Crystal structure of cis-2-(2-carb­oxy­cyclo­prop­yl)glycine (CCG-III) monohydrate

Lindeman, S.; Wallock, N.J.; Donaldson, W.A.

doi:10.1107/S2056989015011500

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Volume 71| Part 7| July 2015| Pages 844-846

doi:10.1107/S2056989015011500

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Crystal structure of cis-2-(2-carboxycyclopropyl)glycine (CCG-III) monohydrate

Sergey Lindeman,^a Nathaniel J. Wallock ^a and William A. Donaldson ^a ^*

^aDepartment of Chemistry, Marquette University, PO Box 1881, Milwaukee, WI 53201-1881, USA
^*Correspondence e-mail: william.donaldson@marquette.edu

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 April 2015; accepted 14 June 2015; online 24 June 2015)

The title compound, C₆H₉NO₄·H₂O [systematic name: (αR,1R,2S)-rel-α-amino-2-carboxycyclopropaneacetic acid monohydrate], crystallizes with two organic molecules and two water molecules in the asymmetric unit. The space group is P2₁ and the organic molecules are enantiomers, thus this is an example of a `false conglomerate' with two molecules of opposite handedness in the asymmetric unit (r.m.s. overlay fit = 0.056 Å for one molecule and its inverted partner). Each molecule exists as a zwitterion, with proton transfer from the amino acid carboxylic acid group to the amine group. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, generating (100) sheets. Conformationally restricted glutamate analogs are of interest due to their selective activation of different glutamate receptors, and the naturally occurring (+)-CCG-III is an inhibitor of glutamate uptake and the key geometrical parameters are discussed.

Keywords: crystal structure; cyclopropane; conformationally restricted glutamate analog.

CCDC reference: 1406594

1. Chemical context

2-(2′-Carboxycyclopropyl)glycines CCG-I, CCG-III and CCG-IV (Fig. 1) are naturally occuring conformationally restricted analogs of glutamate isolated from Aesculus parviflora, Blighia sapida (Fowden, et al., 1969 ), Ephedra foeminea (Caveney & Starratt, 1994 ), and Ephedra altissima (Starratt & Caveney, 1995 ). While not naturally occurring, both enantiomers of CCG-II (Fig. 1) have been prepared in the laboratory (Shimamoto, et al., 1991 ) and all of the diastereomeric CCGs are useful tools for investigating the mechanism of glutamate function. The crystal structure of the title hydrate, (±)-CCG-III·H₂O, is now reported.

Figure 1
Structures of the diastereomers of 2-(2′-carboxycyclopropyl)glycine.

2. Structural commentary

The racemic title compound (Fig. 2) crystallizes as a `false conglomerate' with two molecules of opposite handedness in the asymmetric unit. Each of molecules of 2-(2′-carboxycyclopropyl)glycine has a molecule of water hydrogen bonded to the glycine carboxylate group. It has been estimated that only 1% of organic compounds are false conglomerates (Bishop & Scudder, 2009 ).

Figure 2
The asymmetic unit of the title compound, showing 50% displacement ellipsoids.

The torsion angles O3—C6—C2—X = −4.3° and O3A—C6A—C2A—X = −11.1° (where X is the midpoint of the distal cyclopropane bond) indicate that the carboxylic acid attached to the cyclpropane ring adopts a bisected conformation (Allen, 1980 ). The cyclopropane C—C bonds proximal to the C2 carboxylic group are roughly equal [C1—C2 = 1.532 (3); C2—C3 = 1.512 (3); C1A—C2A = 1.520 (3); C2A—C3A = 1.516 (2) Å] and are longer than the cyclopropane bonds distal to the C2 carboxylic acid [C1—C3 = 1.489 (2); C1A—C3A = 1.484 (2) Å]. These distances and torsion angles are consistent with other cyclopropane carboxylic acids (Allen, 1980).

Conformationally restricted glutamic acid analogs can be classified into one of four categories, which are characterized by the distances between the nitrogen atom of the amino group and the γ-carboxylate carbon atom (d₁), between the α- and γ-carboxylate carbon atoms (d₂), and their sum (d₁ + d₂). The classifications `folded', `semi-folded', `semi-extended', and `extended' are defined by (d₁ + d₂) ≤ 7.5 Å, 7.5 Å ≤ (d₁ + d₂) ≤ 8.0 Å, 8.0 Å ≤ (d₁ + d₂) ≤ 8.5 Å, and (d₁ + d₂) ≥ 8.5 Å, respectively (Pellicciari, et al., 2002 ). The two enantiomeric moleclules in the crystal structure evidence the following distances/sums: d₁, 3.65 and 3.71 Å; d₂, 4.59 and 4.59 Å; (d₁ + d₂), 8.24 and 8.30 Å, respectively. From these values, these conformers of CCG-III can be considered to be in the `semi-extended' class.

3. Supramolecular features

In the crystal, the molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming sheets parallel to (100); Table 1 and Fig. 3.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3Aⁱ	0.94 (2)	2.03 (2)	2.9444 (18)	162.1 (17)
N1—H1B⋯O2Aⁱⁱ	0.86 (2)	2.39 (2)	2.9454 (18)	123.1 (16)
N1—H1C⋯O1WAⁱ	0.98 (3)	1.83 (3)	2.795 (2)	167 (2)
O4—H4⋯O1ⁱⁱⁱ	0.81 (3)	1.79 (3)	2.5851 (18)	166 (3)
O1W—H1WA⋯O2A^iv	0.82 (3)	2.01 (3)	2.8072 (19)	166 (2)
O1W—H1WB⋯O1	0.86 (2)	1.90 (2)	2.7449 (16)	169 (2)
N1A—H1AA⋯O3^v	0.90 (2)	2.01 (2)	2.9087 (18)	173 (2)
N1A—H1AB⋯O3A^vi	0.87 (2)	2.38 (2)	3.1151 (19)	141.7 (17)
N1A—H1AC⋯O1W^v	0.93 (2)	1.87 (2)	2.785 (2)	165.6 (18)
O4A—H4AA⋯O1A^vii	0.98 (3)	1.60 (3)	2.5672 (16)	168 (2)
O1WA—H1WC⋯O2^viii	0.83 (3)	2.07 (3)	2.8628 (19)	158 (2)
O1WA—H1WD⋯O1A	0.81 (2)	1.98 (3)	2.7717 (17)	166 (3)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (ii) x-1, y-1, z-1; (iii) x, y+1, z; (iv) $[-x+1, y-{\script{3\over 2}}, -z+1]$ ; (v) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (vi) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (vii) x, y-1, z; (viii) $[-x+1, y+{\script{3\over 2}}, -z]$ .

Figure 3
The packing for the title compound viewed approximately down [100], with hydrogen bonds shown as dashed lines.

4. Synthesis and crystallization

The racemic title compound was prepared according to the literature procedure (Wallock & Donaldson, 2004 ). A sample for X-ray diffraction analysis was recrystallized from water.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₉NO₄·H₂O
M_r	177.16
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	8.9688 (8), 8.0063 (8), 10.9628 (10)
β (°)	106.015 (4)
V (Å³)	756.65 (12)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.18
Crystal size (mm)	0.37 × 0.32 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD detector
Absorption correction	Multi-scan (SADABS; Bruker, 2005 )
T_min, T_max	0.669, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	6086, 2164, 2154
R_int	0.018
θ_max (°)	61.0
(sin θ/λ)_max (Å⁻¹)	0.567

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.055, 1.06
No. of reflections	2164
No. of parameters	305
No. of restraints	1
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16
Absolute structure	Flack (1983 ), 836 Friedel pairs
Absolute structure parameter	0.57 (15)
Computer programs: APEX2 and SAINT (Bruker, 2005), SHELXTL and SHELXL97 (Sheldrick, 2008 ).

Supporting information

CCDC reference: 1406594

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S2056989015011500/hb7407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015011500/hb7407Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015011500/hb7407Isup3.cml

checkCIF report

Chemical context top

2-(2'-Carboxycyclopropyl)glycines CCG-I, CCG-III and CCG-IV (Fig. 1) are naturally occuring conformationally restricted analogs of glutamate isolated from Aesculus parviflora, Blighia sapida (Fowden, et al., 1969), Ephedra foeminea (Caveney & Starratt, 1994), and Ephedra altissima (Starratt & Caveney, 1995). While not naturally occurring, both enantiomers of CCG-II (Fig. 1) have been prepared in the laboratory (Shimamoto, et al., 1991) and all of the diastereomeric CCGs are useful tools for investigating the mechanism of glutamate function. The crystal structure of the title hydrate, (±)-CCG-III·H₂O, is now reported.

Structural commentary top

The racemic title compound crystallizes as a `false conglomerate' with two molecules of opposite handedness in the asymmetric unit. Each of molecules of 2-(2'-carboxycyclopropyl)glycine has a molecule of water hydrogen bonded to the glycine carboxylate group. It has been estimated that only 1% of organic compounds are false conglomerates (Bishop & Scudder, 2009).

The torsion angles t, O3—C6—C2—X = –4.3° and O3A—C6A—C2A—X = –11.1° (where X is the midpoint of the distal cyclopropane bond) indicate that the carboxylic acid attached to the cyclpropane ring adopts a bisected conformation (Allen, 1980). The cyclopropane C—C bonds proximal to the C2 carboxylic group are roughly equal [C1—C2 = 1.532 (3); C2—C3 = 1.512 (3); C1A—C2A = 1.520 (3); C2A—C3A = 1.516 (2) Å] and are longer than the cyclopropane bonds distal to the C2 carboxylic acid [C1—C3 = 1.489 (2); C1A—C3A = 1.484 (2) Å]. These distances and torsion angles are consistent with other cyclopropane carboxylic acids (Allen, 1980).

Conformationally restricted glutamic acid analogs can be classified into one of four categories, which are characterized by the distances between the nitrogen atom of the amino group and the γ-carboxylate carbon atom (d₁), between the α- and γ-carboxylate carbon atoms (d₂), and their sum (d₁ + d₂). The classifications `folded', `semi-folded', `semi-extended', and `extended' are defined by (d₁ + d₂) ≤ 7.5 Å, 7.5 Å ≤ (d₁ + d₂) ≤ 8.0 Å, 8.0 Å ≤ (d₁ + d₂) ≤ 8.5 Å, and (d₁ + d₂) ≥ 8.5 Å, respectively (Pellicciari, et al., 2002). The two enantiomeric moleclules in the crystal structure evidence the following distances/sums: d₁, 3.65 and 3.71 Å; d₂, 4.59 and 4.59 Å; (d₁ + d₂), 8.24 and 8.30 Å, respectively. From these values, these conformers of CCG-III can be considered to be in the `semi-extended' class.

Supramolecular features top

In the crystal, the molecules are linked by N—H···O and O—H···O hydrogen bonds, generating a three-dimensional network (Table 1 and Fig. 2).

Synthesis and crystallization top

The racemic title compound was prepared according to the literature procedure (Wallock & Donaldson, 2004). A sample for X-ray diffraction analysis was recrystallized from water.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2.

Related literature top

For related structures, see: Avery et al. (2008); Monn et al. (2013, 2015); Panjouhesh (2003); Pellicciari (2002, 2007); Risgaard (2013).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Structures of the diastereomers of 2-(2'-carboxycyclopropyl)glycine.
	Fig. 2. The asymmetic unit of the title compound, showing 50% displacement ellipsoids.
	Fig. 3. The packing for the title compound viewed approximately down [100], with hydrogen bonds shown as dashed lines.

(αR,1R,2S)-rel-α-Amino-2-carboxycyclopropaneacetic acid monohydrate top

Crystal data top

C₆H₉NO₄·H₂O	F(000) = 376
M_r = 177.16	D_x = 1.555 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54178 Å
a = 8.9688 (8) Å	Cell parameters from 5577 reflections
b = 8.0063 (8) Å	θ = 4–61°
c = 10.9628 (10) Å	µ = 1.18 mm⁻¹
β = 106.015 (4)°	T = 100 K
V = 756.65 (12) Å³	Plate, colorless
Z = 4	0.37 × 0.32 × 0.10 mm

Data collection top

Bruker APEXII CCD detector diffractometer	2164 independent reflections
Radiation source: fine-focus sealed tube	2154 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 61.0°, θ_min = 4.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→9
T_min = 0.669, T_max = 0.891	k = −8→9
6086 measured reflections	l = 0→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.021	All H-atom parameters refined
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0523P)² + 0.0652P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2164 reflections	Δρ_max = 0.15 e Å⁻³
305 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 836 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.57 (15)

Crystal data top

C₆H₉NO₄·H₂O	V = 756.65 (12) Å³
M_r = 177.16	Z = 4
Monoclinic, P2₁	Cu Kα radiation
a = 8.9688 (8) Å	µ = 1.18 mm⁻¹
b = 8.0063 (8) Å	T = 100 K
c = 10.9628 (10) Å	0.37 × 0.32 × 0.10 mm
β = 106.015 (4)°

Data collection top

Bruker APEXII CCD detector diffractometer	2164 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2154 reflections with I > 2σ(I)
T_min = 0.669, T_max = 0.891	R_int = 0.018
6086 measured reflections	θ_max = 61.0°

Refinement top

R[F² > 2σ(F²)] = 0.021	All H-atom parameters refined
wR(F²) = 0.055	Δρ_max = 0.15 e Å⁻³
S = 1.06	Δρ_min = −0.16 e Å⁻³
2164 reflections	Absolute structure: Flack (1983), 836 Friedel pairs
305 parameters	Absolute structure parameter: 0.57 (15)
1 restraint

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.16905 (12)	−0.14281 (15)	0.09397 (9)	0.0171 (3)
O2	0.16680 (12)	−0.14746 (15)	−0.11118 (10)	0.0182 (3)
O3	0.17732 (12)	0.43933 (15)	0.13921 (10)	0.0179 (3)
O4	0.36153 (14)	0.61213 (15)	0.11160 (11)	0.0187 (3)
N1	0.10810 (17)	0.18398 (19)	−0.14010 (12)	0.0163 (3)
C1	0.34487 (17)	0.1610 (2)	0.03879 (15)	0.0167 (3)
C2	0.40767 (18)	0.3278 (2)	0.10039 (15)	0.0169 (3)
C3	0.42184 (19)	0.1692 (3)	0.17765 (16)	0.0203 (4)
C4	0.17508 (18)	0.1174 (2)	−0.00932 (14)	0.0147 (4)
C5	0.16579 (16)	−0.0746 (2)	−0.01143 (14)	0.0143 (4)
C6	0.30359 (18)	0.4620 (2)	0.11880 (14)	0.0139 (4)
H1A	0.150 (2)	0.128 (3)	−0.1987 (17)	0.020 (5)*
H1B	0.010 (3)	0.166 (3)	−0.1641 (18)	0.029 (5)*
H1C	0.131 (3)	0.303 (4)	−0.143 (2)	0.050 (7)*
H4	0.297 (3)	0.681 (4)	0.115 (2)	0.044 (7)*
H1	0.407 (2)	0.114 (2)	−0.0118 (16)	0.020 (5)*
H2	0.499 (2)	0.364 (2)	0.0793 (15)	0.017 (4)*
H3A	0.522 (2)	0.127 (3)	0.2107 (17)	0.020 (4)*
H3B	0.354 (2)	0.154 (3)	0.2312 (15)	0.017 (4)*
H4A	0.1176 (17)	0.159 (3)	0.0430 (14)	0.006 (4)*
O1W	0.15198 (15)	−0.01307 (17)	0.32148 (12)	0.0218 (3)
H1WA	0.152 (3)	−0.106 (3)	0.352 (2)	0.038 (7)*
H1WB	0.149 (2)	−0.042 (3)	0.246 (2)	0.034 (6)*
O1A	0.81679 (12)	1.13479 (15)	0.40666 (10)	0.0161 (3)
O2A	0.86473 (13)	1.14792 (16)	0.61824 (10)	0.0175 (3)
O3A	0.80378 (12)	0.55765 (16)	0.36274 (10)	0.0177 (3)
O4A	0.63822 (12)	0.38208 (15)	0.41642 (10)	0.0162 (3)
N1A	0.92671 (16)	0.8177 (2)	0.64801 (12)	0.0142 (3)
C1A	0.66918 (17)	0.8314 (2)	0.49476 (14)	0.0144 (4)
C2A	0.59847 (17)	0.6653 (2)	0.44103 (14)	0.0156 (3)
C3A	0.56440 (18)	0.8249 (2)	0.36381 (16)	0.0173 (4)
C4A	0.83802 (17)	0.8786 (2)	0.51986 (14)	0.0133 (4)
C5A	0.84454 (16)	1.0708 (2)	0.51702 (14)	0.0129 (4)
C6A	0.69085 (18)	0.5329 (2)	0.40323 (13)	0.0149 (4)
H1AA	0.892 (2)	0.864 (3)	0.710 (2)	0.028 (5)*
H1AB	1.025 (2)	0.842 (3)	0.6644 (16)	0.018 (4)*
H1AC	0.917 (2)	0.703 (3)	0.6570 (18)	0.024 (5)*
H4AA	0.709 (3)	0.295 (3)	0.404 (2)	0.044 (6)*
H1AD	0.6284 (17)	0.868 (2)	0.5597 (16)	0.008 (4)*
H2A	0.522 (2)	0.630 (2)	0.4774 (15)	0.013 (4)*
H3AA	0.6122 (17)	0.830 (3)	0.2982 (15)	0.006 (4)*
H3AB	0.465 (2)	0.868 (2)	0.3501 (14)	0.011 (4)*
H4AB	0.8848 (19)	0.827 (3)	0.4588 (16)	0.016 (4)*
O1WA	0.79114 (15)	1.00902 (16)	0.16619 (12)	0.0216 (3)
H1WC	0.796 (3)	1.099 (3)	0.130 (2)	0.041 (7)*
H1WD	0.804 (3)	1.030 (3)	0.241 (2)	0.041 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0227 (6)	0.0139 (7)	0.0160 (6)	0.0011 (5)	0.0077 (4)	0.0020 (5)
O2	0.0242 (6)	0.0144 (7)	0.0163 (6)	0.0019 (5)	0.0061 (4)	−0.0010 (5)
O3	0.0197 (6)	0.0162 (7)	0.0203 (6)	−0.0010 (5)	0.0093 (5)	−0.0007 (5)
O4	0.0202 (6)	0.0130 (7)	0.0240 (6)	−0.0006 (5)	0.0082 (5)	−0.0009 (5)
N1	0.0187 (8)	0.0155 (9)	0.0154 (7)	0.0016 (7)	0.0057 (6)	0.0006 (6)
C1	0.0181 (8)	0.0125 (9)	0.0217 (8)	0.0024 (7)	0.0090 (6)	0.0006 (8)
C2	0.0145 (7)	0.0144 (9)	0.0217 (8)	−0.0031 (7)	0.0051 (6)	0.0013 (7)
C3	0.0160 (8)	0.0160 (9)	0.0258 (9)	−0.0004 (8)	0.0006 (7)	0.0015 (8)
C4	0.0188 (8)	0.0143 (10)	0.0129 (8)	0.0016 (7)	0.0075 (7)	0.0003 (6)
C5	0.0116 (7)	0.0148 (10)	0.0164 (9)	0.0006 (7)	0.0036 (6)	−0.0009 (7)
C6	0.0180 (9)	0.0130 (9)	0.0098 (7)	−0.0023 (7)	0.0022 (6)	0.0011 (6)
O1W	0.0361 (7)	0.0127 (7)	0.0171 (6)	0.0008 (6)	0.0081 (5)	−0.0008 (5)
O1A	0.0212 (6)	0.0127 (7)	0.0160 (5)	0.0013 (5)	0.0080 (4)	0.0014 (5)
O2A	0.0230 (6)	0.0144 (6)	0.0145 (5)	0.0006 (5)	0.0039 (4)	−0.0032 (5)
O3A	0.0196 (6)	0.0160 (7)	0.0203 (6)	−0.0017 (5)	0.0099 (5)	−0.0011 (5)
O4A	0.0178 (5)	0.0092 (7)	0.0228 (6)	−0.0013 (5)	0.0074 (5)	0.0003 (5)
N1A	0.0147 (7)	0.0116 (9)	0.0170 (7)	0.0001 (6)	0.0057 (6)	−0.0005 (6)
C1A	0.0184 (8)	0.0107 (9)	0.0159 (8)	0.0015 (7)	0.0076 (6)	0.0018 (7)
C2A	0.0143 (8)	0.0151 (9)	0.0177 (7)	−0.0001 (7)	0.0050 (6)	0.0011 (7)
C3A	0.0144 (8)	0.0155 (10)	0.0215 (8)	0.0015 (7)	0.0044 (7)	0.0006 (7)
C4A	0.0154 (8)	0.0112 (10)	0.0140 (8)	0.0005 (7)	0.0052 (6)	−0.0006 (6)
C5A	0.0101 (7)	0.0131 (10)	0.0166 (9)	0.0004 (7)	0.0056 (6)	0.0011 (7)
C6A	0.0155 (8)	0.0163 (10)	0.0108 (7)	−0.0012 (7)	0.0000 (6)	0.0015 (7)
O1WA	0.0342 (7)	0.0147 (7)	0.0160 (6)	0.0014 (6)	0.0068 (5)	−0.0003 (6)

Geometric parameters (Å, º) top

O1—C5	1.271 (2)	O1A—C5A	1.273 (2)
O2—C5	1.2417 (19)	O2A—C5A	1.239 (2)
O3—C6	1.2270 (19)	O3A—C6A	1.2289 (19)
O4—C6	1.320 (2)	O4A—C6A	1.319 (2)
O4—H4	0.81 (3)	O4A—H4AA	0.98 (3)
N1—C4	1.492 (2)	N1A—C4A	1.492 (2)
N1—H1A	0.94 (2)	N1A—H1AA	0.90 (2)
N1—H1B	0.86 (2)	N1A—H1AB	0.87 (2)
N1—H1C	0.98 (3)	N1A—H1AC	0.93 (2)
C1—C2	1.532 (3)	C1A—C2A	1.520 (3)
C1—C3	1.489 (2)	C1A—C3A	1.484 (2)
C1—C4	1.509 (2)	C1A—C4A	1.510 (2)
C1—H1	0.963 (19)	C1A—H1AD	0.933 (17)
C2—C3	1.512 (3)	C2A—C3A	1.516 (2)
C2—C6	1.473 (2)	C2A—C6A	1.474 (3)
C2—H2	0.953 (18)	C2A—H2A	0.925 (17)
C3—H3A	0.93 (2)	C3A—H3AA	0.934 (16)
C3—H3B	0.965 (18)	C3A—H3AB	0.929 (18)
C4—C5	1.539 (2)	C4A—C5A	1.541 (2)
C4—H4A	0.932 (17)	C4A—H4AB	0.976 (19)
O1W—H1WA	0.82 (3)	O1WA—H1WC	0.83 (3)
O1W—H1WB	0.86 (2)	O1WA—H1WD	0.81 (2)

C6—O4—H4	108.5 (19)	C6A—O4A—H4AA	111.5 (14)
C4—N1—H1A	110.8 (12)	C4A—N1A—H1AA	111.9 (13)
C4—N1—H1B	110.0 (14)	C4A—N1A—H1AB	111.6 (12)
C4—N1—H1C	110.3 (14)	C4A—N1A—H1AC	112.4 (11)
H1A—N1—H1B	106.2 (19)	H1AA—N1A—H1AB	107.1 (18)
H1A—N1—H1C	108.4 (19)	H1AA—N1A—H1AC	105 (2)
H1B—N1—H1C	111 (2)	H1AB—N1A—H1AC	108.5 (19)
C2—C1—H1	113.3 (11)	C2A—C1A—H1AD	111.2 (10)
C3—C1—C2	60.03 (12)	C3A—C1A—C2A	60.61 (11)
C3—C1—C4	120.41 (14)	C3A—C1A—C4A	121.37 (13)
C3—C1—H1	115.3 (10)	C3A—C1A—H1AD	118.2 (9)
C4—C1—C2	124.66 (14)	C4A—C1A—C2A	125.40 (14)
C4—C1—H1	113.3 (10)	C4A—C1A—H1AD	111.5 (9)
C1—C2—H2	113.0 (11)	C1A—C2A—H2A	112.3 (11)
C3—C2—C1	58.57 (11)	C3A—C2A—C1A	58.51 (11)
C3—C2—H2	116.3 (11)	C3A—C2A—H2A	116.0 (11)
C6—C2—C1	121.77 (14)	C6A—C2A—C1A	122.11 (13)
C6—C2—C3	119.62 (14)	C6A—C2A—C3A	119.45 (14)
C6—C2—H2	115.7 (11)	C6A—C2A—H2A	116.1 (11)
C1—C3—C2	61.40 (11)	C1A—C3A—C2A	60.89 (12)
C1—C3—H3A	120.3 (11)	C1A—C3A—H3AA	116.1 (9)
C1—C3—H3B	115.1 (10)	C1A—C3A—H3AB	117.8 (10)
C2—C3—H3A	116.6 (12)	C2A—C3A—H3AA	113.7 (12)
C2—C3—H3B	118.6 (12)	C2A—C3A—H3AB	115.9 (11)
H3A—C3—H3B	114.6 (15)	H3AA—C3A—H3AB	119.0 (14)
N1—C4—C1	110.69 (13)	N1A—C4A—C1A	109.69 (13)
N1—C4—C5	109.68 (13)	N1A—C4A—C5A	109.39 (13)
N1—C4—H4A	108.6 (10)	N1A—C4A—H4AB	106.7 (11)
C1—C4—C5	106.36 (14)	C1A—C4A—C5A	106.73 (14)
C1—C4—H4A	112.3 (10)	C1A—C4A—H4AB	111.6 (11)
C5—C4—H4A	109.2 (12)	C5A—C4A—H4AB	112.7 (13)
O1—C5—C4	115.33 (14)	O1A—C5A—C4A	114.98 (14)
O2—C5—O1	126.49 (17)	O2A—C5A—O1A	126.36 (17)
O2—C5—C4	117.97 (14)	O2A—C5A—C4A	118.46 (14)
O3—C6—O4	122.97 (16)	O3A—C6A—O4A	122.89 (16)
O3—C6—C2	124.64 (16)	O3A—C6A—C2A	124.66 (17)
O4—C6—C2	112.39 (14)	O4A—C6A—C2A	112.45 (14)
H1WA—O1W—H1WB	99 (2)	H1WC—O1WA—H1WD	107 (3)

N1—C4—C5—O1	−157.34 (12)	N1A—C4A—C5A—O1A	159.17 (12)
N1—C4—C5—O2	27.53 (18)	N1A—C4A—C5A—O2A	−25.74 (18)
C1—C2—C6—O3	31.9 (2)	C1A—C2A—C6A—O3A	−30.4 (2)
C1—C2—C6—O4	−148.40 (15)	C1A—C2A—C6A—O4A	150.15 (14)
C1—C4—C5—O1	82.93 (15)	C1A—C4A—C5A—O1A	−82.23 (15)
C1—C4—C5—O2	−92.20 (16)	C1A—C4A—C5A—O2A	92.87 (16)
C2—C1—C4—N1	83.47 (18)	C2A—C1A—C4A—N1A	−85.57 (18)
C2—C1—C4—C5	−157.45 (15)	C2A—C1A—C4A—C5A	156.02 (14)
C3—C1—C2—C6	−107.63 (17)	C3A—C1A—C2A—C6A	107.23 (16)
C3—C1—C4—N1	156.11 (16)	C3A—C1A—C4A—N1A	−159.79 (16)
C3—C1—C4—C5	−84.81 (19)	C3A—C1A—C4A—C5A	81.8 (2)
C3—C2—C6—O3	−37.4 (2)	C3A—C2A—C6A—O3A	38.8 (2)
C3—C2—C6—O4	142.30 (14)	C3A—C2A—C6A—O4A	−140.58 (14)
C4—C1—C2—C3	108.16 (17)	C4A—C1A—C2A—C3A	−109.43 (17)
C4—C1—C2—C6	0.5 (2)	C4A—C1A—C2A—C6A	−2.2 (2)
C4—C1—C3—C2	−115.01 (18)	C4A—C1A—C3A—C2A	115.80 (19)
C6—C2—C3—C1	111.25 (16)	C6A—C2A—C3A—C1A	−111.72 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3Aⁱ	0.94 (2)	2.03 (2)	2.9444 (18)	162.1 (17)
N1—H1B···O2Aⁱⁱ	0.86 (2)	2.39 (2)	2.9454 (18)	123.1 (16)
N1—H1C···O1WAⁱ	0.98 (3)	1.83 (3)	2.795 (2)	167 (2)
O4—H4···O1ⁱⁱⁱ	0.81 (3)	1.79 (3)	2.5851 (18)	166 (3)
O1W—H1WA···O2A^iv	0.82 (3)	2.01 (3)	2.8072 (19)	166 (2)
O1W—H1WB···O1	0.86 (2)	1.90 (2)	2.7449 (16)	169 (2)
N1A—H1AA···O3^v	0.90 (2)	2.01 (2)	2.9087 (18)	173 (2)
N1A—H1AB···O3A^vi	0.87 (2)	2.38 (2)	3.1151 (19)	141.7 (17)
N1A—H1AC···O1W^v	0.93 (2)	1.87 (2)	2.785 (2)	165.6 (18)
O4A—H4AA···O1A^vii	0.98 (3)	1.60 (3)	2.5672 (16)	168 (2)
O1WA—H1WC···O2^viii	0.83 (3)	2.07 (3)	2.8628 (19)	158 (2)
O1WA—H1WD···O1A	0.81 (2)	1.98 (3)	2.7717 (17)	166 (3)

Symmetry codes: (i) −x+1, y−1/2, −z; (ii) x−1, y−1, z−1; (iii) x, y+1, z; (iv) −x+1, y−3/2, −z+1; (v) −x+1, y+1/2, −z+1; (vi) −x+2, y+1/2, −z+1; (vii) x, y−1, z; (viii) −x+1, y+3/2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3Aⁱ	0.94 (2)	2.03 (2)	2.9444 (18)	162.1 (17)
N1—H1B···O2Aⁱⁱ	0.86 (2)	2.39 (2)	2.9454 (18)	123.1 (16)
N1—H1C···O1WAⁱ	0.98 (3)	1.83 (3)	2.795 (2)	167 (2)
O4—H4···O1ⁱⁱⁱ	0.81 (3)	1.79 (3)	2.5851 (18)	166 (3)
O1W—H1WA···O2A^iv	0.82 (3)	2.01 (3)	2.8072 (19)	166 (2)
O1W—H1WB···O1	0.86 (2)	1.90 (2)	2.7449 (16)	169 (2)
N1A—H1AA···O3^v	0.90 (2)	2.01 (2)	2.9087 (18)	173 (2)
N1A—H1AB···O3A^vi	0.87 (2)	2.38 (2)	3.1151 (19)	141.7 (17)
N1A—H1AC···O1W^v	0.93 (2)	1.87 (2)	2.785 (2)	165.6 (18)
O4A—H4AA···O1A^vii	0.98 (3)	1.60 (3)	2.5672 (16)	168 (2)
O1WA—H1WC···O2^viii	0.83 (3)	2.07 (3)	2.8628 (19)	158 (2)
O1WA—H1WD···O1A	0.81 (2)	1.98 (3)	2.7717 (17)	166 (3)

Experimental details

Crystal data
Chemical formula	C₆H₉NO₄·H₂O
M_r	177.16
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	8.9688 (8), 8.0063 (8), 10.9628 (10)
β (°)	106.015 (4)
V (Å³)	756.65 (12)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.18
Crystal size (mm)	0.37 × 0.32 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.669, 0.891
No. of measured, independent and observed [I > 2σ(I)] reflections	6086, 2164, 2154
R_int	0.018
θ_max (°)	61.0
(sin θ/λ)_max (Å⁻¹)	0.567

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.055, 1.06
No. of reflections	2164
No. of parameters	305
No. of restraints	1
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.16
Absolute structure	Flack (1983), 836 Friedel pairs
Absolute structure parameter	0.57 (15)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

References

Allen, F. H. (1980). Acta Cryst. B36, 81–96. CrossRef IUCr Journals Web of Science Google Scholar
Bishop, R. & Scudder, M. L. (2009). Cryst. Growth Des. 9, 2890–2894. Web of Science CrossRef CAS Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madision, Wisconsin, USA. Google Scholar
Caveney, S. & Starratt, A. (1994). Nature, 372, 509. CrossRef Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Fowden, L., Smith, A., Millington, D. S. & Sheppard, R. C. (1969). Phytochemistry, 8, 437–443. CrossRef CAS Google Scholar
Pellicciari, R., Marinozzi, M., Camaioni, E., del Carmen Nùnez, M., Costantino, G., Gasparini, F., Giorgi, G., Macchiarulo, A. & Subramanian, N. (2002). J. Org. Chem. 67, 5497–5507. CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shimamoto, K., Ishida, M., Shinozaki, H. & Ohfune, Y. (1991). J. Org. Chem. 56, 4167–4176. CrossRef CAS Google Scholar
Starratt, A. N. & Caveney, S. (1995). Phytochemistry, 40, 479–481. CrossRef CAS Google Scholar
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Volume 71| Part 7| July 2015| Pages 844-846

doi:10.1107/S2056989015011500

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of cis-2-(2-carb­­oxy­cyclo­prop­yl)glycine (CCG-III) monohydrate

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Synthesis and crystallization

5. Refinement

Supporting information

References

research communications

Crystal structure of cis-2-(2-carboxycyclopropyl)glycine (CCG-III) monohydrate

3. Supramolecular features