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Acta Cryst. (2009). E65, o2341    [ doi:10.1107/S1600536809034540 ]

(4-Hydroxyphenyl)methanaminium 2-(4-sulfanylphenyl)acetate

Y.-J. Cai, X.-B. Dai, L. Liu, J. Li and H.-Y. Li

Abstract top

In the title molecular salt, C7H10NO+·C8H7O2S-, the crystal structure is stabilized by intermolecular N-H...O, O-H...N and C-H...O hydrogen bonds.

Comment top

There has been much research interest in the intermolecular interactions between carboxylic acid and amine. (Xia et al., 2003; He et al., 2008). The title compound (I) is presented in Fig.1, all bond lengths are within normal ranges (Allen et al., 1987) (Table 1). The carboxylate cation and aminium anion are linked via N—H···O, O—H···N and C—H···O intermolecular hydrogen bonds (Table 2) into three network along the a axis. (Fig. 2).

Related literature top

For related molecular salts, see: Xia et al. (2003); He et al. (2008). For reference structural data, see: Allen et al. (1987).

Experimental top

A mixture of 2-(4-mercaptophenyl)acetic acid (336 mg, 2 mmol), and 4-(aminomethyl)phenol (246 mg, 2 mmol) was stirred in methanol (10 ml) for 1 h. After keeping the solution in air for 3 d, colourless blocks of (I) were formed.

Refinement top

All the H atoms, except for H1A, H1B and H1C attached to N1, H1D attached to S1, were placed in idealized positions (C—H = 0.93–0.97 Å, O—H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(O). Atoms H1A, H1B and H1C and H1D were located from a difference map and their positions were freely refined.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); 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) showing 35% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing of (I), showing intermolecular hydrogen bonds (dashed lines) along the a axis.
(4-Hydroxyphenyl)methanaminium 2-(4-sulfanylphenyl)acetate top
Crystal data top
C7H10NO+·C8H7O2S−F(000) = 616
Mr = 291.37Dx = 1.391 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1267 reflections
a = 6.545 (5) Åθ = 2.4–24.4°
b = 14.792 (12) ŵ = 0.24 mm−1
c = 14.868 (11) ÅT = 293 K
β = 104.78 (4)°Block, colourless
V = 1391.8 (19) Å30.32 × 0.28 × 0.26 mm
Z = 4
Data collection top
Enraf–Nonius CAD-4
diffractometer		2447 independent reflections
Radiation source: fine-focus sealed tube1895 reflections with I > 2σ(I)
graphiteRint = 0.061
ω/2θ scansθmax = 25.0°, θmin = 2.0°
Absorption correction: ψ scan
(North et al., 1968)		h = −7→7
Tmin = 0.927, Tmax = 0.940k = −17→17
6838 measured reflectionsl = −14→17
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)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.182H atoms treated by a mixture of independent and constrained refinement
S = 1.11 w = 1/[σ2(Fo2) + (0.1018P)2 + 0.3741P]
where P = (Fo2 + 2Fc2)/3
2447 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.38 e Å−3
22 restraintsΔρmin = −0.45 e Å−3
Crystal data top
C7H10NO+·C8H7O2S−V = 1391.8 (19) Å3
Mr = 291.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.545 (5) ŵ = 0.24 mm−1
b = 14.792 (12) ÅT = 293 K
c = 14.868 (11) Å0.32 × 0.28 × 0.26 mm
β = 104.78 (4)°
Data collection top
Enraf–Nonius CAD-4
diffractometer		1895 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.061
Tmin = 0.927, Tmax = 0.940θmax = 25.0°
6838 measured reflectionsStandard reflections: ?
2447 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.054H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.182Δρmax = 0.38 e Å−3
S = 1.11Δρmin = −0.45 e Å−3
2447 reflectionsAbsolute structure: ?
191 parametersFlack parameter: ?
22 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
S10.76277 (18)0.46123 (6)0.14786 (7)0.0712 (4)
O11.3152 (3)0.89080 (12)−0.02444 (14)0.0493 (5)
O21.0949 (3)0.85420 (13)0.06100 (13)0.0495 (5)
C10.9143 (5)0.53974 (18)0.1055 (2)0.0491 (7)
C20.8159 (5)0.59649 (19)0.0354 (2)0.0511 (7)
H20.67110.59230.00960.061*
C30.9338 (5)0.65976 (19)0.0038 (2)0.0482 (7)
H3A0.86690.6986−0.04380.058*
C41.1530 (5)0.66758 (18)0.04140 (18)0.0425 (6)
C51.2476 (5)0.60815 (19)0.1105 (2)0.0490 (7)
H51.39310.61050.13540.059*
C61.1284 (6)0.54461 (19)0.1435 (2)0.0542 (8)
H61.19350.50550.19120.065*
C71.2790 (5)0.73591 (19)0.0050 (2)0.0501 (7)
H7A1.26290.7240−0.06060.060*
H7B1.42690.72730.03640.060*
C81.2232 (4)0.83435 (18)0.01580 (18)0.0385 (6)
O30.6854 (4)0.88722 (13)0.17658 (14)0.0603 (6)
H3B0.70230.87650.12480.090*
N10.7229 (4)0.56517 (17)0.46681 (18)0.0451 (6)
C90.6981 (5)0.8088 (2)0.22552 (19)0.051
C100.5344 (5)0.7868 (2)0.2620 (2)0.0560 (8)
H100.41830.82490.25470.067*
C110.5448 (5)0.7067 (2)0.3100 (2)0.0494 (7)
H110.43380.68970.33480.059*
C120.7227 (4)0.65084 (18)0.32159 (17)0.0423 (6)
C130.8840 (5)0.6771 (2)0.28458 (19)0.0479 (7)
H131.00240.64020.29270.058*
C140.8762 (5)0.7568 (2)0.23553 (19)0.0525 (7)
H140.98640.77440.21040.063*
C150.7290 (6)0.5601 (2)0.3675 (2)0.0561 (8)
H15A0.60970.52450.33340.067*
H15B0.85700.52900.36370.067*
H1B0.719 (5)0.5117 (15)0.4910 (19)0.054 (9)*
H1C0.851 (5)0.585 (4)0.496 (3)0.13 (2)*
H1A0.616 (4)0.594 (2)0.473 (3)0.080 (13)*
H1D0.719 (10)0.455 (4)0.229 (2)0.18 (2)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.1102 (8)0.0416 (5)0.0790 (6)−0.0173 (5)0.0555 (6)−0.0050 (4)
O10.0561 (12)0.0336 (11)0.0632 (12)−0.0046 (9)0.0246 (10)−0.0015 (9)
O20.0546 (12)0.0400 (11)0.0605 (12)0.0055 (9)0.0269 (10)−0.0029 (9)
C10.074 (2)0.0309 (15)0.0500 (16)−0.0040 (13)0.0295 (15)−0.0075 (12)
C20.0570 (18)0.0426 (17)0.0537 (16)−0.0055 (13)0.0144 (14)−0.0068 (13)
C30.0542 (18)0.0389 (16)0.0494 (16)0.0002 (13)0.0092 (13)0.0027 (12)
C40.0561 (17)0.0292 (14)0.0457 (14)−0.0001 (12)0.0192 (12)−0.0055 (11)
C50.0552 (18)0.0382 (15)0.0513 (16)0.0052 (13)0.0097 (13)−0.0038 (12)
C60.079 (2)0.0376 (17)0.0454 (15)0.0083 (15)0.0148 (15)0.0061 (12)
C70.0582 (18)0.0348 (15)0.0645 (18)0.0005 (13)0.0290 (14)−0.0042 (12)
C80.0390 (14)0.0337 (14)0.0422 (13)−0.0005 (11)0.0094 (11)−0.0037 (11)
O30.0993 (17)0.0344 (11)0.0446 (11)0.0015 (11)0.0138 (11)0.0139 (8)
N10.0511 (15)0.0340 (13)0.0545 (14)−0.0007 (12)0.0211 (12)0.0041 (11)
C90.0710.0390.041−0.0020.0110.000
C100.065 (2)0.0479 (19)0.0520 (16)0.0133 (15)0.0091 (14)−0.0038 (14)
C110.0512 (17)0.0486 (17)0.0516 (16)−0.0018 (14)0.0192 (13)−0.0057 (13)
C120.0546 (16)0.0352 (14)0.0374 (13)−0.0009 (12)0.0124 (12)−0.0066 (11)
C130.0521 (17)0.0464 (17)0.0472 (15)0.0062 (13)0.0163 (13)−0.0046 (12)
C140.0578 (18)0.0570 (19)0.0468 (15)−0.0053 (15)0.0208 (13)−0.0036 (13)
C150.082 (2)0.0366 (16)0.0501 (16)−0.0017 (15)0.0187 (15)−0.0030 (12)
Geometric parameters (Å, °) top
S1—C11.746 (3)O3—H3B0.8200
S1—H1D1.31 (2)N1—C151.490 (4)
O1—C81.266 (3)N1—H1B0.872 (18)
O2—C81.237 (3)N1—H1C0.89 (2)
C1—C21.365 (4)N1—H1A0.845 (19)
C1—C61.373 (5)C9—C101.358 (5)
C2—C31.370 (4)C9—C141.373 (5)
C2—H20.9300C10—C111.376 (4)
C3—C41.405 (4)C10—H100.9300
C3—H3A0.9300C11—C121.402 (4)
C4—C51.374 (4)C11—H110.9300
C4—C71.491 (4)C12—C131.366 (4)
C5—C61.389 (4)C12—C151.501 (4)
C5—H50.9300C13—C141.380 (4)
C6—H60.9300C13—H130.9300
C7—C81.520 (4)C14—H140.9300
C7—H7A0.9700C15—H15A0.9700
C7—H7B0.9700C15—H15B0.9700
O3—C91.361 (4)
C1—S1—H1D131 (3)C15—N1—H1C104 (4)
C2—C1—C6121.0 (3)H1B—N1—H1C102 (4)
C2—C1—S1118.9 (3)C15—N1—H1A112 (3)
C6—C1—S1120.0 (2)H1B—N1—H1A107 (3)
C1—C2—C3119.0 (3)H1C—N1—H1A119 (5)
C1—C2—H2120.5C10—C9—O3118.1 (3)
C3—C2—H2120.5C10—C9—C14123.9 (3)
C2—C3—C4121.8 (3)O3—C9—C14118.0 (3)
C2—C3—H3A119.1C9—C10—C11118.3 (3)
C4—C3—H3A119.1C9—C10—H10120.9
C5—C4—C3117.7 (3)C11—C10—H10120.9
C5—C4—C7121.3 (3)C10—C11—C12120.1 (3)
C3—C4—C7121.0 (3)C10—C11—H11120.0
C4—C5—C6120.7 (3)C12—C11—H11120.0
C4—C5—H5119.6C13—C12—C11119.1 (3)
C6—C5—H5119.6C13—C12—C15120.2 (3)
C1—C6—C5119.8 (3)C11—C12—C15120.6 (3)
C1—C6—H6120.1C12—C13—C14121.9 (3)
C5—C6—H6120.1C12—C13—H13119.1
C4—C7—C8116.2 (2)C14—C13—H13119.1
C4—C7—H7A108.2C9—C14—C13116.8 (3)
C8—C7—H7A108.2C9—C14—H14121.6
C4—C7—H7B108.2C13—C14—H14121.6
C8—C7—H7B108.2N1—C15—C12113.7 (2)
H7A—C7—H7B107.4N1—C15—H15A108.8
O2—C8—O1124.8 (2)C12—C15—H15A108.8
O2—C8—C7120.0 (2)N1—C15—H15B108.8
O1—C8—C7115.2 (2)C12—C15—H15B108.8
C9—O3—H3B109.4H15A—C15—H15B107.7
C15—N1—H1B112 (2)
C6—C1—C2—C3−0.8 (4)C4—C7—C8—O1−172.5 (2)
S1—C1—C2—C3178.3 (2)O3—C9—C10—C11178.8 (2)
C1—C2—C3—C40.2 (4)C14—C9—C10—C11−1.6 (5)
C2—C3—C4—C51.2 (4)C9—C10—C11—C121.0 (4)
C2—C3—C4—C7179.0 (3)C10—C11—C12—C130.0 (4)
C3—C4—C5—C6−1.9 (4)C10—C11—C12—C15−175.3 (3)
C7—C4—C5—C6−179.8 (3)C11—C12—C13—C14−0.5 (4)
C2—C1—C6—C50.0 (4)C15—C12—C13—C14174.8 (3)
S1—C1—C6—C5−179.0 (2)C10—C9—C14—C131.1 (4)
C4—C5—C6—C11.3 (4)O3—C9—C14—C13−179.3 (2)
C5—C4—C7—C8−119.7 (3)C12—C13—C14—C90.0 (4)
C3—C4—C7—C862.5 (4)C13—C12—C15—N1120.6 (3)
C4—C7—C8—O27.1 (4)C11—C12—C15—N1−64.2 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.85 (2)1.99 (2)2.782 (4)156 (4)
N1—H1C···O2ii0.89 (2)1.87 (2)2.752 (4)169 (5)
N1—H1B···O1iii0.87 (2)1.89 (2)2.749 (4)171 (3)
O3—H3B···N1iv0.822.543.267 (4)149
C6—H6···O3iii0.932.603.521 (4)171
Symmetry codes: (i) x−1, −y+3/2, z+1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+2, y−1/2, −z+1/2; (iv) x, −y+3/2, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.85 (2)1.99 (2)2.782 (4)156 (4)
N1—H1C···O2ii0.89 (2)1.87 (2)2.752 (4)169 (5)
N1—H1B···O1iii0.87 (2)1.89 (2)2.749 (4)171 (3)
O3—H3B···N1iv0.822.543.267 (4)149
C6—H6···O3iii0.932.603.521 (4)171
Symmetry codes: (i) x−1, −y+3/2, z+1/2; (ii) x, −y+3/2, z+1/2; (iii) −x+2, y−1/2, −z+1/2; (iv) x, −y+3/2, z−1/2.
Acknowledgements top

This project was supported by the Education Commission of Hubei Province (D20091703) and the Natural Science Foundation of Hubei Province (2008CDB038).

references
References top

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North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

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

Xia, J., Wang, X.-J., Sun, X.-J., Zhu, H.-L. & Wang, D.-Q. (2003). Z. Kristallogr. New Cryst. Struct. 218, 247–248.