Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803014041/ci6237sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803014041/ci6237Isup2.hkl |
CCDC reference: 217624
The title compound was crystallized from the aqueous solution when attempts were made to grow the single crystals of L-aspartic acid with sulfuric acid.
The H atoms of the water molecule were located from a difference Fourier map and their isotropic displacement parameters were refined [Uiso(H) = 0.04 (1) and 0.07 (2) Å2]. All other H atoms were placed in geometrically calculated positions and included in the refinement in the riding-model approximation, with Uiso equal to 1.2Ueq of the carrier atom. Intensities for 442 Friedel pairs were measured, resulting in a Flack parameter of 0(3). Though the absolute structure could not be confirmed as a result of weak anamalous signal, the Friedel pairs were not merged due to resulting low r/p ratio.
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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.
C4H7NO4·H2O | F(000) = 320 |
Mr = 151.12 | Dx = 1.548 Mg m−3 Dm = 1.54 Mg m−3 Dm measured by Flotation in a mixture of carbon tetrachloride and xylene |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.70165 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 25 reflections |
a = 5.587 (4) Å | θ = 8.0–13.8° |
b = 9.822 (5) Å | µ = 0.14 mm−1 |
c = 11.813 (9) Å | T = 293 K |
V = 648.2 (8) Å3 | Block, colorless |
Z = 4 | 0.3 × 0.3 × 0.3 mm |
Enraf-Nonius CAD-4 diffractometer | 1091 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.085 |
Graphite monochromator | θmax = 24.6°, θmin = 2.7° |
ω–2θ scans | h = 0→6 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→11 |
Tmin = 0.958, Tmax = 0.958 | l = −14→14 |
1318 measured reflections | 3 standard reflections every 60 min |
1132 independent reflections | intensity decay: none |
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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.173 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.136P)2 + 0.3381P] where P = (Fo2 + 2Fc2)/3 |
1132 reflections | (Δ/σ)max < 0.001 |
93 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
C4H7NO4·H2O | V = 648.2 (8) Å3 |
Mr = 151.12 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.587 (4) Å | µ = 0.14 mm−1 |
b = 9.822 (5) Å | T = 293 K |
c = 11.813 (9) Å | 0.3 × 0.3 × 0.3 mm |
Enraf-Nonius CAD-4 diffractometer | 1091 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.085 |
Tmin = 0.958, Tmax = 0.958 | 3 standard reflections every 60 min |
1318 measured reflections | intensity decay: none |
1132 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.173 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.33 e Å−3 |
1132 reflections | Δρmin = −0.54 e Å−3 |
93 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 | ||
O1 | 0.8829 (4) | 0.1742 (2) | −0.00394 (19) | 0.0281 (6) | |
O2 | 0.9943 (4) | −0.0435 (2) | 0.0011 (2) | 0.0322 (6) | |
C1 | 0.8759 (5) | 0.0573 (3) | 0.0356 (2) | 0.0211 (7) | |
C2 | 0.6928 (5) | 0.0265 (3) | 0.1294 (2) | 0.0204 (7) | |
H2 | 0.5635 | −0.0266 | 0.0948 | 0.025* | |
N1 | 0.5849 (5) | 0.1570 (3) | 0.1709 (2) | 0.0225 (6) | |
H1A | 0.5289 | 0.2043 | 0.1123 | 0.034* | |
H1B | 0.6961 | 0.2057 | 0.2066 | 0.034* | |
H1C | 0.4656 | 0.1386 | 0.2184 | 0.034* | |
C3 | 0.7905 (5) | −0.0570 (3) | 0.2273 (3) | 0.0236 (7) | |
H3A | 0.8240 | −0.1484 | 0.2008 | 0.028* | |
H3B | 0.6686 | −0.0634 | 0.2855 | 0.028* | |
C4 | 1.0170 (6) | 0.0020 (3) | 0.2793 (3) | 0.0215 (7) | |
O3 | 1.1118 (4) | 0.1059 (2) | 0.2390 (2) | 0.0301 (6) | |
O4 | 1.1037 (5) | −0.0630 (3) | 0.3683 (2) | 0.0451 (7) | |
H4 | 1.2247 | −0.0242 | 0.3907 | 0.068* | |
O11 | 0.3015 (6) | 0.7701 (3) | 0.1132 (2) | 0.0430 (7) | |
H11 | 0.2037 | 0.8162 | 0.0855 | 0.037 (11)* | |
H12 | 0.3390 | 0.7142 | 0.0674 | 0.072 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0359 (11) | 0.0217 (11) | 0.0268 (11) | −0.0021 (9) | 0.0069 (10) | 0.0077 (10) |
O2 | 0.0363 (12) | 0.0256 (11) | 0.0348 (12) | 0.0058 (10) | 0.0098 (11) | −0.0020 (10) |
C1 | 0.0208 (14) | 0.0244 (14) | 0.0179 (13) | −0.0016 (11) | 0.0004 (11) | 0.0007 (12) |
C2 | 0.0206 (14) | 0.0162 (14) | 0.0246 (15) | −0.0016 (12) | 0.0014 (12) | −0.0001 (11) |
N1 | 0.0232 (12) | 0.0187 (12) | 0.0256 (13) | 0.0034 (10) | 0.0022 (10) | 0.0019 (10) |
C3 | 0.0257 (15) | 0.0171 (14) | 0.0280 (15) | −0.0026 (12) | 0.0053 (13) | 0.0077 (12) |
C4 | 0.0220 (13) | 0.0180 (14) | 0.0244 (14) | 0.0025 (11) | 0.0054 (12) | 0.0027 (12) |
O3 | 0.0275 (11) | 0.0237 (12) | 0.0391 (12) | −0.0059 (9) | −0.0041 (10) | 0.0068 (10) |
O4 | 0.0454 (16) | 0.0453 (16) | 0.0445 (14) | −0.0009 (14) | −0.0070 (14) | 0.0067 (13) |
O11 | 0.0516 (16) | 0.0395 (14) | 0.0380 (14) | 0.0107 (13) | −0.0034 (13) | −0.0022 (12) |
O1—C1 | 1.240 (4) | C3—C4 | 1.522 (5) |
O2—C1 | 1.259 (4) | C3—H3A | 0.97 |
C1—C2 | 1.538 (4) | C3—H3B | 0.97 |
C2—N1 | 1.499 (3) | C4—O3 | 1.244 (4) |
C2—C3 | 1.519 (4) | C4—O4 | 1.322 (4) |
C2—H2 | 0.98 | O4—H4 | 0.82 |
N1—H1A | 0.89 | O11—H11 | 0.78 |
N1—H1B | 0.89 | O11—H12 | 0.80 |
N1—H1C | 0.89 | ||
O1—C1—O2 | 126.2 (3) | H1A—N1—H1C | 109.5 |
O1—C1—C2 | 118.3 (3) | H1B—N1—H1C | 109.5 |
O2—C1—C2 | 115.3 (3) | C2—C3—C4 | 113.6 (2) |
N1—C2—C3 | 110.9 (2) | C2—C3—H3A | 108.8 |
N1—C2—C1 | 109.5 (2) | C4—C3—H3A | 108.8 |
C3—C2—C1 | 114.6 (2) | C2—C3—H3B | 108.8 |
N1—C2—H2 | 107.2 | C4—C3—H3B | 108.8 |
C3—C2—H2 | 107.2 | H3A—C3—H3B | 107.7 |
C1—C2—H2 | 107.2 | O3—C4—O4 | 123.0 (3) |
C2—N1—H1A | 109.5 | O3—C4—C3 | 120.8 (3) |
C2—N1—H1B | 109.5 | O4—C4—C3 | 116.2 (3) |
H1A—N1—H1B | 109.5 | C4—O4—H4 | 109.5 |
C2—N1—H1C | 109.5 | H11—O11—H12 | 107.5 |
O1—C1—C2—N1 | −10.8 (4) | N1—C2—C3—C4 | −71.9 (3) |
O2—C1—C2—N1 | 173.9 (3) | C1—C2—C3—C4 | 52.8 (3) |
O1—C1—C2—C3 | −136.2 (3) | C2—C3—C4—O3 | −2.9 (4) |
O2—C1—C2—C3 | 48.5 (3) | C2—C3—C4—O4 | 177.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.89 | 1.93 | 2.813 (4) | 171 |
N1—H1C···O3ii | 0.89 | 2.02 | 2.809 (4) | 147 |
O4—H4···O2iii | 0.82 | 2.15 | 2.933 (4) | 161 |
N1—H1B···O11iv | 0.89 | 2.22 | 2.854 (4) | 128 |
O11—H11···O2v | 0.78 | 2.06 | 2.837 (4) | 170 |
O11—H12···O2i | 0.80 | 2.05 | 2.817 (4) | 160 |
N1—H1B···O3 | 0.89 | 2.55 | 3.093 (4) | 120 |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x−1, y, z; (iii) −x+5/2, −y, z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x−1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C4H7NO4·H2O |
Mr | 151.12 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 5.587 (4), 9.822 (5), 11.813 (9) |
V (Å3) | 648.2 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.3 × 0.3 × 0.3 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.958, 0.958 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1318, 1132, 1091 |
Rint | 0.085 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.173, 1.06 |
No. of reflections | 1132 |
No. of parameters | 93 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.54 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1999), SHELXL97.
O1—C1 | 1.240 (4) | C4—O3 | 1.244 (4) |
O2—C1 | 1.259 (4) | C4—O4 | 1.322 (4) |
O1—C1—O2 | 126.2 (3) | O2—C1—C2 | 115.3 (3) |
O1—C1—C2 | 118.3 (3) | ||
O1—C1—C2—N1 | −10.8 (4) | N1—C2—C3—C4 | −71.9 (3) |
O2—C1—C2—N1 | 173.9 (3) | C1—C2—C3—C4 | 52.8 (3) |
O1—C1—C2—C3 | −136.2 (3) | C2—C3—C4—O3 | −2.9 (4) |
O2—C1—C2—C3 | 48.5 (3) | C2—C3—C4—O4 | 177.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.89 | 1.93 | 2.813 (4) | 171 |
N1—H1C···O3ii | 0.89 | 2.02 | 2.809 (4) | 147 |
O4—H4···O2iii | 0.82 | 2.15 | 2.933 (4) | 161 |
N1—H1B···O11iv | 0.89 | 2.22 | 2.854 (4) | 128 |
O11—H11···O2v | 0.78 | 2.06 | 2.837 (4) | 170 |
O11—H12···O2i | 0.80 | 2.05 | 2.817 (4) | 160 |
N1—H1B···O3 | 0.89 | 2.55 | 3.093 (4) | 120 |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) x−1, y, z; (iii) −x+5/2, −y, z+1/2; (iv) −x+1, y−1/2, −z+1/2; (v) x−1, y+1, z. |
Aspartic acid is non-essential amino acid, widely distributed in proteins, which plays a major role in the energy cycle of the human body. The crystal structures of L-aspartic acid (Derissen et al., 1968), DL-aspartic acid (Rao, 1973; Sequeria et al., 1989), DL-aspartic acid nitrate monohydrate (Asath Bahadur & Rajaram, 1995), bis(DL-aspartic acid) sulfate (Srinivasan et al., 2001) and L-aspartic acid nitrate–L-aspartic acid (1/1) (Sridhar et al., 2002) have been reported. In the present paper, the crystal structure of L-aspartic acid monohydrate, (I), is reported.
The asymmetric unit of (I) contains one aspartic acid residue and one water molecule (Fig. 1). The equality of C—O bond distances [1.240 (4) and 1.259 (4) Å] and O—C—C bond angles [118.3 (3) and 115.3 (3)°] (Table 1) represent the deprotonated carboxylate group. The backbone conformation angle ψ1 of −10.8 (4)° indicates the cis form. The side chain shows a gauche II conformation [χ1 = −71.8 (3)°]. The branched chain conformation angles χ11 and χ21 are in cis and trans form. The Cγ atom is in the gauche I [52.7 (3)°] conformation with respect to C' atom. The molecular structure is stabilized by a weak intramolecular N1—H1B···O3 hydrogen bond.
The screw-related aspartic acid molecules are linked along the a axis by N1—H1A···O1i hydrogen bonds to form a helical structure (Table 2 and Fig.1). This helical structure is further stabilized by N1—H1C···O3ii hydrogen bonds which link the molecules translated a unit along the a axis. The adjacent helices are interlinked through O4—H4···O2iii hydrogen bonds and also by the water molecules through N1—H1B···O11iv, O11—H11···O2v and O11—H12···O2i hydrogen bonds, to form a three-dimensional network. Within the network, the O4—H4···O2iii hydrogen bonds link the screw related molecules, to form zigzag chains along the c axis. Class II hydrogen-bonding pattern is observed in the present structure having two two-centered hydrogen bonding and one three-centered hydrogen bonding (Jeffrey & Saegner, 1991). In the present study, the water molecule shows planar 1B-1/one-dimensional orientation (Jeffrey & Saegner, 1991). All the symmetry codes are as in Table 2. A view of the molecular packing down the a axis is shown in Fig. 2.