Redetermination of 1-carboxy­cyclo­hexan-1-aminium chloride

Belandria, L.M.; Delgado, G.E.; Mora, A.J.; Seijas, L.E.; González, T.

doi:10.1107/S1600536808044243

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 2| February 2009| Page o245

doi:10.1107/S1600536808044243

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Redetermination of 1-carboxycyclohexan-1-aminium chloride

Lusbely M. Belandria,^a Gerzon E. Delgado,^a ^* Asiloé J. Mora,^a Luis E. Seijas ^a and Teresa González ^b

^aLaboratorio de Cristalografía, Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, Mérida 5101, Venezuela, and ^bCentro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Apartado 21827, Caracas 1020-A, Venezuela
^*Correspondence e-mail: gerzon@ula.ve

(Received 2 December 2008; accepted 30 December 2008; online 8 January 2009)

The crystal structure of the title compound, C₇H₁₄NO₂⁺·Cl⁻, was reported previously [Chacko, Srinivasan & Zand (1975 ). J. Cryst. Mol. Struct. 5, 353–357] from Weissenberg photographic data with R = 0.113. It has now been redetermined, providing a significant increase in the precision of the derived geometric parameters, viz. mean σ(C—C) = 0.003 Å in the present work compared with 0.021 Å for the previous work. The complete cation is generated by crystallographic mirrror symmetry, with three C atoms, two O atoms and the N atom lying on the reflecting plane; the chloride anion also has m site symmetry. The crystal structure is established by a two-dimensional network of O—H⋯Cl and N—H⋯Cl hydrogen bonds, generating C¹₂(4) and C¹₂(7) chains, and R²₄(8) and R²₄(14) rings.

Related literature

For the earlier structure determination of the title salt, see: Chacko et al. (1971 , 1975). For related literature, see Rodríguez-Ropero et al. (2008 ). For the crystal structure of the pure amino acid, see: Valle et al. (1988 ). For ring conformation analysis, see: Cremer & Pople (1975 ). For hydrogen-bond motifs in graph-set notation, see: Etter (1990 ).

Experimental

Crystal data

C₇H₁₄NO₂⁺·Cl⁻
M_r = 179.64
Monoclinic, P 2₁ /m
a = 7.382 (3) Å
b = 6.357 (2) Å
c = 9.374 (3) Å
β = 96.239 (10)°
V = 437.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.39 mm⁻¹
T = 298 (2) K
0.31 × 0.27 × 0.18 mm

Data collection

Rigaku AFC-7S Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ) T_min = 0.880, T_max = 0.930
4638 measured reflections
845 independent reflections
789 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.088
S = 1.01
845 reflections
85 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cl	0.90 (3)	2.34 (3)	3.196 (2)	158 (2)
N1—H1A⋯Clⁱ	0.88 (2)	2.58 (2)	3.3816 (13)	152.4 (17)
O1—H1⋯Clⁱⁱ	0.89 (4)	2.15 (4)	3.027 (2)	168 (3)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) x, y, z-1.

Data collection: CrystalClear (Rigaku, 2002 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: PLATON (Spek, 2003 ) and publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808044243/bh2212sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808044243/bh2212Isup2.hkl

checkCIF report

Comment top

1-Amino-cyclohexanecarboxylic acid is a promising amino acid candidate to serve as basic piece in redesigned protein motifs which constitute the basic modules in synthetic nanoconstructs (Rodríguez-Ropero et al., 2008). It structure was reported by Valle et al. (1988). The title compound, (I), 1-amino-cyclohexanecarboxylic acid hydrochloride, C₇H₁₄NO₂⁺.Cl^-, was first reported in the noncentric space group P2₁ (Chacko et al., 1971) and later reported in the centrosymmetric space group P2₁/m (Chacko et al., 1975) with R = 0.113. The present paper reports a redetermination of the crystal structure of (I), with greater precision and accuracy. Both, the cation and anion are located on a mirror plane, which confirms the space group P2₁/m instead of P2₁. In this compound, the cyclohexane ring adopts a chair conformation, with the ammonium and carboxylate groups in axial and equatorial positions, respectively (Cremer & Pople, 1975), while the pure amino acid has an opposite conformation (Valle et al., 1988). In (I), 1-amino-cyclohexanecarboxylic acid is protonated and is linked to the Cl^- anion by a O—H···Cl hydrogen bond (Fig. 1, Table 1). The hydrogen bonds O1—H1···Cl1 (x, y, z - 1) and N1—H1B···Cl1 (1 - x, y - 1/2, 1 - z) form infinite chains running along the [001] direction (Fig. 2) and may be described in graph-set notation as C¹₂(7) (Etter, 1990). The intramolecular hydrogen bonds N1—H1A···Cl1 form infinite chains, with graph-set C¹₂(4), running along the b cell axis. The combination of these interactions produces rings with graph-set R²₄(8) and R²₄(14), parallel to the bc plane (Fig. 2).

Related literature top

For the earlier structure determination of the title salt, see: Chacko et al. (1971, 1975). For related literature, see Rodríguez-Ropero et al. (2008). For the crystal structure of the pure amino acid, see: Valle et al. (1988). For ring conformation analysis, see: Cremer & Pople (1975). For hydrogen-bond motifs in graph-set notation, see: Etter (1990).

Experimental top

1-Amino-cyclohexanecarboxylic acid and hydrochloric acid in equal molar ratio were mixed together with enough water, and heated to a temperature where a clear solution was obtained. Colorless crystals of (I) suitable for X-ray diffraction analysis were grown by slow evaporation of this solution.

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Figures top

	Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. A partial packing view of (I). Hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity. Symmetry codes: (i) x, y, z - 1; (ii) 1 - x, y - 1/2, 1 - z.

1-carboxycyclohexan-1-aminium chloride top

Crystal data top

C₇H₁₄NO₂⁺·Cl⁻	F(000) = 192
M_r = 179.64	D_x = 1.364 Mg m⁻³
Monoclinic, P2₁/m	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2yb	Cell parameters from 1650 reflections
a = 7.382 (3) Å	θ = 2.2–27.2°
b = 6.357 (2) Å	µ = 0.39 mm⁻¹
c = 9.374 (3) Å	T = 298 K
β = 96.239 (10)°	Block, colourless
V = 437.3 (3) Å³	0.31 × 0.27 × 0.18 mm
Z = 2

Data collection top

Rigaku AFC-7S Mercury diffractometer	845 independent reflections
Radiation source: Normal-focus sealed tube	789 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 14.6306 pixels mm^-1	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = −8→8
Absorption correction: multi-scan (Jacobson, 1998)	k = −6→7
T_min = 0.880, T_max = 0.930	l = −11→11
4638 measured reflections

Refinement top

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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.047P)² + 0.1831P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
845 reflections	Δρ_max = 0.18 e Å⁻³
85 parameters	Δρ_min = −0.15 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 constraints	Extinction coefficient: 0.042 (10)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₇H₁₄NO₂⁺·Cl⁻	V = 437.3 (3) Å³
M_r = 179.64	Z = 2
Monoclinic, P2₁/m	Mo Kα radiation
a = 7.382 (3) Å	µ = 0.39 mm⁻¹
b = 6.357 (2) Å	T = 298 K
c = 9.374 (3) Å	0.31 × 0.27 × 0.18 mm
β = 96.239 (10)°

Data collection top

Rigaku AFC-7S Mercury diffractometer	845 independent reflections
Absorption correction: multi-scan (Jacobson, 1998)	789 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.930	R_int = 0.023
4638 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.18 e Å⁻³
845 reflections	Δρ_min = −0.15 e Å⁻³
85 parameters

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

	x	y	z	U_iso*/U_eq
Cl	0.41343 (8)	0.2500	0.64377 (6)	0.0414 (3)
O2	0.5446 (2)	0.2500	0.04758 (18)	0.0511 (5)
O1	0.2629 (3)	0.2500	−0.06850 (18)	0.0528 (5)
H1	0.324 (5)	0.2500	−0.146 (4)	0.079*
N1	0.4370 (3)	0.2500	0.3054 (2)	0.0343 (5)
H1A	0.506 (3)	0.138 (3)	0.300 (2)	0.051*
H1B	0.398 (4)	0.2500	0.393 (3)	0.051*
C1	0.2863 (3)	0.2500	0.1837 (2)	0.0292 (5)
C2	0.1715 (2)	0.4484 (3)	0.19289 (19)	0.0408 (5)
H2A	0.251 (3)	0.566 (3)	0.1923 (19)	0.049*
H2B	0.090 (3)	0.452 (3)	0.107 (2)	0.049*
C3	0.0597 (3)	0.4450 (4)	0.3193 (2)	0.0539 (6)
H3A	0.140 (3)	0.449 (4)	0.409 (2)	0.065*
H3B	−0.018 (3)	0.571 (4)	0.315 (2)	0.065*
C4	−0.0557 (4)	0.2500	0.3201 (3)	0.0626 (9)
H4A	−0.145 (5)	0.2500	0.232 (4)	0.075*
H4B	−0.148 (5)	0.2500	0.397 (4)	0.075*
C5	0.3819 (3)	0.2500	0.0475 (2)	0.0358 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.0457 (4)	0.0544 (4)	0.0238 (4)	0.000	0.0025 (2)	0.000
O2	0.0359 (10)	0.0837 (14)	0.0345 (10)	0.000	0.0078 (7)	0.000
O1	0.0443 (11)	0.0932 (15)	0.0205 (9)	0.000	0.0023 (7)	0.000
N1	0.0335 (11)	0.0449 (12)	0.0238 (10)	0.000	−0.0002 (8)	0.000
C1	0.0303 (11)	0.0355 (12)	0.0211 (11)	0.000	−0.0004 (8)	0.000
C2	0.0439 (10)	0.0402 (10)	0.0373 (10)	0.0074 (8)	−0.0004 (8)	0.0024 (7)
C3	0.0497 (11)	0.0707 (14)	0.0412 (10)	0.0221 (10)	0.0052 (9)	−0.0058 (10)
C4	0.0386 (15)	0.105 (3)	0.0449 (17)	0.000	0.0076 (13)	0.000
C5	0.0385 (13)	0.0425 (13)	0.0262 (12)	0.000	0.0025 (10)	0.000

Geometric parameters (Å, º) top

O2—C5	1.201 (3)	C2—C3	1.516 (3)
O1—C5	1.322 (3)	C2—H2A	0.95 (2)
O1—H1	0.89 (4)	C2—H2B	0.95 (2)
N1—C1	1.504 (3)	C3—C4	1.505 (3)
N1—H1A	0.88 (2)	C3—H3A	0.97 (2)
N1—H1B	0.90 (3)	C3—H3B	0.98 (2)
C1—C5	1.524 (3)	C4—H4A	0.99 (3)
C1—C2	1.528 (2)	C4—H4B	1.05 (4)

C5—O1—H1	109 (2)	C4—C3—C2	111.85 (19)
C1—N1—H1A	110.2 (13)	C4—C3—H3A	107.9 (13)
C1—N1—H1B	114.0 (18)	C2—C3—H3A	109.9 (12)
H1A—N1—H1B	107.1 (16)	C4—C3—H3B	110.2 (13)
N1—C1—C5	105.28 (18)	C2—C3—H3B	108.4 (13)
N1—C1—C2	109.04 (12)	H3A—C3—H3B	108.5 (17)
C5—C1—C2	110.97 (12)	C3—C4—H4A	108.6 (10)
C3—C2—C1	112.64 (16)	C3—C4—H4B	114.6 (8)
C3—C2—H2A	113.8 (11)	H4A—C4—H4B	99 (3)
C1—C2—H2A	107.7 (12)	O2—C5—O1	125.2 (2)
C3—C2—H2B	108.3 (11)	O2—C5—C1	123.6 (2)
C1—C2—H2B	105.8 (12)	O1—C5—C1	111.2 (2)
H2A—C2—H2B	108.2 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl	0.90 (3)	2.34 (3)	3.196 (2)	158 (2)
N1—H1A···Clⁱ	0.88 (2)	2.58 (2)	3.3816 (13)	152.4 (17)
O1—H1···Clⁱⁱ	0.89 (4)	2.15 (4)	3.027 (2)	168 (3)

Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₇H₁₄NO₂⁺·Cl⁻
M_r	179.64
Crystal system, space group	Monoclinic, P2₁/m
Temperature (K)	298
a, b, c (Å)	7.382 (3), 6.357 (2), 9.374 (3)
β (°)	96.239 (10)
V (Å³)	437.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.39
Crystal size (mm)	0.31 × 0.27 × 0.18

Data collection
Diffractometer	Rigaku AFC-7S Mercury diffractometer
Absorption correction	Multi-scan (Jacobson, 1998)
T_min, T_max	0.880, 0.930
No. of measured, independent and observed [I > 2σ(I)] reflections	4638, 845, 789
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.088, 1.01
No. of reflections	845
No. of parameters	85
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15

Computer programs: CrystalClear (Rigaku, 2002), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl	0.90 (3)	2.34 (3)	3.196 (2)	158 (2)
N1—H1A···Clⁱ	0.88 (2)	2.58 (2)	3.3816 (13)	152.4 (17)
O1—H1···Clⁱⁱ	0.89 (4)	2.15 (4)	3.027 (2)	168 (3)

Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) x, y, z−1.

Acknowledgements

This work was supported by CDCHT-ULA (grant Nos. C-1618-08-A, C-1615-08-B and C-1620-08-08-Em) and FONACIT (grant No. LAB-97000821).

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