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The crystal structure of (R,R)-N-methyltartramic acid monohydrate is presented and compared with that of the parent compound, (R,R)-tartaric acid. Despite some conformational differences between the two molecules the packing is very similar, as it is dictated by the carboxyl rather than the amide function. Particular attention is paid to a mediated three-centre hydrogen bond as one of the packing motifs involving the α-hydroxycarboxyl moiety. The stability and geometry of such structures in the gas phase and in solution are examined via theoretical ab initio methods using the RHF/6-311++G** and RHF/6-311++G**/Onsager models, respectively. Liquid media, in particular those of high polarity, are found to stabilize the structures considerably.
Supporting information
![cif](https://journals.iucr.org//../logos/filetypeicons/bw/b1/ciflogo.png) | Crystallographic Information File (CIF) Contains datablock mma |
![fcf](https://journals.iucr.org//../logos/filetypeicons/bw/b1/fcflogo.png) | Structure factor file (CIF format) Contains datablock hoh2 |
CCDC reference: 134771
Data collection: KM4; cell refinement: KM4; data reduction: DATARED; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SIEMENS STEREOCHEMICAL WORKSTATION.
(
R,
R)-Tartaric Acid Mono (
N-Methylamide) Monohydrate
top
Crystal data top
C5H9NO5·H2O | Dx = 1.553 Mg m−3 Dm = 1.533 Mg m−3 Dm measured by flotation in KI |
Mr = 181.15 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 36 reflections |
a = 7.301 (1) Å | θ = 8.4–14.8° |
b = 7.658 (2) Å | µ = 0.14 mm−1 |
c = 13.855 (3) Å | T = 293 K |
V = 774.6 (3) Å3 | Prism, transparent |
Z = 4 | 0.6 × 0.25 × 0.2 mm |
F(000) = 384 | |
Data collection top
KM-4 diffractometer | Rint = 0.021 |
Radiation source: fine-focus sealed tube | θmax = 28.1°, θmin = 2.9° |
Graphite monochromator | h = −9→9 |
θ–2θ scans | k = 0→10 |
2066 measured reflections | l = 0→18 |
1875 independent reflections | 2 standard reflections every 100 reflections |
1485 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.031 | Calculated w = 1/[σ2(Fo2) + (0.0445P)2 + 0.0586P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.084 | (Δ/σ)max < 0.001 |
S = 1.07 | Δρmax = 0.18 e Å−3 |
1874 reflections | Δρmin = −0.17 e Å−3 |
129 parameters | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
0 restraints | Absolute structure parameter: −0.70 (130) |
Primary atom site location: structure-invariant direct methods | |
Crystal data top
C5H9NO5·H2O | V = 774.6 (3) Å3 |
Mr = 181.15 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.301 (1) Å | µ = 0.14 mm−1 |
b = 7.658 (2) Å | T = 293 K |
c = 13.855 (3) Å | 0.6 × 0.25 × 0.2 mm |
Data collection top
KM-4 diffractometer | Rint = 0.021 |
2066 measured reflections | 2 standard reflections every 100 reflections |
1875 independent reflections | intensity decay: none |
1485 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.084 | Δρmax = 0.18 e Å−3 |
S = 1.07 | Δρmin = −0.17 e Å−3 |
1874 reflections | Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881 |
129 parameters | Absolute structure parameter: −0.70 (130) |
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 | 0.2930 (2) | 0.4182 (2) | 0.41106 (12) | 0.0259 (3) | |
C2 | 0.5003 (2) | 0.4140 (2) | 0.40321 (11) | 0.0228 (3) | |
H2 | 0.5490 (2) | 0.3583 (2) | 0.45972 (11) | 0.027* | |
C3 | 0.5602 (2) | 0.3101 (2) | 0.31528 (12) | 0.0239 (3) | |
H3 | 0.5291 (2) | 0.1897 (2) | 0.32537 (12) | 0.029* | |
C4 | 0.7664 (2) | 0.3249 (2) | 0.30344 (12) | 0.0244 (3) | |
C40 | 1.0165 (3) | 0.3828 (3) | 0.19197 (15) | 0.0399 (5) | |
H401 | 1.0819 (3) | 0.4648 (3) | 0.23146 (15) | 0.048* | |
H402 | 1.0285 (3) | 0.4179 (3) | 0.12574 (15) | 0.048* | |
H403 | 1.0652 (3) | 0.2675 (3) | 0.20078 (15) | 0.048* | |
N4 | 0.8254 (2) | 0.3773 (2) | 0.21926 (10) | 0.0326 (4) | |
H4 | 0.7420 (2) | 0.4135 (2) | 0.17582 (10) | 0.039* | |
O1 | 0.2101 (2) | 0.5480 (2) | 0.43369 (13) | 0.0463 (4) | |
O2 | 0.5651 (2) | 0.5878 (2) | 0.40023 (9) | 0.0289 (3) | |
H2O | 0.668 (4) | 0.601 (4) | 0.443 (2) | 0.070 (8)* | |
O3 | 0.4658 (2) | 0.3721 (2) | 0.23251 (9) | 0.0321 (3) | |
H3O | 0.444 (4) | 0.284 (4) | 0.193 (2) | 0.075 (9)* | |
O4 | 0.8662 (2) | 0.2838 (2) | 0.37232 (9) | 0.0324 (3) | |
O10 | 0.2160 (2) | 0.2688 (2) | 0.39214 (9) | 0.0303 (3) | |
H10 | 0.088 (5) | 0.279 (4) | 0.377 (3) | 0.088 (10)* | |
O(W) | 0.1486 (2) | 0.1173 (2) | 0.98452 (10) | 0.0358 (3) | |
H1W | 0.047 (4) | 0.086 (4) | 1.005 (2) | 0.056 (8)* | |
H2W | 0.138 (5) | 0.230 (5) | 0.969 (3) | 0.098 (11)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0232 (8) | 0.0306 (9) | 0.0240 (8) | 0.0014 (7) | −0.0001 (6) | 0.0001 (7) |
C2 | 0.0219 (7) | 0.0246 (8) | 0.0218 (7) | 0.0011 (6) | −0.0025 (6) | 0.0000 (6) |
C3 | 0.0192 (7) | 0.0253 (8) | 0.0270 (8) | 0.0009 (6) | −0.0024 (7) | −0.0023 (6) |
C4 | 0.0208 (8) | 0.0232 (8) | 0.0294 (8) | 0.0009 (6) | 0.0012 (6) | −0.0044 (7) |
C40 | 0.0295 (9) | 0.0530 (12) | 0.0371 (10) | −0.0018 (9) | 0.0075 (8) | 0.0070 (9) |
N4 | 0.0238 (8) | 0.0443 (9) | 0.0296 (8) | 0.0010 (7) | 0.0000 (6) | 0.0033 (7) |
O1 | 0.0257 (7) | 0.0388 (8) | 0.0744 (11) | 0.0029 (6) | 0.0065 (7) | −0.0184 (7) |
O2 | 0.0253 (6) | 0.0257 (6) | 0.0358 (7) | −0.0029 (5) | −0.0058 (5) | −0.0049 (5) |
O3 | 0.0278 (7) | 0.0423 (8) | 0.0262 (6) | 0.0034 (6) | −0.0062 (5) | −0.0059 (6) |
O4 | 0.0203 (6) | 0.0462 (7) | 0.0309 (6) | 0.0019 (6) | −0.0017 (5) | 0.0048 (5) |
O10 | 0.0219 (6) | 0.0306 (6) | 0.0384 (7) | −0.0012 (5) | −0.0007 (5) | 0.0013 (5) |
O(W) | 0.0307 (7) | 0.0369 (8) | 0.0398 (7) | 0.0012 (7) | −0.0033 (6) | 0.0097 (6) |
Geometric parameters (Å, º) top
C1—O1 | 1.205 (2) | C40—N4 | 1.446 (2) |
C1—O10 | 1.302 (2) | C40—H401 | 0.96 |
C1—C2 | 1.518 (2) | C40—H402 | 0.96 |
C2—O2 | 1.413 (2) | C40—H403 | 0.96 |
C2—C3 | 1.519 (2) | N4—H4 | 0.90 |
C2—H2 | 0.96 | O2—H2O | 0.96 (3) |
C3—O3 | 1.419 (2) | O3—H3O | 0.88 (3) |
C3—C4 | 1.519 (2) | O10—H10 | 0.96 (3) |
C3—H3 | 0.96 | O(W)—H1W | 0.83 (3) |
C4—O4 | 1.241 (2) | O(W)—H2W | 0.89 (4) |
C4—N4 | 1.307 (2) | | |
| | | |
O1—C1—O10 | 124.1 (2) | O4—C4—C3 | 118.7 (2) |
O1—C1—C2 | 122.5 (2) | N4—C4—C3 | 116.5 (2) |
O10—C1—C2 | 113.44 (14) | N4—C40—H401 | 110.50 (11) |
O2—C2—C1 | 108.42 (13) | N4—C40—H402 | 110.24 (10) |
O2—C2—C3 | 111.93 (14) | H401—C40—H402 | 108.5 |
C1—C2—C3 | 110.82 (13) | N4—C40—H403 | 107.29 (12) |
O2—C2—H2 | 108.58 (8) | H401—C40—H403 | 110.2 |
C1—C2—H2 | 108.67 (9) | H402—C40—H403 | 110.2 |
C3—C2—H2 | 108.35 (9) | C4—N4—C40 | 124.1 (2) |
O3—C3—C4 | 111.66 (14) | C4—N4—H4 | 117.94 (10) |
O3—C3—C2 | 109.47 (13) | C40—N4—H4 | 117.97 (10) |
C4—C3—C2 | 109.44 (14) | C2—O2—H2O | 109.8 (19) |
O3—C3—H3 | 108.89 (9) | C3—O3—H3O | 110 (2) |
C4—C3—H3 | 108.78 (9) | C1—O10—H10 | 113 (2) |
C2—C3—H3 | 108.54 (9) | H1W—O(W)—H2W | 106 (3) |
O4—C4—N4 | 124.8 (2) | | |
| | | |
O1—C1—C2—O2 | −15.7 (2) | C1—C2—C3—C4 | 173.93 (13) |
O10—C1—C2—O2 | 165.06 (13) | O3—C3—C4—O4 | 176.33 (14) |
O1—C1—C2—C3 | −138.9 (2) | C2—C3—C4—O4 | 55.0 (2) |
O10—C1—C2—C3 | 41.8 (2) | O3—C3—C4—N4 | −5.1 (2) |
O2—C2—C3—O3 | −69.9 (2) | C2—C3—C4—N4 | −126.4 (2) |
C1—C2—C3—O3 | 51.3 (2) | O4—C4—N4—C40 | 4.7 (3) |
O2—C2—C3—C4 | 52.8 (2) | C3—C4—N4—C40 | −173.8 (2) |
Experimental details
Crystal data |
Chemical formula | C5H9NO5·H2O |
Mr | 181.15 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.301 (1), 7.658 (2), 13.855 (3) |
V (Å3) | 774.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.6 × 0.25 × 0.2 |
|
Data collection |
Diffractometer | KM-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2066, 1875, 1485 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.662 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.084, 1.07 |
No. of reflections | 1874 |
No. of parameters | 129 |
Δρmax, Δρmin (e Å−3) | 0.18, −0.17 |
Absolute structure | Flack H D (1983), Acta Cryst. A39, 876-881 |
Absolute structure parameter | −0.70 (130) |
Selected torsion angles (º) topO1—C1—C2—O2 | −15.7 (2) | C1—C2—C3—C4 | 173.93 (13) |
O10—C1—C2—O2 | 165.06 (13) | O3—C3—C4—O4 | 176.33 (14) |
O1—C1—C2—C3 | −138.9 (2) | C2—C3—C4—O4 | 55.0 (2) |
O10—C1—C2—C3 | 41.8 (2) | O3—C3—C4—N4 | −5.1 (2) |
O2—C2—C3—O3 | −69.9 (2) | C2—C3—C4—N4 | −126.4 (2) |
C1—C2—C3—O3 | 51.3 (2) | O4—C4—N4—C40 | 4.7 (3) |
O2—C2—C3—C4 | 52.8 (2) | C3—C4—N4—C40 | −173.8 (2) |
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