Diisopropyl­ammonium 4-meth­oxy­benzoate

Wei, B.

doi:10.1107/S1600536811023762

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1865

doi:10.1107/S1600536811023762

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Diisopropylammonium 4-methoxybenzoate

Bin Wei ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: seuwei@126.com

(Received 9 May 2011; accepted 17 June 2011; online 30 June 2011)

In the crystal structure of the title compound, C₆H₁₆N⁺·C₈H₇O₃⁻, intermolecular N—H⋯O hydrogen bonds link the cations and anions into arrangements consisting of two cations and two anions each.

Related literature

For background to organic phase-transition materials, see: Fu et al. (2009 ); Rheinstädter et al. (2002 ); Wu et al. (2011 ).

Experimental

Crystal data

C₆H₁₆N⁺·C₈H₇O₃⁻
M_r = 253.33
Triclinic, $[P \overline 1]$
a = 7.3265 (15) Å
b = 8.8808 (18) Å
c = 12.107 (2) Å
α = 87.83 (3)°
β = 77.83 (3)°
γ = 83.44 (3)°
V = 764.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.842, T_max = 1.000
7992 measured reflections
3501 independent reflections
1945 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.163
S = 1.04
3501 reflections
168 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3ⁱ	0.90	1.84	2.720 (2)	166
N1—H1A⋯O2ⁱⁱ	0.90	1.83	2.721 (2)	169
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y+1, -z+1.

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/S1600536811023762/im2287sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023762/im2287Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811023762/im2287Isup3.cml

checkCIF report

Comment top

One of our main research topics is the search for new dielectric-ferroelectric materials. Recent studies have revealed that organic salts might also have this kind of character (Fu et al., 2009; Rheinstädter et al., 2002; Wu et al., 2011). The dielectric constant of the title compound, diisopropylammonium 4-methoxy-benzoate, as a function of temperature indicates that the permittivity is basically temperature-independent. Below the melting point (438–440 K) of the title compound, we have found no dielectric disuniform 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 diisopropylammonium cation and a 4-methoxybenzoate anion (Fig. 1). Intermolecular N—H···O hydrogen bonds (N1–H1A···O2 1.832 (2) Å, N1–H1B···O3 1.838 (2) Å) link the cations and anions into planar arrangements of two cations and anions each (Fig. 2 and Tab. 1).

Related literature top

For background to organic phase-transition materials, see: Fu et al. (2009); Rheinstädter et al. (2002); Wu et al. (2011).

Experimental top

The title compound was obtained by the addition of para-methoxybenzoic acid (1.52 g, 0.01 mol) to a solution of diisopropylamine (1.02 g, 0.01 mol) in methanol in a 1: 1 ratio. Good quality single crystals were obtained by slow evaporation of the solvent after two days (yield: 37%).

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: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Packing of the title compound, stacking along the a axis. Dashed lines indicate hydrogen bonds.

Diisopropylammonium 4-methoxybenzoate top

Crystal data top

C₆H₁₆N⁺·C₈H₇O₃⁻	V = 764.9 (3) Å³
M_r = 253.33	Z = 2
Triclinic, P1	F(000) = 276
Hall symbol: -P 1	D_x = 1.100 Mg m⁻³
a = 7.3265 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8808 (18) Å	θ = 6.2–55.3°
c = 12.107 (2) Å	µ = 0.08 mm⁻¹
α = 87.83 (3)°	T = 293 K
β = 77.83 (3)°	Prism, colorless
γ = 83.44 (3)°	0.20 × 0.20 × 0.20 mm

Data collection top

Rigaku Mercury CCD diffractometer	3501 independent reflections
Radiation source: fine-focus sealed tube	1945 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −11→11
T_min = 0.842, T_max = 1.000	l = −15→15
7992 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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.163	w = 1/[σ²(F_o²) + (0.0667P)² + 0.0936P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
3501 reflections	Δρ_max = 0.14 e Å⁻³
168 parameters	Δρ_min = −0.20 e Å⁻³
0 restraints	Extinction correction: SHELXS97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0000

Crystal data top

C₆H₁₆N⁺·C₈H₇O₃⁻	γ = 83.44 (3)°
M_r = 253.33	V = 764.9 (3) Å³
Triclinic, P1	Z = 2
a = 7.3265 (15) Å	Mo Kα radiation
b = 8.8808 (18) Å	µ = 0.08 mm⁻¹
c = 12.107 (2) Å	T = 293 K
α = 87.83 (3)°	0.20 × 0.20 × 0.20 mm
β = 77.83 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	3501 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1945 reflections with I > 2σ(I)
T_min = 0.842, T_max = 1.000	R_int = 0.027
7992 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.163	H-atom parameters constrained
S = 1.04	Δρ_max = 0.14 e Å⁻³
3501 reflections	Δρ_min = −0.20 e Å⁻³
168 parameters

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
C5	0.3367 (2)	0.7243 (2)	0.69733 (13)	0.0464 (4)
O2	0.4300 (2)	0.49545 (18)	0.78584 (12)	0.0787 (5)
C2	0.2819 (3)	0.8953 (2)	0.50734 (15)	0.0535 (5)
N1	0.2941 (2)	0.64829 (17)	0.11683 (11)	0.0526 (4)
H1A	0.3909	0.5944	0.1403	0.063*
H1B	0.3233	0.6510	0.0408	0.063*
C3	0.3349 (3)	0.7417 (2)	0.49873 (15)	0.0610 (5)
H3	0.3531	0.6951	0.4292	0.073*
C6	0.2841 (2)	0.8778 (2)	0.70400 (14)	0.0533 (5)
H6	0.2659	0.9246	0.7735	0.064*
O1	0.2546 (2)	0.96828 (17)	0.40924 (11)	0.0763 (5)
C8	0.3735 (3)	0.6323 (3)	0.79925 (16)	0.0570 (5)
C7	0.2573 (3)	0.9648 (2)	0.60979 (16)	0.0572 (5)
H7	0.2232	1.0688	0.6159	0.069*
O3	0.3476 (2)	0.70132 (19)	0.89014 (11)	0.0877 (5)
C4	0.3609 (3)	0.6570 (2)	0.59302 (15)	0.0541 (5)
H4	0.3951	0.5531	0.5866	0.065*
C12	0.2805 (3)	0.8068 (2)	0.15741 (17)	0.0678 (6)
H12	0.2411	0.8061	0.2400	0.081*
C1	0.2132 (3)	1.1280 (3)	0.4104 (2)	0.0807 (7)
H1C	0.0956	1.1550	0.4615	0.121*
H1D	0.2050	1.1645	0.3358	0.121*
H1E	0.3110	1.1729	0.4347	0.121*
C9	0.1253 (3)	0.5634 (3)	0.15227 (18)	0.0706 (6)
H9	0.0195	0.6204	0.1260	0.085*
C10	0.1664 (3)	0.4115 (3)	0.0961 (2)	0.0842 (7)
H10A	0.2012	0.4256	0.0157	0.126*
H10B	0.0565	0.3585	0.1142	0.126*
H10C	0.2677	0.3533	0.1227	0.126*
C13	0.1367 (4)	0.9106 (3)	0.1084 (2)	0.1088 (10)
H13A	0.1710	0.9092	0.0274	0.163*
H13B	0.1334	1.0121	0.1340	0.163*
H13C	0.0150	0.8760	0.1329	0.163*
C14	0.4734 (4)	0.8603 (3)	0.1257 (2)	0.0937 (8)
H14A	0.5591	0.7954	0.1610	0.141*
H14B	0.4676	0.9623	0.1507	0.141*
H14C	0.5162	0.8570	0.0451	0.141*
C11	0.0733 (4)	0.5482 (4)	0.2805 (2)	0.1119 (10)
H11A	0.1810	0.5040	0.3084	0.168*
H11B	−0.0262	0.4844	0.3013	0.168*
H11C	0.0323	0.6466	0.3127	0.168*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C5	0.0389 (9)	0.0635 (12)	0.0368 (9)	−0.0063 (8)	−0.0079 (7)	0.0001 (8)
O2	0.1004 (12)	0.0710 (10)	0.0741 (10)	−0.0030 (9)	−0.0451 (9)	0.0112 (8)
C2	0.0514 (11)	0.0669 (13)	0.0438 (10)	−0.0079 (9)	−0.0145 (8)	0.0084 (9)
N1	0.0586 (9)	0.0630 (10)	0.0373 (7)	−0.0025 (8)	−0.0151 (7)	0.0005 (6)
C3	0.0759 (14)	0.0706 (14)	0.0386 (10)	−0.0052 (11)	−0.0176 (9)	−0.0056 (9)
C6	0.0517 (11)	0.0665 (13)	0.0408 (10)	−0.0013 (9)	−0.0092 (8)	−0.0081 (8)
O1	0.0980 (11)	0.0798 (10)	0.0548 (8)	−0.0058 (8)	−0.0292 (8)	0.0167 (7)
C8	0.0519 (11)	0.0781 (15)	0.0445 (10)	−0.0100 (10)	−0.0173 (8)	0.0063 (9)
C7	0.0594 (12)	0.0556 (11)	0.0563 (11)	−0.0009 (9)	−0.0144 (9)	−0.0006 (9)
O3	0.1175 (13)	0.1062 (12)	0.0389 (8)	0.0002 (10)	−0.0225 (8)	0.0049 (8)
C4	0.0600 (11)	0.0559 (11)	0.0471 (10)	−0.0022 (9)	−0.0144 (8)	−0.0029 (8)
C12	0.0924 (16)	0.0619 (13)	0.0492 (11)	−0.0001 (12)	−0.0180 (11)	−0.0074 (9)
C1	0.0791 (16)	0.0799 (16)	0.0873 (16)	−0.0149 (13)	−0.0294 (12)	0.0331 (12)
C9	0.0568 (12)	0.0953 (17)	0.0628 (13)	−0.0142 (12)	−0.0156 (10)	−0.0068 (11)
C10	0.0764 (16)	0.0961 (18)	0.0887 (17)	−0.0278 (13)	−0.0257 (13)	−0.0091 (14)
C13	0.124 (2)	0.0868 (18)	0.108 (2)	0.0388 (17)	−0.0293 (18)	−0.0183 (15)
C14	0.116 (2)	0.0678 (15)	0.1050 (19)	−0.0272 (15)	−0.0328 (16)	0.0033 (13)
C11	0.109 (2)	0.157 (3)	0.0698 (16)	−0.069 (2)	0.0121 (14)	−0.0062 (16)

Geometric parameters (Å, º) top

C5—C6	1.374 (2)	C12—C13	1.520 (3)
C5—C4	1.387 (2)	C12—H12	0.9800
C5—C8	1.509 (2)	C1—H1C	0.9600
O2—C8	1.244 (2)	C1—H1D	0.9600
C2—O1	1.372 (2)	C1—H1E	0.9600
C2—C7	1.375 (3)	C9—C10	1.505 (3)
C2—C3	1.376 (3)	C9—C11	1.523 (3)
N1—C12	1.494 (2)	C9—H9	0.9800
N1—C9	1.499 (2)	C10—H10A	0.9600
N1—H1A	0.9000	C10—H10B	0.9600
N1—H1B	0.9000	C10—H10C	0.9600
C3—C4	1.379 (2)	C13—H13A	0.9600
C3—H3	0.9300	C13—H13B	0.9600
C6—C7	1.389 (3)	C13—H13C	0.9600
C6—H6	0.9300	C14—H14A	0.9600
O1—C1	1.417 (3)	C14—H14B	0.9600
C8—O3	1.249 (2)	C14—H14C	0.9600
C7—H7	0.9300	C11—H11A	0.9600
C4—H4	0.9300	C11—H11B	0.9600
C12—C14	1.511 (3)	C11—H11C	0.9600

C6—C5—C4	117.94 (16)	O1—C1—H1D	109.5
C6—C5—C8	121.22 (16)	H1C—C1—H1D	109.5
C4—C5—C8	120.81 (17)	O1—C1—H1E	109.5
O1—C2—C7	124.49 (18)	H1C—C1—H1E	109.5
O1—C2—C3	115.47 (17)	H1D—C1—H1E	109.5
C7—C2—C3	120.04 (17)	N1—C9—C10	108.59 (17)
C12—N1—C9	117.80 (16)	N1—C9—C11	110.65 (17)
C12—N1—H1A	107.9	C10—C9—C11	111.9 (2)
C9—N1—H1A	107.9	N1—C9—H9	108.5
C12—N1—H1B	107.9	C10—C9—H9	108.5
C9—N1—H1B	107.9	C11—C9—H9	108.5
H1A—N1—H1B	107.2	C9—C10—H10A	109.5
C2—C3—C4	120.11 (17)	C9—C10—H10B	109.5
C2—C3—H3	119.9	H10A—C10—H10B	109.5
C4—C3—H3	119.9	C9—C10—H10C	109.5
C5—C6—C7	121.78 (17)	H10A—C10—H10C	109.5
C5—C6—H6	119.1	H10B—C10—H10C	109.5
C7—C6—H6	119.1	C12—C13—H13A	109.5
C2—O1—C1	118.28 (16)	C12—C13—H13B	109.5
O2—C8—O3	125.35 (18)	H13A—C13—H13B	109.5
O2—C8—C5	117.80 (17)	C12—C13—H13C	109.5
O3—C8—C5	116.83 (19)	H13A—C13—H13C	109.5
C2—C7—C6	119.14 (18)	H13B—C13—H13C	109.5
C2—C7—H7	120.4	C12—C14—H14A	109.5
C6—C7—H7	120.4	C12—C14—H14B	109.5
C3—C4—C5	120.98 (18)	H14A—C14—H14B	109.5
C3—C4—H4	119.5	C12—C14—H14C	109.5
C5—C4—H4	119.5	H14A—C14—H14C	109.5
N1—C12—C14	108.13 (18)	H14B—C14—H14C	109.5
N1—C12—C13	111.18 (18)	C9—C11—H11A	109.5
C14—C12—C13	111.6 (2)	C9—C11—H11B	109.5
N1—C12—H12	108.6	H11A—C11—H11B	109.5
C14—C12—H12	108.6	C9—C11—H11C	109.5
C13—C12—H12	108.6	H11A—C11—H11C	109.5
O1—C1—H1C	109.5	H11B—C11—H11C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3ⁱ	0.90	1.84	2.720 (2)	166
N1—H1A···O2ⁱⁱ	0.90	1.83	2.721 (2)	169

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

Experimental details

Crystal data
Chemical formula	C₆H₁₆N⁺·C₈H₇O₃⁻
M_r	253.33
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.3265 (15), 8.8808 (18), 12.107 (2)
α, β, γ (°)	87.83 (3), 77.83 (3), 83.44 (3)
V (Å³)	764.9 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.20 × 0.20 × 0.20

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	7992, 3501, 1945
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.163, 1.04
No. of reflections	3501
No. of parameters	168
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.20

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3ⁱ	0.90	1.84	2.720 (2)	166
N1—H1A···O2ⁱⁱ	0.90	1.83	2.721 (2)	169

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

Acknowledgements

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

References

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