Cyclo­hexyl­ammonium 4-meth­oxy­benzoate

Wei, B.

doi:10.1107/S1600536811027127

organic compounds

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Volume 67| Part 8| August 2011| Page o2185

doi:10.1107/S1600536811027127

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Cyclohexylammonium 4-methoxybenzoate

Bin Wei ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: seuwei@126.com

(Received 11 June 2011; accepted 6 July 2011; online 30 July 2011)

In the crystal of the title molecular salt, C₆H₁₄N⁺·C₈H₇O₃⁻, strong N—H⋯O hydrogen bonds are formed between the ammonium H atoms and the carboxylate O atoms. The resulting supramolecular structure is based on chains running in the [010] direction. The dihedral angle between the –CO₂ group and the benzene ring is 8.94 (17)° and the methoxy C atom deviates by 1.374 Å from the ring.

Related literature

The title compound was studied during our search for aromatic compounds containing ammonium salts or amidogens having dielectric–ferroelectric properties (Wu et al., 2011 ). For general background on ferroelectric metal-organic frameworks, see: Ye et al. (2006 ); Zhang et al. (2008 , 2010 ); Fu et al. (2009 ).

Experimental

Crystal data

C₆H₁₄N⁺·C₈H₇O₃⁻
M_r = 251.32
Monoclinic, P 2₁
a = 8.9076 (18) Å
b = 6.6025 (13) Å
c = 11.778 (2) Å
β = 102.85 (3)°
V = 675.3 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.2 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.842, T_max = 1.000
7050 measured reflections
1685 independent reflections
1460 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.095
S = 1.08
1685 reflections
165 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O1	0.89	1.86	2.744 (3)	173
N1—H1A⋯O2ⁱ	0.89	1.91	2.787 (2)	167
N1—H1B⋯O2ⁱⁱ	0.89	1.95	2.830 (3)	168
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+1]$ ; (ii) x, y+1, z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811027127/bh2364sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027127/bh2364Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027127/bh2364Isup3.cml

checkCIF report

Comment top

Our research deals with new dielectric-ferroelectric materials. Recent studies have revealed that organic salt compounds which have one or more amidogens probably have this kind of property (Fu et al., 2009; Zhang et al., 2008, 2010; Ye et al., 2006). Thus, we are searching for aromatic compounds containing amidogens having dielectric-ferroelectric properties (Wu et al., 2011). Unfortunately, the dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent below the melting point of the salt (413 K – 415 K). We have found that cyclohexylammonium 4-methoxybenzoate has no dielectric inhomogeneity from 80 K to 405 K. Herein, we describe the crystal structure of this compound.

The asymmetric unit of the title compound consists of a cyclohexylammonium cation, and a 4-methoxybenzoate anion (Fig. 1). Strong N—H···O hydrogen bonds are formed between the H atoms of the ammonium group and the O atoms of the carboxylate group, which also make great contribution to the stability of the crystal structure, linking the cations and anions into chains along the b axis (Table 1 and Fig. 2).

Related literature top

The title compound was studied during our search for aromatic compounds containing amidogens having dielectric-ferroelectric properties (Wu et al., 2011). For general background on ferroelectric metal-organic frameworks, see: Ye et al. (2006); Zhang et al. (2008, 2010); Fu et al. (2009).

Experimental top

The title compound was obtained by addition of para-methoxybenzoic acid (1.52 g, 0.01 mol) to a solution of cyclohexylamine (1.02 g, 0.01 mol) in methanol, in the stoichiometric ratio 1:1. Good quality single crystals were obtained by slow evaporation after two days (the chemical yield is 45%).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, along the a axis. Dashed lines indicate hydrogen bonds.

Cyclohexylammonium 4-methoxybenzoate top

Crystal data top

C₆H₁₄N⁺·C₈H₇O₃⁻	F(000) = 272
M_r = 251.32	D_x = 1.236 Mg m⁻³
Monoclinic, P2₁	Melting point: 413 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 8.9076 (18) Å	θ = 6.2–55.3°
b = 6.6025 (13) Å	µ = 0.09 mm⁻¹
c = 11.778 (2) Å	T = 293 K
β = 102.85 (3)°	Prism, colourless
V = 675.3 (2) Å³	0.2 × 0.2 × 0.2 mm
Z = 2

Data collection top

Rigaku Mercury CCD diffractometer	1685 independent reflections
Radiation source: fine-focus sealed tube	1460 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.2°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −8→8
T_min = 0.842, T_max = 1.000	l = −15→15
7050 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0414P)² + 0.1056P] where P = (F_o² + 2F_c²)/3
1685 reflections	(Δ/σ)_max < 0.001
165 parameters	Δρ_max = 0.14 e Å⁻³
1 restraint	Δρ_min = −0.18 e Å⁻³
0 constraints

Crystal data top

C₆H₁₄N⁺·C₈H₇O₃⁻	V = 675.3 (2) Å³
M_r = 251.32	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 8.9076 (18) Å	µ = 0.09 mm⁻¹
b = 6.6025 (13) Å	T = 293 K
c = 11.778 (2) Å	0.2 × 0.2 × 0.2 mm
β = 102.85 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	1685 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1460 reflections with I > 2σ(I)
T_min = 0.842, T_max = 1.000	R_int = 0.030
7050 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	1 restraint
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	Δρ_max = 0.14 e Å⁻³
1685 reflections	Δρ_min = −0.18 e Å⁻³
165 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.1890 (3)	−0.1036 (5)	1.0959 (2)	0.0572 (7)
H1D	0.1425	−0.1725	1.0250	0.086*
H1E	0.1322	−0.1329	1.1543	0.086*
H1F	0.2934	−0.1488	1.1222	0.086*
C2	0.2544 (3)	0.1768 (4)	0.9883 (2)	0.0408 (6)
C3	0.2302 (3)	0.3798 (4)	0.9597 (2)	0.0459 (6)
H3	0.1750	0.4605	1.0007	0.055*
C4	0.2879 (3)	0.4619 (3)	0.8707 (2)	0.0390 (5)
H4	0.2723	0.5987	0.8530	0.047*
C5	0.3689 (2)	0.3440 (3)	0.80676 (18)	0.0320 (5)
C6	0.3940 (3)	0.1422 (4)	0.83805 (19)	0.0381 (5)
H6	0.4490	0.0612	0.7971	0.046*
C7	0.3391 (3)	0.0583 (4)	0.9290 (2)	0.0420 (6)
H7	0.3592	−0.0766	0.9498	0.050*
C8	0.4250 (2)	0.4355 (3)	0.70654 (19)	0.0338 (5)
C9	0.7266 (2)	0.9048 (4)	0.64892 (18)	0.0352 (5)
H9	0.7382	0.9081	0.7336	0.042*
C10	0.7925 (3)	0.7064 (4)	0.6172 (3)	0.0476 (6)
H10A	0.7763	0.6960	0.5332	0.057*
H10B	0.7396	0.5943	0.6445	0.057*
C11	0.9646 (3)	0.6941 (4)	0.6720 (3)	0.0562 (7)
H11A	0.9796	0.6892	0.7561	0.067*
H11B	1.0061	0.5703	0.6468	0.067*
C12	1.0512 (3)	0.8741 (5)	0.6383 (2)	0.0534 (7)
H12A	1.1587	0.8656	0.6782	0.064*
H12B	1.0458	0.8710	0.5552	0.064*
C13	0.9841 (3)	1.0711 (4)	0.6698 (3)	0.0533 (7)
H13A	1.0376	1.1837	0.6435	0.064*
H13B	0.9994	1.0805	0.7538	0.064*
C14	0.8118 (3)	1.0854 (4)	0.6142 (2)	0.0435 (6)
H14A	0.7704	1.2094	0.6391	0.052*
H14B	0.7970	1.0896	0.5301	0.052*
N1	0.5590 (2)	0.9176 (3)	0.59367 (15)	0.0354 (4)
H1A	0.5457	0.9073	0.5167	0.053*
H1B	0.5221	1.0358	0.6114	0.053*
H1C	0.5093	0.8172	0.6199	0.053*
O1	0.4131 (2)	0.6223 (3)	0.69286 (16)	0.0517 (5)
O2	0.47886 (19)	0.3187 (3)	0.64103 (13)	0.0452 (4)
O3	0.1875 (2)	0.1079 (3)	1.07544 (16)	0.0599 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0654 (16)	0.0534 (16)	0.0579 (16)	−0.0038 (15)	0.0249 (13)	0.0187 (15)
C2	0.0483 (13)	0.0402 (13)	0.0366 (12)	−0.0055 (11)	0.0155 (10)	0.0006 (10)
C3	0.0602 (15)	0.0351 (12)	0.0500 (14)	−0.0010 (12)	0.0284 (11)	−0.0100 (11)
C4	0.0459 (13)	0.0288 (11)	0.0453 (13)	0.0011 (10)	0.0162 (10)	−0.0006 (9)
C5	0.0312 (10)	0.0313 (12)	0.0329 (10)	−0.0017 (9)	0.0058 (8)	−0.0004 (9)
C6	0.0429 (12)	0.0343 (12)	0.0392 (12)	0.0056 (10)	0.0138 (9)	0.0000 (10)
C7	0.0534 (14)	0.0319 (12)	0.0426 (13)	0.0034 (11)	0.0148 (11)	0.0049 (10)
C8	0.0316 (10)	0.0354 (13)	0.0351 (11)	0.0018 (9)	0.0089 (8)	0.0038 (9)
C9	0.0406 (11)	0.0329 (11)	0.0327 (11)	0.0030 (10)	0.0096 (8)	0.0015 (9)
C10	0.0499 (15)	0.0259 (12)	0.0675 (18)	0.0038 (10)	0.0138 (13)	−0.0009 (11)
C11	0.0535 (16)	0.0412 (15)	0.0723 (19)	0.0159 (13)	0.0103 (14)	0.0038 (13)
C12	0.0419 (13)	0.0561 (18)	0.0619 (16)	0.0085 (13)	0.0111 (11)	−0.0013 (14)
C13	0.0448 (14)	0.0416 (16)	0.0712 (18)	−0.0015 (12)	0.0085 (13)	−0.0071 (13)
C14	0.0449 (14)	0.0298 (12)	0.0561 (15)	0.0005 (10)	0.0115 (12)	−0.0008 (11)
N1	0.0432 (10)	0.0296 (9)	0.0365 (9)	0.0016 (8)	0.0155 (7)	0.0016 (8)
O1	0.0631 (11)	0.0335 (9)	0.0680 (12)	0.0048 (9)	0.0350 (9)	0.0120 (9)
O2	0.0629 (11)	0.0387 (9)	0.0398 (9)	0.0088 (8)	0.0241 (8)	0.0046 (8)
O3	0.0912 (14)	0.0467 (11)	0.0552 (11)	−0.0064 (11)	0.0446 (10)	0.0020 (9)

Geometric parameters (Å, º) top

C1—O3	1.417 (3)	C9—C14	1.518 (3)
C1—H1D	0.9600	C9—H9	0.9800
C1—H1E	0.9600	C10—C11	1.528 (4)
C1—H1F	0.9600	C10—H10A	0.9700
C2—O3	1.374 (3)	C10—H10B	0.9700
C2—C7	1.380 (3)	C11—C12	1.517 (4)
C2—C3	1.387 (4)	C11—H11A	0.9700
C3—C4	1.376 (3)	C11—H11B	0.9700
C3—H3	0.9300	C12—C13	1.511 (4)
C4—C5	1.392 (3)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C5—C6	1.387 (3)	C13—C14	1.532 (4)
C5—C8	1.507 (3)	C13—H13A	0.9700
C6—C7	1.389 (3)	C13—H13B	0.9700
C6—H6	0.9300	C14—H14A	0.9700
C7—H7	0.9300	C14—H14B	0.9700
C8—O1	1.246 (3)	N1—H1A	0.8900
C8—O2	1.259 (3)	N1—H1B	0.8900
C9—N1	1.492 (3)	N1—H1C	0.8900
C9—C10	1.516 (3)

O3—C1—H1D	109.5	C11—C10—H10A	109.6
O3—C1—H1E	109.5	C9—C10—H10B	109.6
H1D—C1—H1E	109.5	C11—C10—H10B	109.6
O3—C1—H1F	109.5	H10A—C10—H10B	108.1
H1D—C1—H1F	109.5	C12—C11—C10	111.6 (2)
H1E—C1—H1F	109.5	C12—C11—H11A	109.3
O3—C2—C7	124.6 (2)	C10—C11—H11A	109.3
O3—C2—C3	115.6 (2)	C12—C11—H11B	109.3
C7—C2—C3	119.9 (2)	C10—C11—H11B	109.3
C4—C3—C2	120.1 (2)	H11A—C11—H11B	108.0
C4—C3—H3	119.9	C13—C12—C11	111.0 (2)
C2—C3—H3	119.9	C13—C12—H12A	109.4
C3—C4—C5	121.2 (2)	C11—C12—H12A	109.4
C3—C4—H4	119.4	C13—C12—H12B	109.4
C5—C4—H4	119.4	C11—C12—H12B	109.4
C6—C5—C4	117.8 (2)	H12A—C12—H12B	108.0
C6—C5—C8	122.08 (19)	C12—C13—C14	111.2 (2)
C4—C5—C8	120.14 (19)	C12—C13—H13A	109.4
C5—C6—C7	121.7 (2)	C14—C13—H13A	109.4
C5—C6—H6	119.2	C12—C13—H13B	109.4
C7—C6—H6	119.2	C14—C13—H13B	109.4
C2—C7—C6	119.4 (2)	H13A—C13—H13B	108.0
C2—C7—H7	120.3	C9—C14—C13	110.5 (2)
C6—C7—H7	120.3	C9—C14—H14A	109.6
O1—C8—O2	124.1 (2)	C13—C14—H14A	109.6
O1—C8—C5	117.7 (2)	C9—C14—H14B	109.6
O2—C8—C5	118.20 (19)	C13—C14—H14B	109.6
N1—C9—C10	110.26 (19)	H14A—C14—H14B	108.1
N1—C9—C14	110.48 (18)	C9—N1—H1A	109.5
C10—C9—C14	111.59 (17)	C9—N1—H1B	109.5
N1—C9—H9	108.1	H1A—N1—H1B	109.5
C10—C9—H9	108.1	C9—N1—H1C	109.5
C14—C9—H9	108.1	H1A—N1—H1C	109.5
C9—C10—C11	110.5 (2)	H1B—N1—H1C	109.5
C9—C10—H10A	109.6	C2—O3—C1	117.6 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	1.86	2.744 (3)	173
N1—H1A···O2ⁱ	0.89	1.91	2.787 (2)	167
N1—H1B···O2ⁱⁱ	0.89	1.95	2.830 (3)	168

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

Experimental details

Crystal data
Chemical formula	C₆H₁₄N⁺·C₈H₇O₃⁻
M_r	251.32
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	8.9076 (18), 6.6025 (13), 11.778 (2)
β (°)	102.85 (3)
V (Å³)	675.3 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.842, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7050, 1685, 1460
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.095, 1.08
No. of reflections	1685
No. of parameters	165
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.18

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O1	0.89	1.86	2.744 (3)	172.9
N1—H1A···O2ⁱ	0.89	1.91	2.787 (2)	166.5
N1—H1B···O2ⁱⁱ	0.89	1.95	2.830 (3)	168.0

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

Acknowledgements

The author is grateful to the starter fund of Southeast University for the purchase of the diffractometer.

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