L Aspartic acid monohydrate

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Acta Cryst.(2003). E59, o1073±o1075 DOI: 10.1107/S1600536803014041 K. Umadeviet al. C₄H₇NO₄H₂O

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organic papers

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

L

-Aspartic acid monohydrate

K. Umadevi,a_{K. Anitha,}a B. Sridhar,a_{N. Srinivasan}b _and R. K. Rajarama_*

a_{Department of Physics, Madurai Kamaraj}

University, Madurai 625 021, India, and

b_{Department of Physics, Thiagarajar College,}

Madurai 625 009, India

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.004 AÊ

Rfactor = 0.061

wRfactor = 0.173

Data-to-parameter ratio = 12.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

In the title compound, C4H7NO4H2O, the screw-related

aspartic acid molecules are linked along the a axis by NÐ

H O hydrogen bonds to form helical structures. The

adjacent helices are inter-linked through OÐH O hydrogen

bonds and also by the water molecules through NÐH O(W)

and O(W)ÐH O hydrogen bonds, to form a

three-dimen-sional network.

Comment

Aspartic acid is a 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

(Derissenet al., 1968),dl-aspartic acid (Rao, 1973; Sequeiraet

al., 1989), dl-aspartic acid nitrate monohydrate (Asath

Bahadur & Rajaram, 1995), bis(dl-aspartic acid) sulfate

(Srinivasanet al., 2001) andl-aspartic acid nitrate±l-aspartic

acid (1/1) (Sridhar et al., 2002) have been reported. In the

present paper, the crystal structure ofl-aspartic acid

mono-hydrate, (I), is reported.

The asymmetric unit of (I) contains one aspartic acid molecule and one water molecule (Fig. 1). The equality of CÐ O bond distances [1.240 (4) and 1.259 (4) AÊ] and OÐCÐC

bond angles [118.3 (3) and 115.3 (3)_{] (Table 1) characterize}

the deprotonated carboxylate group. The backbone

conformation angle 1 _of _ÿ_{10.8 (4)} _{indicates the} _cis_form.

The side chain shows a gauche II conformation [1 ₌

ÿ71.8 (3)_{]. The branched chain conformation angles}11_and

21_{correspond to the}_cis_and_trans_{forms. The C}_{atom is in the} gaucheI [52.7 (3)_{] conformation with respect to the C}0_atom.

The molecular structure is stabilized by a weak intramolecular

N1ÐH1B O3 hydrogen bond.

The screw-related aspartic acid molecules are linked along

the a axis by N1ÐH1A O1i _{hydrogen bonds to form a}

helical structure (Table 2 and Fig. 2). This helical structure is

further stabilized by N1ÐH1C O3ii_{hydrogen bonds, which}

link the molecules translated by one unit along theaaxis. The

adjacent helices are interlinked through O4ÐH4 O2iii

hydrogen bonds and also by the water molecules through

N1ÐH1B O11iv_{, O11ÐH11}_O2v _{and O11ÐH12}_O2i

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K. Umadeviet al. C₄H₇NO₄H₂O Acta Cryst.(2003). E59, o1073±o1075

hydrogen bonds, to form a three-dimensional network. Within

the network, the O4ÐH4 O2iii _{hydrogen bonds link the}

screw-related molecules, to form zigzag chains along thecaxis. A class II hydrogen-bonding pattern is observed in the present structure, having two two-centered hydrogen bonds and one three-centered hydrogen bond (Jeffrey & Saenger, 1991). In the present study, the water molecule shows a planar 1B-1/1D

orientation (Jeffrey & Saenger, 1991). All the symmetry codes

are as in Table 2. A view of the molecular packing down thea

axis is shown in Fig. 3.

Experimental

The title compound was crystallized from an aqueous solution when attempts were made to grow single crystals of a complex ofl-aspartic acid with sulfuric acid.

Crystal data

C4H7NO4H2O Mr= 151.12

Orthorhombic,P212121 a= 5.587 (4) AÊ

b= 9.822 (5) AÊ

c= 11.813 (9) AÊ

V= 648.2 (8) AÊ3 Z= 4

Dx= 1.548 Mg mÿ3

Dm= 1.54 Mg mÿ3

Dmmeasured by ¯otation in a

mixture of carbon tetrachloride and xylene

MoKradiation Cell parameters from 25

re¯ections

= 8.0±13.8 = 0.14 mmÿ1 T= 293 (2) K Block, colorless 0.30.30.3 mm

Data collection

Enraf±Nonius CAD-4 diffractometer

!±2scans

Absorption correction: scan (Northet al., 1968)

Tmin= 0.958,Tmax= 0.958

1318 measured re¯ections 1132 independent re¯ections 1091 re¯ections withI> 2(I)

Rint= 0.085 max= 24.6 h= 0!6

k= 0!11

l=ÿ14!14 3 standard re¯ections

frequency: 60 min intensity decay: none

Re®nement

Re®nement onF2 R[F2_{> 2}₍_F2_{)] = 0.061} wR(F2_{) = 0.173} S= 1.06 1132 re¯ections 93 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2₍_F

o2) + (0.136P)2

+ 0.3381P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.33 e AÊÿ3

min=ÿ0.54 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,_).

O1ÐC1 1.240 (4)

O2ÐC1 1.259 (4) C4ÐO3C4ÐO4 1.244 (4)1.322 (4) O1ÐC1ÐO2 126.2 (3)

O1ÐC1ÐC2 118.3 (3) O2ÐC1ÐC2 115.3 (3) O1ÐC1ÐC2ÐN1 ÿ10.8 (4)

O2ÐC1ÐC2ÐN1 173.9 (3) O1ÐC1ÐC2ÐC3 ÿ136.2 (3) O2ÐC1ÐC2ÐC3 48.5 (3)

N1ÐC2ÐC3ÐC4 ÿ71.9 (3) C1ÐC2ÐC3ÐC4 52.8 (3) C2ÐC3ÐC4ÐO3 ÿ2.9 (4) C2ÐC3ÐC4ÐO4 177.0 (3)

Figure 2

A view of the helical structures formed along theaaxis. For clarity, all H

atoms except H1Ahave been omitted.

Figure 3

Hydrogen-bonding network, viewed down theaaxis.

Figure 1

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Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N1ÐH1A O1i _0.89 _1.93 _{2.813 (4)} ₁₇₁

N1ÐH1C O3ii _0.89 _2.02 _{2.809 (4)} ₁₄₇

O4ÐH4 O2iii _0.82 _2.15 _{2.933 (4)} ₁₆₁

N1ÐH1B O11iv _0.89 _2.22 _{2.854 (4)} ₁₂₈

O11ÐH11 O2v _0.78 _2.06 _{2.837 (4)} ₁₇₀

O11ÐH12 O2i _0.80 _2.05 _{2.817 (4)} ₁₆₀

N1ÐH1B O3 0.89 2.55 3.093 (4) 120

Symmetry codes: (i) xÿ1_2;1

2ÿy;ÿz; (ii) xÿ1;y;z; (iii) 52ÿx;ÿy;12z; (iv) 1ÿx;yÿ1_2;1

2ÿz; (v)xÿ1;1y;z.

The H atoms of the water molecule were located from a difference Fourier map and their isotropic displacement parameters were re®ned [Uiso(H) = 0.04 (1) and 0.07 (2) AÊ2_{]. All other H atoms were} placed in geometrically calculated positions and included in the re®nement in the riding-model approximation, with Uiso equal to 1.2Ueqof the carrier atom. The data set includes 442 Friedel pairs; however, the lack of any signi®cant anomalous effects precludes the con®rmation of the absolute con®guration from the diffraction data, and it has been assumed.

Data collection: CAD-4 Software (Enraf±Nonius, 1989); cell re®nement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); molecular graphics:PLATON(Spek, 1999); software used to prepare material for publication:SHELXL97.

BS thanks the Council of Scienti®c and Industrial Research (CSIR), Government of India, for ®nancial assistance. RKR thanks the Department of Science and Technology (DST), Government of India, for ®nancial support. Financial support from the UGC is also gratefully acknowledged.

References

Asath Bahadur, S. & Rajaram. R. K. (1995).Z. Kristallogr.210, 276±278. Derissen, J. L., Endeman, H. J. & Peerdeman, A. F. (1968).Acta Cryst.B24,

1349±1354.

Enraf±Nonius (1989).CAD-4Software. Version 5.0. Enraf±Nonius, Delft, The Netherlands.

Jeffrey, G. A. & Saenger, W. (1991). In Hydrogen Bonding in Biological Structures. Berlin, Heidelberg, New York: Springer-Verlag.

Johnson, C. K. (1976).ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.

Rao, S. T. (1973).Acta Cryst.B29, 1718±1720.

Sequeira, A., Rajagopal, H. & Ramanadham, M. (1989).Acta Cryst.C45, 906± 908.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of GoÈttingen, Germany.

Spek, A. L. (1999).PLATON.Utrecht University, The Netherlands. Sridhar, B., Srinivasan, N. & Rajaram, R. K. (2002).Acta Cryst.E58, o1372±

o1374.

Srinivasan, N., Sridhar, B. & Rajaram, R. K. (2001).Acta Cryst.E57, o679± o681.

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Acta Cryst. (2003). E59, o1073–o1075

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Acta Cryst. (2003). E59, o1073–o1075 [doi:10.1107/S1600536803014041]

L

-Aspartic acid monohydrate

K. Umadevi, K. Anitha, B. Sridhar, N. Srinivasan and R. K. Rajaram

S1. Comment

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···O2}v_{and O11—H12···O2}i_{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.

S2. Experimental

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.

S3. Refinement

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

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Acta Cryst. (2003). E59, o1073–o1075

Figure 1

The structure of the title compound, showing 50% probability displacement ellipsoids (Johnson, 1976) and the

atom-numbering scheme.

Figure 2

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Acta Cryst. (2003). E59, o1073–o1075

Figure 3

Hydrogen-bonding network viewed down the a axis.

′L-aspartic acid monohydrate′

Crystal data

C4H7NO4·H2O

Mr = 151.12

Orthorhombic, P212121 Hall symbol: P 2ac 2ab

a = 5.587 (4) Å

b = 9.822 (5) Å

c = 11.813 (9) Å

V = 648.2 (8) Å3

Z = 4

F(000) = 320

Dx = 1.548 Mg m−3

Dm = 1.54 Mg m−3

Dm measured by Flotation in a mixture of carbon tetrachloride and xylene

Mo Kα radiation, λ = 0.70165 Å Cell parameters from 25 reflections

θ = 8.0–13.8°

µ = 0.14 mm−1

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Data collection

Enraf-Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω–2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.958, Tmax = 0.958 1318 measured reflections

1132 independent reflections 1091 reflections with I > 2σ(I)

Rint = 0.085

θmax = 24.6°, θmin = 2.7°

h = 0→6

k = 0→11

l = −14→14

3 standard reflections every 60 min intensity decay: none

Refinement

Refinement on F2 Least-squares matrix: full

R[F2_{> 2}_σ₍_F2_{)] = 0.061}

wR(F2_{) = 0.173}

S = 1.06 1132 reflections 93 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2₍_F

o2) + (0.136P)2 + 0.3381P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.33 e Å−3 Δρmin = −0.54 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

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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)*

Atomic displacement parameters (Å2₎

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)

Geometric parameters (Å, º)

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

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O2—C1—C2—C3 48.5 (3) C2—C3—C4—O4 177.0 (3)

Hydrogen-bond geometry (Å, º)

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