Diethyl­ammonium 4-hy­droxy­benzoate

Lu, Y.-H.

doi:10.1107/S1600536810040523

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2920

https://doi.org/10.1107/S1600536810040523

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Diethylammonium 4-hydroxybenzoate

Yong-Hong Lu ^a ^*

^aOrdered Matter Science Reserch Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: chmsunbw@seu.edu.cn

(Received 21 June 2010; accepted 9 October 2010; online 23 October 2010)

In the crystal structure of the title compound, C₄H₁₂N⁺·C₇H₅O₃⁻, the cations and anions are linked by N—H⋯O and O—H⋯O hydrogen bonds, leading to the formation of a three-dimensional network.

Related literature

Hydrogen bonds in co-crystals have been widely used to design and synthesize one-, two- and three-dimensional supramolecular compounds, see: Aakeroÿ et al. (2002 ). 4-Hydroxybenzoic acid is a good hydrogen bond donor and can form co-crystals with other organic molecules, see: Vishweshwar et al. (2003 ).

Experimental

Crystal data

C₄H₁₂N⁺·C₇H₅O₃⁻
M_r = 211.26
Orthorhombic, P b c a
a = 12.1270 (13) Å
b = 10.6829 (11) Å
c = 17.6066 (15) Å
V = 2281.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.43 × 0.41 × 0.20 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.963, T_max = 0.982
8818 measured reflections
2016 independent reflections
1155 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.130
S = 1.06
2016 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.90	2.15	2.873 (3)	137
N1—H1A⋯O1ⁱ	0.90	2.16	3.022 (3)	162
N1—H1B⋯O2ⁱⁱ	0.90	1.83	2.724 (3)	174
O3—H3⋯O1ⁱⁱⁱ	0.82	1.82	2.635 (3)	170
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (iii) $[x+{\script{1\over 2}}, y, -z+{\script{3\over 2}}]$ .

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 global, I. DOI: https://doi.org/10.1107/S1600536810040523/fl2305sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040523/fl2305Isup2.hkl

checkCIF report

Comment top

In recent years, study of co-crystals has attracted a great many chemists' interest since they can be exploited to improve the physical and/or chemical properties of active pharmaceutical ingredients (APIs). The hydrogen bonds in co-crystals have been widely used to design and synthesize one-, two- and three-dimensional supramolecular compounds (Aakeroÿ et al., 2002).Research into hydrogen bonds experienced a stagnant period in the 1980 s, but re-opened around 1990, and has been in rapid development since then. 4-Hydroxybenzoic acid is a good hydrogen bond donor and can form co-crystals with other organic molecules (Vishweshwar et al., 2003). In this paper, we used 4-Hydroxybenzoic acid and diethylamine to synthesize the co-crystal compound (I).

Compound (I) consists of a diethylamine cation and a 4-hydroxybenzoic acid anion (Fig. 1), therefore, it is a molecular salt. The –NH2 groups of the cations act as hydrogen-bond donors to the O atoms of the carboxyl group of the anions. Moreover, the hydroxyl H atom of the anions also act as hydrogen-bond donors to tone of the O atoms of a neighboring carboxyl group of the 4-hydroxybenzoic acid anions to form a three-dimension network (Fig. 2 and Table 1). One of the H atoms of the –NH2 group links to both O atoms of the –COOH group in an adjacent molecule via two N—H···O bonds such that two cations and two anions are linked by hydrogen bonds to form an eight-membered ring.

Related literature top

Hydrogen bonds in co-crystals have been widely used to design and synthesize one-, two- and three-dimensional supramolecular compounds, see: Aakeroÿ et al. (2002). 4-Hydroxybenzoic acid is a good hydrogen bond donor and can form co-crystals with other organic molecules, see: Vishweshwar et al. (2003).

Experimental top

All reagents were commercially available and of analytical grade. 4- Hydroxybenzoic acid (0.78 mmol, 0.108 g) and diethylamine (0.78 mmol, 0.057 g) were dissolved in ethanol (15 ml). The mixture was stirred for 10 min at room temperature and then filtered. Colorless crystals suitable for data collection were obtained after several days.

Structure description top

Hydrogen bonds in co-crystals have been widely used to design and synthesize one-, two- and three-dimensional supramolecular compounds, see: Aakeroÿ et al. (2002). 4-Hydroxybenzoic acid is a good hydrogen bond donor and can form co-crystals with other organic molecules, see: Vishweshwar et al. (2003).

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 (I)
	Fig. 2. A view of the hydrogen-bonding patterns in (I). Dashed lines indicate hydrgen bonding.

Diethylammonium 4-hydroxybenzoate top

Crystal data top

C₄H₁₂N⁺·C₇H₅O₃⁻	F(000) = 912
M_r = 211.26	D_x = 1.230 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 4113 reflections
a = 12.1270 (13) Å	θ = 2.4–27.4°
b = 10.6829 (11) Å	µ = 0.09 mm⁻¹
c = 17.6066 (15) Å	T = 298 K
V = 2281.0 (4) Å³	Prism, colourless
Z = 8	0.43 × 0.41 × 0.20 mm

Data collection top

Rigaku Mercury diffractometer	2016 independent reflections
Radiation source: fine-focus sealed tube	1155 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −7→14
T_min = 0.963, T_max = 0.982	k = −12→9
8818 measured reflections	l = −20→20

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0464P)² + 0.8922P] where P = (F_o² + 2F_c²)/3
2016 reflections	(Δ/σ)_max < 0.001
138 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₄H₁₂N⁺·C₇H₅O₃⁻	V = 2281.0 (4) Å³
M_r = 211.26	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.1270 (13) Å	µ = 0.09 mm⁻¹
b = 10.6829 (11) Å	T = 298 K
c = 17.6066 (15) Å	0.43 × 0.41 × 0.20 mm

Data collection top

Rigaku Mercury diffractometer	2016 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1155 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.982	R_int = 0.048
8818 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.06	Δρ_max = 0.21 e Å⁻³
2016 reflections	Δρ_min = −0.21 e Å⁻³
138 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
N1	0.15290 (17)	0.4229 (2)	0.46227 (12)	0.0500 (6)
H1A	0.1303	0.3844	0.5050	0.060*
H1B	0.0985	0.4747	0.4474	0.060*
O1	0.39118 (14)	0.74534 (19)	0.59243 (10)	0.0538 (5)
O2	0.49892 (17)	0.9105 (2)	0.58731 (11)	0.0685 (6)
O3	0.75558 (15)	0.59440 (17)	0.83491 (10)	0.0597 (6)
H3	0.7969	0.6470	0.8534	0.090*
C1	0.4739 (2)	0.8063 (3)	0.61463 (14)	0.0449 (7)
C2	0.54591 (19)	0.7521 (2)	0.67521 (13)	0.0371 (6)
C3	0.62071 (19)	0.8261 (2)	0.71431 (13)	0.0420 (6)
H3A	0.6239	0.9113	0.7038	0.050*
C4	0.69034 (19)	0.7768 (2)	0.76835 (13)	0.0417 (6)
H4	0.7389	0.8286	0.7944	0.050*
C5	0.68774 (19)	0.6501 (2)	0.78369 (13)	0.0412 (6)
C6	0.61259 (19)	0.5748 (2)	0.74597 (14)	0.0451 (7)
H6	0.6095	0.4896	0.7567	0.054*
C7	0.54265 (19)	0.6254 (2)	0.69286 (13)	0.0420 (6)
H7	0.4922	0.5740	0.6683	0.050*
C8	0.2517 (3)	0.4991 (3)	0.48039 (17)	0.0638 (8)
H8A	0.2304	0.5662	0.5144	0.077*
H8B	0.2791	0.5368	0.4340	0.077*
C9	0.3426 (2)	0.4254 (3)	0.51642 (18)	0.0724 (9)
H9A	0.3139	0.3792	0.5588	0.109*
H9B	0.3992	0.4815	0.5337	0.109*
H9C	0.3730	0.3684	0.4799	0.109*
C10	0.1689 (2)	0.3275 (3)	0.40308 (15)	0.0575 (8)
H10A	0.2266	0.2702	0.4187	0.069*
H10B	0.1924	0.3679	0.3565	0.069*
C11	0.0657 (3)	0.2559 (3)	0.3885 (2)	0.0845 (11)
H11A	0.0446	0.2118	0.4338	0.127*
H11B	0.0780	0.1969	0.3483	0.127*
H11C	0.0080	0.3126	0.3742	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0416 (13)	0.0629 (15)	0.0456 (12)	0.0035 (11)	0.0090 (10)	0.0040 (11)
O1	0.0427 (11)	0.0719 (13)	0.0467 (11)	−0.0014 (10)	−0.0083 (9)	0.0082 (9)
O2	0.0711 (14)	0.0676 (14)	0.0668 (13)	−0.0052 (11)	−0.0119 (11)	0.0315 (11)
O3	0.0530 (11)	0.0591 (12)	0.0670 (12)	−0.0036 (10)	−0.0217 (10)	0.0170 (10)
C1	0.0431 (16)	0.0561 (18)	0.0356 (14)	0.0077 (14)	0.0067 (12)	0.0044 (13)
C2	0.0336 (13)	0.0426 (15)	0.0352 (13)	0.0021 (12)	0.0047 (11)	0.0047 (11)
C3	0.0465 (15)	0.0369 (15)	0.0426 (14)	−0.0032 (12)	0.0029 (13)	0.0063 (12)
C4	0.0405 (15)	0.0444 (16)	0.0402 (14)	−0.0072 (12)	−0.0015 (12)	0.0011 (12)
C5	0.0359 (14)	0.0486 (16)	0.0390 (13)	0.0030 (12)	0.0003 (12)	0.0070 (12)
C6	0.0424 (15)	0.0390 (15)	0.0539 (16)	−0.0020 (13)	−0.0045 (13)	0.0076 (13)
C7	0.0350 (14)	0.0441 (16)	0.0467 (15)	−0.0049 (12)	−0.0022 (12)	0.0005 (13)
C8	0.067 (2)	0.0595 (19)	0.0652 (19)	−0.0111 (16)	0.0033 (16)	−0.0082 (16)
C9	0.0508 (19)	0.092 (2)	0.074 (2)	−0.0046 (18)	−0.0058 (16)	−0.0123 (19)
C10	0.0637 (19)	0.0506 (18)	0.0584 (17)	0.0002 (15)	0.0068 (15)	−0.0044 (14)
C11	0.076 (2)	0.086 (3)	0.091 (3)	−0.018 (2)	−0.028 (2)	−0.003 (2)

Geometric parameters (Å, º) top

N1—C10	1.470 (3)	C6—C7	1.373 (3)
N1—C8	1.483 (3)	C6—H6	0.9300
N1—H1A	0.9000	C7—H7	0.9300
N1—H1B	0.9000	C8—C9	1.495 (4)
O1—C1	1.259 (3)	C8—H8A	0.9700
O2—C1	1.249 (3)	C8—H8B	0.9700
O3—C5	1.358 (3)	C9—H9A	0.9600
O3—H3	0.8200	C9—H9B	0.9600
C1—C2	1.495 (3)	C9—H9C	0.9600
C2—C3	1.386 (3)	C10—C11	1.489 (4)
C2—C7	1.388 (3)	C10—H10A	0.9700
C3—C4	1.377 (3)	C10—H10B	0.9700
C3—H3A	0.9300	C11—H11A	0.9600
C4—C5	1.381 (3)	C11—H11B	0.9600
C4—H4	0.9300	C11—H11C	0.9600
C5—C6	1.385 (3)

C10—N1—C8	115.2 (2)	C6—C7—H7	119.4
C10—N1—H1A	108.5	C2—C7—H7	119.4
C8—N1—H1A	108.5	N1—C8—C9	113.4 (2)
C10—N1—H1B	108.5	N1—C8—H8A	108.9
C8—N1—H1B	108.5	C9—C8—H8A	108.9
H1A—N1—H1B	107.5	N1—C8—H8B	108.9
C5—O3—H3	109.5	C9—C8—H8B	108.9
O2—C1—O1	122.3 (2)	H8A—C8—H8B	107.7
O2—C1—C2	118.6 (3)	C8—C9—H9A	109.5
O1—C1—C2	119.1 (2)	C8—C9—H9B	109.5
C3—C2—C7	117.6 (2)	H9A—C9—H9B	109.5
C3—C2—C1	121.0 (2)	C8—C9—H9C	109.5
C7—C2—C1	121.4 (2)	H9A—C9—H9C	109.5
C4—C3—C2	121.8 (2)	H9B—C9—H9C	109.5
C4—C3—H3A	119.1	N1—C10—C11	111.6 (2)
C2—C3—H3A	119.1	N1—C10—H10A	109.3
C3—C4—C5	119.7 (2)	C11—C10—H10A	109.3
C3—C4—H4	120.1	N1—C10—H10B	109.3
C5—C4—H4	120.1	C11—C10—H10B	109.3
O3—C5—C4	123.1 (2)	H10A—C10—H10B	108.0
O3—C5—C6	117.6 (2)	C10—C11—H11A	109.5
C4—C5—C6	119.4 (2)	C10—C11—H11B	109.5
C7—C6—C5	120.3 (2)	H11A—C11—H11B	109.5
C7—C6—H6	119.9	C10—C11—H11C	109.5
C5—C6—H6	119.9	H11A—C11—H11C	109.5
C6—C7—C2	121.2 (2)	H11B—C11—H11C	109.5

O2—C1—C2—C3	16.5 (3)	C3—C4—C5—C6	−1.9 (4)
O1—C1—C2—C3	−164.2 (2)	O3—C5—C6—C7	−179.2 (2)
O2—C1—C2—C7	−161.6 (2)	C4—C5—C6—C7	1.1 (4)
O1—C1—C2—C7	17.7 (3)	C5—C6—C7—C2	0.5 (4)
C7—C2—C3—C4	0.5 (3)	C3—C2—C7—C6	−1.3 (4)
C1—C2—C3—C4	−177.6 (2)	C1—C2—C7—C6	176.8 (2)
C2—C3—C4—C5	1.1 (4)	C10—N1—C8—C9	−66.5 (3)
C3—C4—C5—O3	178.5 (2)	C8—N1—C10—C11	−179.9 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.90	2.15	2.873 (3)	137
N1—H1A···O1ⁱ	0.90	2.16	3.022 (3)	162
N1—H1B···O2ⁱⁱ	0.90	1.83	2.724 (3)	174
O3—H3···O1ⁱⁱⁱ	0.82	1.82	2.635 (3)	170

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x−1/2, −y+3/2, −z+1; (iii) x+1/2, y, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N⁺·C₇H₅O₃⁻
M_r	211.26
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	12.1270 (13), 10.6829 (11), 17.6066 (15)
V (Å³)	2281.0 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.43 × 0.41 × 0.20

Data collection
Diffractometer	Rigaku Mercury
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.963, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	8818, 2016, 1155
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.130, 1.06
No. of reflections	2016
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.21

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—H1A···O2ⁱ	0.90	2.15	2.873 (3)	136.5
N1—H1A···O1ⁱ	0.90	2.16	3.022 (3)	161.5
N1—H1B···O2ⁱⁱ	0.90	1.83	2.724 (3)	174.2
O3—H3···O1ⁱⁱⁱ	0.82	1.82	2.635 (3)	170.4

Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) x−1/2, −y+3/2, −z+1; (iii) x+1/2, y, −z+3/2.

References

Aakeroÿ, C. B., Beatty, A. M. & Helfrich, B. A. (2002). J. Am. Chem. Soc. 124, 14425–14432. Web of Science PubMed Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vishweshwar, P., Nangia, A. & Lynch, V. M. (2003). CrystEngComm, 5, 164–168. Web of Science CSD CrossRef CAS Google Scholar

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Volume 66| Part 11| November 2010| Page o2920

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