Acta Cryst. (2009). E65, o1278 [ doi:10.1107/S1600536809016626 ]
The title compound, C4H12NO3+·C2HCl2O2-, was obtained from dichloroacetic acid and 2-amino-2-(hydroxymethyl)propane-1,3-diol. In the crystal structure, the cations and anions are connected by intermolecular N-H
O and O-HO hydrogen bonding, forming a two-dimensional array parallel to (001). The crystal used for analysis was a merohedral twin, as indicated by the Flack parameter of 0.67 (6).
The crystals were grown by slow evaporation at ambient temperature of the solution prepared by adding dichloroacetic acid to the aqueous solution of tris(hydroxymethyl)aminomethane in a stoichiometric ratio. For the X-ray diffraction analysis, suitable single crystals of compound (I) were obtained after one night by slow evaporation from an filtration water solution.
All H atoms were found from a difference Fourier map but they were treated as riding on their parent atoms with C—H = 0.97 Å (methylene) or 0.98 Å (methine), N—H = 0.89 Å and O—H = 0.82 Å with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(N,O).
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./dn2442fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with the atom labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. H bond is drawn as dashed line. |
![[Figure 2]](./dn2442fig2thm.gif)
| Fig. 2. Partial packing view showing the intricated hydrogen bond framework. H atoms not involved in hydrogen bondings were omitted. [Symmetry code: (i) -x + 1, y + 1/2, -z + 1.] |
| C4H12NO3+·C2HCl2O2– | F000 = 260 |
| Mr = 250.07 | Dx = 1.597 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation λ = 0.71073 Å |
| Hall symbol: P 2yb | Cell parameters from 735 reflections |
| a = 8.6231 (17) Å | θ = 2.8–27.5º |
| b = 6.1376 (12) Å | µ = 0.62 mm−1 |
| c = 9.898 (2) Å | T = 293 K |
| β = 97.03 (3)º | Prism, colourless |
| V = 519.92 (18) Å3 | 0.22 × 0.18 × 0.12 mm |
| Z = 2 |
| Rigaku SCXmini diffractometer | 2044 independent reflections |
| Radiation source: fine-focus sealed tube | 1951 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.025 |
| Detector resolution: 13.6612 pixels mm-1 | θmax = 26.0º |
| T = 293 K | θmin = 3.3º |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −7→7 |
| Tmin = 0.875, Tmax = 0.929 | l = −12→12 |
| 4914 measured reflections |
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.031 | w = 1/[σ2(Fo2) + (0.0218P)2 + 0.166P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.069 | (Δ/σ)max < 0.001 |
| S = 1.10 | Δρmax = 0.23 e Å−3 |
| 2044 reflections | Δρmin = −0.25 e Å−3 |
| 130 parameters | Extinction correction: none |
| 3 restraints | Absolute structure: Flack (1983), 920 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.67 (6) |
| Secondary atom site location: difference Fourier map |
| C4H12NO3+·C2HCl2O2– | V = 519.92 (18) Å3 |
| Mr = 250.07 | Z = 2 |
| Monoclinic, P21 | Mo Kα |
| a = 8.6231 (17) Å | µ = 0.62 mm−1 |
| b = 6.1376 (12) Å | T = 293 K |
| c = 9.898 (2) Å | 0.22 × 0.18 × 0.12 mm |
| β = 97.03 (3)º |
| Rigaku SCXmini diffractometer | 2044 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1951 reflections with I > 2σ(I) |
| Tmin = 0.875, Tmax = 0.929 | Rint = 0.025 |
| 4914 measured reflections |
| R[F2 > 2σ(F2)] = 0.031 | H-atom parameters constrained |
| wR(F2) = 0.069 | Δρmax = 0.23 e Å−3 |
| S = 1.10 | Δρmin = −0.25 e Å−3 |
| 2044 reflections | Absolute structure: Flack (1983), 920 Friedel pairs |
| 130 parameters | Flack parameter: 0.67 (6) |
| 3 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | ||
| Cl1 | 0.86491 (9) | 0.39154 (15) | 0.00483 (7) | 0.0630 (2) | |
| Cl2 | 0.70850 (10) | 0.03942 (11) | 0.13016 (8) | 0.0598 (2) | |
| C1 | 0.6938 (3) | 0.3135 (4) | 0.0737 (2) | 0.0342 (5) | |
| H1 | 0.6046 | 0.3263 | 0.0026 | 0.041* | |
| C2 | 0.6675 (2) | 0.4656 (4) | 0.1919 (2) | 0.0282 (5) | |
| C3 | 0.2265 (2) | 0.2569 (3) | 0.3756 (2) | 0.0215 (4) | |
| C4 | 0.3748 (2) | 0.1471 (3) | 0.3394 (2) | 0.0248 (4) | |
| H4A | 0.3540 | 0.0827 | 0.2496 | 0.030* | |
| H4B | 0.4558 | 0.2562 | 0.3365 | 0.030* | |
| C5 | 0.0883 (2) | 0.0986 (3) | 0.3577 (2) | 0.0249 (4) | |
| H5A | 0.0543 | 0.0801 | 0.2613 | 0.030* | |
| H5B | 0.1226 | −0.0423 | 0.3944 | 0.030* | |
| C6 | 0.1911 (2) | 0.4607 (3) | 0.2892 (2) | 0.0270 (4) | |
| H6A | 0.1841 | 0.4215 | 0.1937 | 0.032* | |
| H6B | 0.0905 | 0.5188 | 0.3058 | 0.032* | |
| N1 | 0.25465 (19) | 0.3243 (3) | 0.52217 (16) | 0.0221 (3) | |
| H1A | 0.3470 | 0.3903 | 0.5382 | 0.033* | |
| H1B | 0.2540 | 0.2070 | 0.5750 | 0.033* | |
| H1C | 0.1797 | 0.4156 | 0.5403 | 0.033* | |
| O1 | 0.54454 (19) | 0.5709 (3) | 0.17435 (18) | 0.0444 (4) | |
| O2 | 0.76863 (19) | 0.4708 (3) | 0.29336 (16) | 0.0403 (4) | |
| O3 | 0.42905 (16) | −0.0160 (2) | 0.43407 (15) | 0.0306 (4) | |
| H3 | 0.3857 | −0.1281 | 0.4071 | 0.046* | |
| O4 | 0.30642 (17) | 0.6233 (2) | 0.31776 (17) | 0.0336 (4) | |
| H4 | 0.3805 | 0.5959 | 0.2759 | 0.050* | |
| O5 | −0.04042 (15) | 0.1704 (3) | 0.42311 (15) | 0.0274 (3) | |
| H5 | −0.0931 | 0.2564 | 0.3735 | 0.041* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0535 (4) | 0.0984 (7) | 0.0405 (4) | −0.0075 (4) | 0.0196 (3) | −0.0042 (4) |
| Cl2 | 0.0872 (5) | 0.0321 (3) | 0.0549 (4) | −0.0001 (4) | −0.0123 (4) | −0.0081 (3) |
| C1 | 0.0339 (12) | 0.0377 (13) | 0.0292 (11) | 0.0008 (10) | −0.0040 (9) | −0.0007 (10) |
| C2 | 0.0274 (11) | 0.0271 (10) | 0.0304 (11) | −0.0002 (10) | 0.0048 (9) | 0.0064 (9) |
| C3 | 0.0185 (9) | 0.0225 (10) | 0.0233 (10) | −0.0014 (8) | 0.0018 (8) | 0.0011 (8) |
| C4 | 0.0213 (10) | 0.0248 (11) | 0.0288 (11) | 0.0005 (9) | 0.0052 (9) | 0.0000 (9) |
| C5 | 0.0191 (9) | 0.0233 (11) | 0.0324 (11) | −0.0007 (8) | 0.0029 (8) | −0.0030 (9) |
| C6 | 0.0247 (10) | 0.0227 (10) | 0.0332 (11) | 0.0007 (9) | 0.0017 (9) | 0.0044 (9) |
| N1 | 0.0180 (7) | 0.0224 (8) | 0.0259 (9) | 0.0000 (7) | 0.0031 (7) | −0.0006 (7) |
| O1 | 0.0347 (9) | 0.0503 (11) | 0.0494 (10) | 0.0142 (8) | 0.0097 (8) | 0.0129 (9) |
| O2 | 0.0424 (9) | 0.0425 (10) | 0.0337 (9) | 0.0120 (8) | −0.0048 (7) | −0.0105 (7) |
| O3 | 0.0238 (7) | 0.0236 (8) | 0.0433 (9) | 0.0036 (6) | −0.0002 (7) | 0.0001 (7) |
| O4 | 0.0293 (8) | 0.0219 (7) | 0.0510 (10) | −0.0038 (6) | 0.0105 (7) | 0.0024 (7) |
| O5 | 0.0179 (7) | 0.0308 (8) | 0.0337 (8) | −0.0002 (6) | 0.0043 (6) | 0.0027 (6) |
| Cl1—C1 | 1.765 (2) | C5—O5 | 1.421 (2) |
| Cl2—C1 | 1.773 (3) | C5—H5A | 0.9700 |
| C1—C2 | 1.536 (3) | C5—H5B | 0.9700 |
| C1—H1 | 0.9800 | C6—O4 | 1.413 (3) |
| C2—O1 | 1.236 (3) | C6—H6A | 0.9700 |
| C2—O2 | 1.247 (3) | C6—H6B | 0.9700 |
| C3—N1 | 1.499 (3) | N1—H1A | 0.8900 |
| C3—C6 | 1.525 (3) | N1—H1B | 0.8900 |
| C3—C4 | 1.527 (3) | N1—H1C | 0.8900 |
| C3—C5 | 1.531 (3) | O3—H3 | 0.8119 |
| C4—O3 | 1.411 (2) | O4—H4 | 0.8205 |
| C4—H4A | 0.9700 | O5—H5 | 0.8200 |
| C4—H4B | 0.9700 | ||
| C2—C1—Cl1 | 109.75 (16) | O5—C5—C3 | 112.99 (16) |
| C2—C1—Cl2 | 110.36 (16) | O5—C5—H5A | 109.0 |
| Cl1—C1—Cl2 | 110.39 (14) | C3—C5—H5A | 109.0 |
| C2—C1—H1 | 108.8 | O5—C5—H5B | 109.0 |
| Cl1—C1—H1 | 108.8 | C3—C5—H5B | 109.0 |
| Cl2—C1—H1 | 108.8 | H5A—C5—H5B | 107.8 |
| O1—C2—O2 | 127.1 (2) | O4—C6—C3 | 112.27 (17) |
| O1—C2—C1 | 114.5 (2) | O4—C6—H6A | 109.2 |
| O2—C2—C1 | 118.38 (19) | C3—C6—H6A | 109.2 |
| N1—C3—C6 | 108.33 (17) | O4—C6—H6B | 109.2 |
| N1—C3—C4 | 107.93 (16) | C3—C6—H6B | 109.2 |
| C6—C3—C4 | 110.28 (16) | H6A—C6—H6B | 107.9 |
| N1—C3—C5 | 108.57 (16) | C3—N1—H1A | 109.5 |
| C6—C3—C5 | 110.83 (16) | C3—N1—H1B | 109.5 |
| C4—C3—C5 | 110.81 (17) | H1A—N1—H1B | 109.5 |
| O3—C4—C3 | 112.12 (16) | C3—N1—H1C | 109.5 |
| O3—C4—H4A | 109.2 | H1A—N1—H1C | 109.5 |
| C3—C4—H4A | 109.2 | H1B—N1—H1C | 109.5 |
| O3—C4—H4B | 109.2 | C4—O3—H3 | 106.3 |
| C3—C4—H4B | 109.2 | C6—O4—H4 | 109.1 |
| H4A—C4—H4B | 107.9 | C5—O5—H5 | 109.5 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.89 | 2.00 | 2.881 (2) | 169 |
| N1—H1B···O2ii | 0.89 | 1.97 | 2.858 (2) | 172 |
| N1—H1C···O5iii | 0.89 | 2.03 | 2.909 (2) | 169 |
| O3—H3···O4iv | 0.81 | 1.85 | 2.654 (2) | 169 |
| O4—H4···O1 | 0.82 | 1.84 | 2.655 (2) | 173 |
| O5—H5···O2v | 0.82 | 1.88 | 2.691 (2) | 168 |
| Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x, y+1/2, −z+1; (iv) x, y−1, z; (v) x−1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1A···O3i | 0.89 | 2.00 | 2.881 (2) | 169 |
| N1—H1B···O2ii | 0.89 | 1.97 | 2.858 (2) | 172 |
| N1—H1C···O5iii | 0.89 | 2.03 | 2.909 (2) | 169 |
| O3—H3···O4iv | 0.81 | 1.85 | 2.654 (2) | 169 |
| O4—H4···O1 | 0.82 | 1.84 | 2.655 (2) | 173 |
| O5—H5···O2v | 0.82 | 1.88 | 2.691 (2) | 168 |
| Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+1, y−1/2, −z+1; (iii) −x, y+1/2, −z+1; (iv) x, y−1, z; (v) x−1, y, z. |
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During the past 15 years, organic crystals for quadratic nonlinear optics have been intensely engineered (Etter & Frankenbach, 1989; Yaghi et al., 1997). Arising from the complexation of organic and inorganic molecules based on acid–base interactions, highly polarisable cations, responsible for NLO properties, are linked to inorganic anions through hydrogen bond networks which generate a noncentrosymmetric structural organization (Etter, 1990). In this paper, a novel nonlinear hybrid molecular crystal, NH2C(CH2OH)3, has been prepared by complexation between dichloroacetic and tris(hydroxymethyl)amino methane.
The structure is built up from cations and anions (Fig. 1) connected through strong intermolecular hydrogen bonds (Table 1, Fig. 2) to form a two-dimensional layer developing parallel to the (001) plane. As suggested by the value of the Flack parameter (Flack, 1983), 0.67 (6), based on 920 Friedel's pairs, the particular crystal is twinned by inversion.