Cyclo­hexa­naminium trichloro­acetate

Abstract

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 R ₄ ⁴(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,

• a = 6.7217 (4) Å

• b = 21.2482 (15) Å

• c = 10.6908 (6) Å

• β = 126.590 (3)°

• V = 1225.98 (14) ų

• 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[F ² > 2σ(F ²)] = 0.066

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

The coordinates of H-atoms attached to N1 and C1 were refined. The other H atoms were positioned geometrically (C—H = 0.97 Å) and refined as riding. The constraint U_iso(H) = 1.2U_eq(carrier) was applied for all H atoms.

Figures

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.

Crystal data

C6H14N+·C2Cl3O2−	F(000) = 544
Mr = 262.55	Dx = 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

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

Refinement

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(Fo2) + (0.1089P)2 + 0.5776P] where P = (Fo2 + 2Fc2)/3
2910 reflections	(Δ/σ)max < 0.001
139 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.