Crystal structure of (S)-2-amino-2-methyl-succinic acid.

The title compound, C5H9NO4, crystallized as a zwitterion. There is an intra-molecular N-H⋯O hydrogen bond involving the trans-succinic acid and the ammonium group, forming an S(6) ring motif. In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds, forming C(7) chains along the c-axis direction. The chains are linked by N-H⋯O and C-H⋯O hydrogen bonds, forming sheets parallel to the bc plane. Further N-H⋯O hydrogen bonds link the sheets to form a three-dimensional framework.

Related literature

For general background and biological properties of 2-methyl­aspartic acid (MeASP), see: Pfeiffer & Heinrich (1936 ▸); Delbaere et al. (1989 ▸); Nobe et al. (1998 ▸). For the absolute configuration and synthesis of the title compound, see: Terashima et al. (1966 ▸). For the crystal structure of related racemic compounds, see: Derricott et al. (1979 ▸); Brewer et al. (2013 ▸). For the crystal structure of dl-ASP, see: Flaig et al. (1998 ▸).

Experimental

Crystal data

C5H9NO4

M = 147.13

Monoclinic,

a = 8.3398 (12) Å

b = 9.6725 (10) Å

c = 8.0671 (10) Å

β = 95.175 (5)°

V = 648.09 (14) Å3

Z = 4

Cu Kα radiation

μ = 1.14 mm−1

T = 297 K

0.4 × 0.2 × 0.2 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▸) T min = 0.76, T max = 0.81

843 measured reflections

700 independent reflections

699 reflections with I > 2σ(I)

R int = 0.019

3 standard reflections every 300 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.096

S = 1.27

700 reflections

109 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▸); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: PLATON (Spek, 2003 ▸) and WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015016709/su5203sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015016709/su5203Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015016709/su5203Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015016709/su5203fig1.tif

A view of the mol­ecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The dashed line indicates the intra­molecular N—H⋯O hydrogen bond (see Table 1).

Click here for additional data file.

. DOI: 10.1107/S2056989015016709/su5203fig2.tif

A partial view of the crystal packing of the title compound. Dashed lines indicate the O—H⋯O and N—H⋯O hydrogen bonds (see Table 1).

Click here for additional data file.

c . DOI: 10.1107/S2056989015016709/su5203fig3.tif

A view along the c axis of the crystal packing of the title compound. Dashed lines indicate the O—H⋯O and N—H⋯O hydrogen bonds (see Table 1), and C-bound H atoms have been omitted for clarity.

CCDC reference: 1422827

Additional supporting information: crystallographic information; 3D view; checkCIF report

C5H9NO4	F(000) = 312
Mr = 147.13	Dx = 1.508 Mg m−3
Monoclinic, C2	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: C 2y	Cell parameters from 25 reflections
a = 8.3398 (12) Å	θ = 20–28°
b = 9.6725 (10) Å	µ = 1.14 mm−1
c = 8.0671 (10) Å	T = 297 K
β = 95.175 (5)°	Rod, colorless
V = 648.09 (14) Å3	0.4 × 0.2 × 0.2 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	699 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube	Rint = 0.019
Graphite monochromator	θmax = 74.0°, θmin = 5.5°
ω/2θ scans	h = −10→1
Absorption correction: ψ scan (North et al., 1968)	k = −12→0
Tmin = 0.76, Tmax = 0.81	l = −10→10
843 measured reflections	3 standard reflections every 300 reflections
700 independent reflections	intensity decay: none

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.034	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096	w = 1/[σ2(Fo2) + (0.0559P)2 + 0.2563P] where P = (Fo2 + 2Fc2)/3
S = 1.27	(Δ/σ)max < 0.001
700 reflections	Δρmax = 0.29 e Å−3
109 parameters	Δρmin = −0.21 e Å−3
2 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2014), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.045 (4)

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.

	x	y	z	Uiso*/Ueq
H8	0.155 (3)	0.434 (4)	0.122 (4)	0.026 (7)*
H7	0.126 (4)	0.416 (4)	0.275 (5)	0.040 (9)*
H6	0.207 (5)	0.170 (5)	0.725 (4)	0.071 (14)*
H9	0.022 (4)	0.340 (4)	0.164 (4)	0.040 (9)*
C1	0.2417 (3)	0.1802 (3)	0.0388 (3)	0.0273 (5)
C2	0.2485 (3)	0.2608 (2)	0.2046 (3)	0.0238 (5)
C3	0.2132 (3)	0.1603 (3)	0.3436 (3)	0.0305 (6)
H3A	0.1108	0.1156	0.3124	0.037*
H3B	0.2954	0.0891	0.3512	0.037*
C4	0.2069 (3)	0.2244 (3)	0.5137 (3)	0.0284 (6)
C5	0.4148 (3)	0.3267 (4)	0.2343 (4)	0.0386 (7)
H5A	0.4277	0.3947	0.1498	0.058*
H5B	0.4959	0.2567	0.2301	0.058*
H5C	0.4254	0.3702	0.3417	0.058*
N1	0.1250 (3)	0.3741 (2)	0.1916 (3)	0.0248 (5)
O1	0.1677 (2)	0.2358 (2)	−0.0871 (2)	0.0378 (5)
O2	0.3164 (3)	0.0705 (2)	0.0427 (3)	0.0525 (7)
O3	0.2242 (3)	0.1339 (2)	0.6334 (2)	0.0392 (6)
O4	0.1831 (4)	0.3463 (2)	0.5370 (2)	0.0554 (7)

	U11	U22	U33	U12	U13	U23
C1	0.0384 (11)	0.0263 (12)	0.0177 (10)	0.0010 (10)	0.0051 (8)	−0.0020 (9)
C2	0.0349 (10)	0.0220 (11)	0.0147 (10)	0.0029 (9)	0.0028 (8)	−0.0013 (8)
C3	0.0520 (14)	0.0239 (13)	0.0157 (10)	0.0039 (11)	0.0039 (9)	−0.0005 (9)
C4	0.0436 (13)	0.0252 (12)	0.0164 (10)	0.0015 (10)	0.0025 (9)	−0.0014 (9)
C5	0.0342 (12)	0.0476 (17)	0.0338 (13)	−0.0022 (12)	0.0020 (10)	−0.0065 (12)
N1	0.0368 (11)	0.0213 (10)	0.0164 (9)	0.0008 (8)	0.0036 (7)	−0.0007 (8)
O1	0.0510 (10)	0.0455 (11)	0.0167 (8)	0.0152 (9)	0.0011 (7)	−0.0039 (8)
O2	0.0930 (17)	0.0383 (13)	0.0257 (10)	0.0290 (13)	0.0023 (10)	−0.0082 (9)
O3	0.0721 (13)	0.0304 (10)	0.0162 (9)	0.0085 (9)	0.0096 (8)	0.0010 (8)
O4	0.118 (2)	0.0290 (12)	0.0200 (9)	0.0126 (12)	0.0102 (10)	−0.0024 (8)

C1—O2	1.229 (3)	C4—O4	1.213 (4)
C1—O1	1.261 (3)	C4—O3	1.301 (3)
C1—C2	1.545 (3)	C5—H5A	0.9600
C2—N1	1.502 (3)	C5—H5B	0.9600
C2—C5	1.525 (3)	C5—H5C	0.9600
C2—C3	1.532 (3)	N1—H8	0.86 (4)
C3—C4	1.511 (3)	N1—H7	0.78 (4)
C3—H3A	0.9700	N1—H9	0.93 (4)
C3—H3B	0.9700	O3—H6	0.84 (2)
O2—C1—O1	126.8 (2)	O4—C4—C3	124.0 (2)
O2—C1—C2	115.7 (2)	O3—C4—C3	112.8 (2)
O1—C1—C2	117.3 (2)	C2—C5—H5A	109.5
N1—C2—C5	108.3 (2)	C2—C5—H5B	109.5
N1—C2—C3	109.79 (18)	H5A—C5—H5B	109.5
C5—C2—C3	112.5 (2)	C2—C5—H5C	109.5
N1—C2—C1	109.67 (18)	H5A—C5—H5C	109.5
C5—C2—C1	107.98 (18)	H5B—C5—H5C	109.5
C3—C2—C1	108.60 (19)	C2—N1—H8	107 (2)
C4—C3—C2	115.4 (2)	C2—N1—H7	112 (3)
C4—C3—H3A	108.4	H8—N1—H7	104 (3)
C2—C3—H3A	108.4	C2—N1—H9	112 (3)
C4—C3—H3B	108.4	H8—N1—H9	113 (3)
C2—C3—H3B	108.4	H7—N1—H9	109 (3)
H3A—C3—H3B	107.5	C4—O3—H6	111 (4)
O4—C4—O3	123.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H7···O4	0.79 (4)	2.23 (4)	2.798 (3)	130 (3)
O3—H6···O1i	0.84 (4)	1.70 (4)	2.543 (2)	177 (5)
N1—H7···O3ii	0.79 (4)	2.53 (4)	3.093 (3)	130 (3)
N1—H8···O2iii	0.86 (3)	1.90 (4)	2.754 (3)	170 (3)
N1—H9···O1iv	0.93 (3)	1.93 (4)	2.844 (3)	168 (4)
C3—H3B···O4v	0.97	2.52	3.279 (4)	135

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H7O4	0.79(4)	2.23(4)	2.798(3)	130(3)
O3H6O1i	0.84(4)	1.70(4)	2.543(2)	177(5)
N1H7O3ii	0.79(4)	2.53(4)	3.093(3)	130(3)
N1H8O2iii	0.86(3)	1.90(4)	2.754(3)	170(3)
N1H9O1iv	0.93(3)	1.93(4)	2.844(3)	168(4)
C3H3BO4v	0.97	2.52	3.279(4)	135

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .