Cyclo­hexa­naminium trichloro­acetate

Shahwar, D.; Tahir, M.N.; Ahmad, N.; Khan, M.A.; Saeed, A.

doi:10.1107/S1600536809017504

organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Page o1313

doi:10.1107/S1600536809017504

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Cyclohexanaminium trichloroacetate

Durre Shahwar,^a M. Nawaz Tahir,^b ^* Naeem Ahmad,^a Muhammad Akmal Khan ^a and Afifa Saeed ^a

^aDepartment of Chemistry, Government College University, Lahore, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 9 May 2009; accepted 10 May 2009; online 20 May 2009)

In the crystal of the title compound, C₆H₁₄N⁺·C₂Cl₃O₂⁻, centrosymmetric assemblies of two cyclohexanaminium cations and two trichloroacetate ions are linked by N—H⋯O hydrogen bonds, thereby forming R₄⁴(12) ring motifs. Further N—H⋯O interactions link the tetramers into chains propagating along the a axis.

Related literature

For related structures, see: Shahwar et al. (2009 ); Wang et al. (2005 ); Jones & Ahrens (1998 ). For reference structural data, see: Allen et al. (1987 ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₆H₁₄N⁺·C₂Cl₃O₂⁻
M_r = 262.55
Monoclinic, P 2₁ /c
a = 6.7217 (4) Å
b = 21.2482 (15) Å
c = 10.6908 (6) Å
β = 126.590 (3)°
V = 1225.98 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 296 K
0.25 × 0.18 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.853, T_max = 0.919
13379 measured reflections
2910 independent reflections
1710 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.215
S = 1.05
2910 reflections
139 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.85 (6)	1.96 (6)	2.788 (6)	167 (4)
N1—H1B⋯O2ⁱⁱ	0.82 (5)	1.96 (5)	2.770 (5)	168 (4)
N1—H1C⋯O1ⁱⁱⁱ	1.02 (4)	1.83 (4)	2.837 (4)	169 (4)
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809017504/hb2970sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809017504/hb2970Isup2.hkl

checkCIF report

Comment top

In continuation of synthesizing various organic ammonium salts (Shahwar et al., 2009), the title compound (I), (Fig. 1) is being reported. The crystal structures of (II) Cyclohexylammonium dichloroacetate (Wang et al., 2005) and (III) Cyclohexylamine cyclohexylammonium chloride (Jones & Ahrens, 1998) have been reported.

In (I), the bond distance and bond angles are within normal ranges (Allen et al., 1987). In the title compound, two cyclohexanaminium ions and two trichloroacetate ions are interlinked through intermolecular H-bonding of N—H···O type (Table 1) forming ring motifs R₄⁴(12) (Bernstein et al., 1995) (Fig. 2). The ring motifs are further connected through the same along the a axis resulting in one-dimensional polymeric chains. The cyclohexanaminium ions are in chair confirmations with N-atoms at a distance of 0.628 (9)Å from the central plane.

Related literature top

For related structures, see: Shahwar et al. (2009); Wang et al. (2005); Jones & Ahrens (1998). For reference structural data, see: Allen et al. (1987). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

A solution of trichloroacetic acid (1.635 g, 0.01 mol) in 20 ml of dichloromethane was prepared. To this solution cyclohexyl amine (1.14 ml, 0.01 mol) was added dropwise and stirred for 30 min. The precipitate were filtered out and recrystallized in hot chloroform to yield colourless rods of (I).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 30% probability level. H-atoms are shown by small spheres of arbitrary radius.
	Fig. 2. The partial packing in (I) showing intermolecular H-bonding between NH₃ and trichloroacetate ions and the resulting ring motif.

Cyclohexanaminium trichloroacetate top

Crystal data top

C₆H₁₄N⁺·C₂Cl₃O₂⁻	F(000) = 544
M_r = 262.55	D_x = 1.422 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2910 reflections
a = 6.7217 (4) Å	θ = 2.6–27.9°
b = 21.2482 (15) Å	µ = 0.72 mm⁻¹
c = 10.6908 (6) Å	T = 296 K
β = 126.590 (3)°	Rod, colorless
V = 1225.98 (14) Å³	0.25 × 0.18 × 0.12 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	2910 independent reflections
Radiation source: fine-focus sealed tube	1710 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 7.50 pixels mm^-1	θ_max = 27.9°, θ_min = 2.6°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −27→26
T_min = 0.853, T_max = 0.919	l = −12→14
13379 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.215	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.1089P)² + 0.5776P] where P = (F_o² + 2F_c²)/3
2910 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.37 e Å⁻³

Crystal data top

C₆H₁₄N⁺·C₂Cl₃O₂⁻	V = 1225.98 (14) Å³
M_r = 262.55	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.7217 (4) Å	µ = 0.72 mm⁻¹
b = 21.2482 (15) Å	T = 296 K
c = 10.6908 (6) Å	0.25 × 0.18 × 0.12 mm
β = 126.590 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	2910 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1710 reflections with I > 2σ(I)
T_min = 0.853, T_max = 0.919	R_int = 0.038
13379 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.215	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.73 e Å⁻³
2910 reflections	Δρ_min = −0.37 e Å⁻³
139 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
N1	0.2904 (5)	0.05714 (15)	0.0547 (4)	0.0480 (10)
C1	0.4574 (6)	0.08854 (16)	0.2093 (4)	0.0463 (10)
C2	0.7215 (6)	0.06696 (19)	0.2878 (5)	0.0568 (11)
C3	0.8922 (7)	0.0967 (2)	0.4465 (5)	0.0731 (15)
C4	0.8100 (8)	0.0827 (3)	0.5472 (6)	0.0816 (18)
C5	0.5457 (8)	0.1032 (2)	0.4704 (5)	0.0764 (17)
C6	0.3726 (7)	0.0733 (2)	0.3100 (5)	0.0626 (15)
Cl1	0.9294 (2)	0.30601 (6)	0.38465 (15)	0.0791 (4)
Cl2	0.7598 (3)	0.28803 (6)	0.57059 (16)	0.1029 (6)
Cl3	0.4167 (2)	0.28226 (6)	0.23280 (17)	0.0950 (5)
O1	0.7893 (5)	0.42783 (12)	0.4227 (4)	0.0711 (9)
O2	0.4297 (5)	0.40429 (14)	0.3696 (3)	0.0680 (10)
C7	0.6272 (5)	0.39152 (15)	0.3948 (3)	0.0406 (9)
C8	0.6778 (7)	0.32022 (15)	0.3937 (4)	0.0488 (10)
H1	0.432 (7)	0.1331 (19)	0.186 (4)	0.0553*
H1A	0.141 (8)	0.0678 (19)	0.011 (5)	0.0575*
H1B	0.333 (7)	0.0632 (19)	−0.002 (5)	0.0575*
H1C	0.285 (7)	0.010 (2)	0.071 (4)	0.0575*
H2A	0.72989	0.02151	0.29833	0.0680*
H2B	0.77440	0.07841	0.22401	0.0680*
H3A	1.05899	0.08085	0.49682	0.0877*
H3B	0.89524	0.14188	0.43499	0.0877*
H4A	0.91813	0.10433	0.64607	0.0973*
H4B	0.82413	0.03787	0.56795	0.0973*
H5A	0.53487	0.14865	0.46040	0.0919*
H5B	0.49516	0.09095	0.53505	0.0919*
H6A	0.20568	0.08903	0.25991	0.0753*
H6B	0.37023	0.02808	0.32080	0.0753*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0401 (14)	0.0439 (17)	0.0601 (19)	0.0011 (12)	0.0300 (14)	0.0040 (13)
C1	0.0436 (16)	0.0341 (17)	0.057 (2)	0.0007 (13)	0.0278 (16)	0.0035 (14)
C2	0.0426 (17)	0.063 (2)	0.066 (2)	0.0015 (16)	0.0331 (17)	0.0043 (18)
C3	0.0463 (19)	0.084 (3)	0.072 (3)	−0.0074 (19)	0.026 (2)	−0.002 (2)
C4	0.066 (2)	0.093 (4)	0.064 (3)	−0.002 (2)	0.027 (2)	−0.007 (2)
C5	0.079 (3)	0.088 (3)	0.068 (3)	0.003 (2)	0.047 (2)	−0.010 (2)
C6	0.0508 (19)	0.072 (3)	0.074 (3)	−0.0019 (18)	0.042 (2)	−0.001 (2)
Cl1	0.0779 (7)	0.0700 (7)	0.0894 (8)	0.0142 (5)	0.0499 (7)	−0.0143 (6)
Cl2	0.1635 (14)	0.0733 (8)	0.0817 (9)	0.0174 (8)	0.0784 (10)	0.0311 (6)
Cl3	0.0748 (7)	0.0673 (8)	0.0937 (9)	−0.0196 (5)	0.0236 (7)	−0.0294 (6)
O1	0.0498 (14)	0.0401 (14)	0.111 (2)	−0.0005 (11)	0.0413 (15)	0.0006 (14)
O2	0.0564 (15)	0.0762 (19)	0.0787 (19)	0.0110 (13)	0.0442 (15)	0.0000 (14)
C7	0.0409 (16)	0.0400 (17)	0.0342 (15)	0.0016 (13)	0.0187 (13)	0.0004 (12)
C8	0.0579 (19)	0.0354 (17)	0.0418 (17)	−0.0009 (14)	0.0236 (16)	0.0005 (13)

Geometric parameters (Å, º) top

Cl1—C8	1.776 (6)	C5—C6	1.523 (6)
Cl2—C8	1.762 (4)	C1—H1	0.97 (4)
Cl3—C8	1.758 (4)	C2—H2B	0.9700
O1—C7	1.218 (5)	C2—H2A	0.9700
O2—C7	1.217 (5)	C3—H3A	0.9700
N1—C1	1.492 (5)	C3—H3B	0.9700
N1—H1A	0.85 (6)	C4—H4A	0.9700
N1—H1C	1.02 (4)	C4—H4B	0.9700
N1—H1B	0.82 (5)	C5—H5B	0.9700
C1—C6	1.523 (7)	C5—H5A	0.9700
C1—C2	1.513 (7)	C6—H6B	0.9700
C2—C3	1.508 (6)	C6—H6A	0.9700
C3—C4	1.504 (8)	C7—C8	1.554 (5)
C4—C5	1.510 (9)

C1—N1—H1C	109 (2)	H3A—C3—H3B	108.00
C1—N1—H1A	111 (3)	C3—C4—H4A	109.00
C1—N1—H1B	113 (3)	C3—C4—H4B	109.00
H1B—N1—H1C	110 (4)	C5—C4—H4A	109.00
H1A—N1—H1B	112 (5)	C5—C4—H4B	109.00
H1A—N1—H1C	102 (4)	H4A—C4—H4B	108.00
N1—C1—C2	109.8 (3)	C4—C5—H5A	110.00
N1—C1—C6	109.7 (4)	C4—C5—H5B	109.00
C2—C1—C6	110.7 (3)	C6—C5—H5A	110.00
C1—C2—C3	110.6 (4)	C6—C5—H5B	109.00
C2—C3—C4	111.4 (4)	H5A—C5—H5B	108.00
C3—C4—C5	111.6 (4)	C1—C6—H6A	109.00
C4—C5—C6	110.7 (4)	C1—C6—H6B	110.00
C1—C6—C5	110.5 (4)	C5—C6—H6A	109.00
N1—C1—H1	105 (2)	C5—C6—H6B	110.00
C2—C1—H1	114 (3)	H6A—C6—H6B	108.00
C6—C1—H1	108 (3)	O1—C7—O2	127.7 (3)
C1—C2—H2A	110.00	O1—C7—C8	116.8 (4)
C1—C2—H2B	110.00	O2—C7—C8	115.5 (3)
C3—C2—H2A	110.00	Cl1—C8—Cl2	107.1 (2)
C3—C2—H2B	110.00	Cl1—C8—Cl3	107.2 (2)
H2A—C2—H2B	108.00	Cl1—C8—C7	112.7 (3)
C2—C3—H3A	109.00	Cl2—C8—Cl3	111.3 (2)
C2—C3—H3B	109.00	Cl2—C8—C7	107.5 (2)
C4—C3—H3A	109.00	Cl3—C8—C7	111.1 (3)
C4—C3—H3B	109.00

N1—C1—C2—C3	−178.3 (3)	C4—C5—C6—C1	−55.8 (5)
C6—C1—C2—C3	−57.1 (4)	O1—C7—C8—Cl1	−15.1 (4)
N1—C1—C6—C5	178.2 (3)	O1—C7—C8—Cl2	102.6 (4)
C2—C1—C6—C5	56.9 (4)	O1—C7—C8—Cl3	−135.5 (3)
C1—C2—C3—C4	56.5 (5)	O2—C7—C8—Cl1	165.9 (2)
C2—C3—C4—C5	−55.9 (6)	O2—C7—C8—Cl2	−76.4 (3)
C3—C4—C5—C6	55.4 (6)	O2—C7—C8—Cl3	45.6 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.85 (6)	1.96 (6)	2.788 (6)	167 (4)
N1—H1B···O2ⁱⁱ	0.82 (5)	1.96 (5)	2.770 (5)	168 (4)
N1—H1C···O1ⁱⁱⁱ	1.02 (4)	1.83 (4)	2.837 (4)	169 (4)

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

Experimental details

Crystal data
Chemical formula	C₆H₁₄N⁺·C₂Cl₃O₂⁻
M_r	262.55
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	6.7217 (4), 21.2482 (15), 10.6908 (6)
β (°)	126.590 (3)
V (Å³)	1225.98 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.25 × 0.18 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.853, 0.919
No. of measured, independent and observed [I > 2σ(I)] reflections	13379, 2910, 1710
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.215, 1.05
No. of reflections	2910
No. of parameters	139
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.37

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.85 (6)	1.96 (6)	2.788 (6)	167 (4)
N1—H1B···O2ⁱⁱ	0.82 (5)	1.96 (5)	2.770 (5)	168 (4)
N1—H1C···O1ⁱⁱⁱ	1.02 (4)	1.83 (4)	2.837 (4)	169 (4)

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

Acknowledgements

NA greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing a Scholarship under the Indigenous PhD Program (PIN 042–120599-PS2–156).

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