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Acta Cryst. (2010). E66, o2920    [ doi:10.1107/S1600536810040523 ]

Diethylammonium 4-hydroxybenzoate

Y.-H. Lu

Abstract top

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.

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.

Refinement top

The H atoms bonded to C atoms were positioned geometrically and refined as riding, with C—H = 0.93–0.97 Å and Uiso (H) = 1.2 or 1.5 Ueq (C) while the H atoms bonded to the N atom and the hydroxy group were located in a difference Fourier map, with N—H = 0.90 Å and O—H = 0.82 Å and then refined with a riding model as was used for the H atoms on the C atoms.

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
[Figure 1] Fig. 1. The molecular structure of (I)
[Figure 2] 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
Mr = 211.26Dx = 1.230 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 4113 reflections
a = 12.1270 (13) Åθ = 2.4–27.4°
b = 10.6829 (11) ŵ = 0.09 mm−1
c = 17.6066 (15) ÅT = 298 K
V = 2281.0 (4) Å3Prism, colourless
Z = 80.43 × 0.41 × 0.20 mm
Data collection top
Rigaku Mercury
diffractometer		2016 independent reflections
Radiation source: fine-focus sealed tube1155 reflections with I > 2σ(I)
graphiteRint = 0.048
ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		h = −7→14
Tmin = 0.963, Tmax = 0.982k = −12→9
8818 measured reflectionsl = −20→20
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0464P)2 + 0.8922P]
where P = (Fo2 + 2Fc2)/3
2016 reflections(Δ/σ)max < 0.001
138 parametersΔρmax = 0.21 e Å−3
0 restraintsΔρmin = −0.21 e Å−3
Crystal data top
C4H12N+·C7H5O3−V = 2281.0 (4) Å3
Mr = 211.26Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 12.1270 (13) ŵ = 0.09 mm−1
b = 10.6829 (11) ÅT = 298 K
c = 17.6066 (15) Å0.43 × 0.41 × 0.20 mm
Data collection top
Rigaku Mercury
diffractometer		1155 reflections with I > 2σ(I)
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)		Rint = 0.048
Tmin = 0.963, Tmax = 0.982θmax = 25.0°
8818 measured reflectionsStandard reflections: ?
2016 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.130Δρmax = 0.21 e Å−3
S = 1.06Δρmin = −0.21 e Å−3
2016 reflectionsAbsolute structure: ?
138 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
N10.15290 (17)0.4229 (2)0.46227 (12)0.0500 (6)
H1A0.13030.38440.50500.060*
H1B0.09850.47470.44740.060*
O10.39118 (14)0.74534 (19)0.59243 (10)0.0538 (5)
O20.49892 (17)0.9105 (2)0.58731 (11)0.0685 (6)
O30.75558 (15)0.59440 (17)0.83491 (10)0.0597 (6)
H30.79690.64700.85340.090*
C10.4739 (2)0.8063 (3)0.61463 (14)0.0449 (7)
C20.54591 (19)0.7521 (2)0.67521 (13)0.0371 (6)
C30.62071 (19)0.8261 (2)0.71431 (13)0.0420 (6)
H3A0.62390.91130.70380.050*
C40.69034 (19)0.7768 (2)0.76835 (13)0.0417 (6)
H40.73890.82860.79440.050*
C50.68774 (19)0.6501 (2)0.78369 (13)0.0412 (6)
C60.61259 (19)0.5748 (2)0.74597 (14)0.0451 (7)
H60.60950.48960.75670.054*
C70.54265 (19)0.6254 (2)0.69286 (13)0.0420 (6)
H70.49220.57400.66830.050*
C80.2517 (3)0.4991 (3)0.48039 (17)0.0638 (8)
H8A0.23040.56620.51440.077*
H8B0.27910.53680.43400.077*
C90.3426 (2)0.4254 (3)0.51642 (18)0.0724 (9)
H9A0.31390.37920.55880.109*
H9B0.39920.48150.53370.109*
H9C0.37300.36840.47990.109*
C100.1689 (2)0.3275 (3)0.40308 (15)0.0575 (8)
H10A0.22660.27020.41870.069*
H10B0.19240.36790.35650.069*
C110.0657 (3)0.2559 (3)0.3885 (2)0.0845 (11)
H11A0.04460.21180.43380.127*
H11B0.07800.19690.34830.127*
H11C0.00800.31260.37420.127*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0416 (13)0.0629 (15)0.0456 (12)0.0035 (11)0.0090 (10)0.0040 (11)
O10.0427 (11)0.0719 (13)0.0467 (11)−0.0014 (10)−0.0083 (9)0.0082 (9)
O20.0711 (14)0.0676 (14)0.0668 (13)−0.0052 (11)−0.0119 (11)0.0315 (11)
O30.0530 (11)0.0591 (12)0.0670 (12)−0.0036 (10)−0.0217 (10)0.0170 (10)
C10.0431 (16)0.0561 (18)0.0356 (14)0.0077 (14)0.0067 (12)0.0044 (13)
C20.0336 (13)0.0426 (15)0.0352 (13)0.0021 (12)0.0047 (11)0.0047 (11)
C30.0465 (15)0.0369 (15)0.0426 (14)−0.0032 (12)0.0029 (13)0.0063 (12)
C40.0405 (15)0.0444 (16)0.0402 (14)−0.0072 (12)−0.0015 (12)0.0011 (12)
C50.0359 (14)0.0486 (16)0.0390 (13)0.0030 (12)0.0003 (12)0.0070 (12)
C60.0424 (15)0.0390 (15)0.0539 (16)−0.0020 (13)−0.0045 (13)0.0076 (13)
C70.0350 (14)0.0441 (16)0.0467 (15)−0.0049 (12)−0.0022 (12)0.0005 (13)
C80.067 (2)0.0595 (19)0.0652 (19)−0.0111 (16)0.0033 (16)−0.0082 (16)
C90.0508 (19)0.092 (2)0.074 (2)−0.0046 (18)−0.0058 (16)−0.0123 (19)
C100.0637 (19)0.0506 (18)0.0584 (17)0.0002 (15)0.0068 (15)−0.0044 (14)
C110.076 (2)0.086 (3)0.091 (3)−0.018 (2)−0.028 (2)−0.003 (2)
Geometric parameters (Å, °) top
N1—C101.470 (3)C6—C71.373 (3)
N1—C81.483 (3)C6—H60.9300
N1—H1A0.9000C7—H70.9300
N1—H1B0.9000C8—C91.495 (4)
O1—C11.259 (3)C8—H8A0.9700
O2—C11.249 (3)C8—H8B0.9700
O3—C51.358 (3)C9—H9A0.9600
O3—H30.8200C9—H9B0.9600
C1—C21.495 (3)C9—H9C0.9600
C2—C31.386 (3)C10—C111.489 (4)
C2—C71.388 (3)C10—H10A0.9700
C3—C41.377 (3)C10—H10B0.9700
C3—H3A0.9300C11—H11A0.9600
C4—C51.381 (3)C11—H11B0.9600
C4—H40.9300C11—H11C0.9600
C5—C61.385 (3)
C10—N1—C8115.2 (2)C6—C7—H7119.4
C10—N1—H1A108.5C2—C7—H7119.4
C8—N1—H1A108.5N1—C8—C9113.4 (2)
C10—N1—H1B108.5N1—C8—H8A108.9
C8—N1—H1B108.5C9—C8—H8A108.9
H1A—N1—H1B107.5N1—C8—H8B108.9
C5—O3—H3109.5C9—C8—H8B108.9
O2—C1—O1122.3 (2)H8A—C8—H8B107.7
O2—C1—C2118.6 (3)C8—C9—H9A109.5
O1—C1—C2119.1 (2)C8—C9—H9B109.5
C3—C2—C7117.6 (2)H9A—C9—H9B109.5
C3—C2—C1121.0 (2)C8—C9—H9C109.5
C7—C2—C1121.4 (2)H9A—C9—H9C109.5
C4—C3—C2121.8 (2)H9B—C9—H9C109.5
C4—C3—H3A119.1N1—C10—C11111.6 (2)
C2—C3—H3A119.1N1—C10—H10A109.3
C3—C4—C5119.7 (2)C11—C10—H10A109.3
C3—C4—H4120.1N1—C10—H10B109.3
C5—C4—H4120.1C11—C10—H10B109.3
O3—C5—C4123.1 (2)H10A—C10—H10B108.0
O3—C5—C6117.6 (2)C10—C11—H11A109.5
C4—C5—C6119.4 (2)C10—C11—H11B109.5
C7—C6—C5120.3 (2)H11A—C11—H11B109.5
C7—C6—H6119.9C10—C11—H11C109.5
C5—C6—H6119.9H11A—C11—H11C109.5
C6—C7—C2121.2 (2)H11B—C11—H11C109.5
O2—C1—C2—C316.5 (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—C71.1 (4)
O1—C1—C2—C717.7 (3)C5—C6—C7—C20.5 (4)
C7—C2—C3—C40.5 (3)C3—C2—C7—C6−1.3 (4)
C1—C2—C3—C4−177.6 (2)C1—C2—C7—C6176.8 (2)
C2—C3—C4—C51.1 (4)C10—N1—C8—C9−66.5 (3)
C3—C4—C5—O3178.5 (2)C8—N1—C10—C11−179.9 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.902.152.873 (3)137
N1—H1A···O1i0.902.163.022 (3)162
N1—H1B···O2ii0.901.832.724 (3)174
O3—H3···O1iii0.821.822.635 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O2i0.902.152.873 (3)137
N1—H1A···O1i0.902.163.022 (3)162
N1—H1B···O2ii0.901.832.724 (3)174
O3—H3···O1iii0.821.822.635 (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.
references
References top

Aakeroÿ, C. B., Beatty, A. M. & Helfrich, B. A. (2002). J. Am. Chem. Soc. 124, 14425–14432.

Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Vishweshwar, P., Nangia, A. & Lynch, V. M. (2003). CrystEngComm, 5, 164–168.