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The molecular packing modes of a series of mono- and diamides of (R,R)-tartaric acid are discussed on the basis of their crystal structures. Derivatives include combinations of methylester, amide, N-methylamide and N,N-dimethylamide groups, both symmetrically and asymmetrically substituted. The symmetrically substituted derivatives do not utilize their C2 symmetry in the crystal. The packing of primary tartramides seems to be driven by NH
O=C hydrogen bonds and supplemented by strong OHO=C and weak NHOH bonds. On the other hand, in derivatives containing methylester and/or methylamide groups OHOHO=C hydrogen-bond patterns seem to dominate. Types of aggregates, characteristic for the investigated derivatives, include cyclic dimers and ring systems analogous to the dimers, but formed by two different although complementary functional groups, as well as sets of chains aligned in a manner resembling the helical arrangement of peptides. The helices are formed along the screw axis with an identity period of approximately 5 Å. In tartramic acids, containing in one molecule both carboxyl and amide functions, in competition between the two groups to control the molecular arrangement, the latter dominates, unless it is N-substituted tartramide, in which case the carboxyl group predominates. Problems with packing, which occur in some of the structures owing to the steric bulk of the methyl groups, are overcome by changes in conformation (esters) or by co-crystallization with solvent water molecules (methylamides and dimethylamides). These derivatives are also more likely to crystallize with multiple asymmetric units.
O=C hydrogen bonds and supplemented by strong OHO=C and weak NHOH bonds. On the other hand, in derivatives containing methylester and/or methylamide groups OHOHO=C hydrogen-bond patterns seem to dominate. Types of aggregates, characteristic for the investigated derivatives, include cyclic dimers and ring systems analogous to the dimers, but formed by two different although complementary functional groups, as well as sets of chains aligned in a manner resembling the helical arrangement of peptides. The helices are formed along the screw axis with an identity period of approximately 5 Å. In tartramic acids, containing in one molecule both carboxyl and amide functions, in competition between the two groups to control the molecular arrangement, the latter dominates, unless it is N-substituted tartramide, in which case the carboxyl group predominates. Problems with packing, which occur in some of the structures owing to the steric bulk of the methyl groups, are overcome by changes in conformation (esters) or by co-crystallization with solvent water molecules (methylamides and dimethylamides). These derivatives are also more likely to crystallize with multiple asymmetric units.Supporting information
 | Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768100004274/cf0011sup1.cif |
 | Structure factor file (CIF format) https://doi.org/10.1107/S0108768100004274/cf0011hoh1sup2.fcf |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108768100004274/cf0011hn12sup3.fcf |
| Structure factor file (CIF format) https://doi.org/10.1107/S0108768100004274/cf0011hn22sup4.fcf |
CCDC references: 153325; 153326; 153327
Computing details top
For all compounds, data collection: Kuma KM-4 Software (Kuma Diffraction, 1991). Cell refinement: Kuma KM-4 Software (Kuma Diffraction, 1991) for hoh1; Kuma KM-4 Software for hn12, hn22. Data reduction: Kuma KM-4 Software (Kuma Diffraction, 1991) for hoh1; Kuma KM-4 Software for hn12, hn22. For all compounds, program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: Simens Analytical X-Ray Instruments (1989); software used to prepare material for publication: SHELXL93 (Sheldrick, 1993).
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(hoh1) (R,R)-(+)-Tartaric acid monoamide top
Crystal data top
| C4H7NO5 | Dx = 1.726 Mg m−3 |
| Mr = 149.11 | Melting point = 443–445 K |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| a = 5.9556 (5) Å | Cell parameters from 46 reflections |
| b = 8.0972 (5) Å | θ = 12.2–15.0° |
| c = 11.8960 (8) Å | µ = 0.16 mm−1 |
| V = 573.67 (7) Å3 | T = 293 K |
| Z = 4 | Square pyramid, colourless |
| F(000) = 312 | 0.5 × 0.5 × 0.5 mm |
Data collection top
| KM-4 four circle diffractometer | Rint = 0.011 |
| Radiation source: fine-focus sealed tube | θmax = 29.1°, θmin = 3.0° |
| Graphite monochromator | h = −8→8 |
| θ–2θ scans | k = 0→11 |
| 1688 measured reflections | l = 0→16 |
| 1534 independent reflections | 2 standard reflections every 100 reflections |
| 1476 reflections with I > σ(I) | intensity decay: 1.0% |
Refinement top
| 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)] = 0.033 | Riding model |
| wR(F2) = 0.099 | Calculated w = 1/[σ2(Fo2) + (0.0485P)2 + 0.1655P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.01 | (Δ/σ)max = −0.054 |
| 1531 reflections | Δρmax = 0.39 e Å−3 |
| 103 parameters | Δρmin = −0.18 e Å−3 |
| 0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.80 (114) |
Crystal data top
| C4H7NO5 | V = 573.67 (7) Å3 |
| Mr = 149.11 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 5.9556 (5) Å | µ = 0.16 mm−1 |
| b = 8.0972 (5) Å | T = 293 K |
| c = 11.8960 (8) Å | 0.5 × 0.5 × 0.5 mm |
Data collection top
| KM-4 four circle diffractometer | Rint = 0.011 |
| 1688 measured reflections | 2 standard reflections every 100 reflections |
| 1534 independent reflections | intensity decay: 1.0% |
| 1476 reflections with I > σ(I) |
Refinement top
| R[F2 > 2σ(F2)] = 0.033 | Riding model |
| wR(F2) = 0.099 | Δρmax = 0.39 e Å−3 |
| S = 1.01 | Δρmin = −0.18 e Å−3 |
| 1531 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| 103 parameters | Absolute structure parameter: 0.80 (114) |
| 0 restraints |
Special details top
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 on F2 for ALL reflections except for 3 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.2145 (2) | −0.5652 (2) | −0.49757 (10) | 0.0206 (2) | |
| C2 | −0.0044 (2) | −0.56737 (15) | −0.43187 (9) | 0.0183 (2) | |
| H2 | −0.0111 (2) | −0.66799 (15) | −0.38932 (9) | 0.020* | |
| C3 | −0.0080 (2) | −0.42239 (15) | −0.34979 (10) | 0.0214 (2) | |
| H3 | 0.1212 (2) | −0.42979 (15) | −0.30182 (10) | 0.020* | |
| C4 | −0.2183 (2) | −0.4313 (2) | −0.27706 (10) | 0.0224 (2) | |
| N4 | −0.3519 (2) | −0.3024 (2) | −0.28003 (11) | 0.0339 (3) | |
| H41 | −0.4785 (2) | −0.3014 (2) | −0.23877 (11) | 0.060* | |
| H42 | −0.3167 (2) | −0.2149 (2) | −0.32325 (11) | 0.060* | |
| O1 | 0.2225 (2) | −0.56502 (14) | −0.59877 (8) | 0.0302 (2) | |
| O2 | −0.19040 (13) | −0.56349 (14) | −0.50508 (8) | 0.0237 (2) | |
| H2O | −0.161 (5) | −0.516 (3) | −0.566 (2) | 0.055 (7)* | |
| O3 | 0.0052 (2) | −0.27569 (13) | −0.41215 (10) | 0.0349 (3) | |
| H3O | 0.071 (4) | −0.211 (3) | −0.375 (2) | 0.044 (6)* | |
| O4 | −0.2518 (2) | −0.55460 (13) | −0.21725 (8) | 0.0297 (2) | |
| O10 | 0.3878 (2) | −0.56387 (15) | −0.42987 (8) | 0.0295 (2) | |
| H10 | 0.506 (4) | −0.552 (3) | −0.4650 (18) | 0.040 (5)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0167 (5) | 0.0224 (5) | 0.0229 (5) | 0.0000 (4) | 0.0018 (4) | −0.0006 (5) |
| C2 | 0.0150 (4) | 0.0225 (5) | 0.0176 (5) | 0.0004 (5) | 0.0005 (4) | −0.0006 (4) |
| C3 | 0.0200 (5) | 0.0235 (5) | 0.0207 (5) | −0.0011 (5) | −0.0003 (4) | −0.0034 (4) |
| C4 | 0.0210 (5) | 0.0278 (5) | 0.0184 (5) | 0.0005 (5) | −0.0010 (4) | −0.0061 (4) |
| N4 | 0.0303 (6) | 0.0334 (6) | 0.0380 (6) | 0.0087 (5) | 0.0044 (5) | −0.0039 (5) |
| O1 | 0.0244 (4) | 0.0455 (5) | 0.0208 (4) | 0.0011 (5) | 0.0038 (3) | 0.0006 (4) |
| O2 | 0.0155 (4) | 0.0360 (5) | 0.0197 (4) | −0.0008 (4) | −0.0013 (3) | −0.0002 (4) |
| O3 | 0.0433 (6) | 0.0236 (4) | 0.0378 (6) | −0.0077 (5) | 0.0044 (5) | 0.0020 (4) |
| O4 | 0.0304 (5) | 0.0336 (5) | 0.0250 (4) | 0.0015 (4) | 0.0062 (4) | 0.0028 (4) |
| O10 | 0.0157 (4) | 0.0475 (6) | 0.0253 (4) | −0.0015 (4) | −0.0001 (3) | −0.0011 (4) |
Geometric parameters (Å, º) top
| C1—O1 | 1.205 (2) | C3—H3 | 0.96 |
| C1—O10 | 1.3089 (15) | C4—O4 | 1.242 (2) |
| C1—C2 | 1.520 (2) | C4—N4 | 1.313 (2) |
| C2—O2 | 1.4093 (13) | N4—H41 | 0.90 |
| C2—C3 | 1.527 (2) | N4—H42 | 0.90 |
| C2—H2 | 0.96 | O2—H2O | 0.84 (3) |
| C3—O3 | 1.403 (2) | O3—H3O | 0.79 (3) |
| C3—C4 | 1.524 (2) | O10—H10 | 0.83 (2) |
| O1—C1—O10 | 125.70 (11) | O3—C3—H3 | 108.80 (7) |
| O1—C1—C2 | 123.20 (10) | C4—C3—H3 | 108.57 (6) |
| O10—C1—C2 | 111.10 (10) | C2—C3—H3 | 108.72 (7) |
| O2—C2—C1 | 110.86 (9) | O4—C4—N4 | 123.84 (12) |
| O2—C2—C3 | 111.54 (10) | O4—C4—C3 | 119.69 (11) |
| C1—C2—C3 | 109.38 (10) | N4—C4—C3 | 116.44 (12) |
| O2—C2—H2 | 108.19 (7) | C4—N4—H41 | 120.02 (8) |
| C1—C2—H2 | 108.43 (6) | C4—N4—H42 | 119.98 (8) |
| C3—C2—H2 | 108.34 (6) | H41—N4—H42 | 120.0 |
| O3—C3—C4 | 112.73 (11) | C2—O2—H2O | 112.2 (18) |
| O3—C3—C2 | 108.18 (10) | C3—O3—H3O | 107.0 (17) |
| C4—C3—C2 | 109.76 (10) | C1—O10—H10 | 111.3 (15) |
(hn12) (R,R)-(+)-Tartaric acid N-methyldiamide top
Crystal data top
| C5H10N2O4 | Melting point = 475–477 K |
| Mr = 162.15 | Mo Kα radiation, λ = 0.71073 Å |
| Tetragonal, P41212 | Cell parameters from 47 reflections |
| a = 10.594 (1) Å | θ = 6.1–12.0° |
| c = 13.771 (3) Å | µ = 0.12 mm−1 |
| V = 1545.6 (4) Å3 | T = 293 K |
| Z = 8 | Tetragonal bipyramid, colourless |
| F(000) = 688 | 0.45 × 0.44 × 0.41 mm |
| Dx = 1.394 Mg m−3 |
Data collection top
| KM-4 four circle diffractometer | Rint = 0.013 |
| Radiation source: fine-focus sealed tube | θmax = 27.1°, θmin = 2.4° |
| Graphite monochromator | h = 0→13 |
| Θ–2Θ scans | k = 0→13 |
| 1939 measured reflections | l = 0→17 |
| 1698 independent reflections | 2 standard reflections every 100 reflections |
| 1408 reflections with I > 2σ(I) | intensity decay: 0.9% |
Refinement top
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | Riding model |
| R[F2 > 2σ(F2)] = 0.042 | Calculated w = 1/[σ2(Fo2) + (0.0699P)2 + 0.2727P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.122 | (Δ/σ)max < 0.001 |
| S = 1.10 | Δρmax = 0.28 e Å−3 |
| 1698 reflections | Δρmin = −0.23 e Å−3 |
| 113 parameters | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0304 (45) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.72 (187) |
Crystal data top
| C5H10N2O4 | Z = 8 |
| Mr = 162.15 | Mo Kα radiation |
| Tetragonal, P41212 | µ = 0.12 mm−1 |
| a = 10.594 (1) Å | T = 293 K |
| c = 13.771 (3) Å | 0.45 × 0.44 × 0.41 mm |
| V = 1545.6 (4) Å3 |
Data collection top
| KM-4 four circle diffractometer | Rint = 0.013 |
| 1939 measured reflections | 2 standard reflections every 100 reflections |
| 1698 independent reflections | intensity decay: 0.9% |
| 1408 reflections with I > 2σ(I) |
Refinement top
| R[F2 > 2σ(F2)] = 0.042 | Riding model |
| wR(F2) = 0.122 | Δρmax = 0.28 e Å−3 |
| S = 1.10 | Δρmin = −0.23 e Å−3 |
| 1698 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| 113 parameters | Absolute structure parameter: 0.72 (187) |
| 0 restraints |
Special details top
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 on F2 for ALL reflections except for 0 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| C1 | 1.0031 (2) | 0.3259 (2) | −0.19146 (15) | 0.0333 (5) | |
| C2 | 0.9944 (2) | 0.2357 (2) | −0.10640 (14) | 0.0318 (5) | |
| H2 | 1.0751 (2) | 0.2327 (2) | −0.07477 (14) | 0.038* | |
| C3 | 0.8969 (2) | 0.2848 (2) | −0.03486 (14) | 0.0337 (5) | |
| H3 | 0.9222 (2) | 0.3666 (2) | −0.01209 (14) | 0.040* | |
| C4 | 0.8908 (2) | 0.1938 (2) | 0.0499 (2) | 0.0389 (5) | |
| C41 | 0.7692 (4) | 0.0247 (6) | 0.1287 (4) | 0.0533 (13) | 0.60 |
| H411 | 0.8349 (4) | 0.0231 (6) | 0.1767 (4) | 0.064* | 0.60 |
| H412 | 0.7710 (4) | −0.0524 (6) | 0.0921 (4) | 0.064* | 0.60 |
| H413 | 0.6887 (4) | 0.0304 (6) | 0.1603 (4) | 0.064* | 0.60 |
| C42 | 0.7585 (16) | 0.0782 (17) | 0.1626 (12) | 0.120 (6)* | 0.40 |
| N1 | 0.9727 (2) | 0.2826 (2) | −0.27842 (13) | 0.0412 (5) | |
| H12 | 0.9602 (2) | 0.1986 (2) | −0.28028 (13) | 0.049* | |
| H11 | 0.9779 (2) | 0.3378 (2) | −0.32794 (13) | 0.049* | |
| N4 | 0.7865 (2) | 0.1311 (3) | 0.0609 (2) | 0.0710 (9) | |
| H4 | 0.7223 (2) | 0.1474 (3) | 0.0199 (2) | 0.085* | |
| O1 | 1.0369 (2) | 0.4354 (2) | −0.17790 (12) | 0.0452 (5) | |
| O2 | 0.9608 (2) | 0.1130 (2) | −0.13644 (12) | 0.0396 (4) | |
| H2O | 1.020 (3) | 0.074 (3) | −0.131 (2) | 0.058 (10)* | |
| O3 | 0.77673 (15) | 0.2933 (2) | −0.07847 (13) | 0.0444 (4) | |
| H3O | 0.772 (3) | 0.364 (4) | −0.090 (2) | 0.062 (10)* | |
| O4 | 0.98510 (15) | 0.1790 (2) | 0.10183 (11) | 0.0423 (4) |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0285 (10) | 0.0376 (11) | 0.0338 (10) | −0.0005 (8) | −0.0039 (8) | 0.0031 (8) |
| C2 | 0.0295 (10) | 0.0339 (10) | 0.0320 (9) | −0.0014 (8) | −0.0042 (8) | 0.0020 (8) |
| C3 | 0.0288 (10) | 0.0361 (11) | 0.0360 (10) | 0.0007 (8) | −0.0035 (8) | 0.0027 (9) |
| C4 | 0.0318 (11) | 0.0479 (13) | 0.0370 (11) | 0.0002 (10) | −0.0005 (9) | 0.0059 (9) |
| C41 | 0.041 (2) | 0.066 (3) | 0.053 (2) | −0.020 (2) | −0.004 (2) | 0.036 (2) |
| N1 | 0.0521 (12) | 0.0393 (10) | 0.0324 (8) | −0.0034 (9) | −0.0060 (8) | 0.0049 (8) |
| N4 | 0.0388 (11) | 0.107 (2) | 0.0672 (15) | −0.0159 (13) | −0.0100 (11) | 0.052 (2) |
| O1 | 0.0595 (11) | 0.0375 (9) | 0.0387 (9) | −0.0131 (7) | −0.0137 (8) | 0.0047 (7) |
| O2 | 0.0406 (9) | 0.0328 (8) | 0.0454 (9) | 0.0004 (7) | −0.0083 (7) | 0.0007 (7) |
| O3 | 0.0289 (8) | 0.0477 (10) | 0.0567 (10) | 0.0031 (7) | −0.0057 (7) | 0.0177 (8) |
| O4 | 0.0380 (9) | 0.0497 (10) | 0.0394 (8) | −0.0024 (7) | −0.0102 (7) | 0.0085 (7) |
Geometric parameters (Å, º) top
| C1—O1 | 1.228 (3) | C41—N4 | 1.476 (4) |
| C1—N1 | 1.322 (3) | C41—H411 | 0.96 |
| C1—C2 | 1.514 (3) | C41—H412 | 0.96 |
| C2—O2 | 1.410 (2) | C41—H413 | 0.96 |
| C2—C3 | 1.519 (3) | C42—N4 | 1.54 (2) |
| C2—H2 | 0.96 | N1—H12 | 0.90 |
| C3—O3 | 1.410 (3) | N1—H11 | 0.90 |
| C3—C4 | 1.515 (3) | N4—H4 | 0.90 |
| C3—H3 | 0.96 | O2—H2O | 0.76 (3) |
| C4—O4 | 1.238 (3) | O3—H3O | 0.76 (4) |
| C4—N4 | 1.298 (3) | ||
| O1—C1—N1 | 122.4 (2) | N4—C41—H411 | 111.0 (2) |
| O1—C1—C2 | 119.7 (2) | N4—C41—H412 | 108.4 (3) |
| N1—C1—C2 | 117.8 (2) | H411—C41—H412 | 109.5 |
| O2—C2—C1 | 111.7 (2) | N4—C41—H413 | 110.4 (2) |
| O2—C2—C3 | 109.5 (2) | H411—C41—H413 | 109.5 |
| C1—C2—C3 | 109.1 (2) | H412—C41—H413 | 108.1 |
| O2—C2—H2 | 109.07 (11) | C1—N1—H12 | 113.87 (13) |
| C1—C2—H2 | 108.53 (11) | C1—N1—H11 | 116.47 (13) |
| C3—C2—H2 | 108.83 (10) | H12—N1—H11 | 129.0 |
| O3—C3—C4 | 109.3 (2) | C4—N4—C41 | 124.8 (3) |
| O3—C3—C2 | 111.1 (2) | C4—N4—C42 | 117.2 (7) |
| C4—C3—C2 | 108.1 (2) | C41—N4—C42 | 28.5 (6) |
| O3—C3—H3 | 109.50 (12) | C4—N4—H4 | 118.18 (14) |
| C4—C3—H3 | 109.54 (12) | C41—N4—H4 | 116.7 (2) |
| C2—C3—H3 | 109.30 (11) | C42—N4—H4 | 119.7 (6) |
| O4—C4—N4 | 123.7 (2) | C2—O2—H2O | 106 (2) |
| O4—C4—C3 | 119.4 (2) | C3—O3—H3O | 102 (3) |
| N4—C4—C3 | 116.8 (2) | ||
| O1—C1—C2—O2 | −176.8 (2) | O3—C3—C4—O4 | −175.5 (2) |
| N1—C1—C2—O2 | 3.6 (3) | C2—C3—C4—O4 | 63.5 (3) |
| O1—C1—C2—C3 | 62.0 (3) | O3—C3—C4—N4 | 7.4 (3) |
| N1—C1—C2—C3 | −117.6 (2) | C2—C3—C4—N4 | −113.6 (3) |
| O2—C2—C3—O3 | −61.9 (2) | O4—C4—N4—C41 | −7.0 (6) |
| C1—C2—C3—O3 | 60.7 (2) | C3—C4—N4—C41 | 169.9 (4) |
| O2—C2—C3—C4 | 58.0 (2) | O4—C4—N4—C42 | 25.1 (8) |
| C1—C2—C3—C4 | −179.4 (2) | C3—C4—N4—C42 | −158.0 (7) |
(hn22) (R,R)-(+)-Tartaric acid N,N'-dimethyldiamide
monohydrate top
Crystal data top
| C6H14N2O5 | Dx = 1.382 Mg m−3 |
| Mr = 194.19 | Melting point = 471–473 K |
| Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
| a = 5.094 (1) Å | Cell parameters from 40 reflections |
| b = 11.243 (2) Å | θ = 5.9–19.1° |
| c = 16.295 (4) Å | µ = 0.12 mm−1 |
| V = 933.2 (3) Å3 | T = 293 K |
| Z = 4 | Needle, colourless |
| F(000) = 416 | 0.3 × 0.3 × 0.2 mm |
Data collection top
| KM-4 four circle diffractometer | Rint = 0.103 |
| Radiation source: fine-focus sealed tube | θmax = 27.1°, θmin = 2.2° |
| Graphite monochromator | h = −6→6 |
| Θ–2Θ scans | k = 0→14 |
| 2216 measured reflections | l = 0→20 |
| 2058 independent reflections | 3 standard reflections every 100 reflections |
| 1696 reflections with I > 2σ(I) | intensity decay: 0.5% |
Refinement top
| 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)] = 0.057 | Riding model |
| wR(F2) = 0.163 | Calculated w = 1/[σ2(Fo2) + (0.1129P)2 + 0.4981P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.04 | (Δ/σ)max < 0.001 |
| 2057 reflections | Δρmax = 0.28 e Å−3 |
| 134 parameters | Δρmin = −0.26 e Å−3 |
| 0 restraints | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −1.63 (188) |
Crystal data top
| C6H14N2O5 | V = 933.2 (3) Å3 |
| Mr = 194.19 | Z = 4 |
| Orthorhombic, P212121 | Mo Kα radiation |
| a = 5.094 (1) Å | µ = 0.12 mm−1 |
| b = 11.243 (2) Å | T = 293 K |
| c = 16.295 (4) Å | 0.3 × 0.3 × 0.2 mm |
Data collection top
| KM-4 four circle diffractometer | Rint = 0.103 |
| 2216 measured reflections | 3 standard reflections every 100 reflections |
| 2058 independent reflections | intensity decay: 0.5% |
| 1696 reflections with I > 2σ(I) |
Refinement top
| R[F2 > 2σ(F2)] = 0.057 | Riding model |
| wR(F2) = 0.163 | Δρmax = 0.28 e Å−3 |
| S = 1.04 | Δρmin = −0.26 e Å−3 |
| 2057 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
| 134 parameters | Absolute structure parameter: −1.63 (188) |
| 0 restraints |
Special details top
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 on F2 for ALL reflections except for 1 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
| x | y | z | Uiso*/Ueq | ||
| C1 | 0.1536 (6) | 0.0027 (2) | 0.5434 (2) | 0.0137 (6) | |
| C2 | 0.2217 (6) | 0.0950 (2) | 0.4793 (2) | 0.0110 (6) | |
| H2 | 0.4085 (6) | 0.0966 (2) | 0.4716 (2) | 0.010* | |
| C3 | 0.0882 (5) | 0.0638 (2) | 0.3981 (2) | 0.0121 (5) | |
| H3 | 0.1671 (5) | −0.0064 (2) | 0.3753 (2) | 0.010* | |
| C4 | 0.1282 (6) | 0.1690 (2) | 0.3392 (2) | 0.0121 (5) | |
| C11 | −0.0636 (8) | −0.0391 (3) | 0.6732 (2) | 0.0267 (7) | |
| H111 | −0.0817 (8) | 0.0068 (3) | 0.7226 (2) | 0.040* | |
| H112 | 0.0621 (8) | −0.1016 (3) | 0.6812 (2) | 0.040* | |
| H113 | −0.2289 (8) | −0.0742 (3) | 0.6586 (2) | 0.040* | |
| C41 | −0.0827 (6) | 0.3090 (2) | 0.2470 (2) | 0.0183 (6) | |
| H411 | −0.2443 (6) | 0.3146 (2) | 0.2170 (2) | 0.030* | |
| H412 | 0.0603 (6) | 0.2981 (2) | 0.2094 (2) | 0.030* | |
| H413 | −0.0532 (6) | 0.3817 (2) | 0.2765 (2) | 0.030* | |
| O1 | 0.2172 (5) | −0.1028 (2) | 0.53222 (14) | 0.0200 (5) | |
| O2 | 0.1340 (4) | 0.2092 (2) | 0.50499 (12) | 0.0124 (4) | |
| H2O | 0.306 (10) | 0.248 (4) | 0.511 (3) | 0.034 (11)* | |
| O3 | −0.1830 (4) | 0.0447 (2) | 0.40978 (13) | 0.0153 (5) | |
| H3O | −0.221 (8) | −0.029 (4) | 0.407 (2) | 0.023 (10)* | |
| O4 | 0.3488 (4) | 0.2097 (2) | 0.32678 (13) | 0.0149 (4) | |
| N1 | 0.0234 (5) | 0.0406 (2) | 0.6085 (2) | 0.0171 (5) | |
| H1 | −0.0119 (5) | 0.1187 (2) | 0.6131 (2) | 0.040* | |
| N4 | −0.0892 (5) | 0.2101 (2) | 0.30444 (14) | 0.0135 (5) | |
| H4 | −0.2441 (5) | 0.1759 (2) | 0.31662 (14) | 0.010* | |
| O1W | −0.4143 (5) | −0.1676 (2) | 0.4156 (2) | 0.0192 (5) | |
| H1W | −0.334 (11) | −0.228 (6) | 0.424 (4) | 0.059 (17)* | |
| H2W | −0.527 (12) | −0.152 (4) | 0.441 (3) | 0.037 (14)* |
Atomic displacement parameters (Å2) top
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0148 (13) | 0.0104 (11) | 0.0161 (13) | 0.0008 (10) | −0.0022 (10) | 0.0022 (10) |
| C2 | 0.0134 (12) | 0.0053 (12) | 0.0145 (13) | 0.0011 (9) | 0.0019 (10) | −0.0008 (10) |
| C3 | 0.0130 (13) | 0.0087 (11) | 0.0145 (13) | 0.0004 (9) | 0.0007 (11) | −0.0006 (9) |
| C4 | 0.0161 (13) | 0.0091 (11) | 0.0112 (13) | 0.0007 (10) | 0.0000 (10) | −0.0024 (9) |
| C11 | 0.044 (2) | 0.0156 (14) | 0.021 (2) | 0.0026 (14) | 0.0097 (14) | 0.0073 (12) |
| C41 | 0.0198 (14) | 0.0155 (13) | 0.0196 (14) | −0.0001 (11) | −0.0021 (12) | 0.0068 (11) |
| O1 | 0.0271 (12) | 0.0084 (9) | 0.0246 (11) | 0.0038 (8) | 0.0053 (9) | 0.0024 (8) |
| O2 | 0.0149 (9) | 0.0054 (8) | 0.0170 (10) | 0.0000 (8) | 0.0006 (8) | −0.0023 (7) |
| O3 | 0.0140 (10) | 0.0081 (9) | 0.0238 (11) | −0.0023 (8) | 0.0001 (8) | 0.0020 (8) |
| O4 | 0.0147 (10) | 0.0137 (9) | 0.0163 (10) | −0.0013 (8) | 0.0013 (8) | 0.0006 (7) |
| N1 | 0.0267 (13) | 0.0082 (10) | 0.0165 (13) | 0.0004 (10) | 0.0035 (10) | 0.0029 (9) |
| N4 | 0.0126 (11) | 0.0129 (10) | 0.0148 (11) | −0.0007 (9) | 0.0003 (9) | 0.0041 (9) |
| O1W | 0.0212 (12) | 0.0092 (9) | 0.0272 (13) | 0.0015 (8) | 0.0048 (10) | 0.0011 (8) |
Geometric parameters (Å, º) top
| C1—O1 | 1.243 (3) | C11—H112 | 0.96 |
| C1—N1 | 1.321 (4) | C11—H113 | 0.96 |
| C1—C2 | 1.512 (4) | C41—N4 | 1.453 (3) |
| C2—O2 | 1.422 (3) | C41—H411 | 0.96 |
| C2—C3 | 1.529 (4) | C41—H412 | 0.96 |
| C2—H2 | 0.96 | C41—H413 | 0.96 |
| C3—O3 | 1.411 (3) | O2—H2O | 0.98 (5) |
| C3—C4 | 1.537 (3) | O3—H3O | 0.85 (5) |
| C3—H3 | 0.96 | N1—H1 | 0.90 |
| C4—O4 | 1.230 (4) | N4—H4 | 0.90 |
| C4—N4 | 1.327 (4) | O1W—H1W | 0.81 (6) |
| C11—N1 | 1.453 (4) | O1W—H2W | 0.73 (6) |
| C11—H111 | 0.96 | ||
| O1—C1—N1 | 123.8 (3) | H111—C11—H112 | 110.2 |
| O1—C1—C2 | 119.6 (3) | N1—C11—H113 | 110.0 (2) |
| N1—C1—C2 | 116.6 (2) | H111—C11—H113 | 110.2 |
| O2—C2—C1 | 110.1 (2) | H112—C11—H113 | 108.5 |
| O2—C2—C3 | 108.8 (2) | N4—C41—H411 | 111.1 (2) |
| C1—C2—C3 | 109.7 (2) | N4—C41—H412 | 109.3 (2) |
| O2—C2—H2 | 109.46 (14) | H411—C41—H412 | 109.4 |
| C1—C2—H2 | 109.3 (2) | N4—C41—H413 | 109.4 (2) |
| C3—C2—H2 | 109.38 (15) | H411—C41—H413 | 109.4 |
| O3—C3—C2 | 110.7 (2) | H412—C41—H413 | 108.0 |
| O3—C3—C4 | 109.4 (2) | C2—O2—H2O | 99 (3) |
| C2—C3—C4 | 107.7 (2) | C3—O3—H3O | 111 (3) |
| O3—C3—H3 | 109.72 (14) | C1—N1—C11 | 122.5 (2) |
| C2—C3—H3 | 109.71 (14) | C1—N1—H1 | 118.79 (15) |
| C4—C3—H3 | 109.59 (14) | C11—N1—H1 | 118.7 (2) |
| O4—C4—N4 | 124.3 (2) | C4—N4—C41 | 121.5 (2) |
| O4—C4—C3 | 120.7 (3) | C4—N4—H4 | 119.25 (15) |
| N4—C4—C3 | 115.1 (2) | C41—N4—H4 | 119.3 (2) |
| N1—C11—H111 | 107.8 (2) | H1W—O1W—H2W | 120 (6) |
| N1—C11—H112 | 110.3 (2) | ||
| O1—C1—C2—O2 | −179.3 (3) | O3—C3—C4—O4 | 172.3 (2) |
| N1—C1—C2—O2 | 1.8 (4) | C2—C3—C4—O4 | 51.9 (3) |
| O1—C1—C2—C3 | 61.0 (4) | O3—C3—C4—N4 | −7.6 (3) |
| N1—C1—C2—C3 | −117.9 (3) | C2—C3—C4—N4 | −128.0 (2) |
| O2—C2—C3—O3 | −68.5 (3) | O1—C1—N1—C11 | −1.3 (5) |
| C1—C2—C3—O3 | 52.0 (3) | C2—C1—N1—C11 | 177.6 (3) |
| O2—C2—C3—C4 | 51.0 (3) | O4—C4—N4—C41 | 0.3 (4) |
| C1—C2—C3—C4 | 171.6 (2) | C3—C4—N4—C41 | −179.7 (2) |
Experimental details
| (hoh1) | (hn12) | (hn22) | |
| Crystal data | |||
| Chemical formula | C4H7NO5 | C5H10N2O4 | C6H14N2O5 |
| Mr | 149.11 | 162.15 | 194.19 |
| Crystal system, space group | Orthorhombic, P212121 | Tetragonal, P41212 | Orthorhombic, P212121 |
| Temperature (K) | 293 | 293 | 293 |
| a, b, c (Å) | 5.9556 (5), 8.0972 (5), 11.8960 (8) | 10.594 (1), 10.594 (1), 13.771 (3) | 5.094 (1), 11.243 (2), 16.295 (4) |
| α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 90, 90 |
| V (Å3) | 573.67 (7) | 1545.6 (4) | 933.2 (3) |
| Z | 4 | 8 | 4 |
| Radiation type | Mo Kα | Mo Kα | Mo Kα |
| µ (mm−1) | 0.16 | 0.12 | 0.12 |
| Crystal size (mm) | 0.5 × 0.5 × 0.5 | 0.45 × 0.44 × 0.41 | 0.3 × 0.3 × 0.2 |
| Data collection | |||
| Diffractometer | KM-4 four circle diffractometer | KM-4 four circle diffractometer | KM-4 four circle diffractometer |
| Absorption correction | – | – | – |
| No. of measured, independent and observed reflections | 1688, 1534, 1476 [I > σ(I)] | 1939, 1698, 1408 [I > 2σ(I)] | 2216, 2058, 1696 [I > 2σ(I)] |
| Rint | 0.011 | 0.013 | 0.103 |
| (sin θ/λ)max (Å−1) | 0.683 | 0.640 | 0.640 |
| Refinement | |||
| R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.099, 1.01 | 0.042, 0.122, 1.10 | 0.057, 0.163, 1.04 |
| No. of reflections | 1531 | 1698 | 2057 |
| No. of parameters | 103 | 113 | 134 |
| H-atom treatment | Riding model | Riding model | Riding model |
| Δρmax, Δρmin (e Å−3) | 0.39, −0.18 | 0.28, −0.23 | 0.28, −0.26 |
| Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 | Flack H D (1983), Acta Cryst. A39, 876-881 |
| Absolute structure parameter | 0.80 (114) | 0.72 (187) | −1.63 (188) |
Computer programs: Kuma KM-4 Software (Kuma Diffraction, 1991), Kuma KM-4 Software, SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), Simens Analytical X-Ray Instruments (1989).
