B—C14B—O14B | −174 (5) |
C15—C12—C14—O14 | 171.8 (2) | N11B—C12B—C15B—O15B | 89 (5) |
N11—C12—C15—O15 | −86.3 (3) | C13B—C12B—C15B—O15B | −33 (6) |
C13—C12—C15—O15 | 35.3 (4) | C14B—C12B—C15B—O15B | −156 (5) |
C14—C12—C15—O15 | 157.3 (3) | O11B—C11B—C21B—O21B | −176 (4) |
C22—N21—C21—C11 | −175.8 (3) | N11B—C11B—C21B—O21B | 3 (6) |
C22—N21—C21—O21 | 4.2 (6) | O11B—C11B—C21B—N21B | 4 (6) |
N11—C11—C21—N21 | 178.8 (4) | N11B—C11B—C21B—N21B | −177 (4) |
N11—C11—C21—O21 | −1.2 (5) | O21B—C21B—N21B—C22B | 1 (10) |
O11—C11—C21—N21 | 0.3 (4) | C11B—C21B—N21B—C22B | −179 (4) |
C21—N21—C22—C23 | 78.7 (4) | C21B—N21B—C22B—C25B | 38 (7) |
C21—N21—C22—C24 | −163.8 (3) | C21B—N21B—C22B—C24B | 158 (6) |
C21—N21—C22—C25 | −45.0 (4) | C21B—N21B—C22B—C23B | −83 (6) |
N21—C22—C23—O23 | 176.5 (2) | N21B—C22B—C23B—O23B | −177 (4) |
C24—C22—C23—O23 | 61.7 (3) | C25B—C22B—C23B—O23B | 63 (6) |
C25—C22—C23—O23 | −58.4 (3) | C24B—C22B—C23B—O23B | −59 (5) |
N21—C22—C24—O24 | −50.7 (3) | N21B—C22B—C24B—O24B | 49 (6) |
C23—C22—C24—O24 | 65.8 (3) | C25B—C22B—C24B—O24B | 171 (5) |
C25—C22—C24—O24 | −172.6 (2) | C23B—C22B—C24B—O24B | −65 (6) |
N21—C22—C25—O25 | 87.9 (3) | N21B—C22B—C25B—O25B | −82 (6) |
C23—C22—C25—O25 | −34.3 (4) | C24B—C22B—C25B—O25B | 158 (5) |
C24—C22—C25—O25 | −155.1 (3) | C23B—C22B—C25B—O25B | 34 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O14i | 0.84 | 1.85 | 2.652 (3) | 158 |
O14—H14···O23ii | 0.84 | 1.82 | 2.650 (3) | 167 |
O15—H15···O11 | 0.84 | 2.03 | 2.765 (4) | 146 |
O23—H23···O24iii | 0.84 | 1.84 | 2.658 (3) | 163 |
O24—H24···O13iv | 0.84 | 1.84 | 2.666 (3) | 171 |
O25—H25···O21 | 0.84 | 2.03 | 2.756 (4) | 144 |
Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y+3/2, z; (iii) x, y+1, z; (iv) x+1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C10H20N2O8 |
Mr | 296.28 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 150 |
a, b, c (Å) | 21.4097 (3), 6.1559 (6), 10.0605 (13) |
V (Å3) | 1325.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.30 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Kappa-CCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.962, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7853, 1573, 1282 |
Rint | 0.101 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.120, 1.02 |
No. of reflections | 1573 |
No. of parameters | 235 |
No. of restraints | 36 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.28 |
Computer programs: Kappa-CCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), PLATON (Spek, 2001), SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).
C11—O11 | 1.242 (4) | C21—O21 | 1.229 (3) |
C11—N11 | 1.323 (4) | C21—N21 | 1.332 (4) |
N11—C12 | 1.470 (4) | N21—C22 | 1.467 (4) |
C11—C21 | 1.535 (4) | ||
O11—C11—N11 | 127.1 (3) | O21—C21—N21 | 126.9 (3) |
O11—C11—C21 | 120.4 (3) | O21—C21—C11 | 120.3 (3) |
N11—C11—C21 | 112.5 (2) | N21—C21—C11 | 112.8 (2) |
C11—N11—C12 | 127.8 (3) | C21—N21—C22 | 126.7 (2) |
C12—N11—C11—C21 | 176.3 (3) | C22—N21—C21—C11 | −175.8 (3) |
C12—N11—C11—O11 | −5.3 (6) | C22—N21—C21—O21 | 4.2 (6) |
O11—C11—C21—O21 | −179.8 (5) | N11—C11—C21—N21 | 178.8 (4) |
C11—N11—C12—C13 | −75.8 (4) | C21—N21—C22—C23 | 78.7 (4) |
C11—N11—C12—C14 | 165.4 (3) | C21—N21—C22—C24 | −163.8 (3) |
C11—N11—C12—C15 | 47.3 (5) | C21—N21—C22—C25 | −45.0 (4) |
N11—C12—C13—O13 | −175.4 (2) | N21—C22—C23—O23 | 176.5 (2) |
N11—C12—C14—O14 | 50.6 (4) | N21—C22—C24—O24 | −50.7 (3) |
N11—C12—C15—O15 | −86.3 (3) | N21—C22—C25—O25 | 87.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O13—H13···O14i | 0.84 | 1.85 | 2.652 (3) | 158 |
O14—H14···O23ii | 0.84 | 1.82 | 2.650 (3) | 167 |
O15—H15···O11 | 0.84 | 2.03 | 2.765 (4) | 146 |
O23—H23···O24iii | 0.84 | 1.84 | 2.658 (3) | 163 |
O24—H24···O13iv | 0.84 | 1.84 | 2.666 (3) | 171 |
O25—H25···O21 | 0.84 | 2.03 | 2.756 (4) | 144 |
Symmetry codes: (i) x, y−1, z; (ii) x−1/2, −y+3/2, z; (iii) x, y+1, z; (iv) x+1/2, −y+1/2, z. |
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Molecules of pentaerythritol, C(CH2OH)4, have crystallographically imposed 4 (S4) symmetry in the solid state and the hydroxyl groups act as both hydrogen-bond donors and hydrogen-bond acceptors; the molecules are linked by the O—H···O hydrogen bonds into sheets built from R44(8) and R22(12) rings arranged in a checkerboard fashion (Ladd, 1979; Eilerman & Rudman, 1979a; Hope & Nichols, 1981; Semmingsen, 1988; Katrusiak, 1995). Although each molecule participates in eight hydrogen bonds, and is thereby linked to four other molecules in a (4, 4) net (Batten & Robson, 1998), the elegant simplicity of the supramolecular structure owes much to the symmetry equivalence of all the hydrogen bonds.
In the ordered orthorhombic phase of the related aminotriol H2NC(CH2OH)3 (Eilerman & Rudman, 1980; Castellari & Ottani, 1997), the amino group and the three hydroxyl groups all act as both donors and acceptors of hydrogen bonds. However, since the molecules lie in general positions, there are four distinct hydrogen bonds in the structure, two of O—H···O type and one each of O—H···N and N—H···O types; the hydrogen bonding is thus of considerable complexity although the supramolecular aggregation is still two-dimensional, as in pentaerythritol. There is also a cubic plastic phase of this material, with Z = 2 in space group Im3m (Eilerman & Rudman, 1980), but the orientational disorder of the molecules in this phase precludes detailed discussion of the hydrogen bonding. By contrast, in tris-hydroxymethyl)acetic acid HOOCC(CH2OH)3 (Eilerman & Rudman, 1979b), the hydrogen bonding generates a three-dimensional supramolecular structure, although the R22(8) motif so characteristic of carboxylic acids is absent: this material also exhibits a disordered cubic phase, with Z = 4 in space group Fm3m (Eilerman & Rudman, 1973).
In view of the two-dimensional aggregation in both C(CH2OH)4 and ordered H2NC(CH2OH)3, and the three-dimensional aggregation in ordered HOOCC(CH2OH)3, it is therefore of interest to investigate the structure of the related hexahydroxy analogue N,N'-bis[tris(hydroxymethyl)methyl]ethanediamide, (HOCH2)3CNHCOCONHC(CH2OH)3, (I), originally synthesized (DuBois et al., 1992) as one of the more recent examples in a long series of adventitious sweetening agents (Exodus, undated; Grami, 1998). \sch
Molecules of (I) (Fig. 1) lie in general positions in space group Pna21; they are disordered over two sets of sites with occupancies 0.94 and 0.06, and the two sets of sites are approximately related to one another by reflection across the plane y = 0.75. Because of the constraints applied to the minor component, only the major component will be discussed. For the major form, the overall dimensions and the conformation indicate that the molecules are close to being centrosymmetric: in particular, corresponding pairs of torsional angles have closely-similar magnitudes with opposite signs. However, a search for possible additional symmetry showed that none was present; this is so even if all the H atoms are ignored. The non-centrosymmetric nature of the molecules in (I) may be contrasted with the behaviour of the derivatives (II)-(IV), in all of which the molecules lie across centres of inversion (Ross et al., 1996a,b). The central portion of the molecule is essentially planar, with neighbouring N—H and C═O units mutually trans: the central C—C bond is long, as typically found in oxalic acid derivatives (de With & Harkema, 1977; Allen et al., 1987; Ross et al., 1996a,b).
Each of the hydroxyl groups in (I) acts both as a hydrogen-bond donor and as a hydrogen-bond acceptor, but the N—H units play no role in the supramolecular aggregation (Table 2). There are two intramolecular O—H···O hydrogen bonds, each of which generates an S(7) motif (Fig. 2). Each molecules therefore acts as a fourfold donor and acceptor in intermolecular hydrogen bonds, and each molecule is thereby linked to six others in the resulting two-dimensional structure, but by adoption of the sub-structure approach (Gregson et al., 2000), the rather complex supramolecular aggregation can readily be analysed in terms of three simple motifs.
Atoms O13 and O23 in the molecule at (x, y, z) act as donors to O14 at (x, -1 + y, z) and to O24 at (x, 1 + y, z), respectively. Propagation of these two hydrogen bonds generates a molecular ladder running parallel to the [010] direction: the two rungs of the ladder consist of independent C(6) chains, while the molecular backbone from O13 to O23 provides the rungs of the ladder (Fig. 2). Between the rungs there are R22(22) rings, in the interior of which are the S(7) rings.
The [010] ladders are linked by two independent spiral-chain motifs. Atom O14 in the molecule at (x, y, z) acts as donor to O23 at (-1/2 + x, 3/2 - y, z), while O14 at (-1/2 + x, 3/2 - y, z) in turn acts as donor to O23 at (-1 + x, y, z); in this manner is generated a C(11) spiral around the 21 screw axis along (x, 3/4, 0). Similarly, O24 at (x, y, z) acts as donor to O13 at (1/2 + x, 1/2 - y, z) and propagation of this interaction generates a second C(11) spiral around the 21 screw axis along (x, 1/2, 0). The combined effect of these two independent C(11) chains along [100] is to link the [010] ladders into a sheet parallel to (001). This sheet is built from two types of R33(10) ring in addition to the R22(22) ring and the two types of S(7) ring noted earlier (Fig. 2). The reference (001) sheet lies in the domain -0.09 < z < 0.47, and a second sheet runs through the unit cell in the domain 0.41 < z < 0.97. There are no hydrogen bonds between adjacent sheets, so that the supramolecular aggregation is two-dimensional.