1-Aza-niumyl-cyclo-butane-1-carboxyl-ate monohydrate.

In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the α-carboxyl-ate group. The cyclo-butane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7) and 0.118 (7). In the crystal, N-H⋯O and O-H⋯O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3 (+)) and donor (through a single carboxylate O from two different aminocyclobutane carb-oxylate moities)], resulting in a two-dimensional layered structure lying parallel to (100).

Related literature

For the eighty amino acids that have been detected in meteorites or comets, see: Burton et al. (2012 ▶); Pizzarello et al. (2004 ▶), (2006 ▶). For the role of the H atom on the α-C atom in enhancing the rate of racemization, see: Yamada et al. (1983 ▶). For the mechanism of racemization of amino acids lacking an α-H atom, see: Pizzarello & Groy (2011 ▶). For the role that crystallization can play in the enrichment of l-isovaline and its structure, see: Butcher et al. (2013 ▶). For normal bond lengths and angles, see: Orpen (1993 ▶). For the hydro­chloride salt of the title compound and related non-proteinogenic amino acids, see: Chacko & Zand (1975 ▶); Butcher et al. (2013 ▶); Brewer et al. (2013 ▶). For conformational studies on model proteins with 1-amino­cyclo­butane-1-carb­oxy­lic acid residues, see: Balaji et al. (1995 ▶). For involvement of the title compound in ethyl­ene production that leads to the ripening and spoilage of fruit, see: Nakatsuka et al. (1998 ▶); Bulantseva et al. (2003 ▶).

Experimental

Crystal data

C5H9NO2·H2O

M = 133.15

Monoclinic,

a = 10.25082 (19) Å

b = 6.13117 (9) Å

c = 10.9209 (2) Å

β = 100.8735 (18)°

V = 674.05 (2) Å3

Z = 4

Cu Kα radiation

μ = 0.92 mm−1

T = 123 K

0.41 × 0.34 × 0.16 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.784, T max = 1.000

4405 measured reflections

1400 independent reflections

1360 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.103

S = 1.06

1400 reflections

119 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.19 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813033217/zs2282sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813033217/zs2282Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536813033217/zs2282Isup3.cml

CCDC reference:

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

C5H9NO2·H2O	F(000) = 288
Mr = 133.15	Dx = 1.312 Mg m−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 4146 reflections
a = 10.25082 (19) Å	θ = 4.1–77.2°
b = 6.13117 (9) Å	µ = 0.92 mm−1
c = 10.9209 (2) Å	T = 123 K
β = 100.8735 (18)°	Prism, colorless
V = 674.05 (2) Å3	0.41 × 0.34 × 0.16 mm
Z = 4

Agilent Xcalibur (Ruby, Gemini) diffractometer	1400 independent reflections
Radiation source: Enhance (Cu) X-ray source	1360 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
Detector resolution: 10.5081 pixels mm-1	θmax = 77.4°, θmin = 8.3°
ω scans	h = −12→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −6→7
Tmin = 0.784, Tmax = 1.000	l = −13→13
4405 measured reflections

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.103	w = 1/[σ2(Fo2) + (0.0616P)2 + 0.2169P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
1400 reflections	Δρmax = 0.36 e Å−3
119 parameters	Δρmin = −0.19 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.016 (4)

Experimental. Absorption correction: CrysAlisPro (Agilent, 2012) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	Occ. (<1)
O1W	0.11907 (10)	0.30045 (14)	0.47599 (9)	0.0268 (3)
H1W1	0.1576 (18)	0.203 (3)	0.5293 (18)	0.037 (4)*
H1W2	0.0713 (19)	0.231 (3)	0.4210 (19)	0.039 (5)*
O2	0.04488 (8)	0.54177 (13)	0.20493 (7)	0.0218 (3)
O1	0.23745 (8)	0.52875 (13)	0.13611 (7)	0.0213 (3)
N1	0.13993 (9)	0.73526 (15)	0.41449 (8)	0.0159 (3)
H1N	0.0661 (18)	0.809 (3)	0.3735 (16)	0.032 (4)*
H2N	0.1799 (15)	0.815 (3)	0.4840 (15)	0.023 (4)*
H3N	0.1179 (16)	0.603 (3)	0.4404 (15)	0.026 (4)*
C1	0.16664 (10)	0.57917 (16)	0.21410 (9)	0.0155 (3)
C2	0.23577 (10)	0.70405 (17)	0.32992 (9)	0.0151 (3)
C3	0.30893 (12)	0.9136 (2)	0.30010 (12)	0.0247 (3)
H3A	0.2845 (16)	0.967 (3)	0.2165 (16)	0.030*
H3B	0.3019 (16)	1.021 (3)	0.3606 (16)	0.030*
C4A	0.44072 (14)	0.7839 (3)	0.32757 (17)	0.0353 (6)	0.882 (7)
H4AA	0.4706	0.7309	0.2518	0.042*	0.882 (7)
H4AB	0.5134	0.8607	0.3837	0.042*	0.882 (7)
C4B	0.4308 (11)	0.845 (2)	0.3984 (14)	0.0353 (6)	0.118
H4BA	0.4366	0.9176	0.4802	0.042*	0.118 (7)
H4BB	0.5162	0.8543	0.3689	0.042*	0.118 (7)
C5	0.37127 (10)	0.6082 (2)	0.39333 (11)	0.0228 (3)
H5A	0.3873 (16)	0.464 (3)	0.3693 (15)	0.027*
H5B	0.3840 (16)	0.615 (3)	0.4822 (16)	0.027*

	U11	U22	U33	U12	U13	U23
O1W	0.0356 (5)	0.0181 (4)	0.0236 (5)	−0.0006 (3)	−0.0028 (4)	0.0030 (3)
O2	0.0172 (4)	0.0236 (5)	0.0229 (4)	−0.0017 (3)	−0.0010 (3)	−0.0053 (3)
O1	0.0237 (4)	0.0252 (5)	0.0150 (4)	0.0027 (3)	0.0035 (3)	−0.0017 (3)
N1	0.0166 (5)	0.0170 (5)	0.0139 (5)	0.0002 (3)	0.0023 (3)	−0.0002 (3)
C1	0.0186 (5)	0.0131 (5)	0.0134 (5)	0.0021 (4)	−0.0006 (4)	0.0021 (4)
C2	0.0143 (5)	0.0163 (5)	0.0141 (5)	0.0002 (4)	0.0017 (4)	0.0004 (4)
C3	0.0271 (6)	0.0214 (6)	0.0273 (6)	−0.0085 (4)	0.0098 (5)	−0.0027 (5)
C4A	0.0195 (8)	0.0404 (10)	0.0476 (11)	−0.0086 (6)	0.0105 (7)	−0.0069 (7)
C4B	0.0195 (8)	0.0404 (10)	0.0476 (11)	−0.0086 (6)	0.0105 (7)	−0.0069 (7)
C5	0.0148 (5)	0.0313 (7)	0.0204 (6)	0.0039 (4)	−0.0018 (4)	−0.0033 (4)

O1W—H1W1	0.87 (2)	C3—C4A	1.547 (2)
O1W—H1W2	0.82 (2)	C3—H3A	0.958 (17)
O2—C1	1.2543 (13)	C3—H3B	0.943 (18)
O1—C1	1.2574 (13)	C4A—C5	1.542 (2)
N1—C2	1.4823 (13)	C4A—H4AA	0.9900
N1—H1N	0.922 (18)	C4A—H4AB	0.9900
N1—H2N	0.930 (17)	C4B—C5	1.570 (12)
N1—H3N	0.902 (17)	C4B—H4BA	0.9900
C1—C2	1.5330 (14)	C4B—H4BB	0.9900
C2—C5	1.5465 (14)	C5—H5A	0.942 (17)
C2—C3	1.5527 (15)	C5—H5B	0.956 (17)
C3—C4B	1.545 (13)
H1W1—O1W—H1W2	105.5 (18)	C2—C3—H3B	108.9 (10)
C2—N1—H1N	109.9 (11)	H3A—C3—H3B	112.9 (14)
C2—N1—H2N	109.5 (9)	C5—C4A—C3	89.22 (9)
H1N—N1—H2N	109.6 (14)	C5—C4A—H4AA	113.8
C2—N1—H3N	108.3 (10)	C3—C4A—H4AA	113.8
H1N—N1—H3N	111.2 (15)	C5—C4A—H4AB	113.8
H2N—N1—H3N	108.2 (14)	C3—C4A—H4AB	113.8
O2—C1—O1	126.43 (10)	H4AA—C4A—H4AB	111.0
O2—C1—C2	117.09 (9)	C3—C4B—C5	88.3 (6)
O1—C1—C2	116.46 (9)	C3—C4B—H4BA	113.9
N1—C2—C1	108.72 (8)	C5—C4B—H4BA	113.9
N1—C2—C5	114.52 (8)	C3—C4B—H4BB	113.9
C1—C2—C5	114.58 (9)	C5—C4B—H4BB	113.9
N1—C2—C3	115.28 (9)	H4BA—C4B—H4BB	111.1
C1—C2—C3	113.99 (9)	C4A—C5—C2	88.88 (9)
C5—C2—C3	88.84 (8)	C2—C5—C4B	88.6 (4)
C4B—C3—C2	89.3 (4)	C4A—C5—H5A	113.8 (10)
C4A—C3—C2	88.44 (9)	C2—C5—H5A	114.8 (10)
C4B—C3—H3A	142.0 (11)	C4B—C5—H5A	141.8 (11)
C4A—C3—H3A	115.0 (10)	C4A—C5—H5B	117.2 (9)
C2—C3—H3A	115.6 (10)	C2—C5—H5B	112.2 (10)
C4B—C3—H3B	82.1 (12)	C4B—C5—H5B	86.9 (11)
C4A—C3—H3B	113.6 (10)	H5A—C5—H5B	109.0 (14)
O2—C1—C2—N1	5.49 (13)	C2—C3—C4A—C5	−16.15 (9)
O1—C1—C2—N1	−176.10 (9)	C4A—C3—C4B—C5	−71.5 (8)
O2—C1—C2—C5	135.05 (10)	C2—C3—C4B—C5	16.8 (5)
O1—C1—C2—C5	−46.54 (13)	C3—C4A—C5—C2	16.21 (10)
O2—C1—C2—C3	−124.62 (10)	C3—C4A—C5—C4B	−72.9 (8)
O1—C1—C2—C3	53.79 (13)	N1—C2—C5—C4A	−133.55 (10)
N1—C2—C3—C4B	99.7 (6)	C1—C2—C5—C4A	99.82 (11)
C1—C2—C3—C4B	−133.6 (6)	C3—C2—C5—C4A	−16.16 (10)
C5—C2—C3—C4B	−17.0 (6)	N1—C2—C5—C4B	−100.6 (6)
N1—C2—C3—C4A	132.80 (10)	C1—C2—C5—C4B	132.7 (6)
C1—C2—C3—C4A	−100.42 (11)	C3—C2—C5—C4B	16.8 (6)
C5—C2—C3—C4A	16.10 (10)	C3—C4B—C5—C4A	73.3 (8)
C4B—C3—C4A—C5	74.9 (8)	C3—C4B—C5—C2	−16.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1i	0.87 (2)	1.92 (2)	2.7935 (12)	175.2 (18)
O1W—H1W2···O2ii	0.82 (2)	2.01 (2)	2.8268 (12)	175.7 (19)
N1—H1N···O2iii	0.922 (18)	1.923 (18)	2.8087 (12)	160.6 (15)
N1—H2N···O1iv	0.930 (17)	1.913 (17)	2.8351 (12)	171.2 (14)
N1—H3N···O1W	0.902 (17)	1.895 (17)	2.7673 (13)	162.3 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1i	0.87 (2)	1.92 (2)	2.7935 (12)	175.2 (18)
O1W—H1W2⋯O2ii	0.82 (2)	2.01 (2)	2.8268 (12)	175.7 (19)
N1—H1N⋯O2iii	0.922 (18)	1.923 (18)	2.8087 (12)	160.6 (15)
N1—H2N⋯O1iv	0.930 (17)	1.913 (17)	2.8351 (12)	171.2 (14)
N1—H3N⋯O1W	0.902 (17)	1.895 (17)	2.7673 (13)	162.3 (15)

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