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

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

doi:10.1107/S1600536809034540

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2341

doi:10.1107/S1600536809034540

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

Ying-Jie Cai,^a Xi-Bin Dai,^a Lian Liu,^a Jin Li ^a and Hai-Yan Li ^a ^*

^aEngineering Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan 430073, People's Republic of China
^*Correspondence e-mail: haiyany_li@163.com

(Received 25 August 2009; accepted 28 August 2009; online 5 September 2009)

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.

Related literature

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

Experimental

Crystal data

C₇H₁₀NO⁺·C₈H₇O₂S⁻
M_r = 291.37
Monoclinic, P 2₁ /c
a = 6.545 (5) Å
b = 14.792 (12) Å
c = 14.868 (11) Å
β = 104.78 (4)°
V = 1391.8 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 293 K
0.32 × 0.28 × 0.26 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.927, T_max = 0.940
6838 measured reflections
2447 independent reflections
1895 reflections with I > 2σ(I)
R_int = 0.061
??? standard reflections every ??? reflections intensity decay: ???%

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.182
S = 1.11
2447 reflections
191 parameters
22 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.845 (19)	1.99 (2)	2.782 (4)	156 (4)
N1—H1C⋯O2ⁱⁱ	0.89 (2)	1.87 (2)	2.752 (4)	169 (5)
N1—H1B⋯O1ⁱⁱⁱ	0.872 (18)	1.885 (19)	2.749 (4)	171 (3)
O3—H3B⋯N1^iv	0.82	2.54	3.267 (4)	149
C6—H6⋯O3ⁱⁱⁱ	0.93	2.60	3.521 (4)	171
Symmetry codes: (i) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034540/hb5068sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034540/hb5068Isup2.hkl

checkCIF report

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.

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

	Fig. 1. The molecular structure of (I) showing 35% probability displacement ellipsoids.
	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
M_r = 291.37	D_x = 1.391 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1267 reflections
a = 6.545 (5) Å	θ = 2.4–24.4°
b = 14.792 (12) Å	µ = 0.24 mm⁻¹
c = 14.868 (11) Å	T = 293 K
β = 104.78 (4)°	Block, colourless
V = 1391.8 (19) Å³	0.32 × 0.28 × 0.26 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	2447 independent reflections
Radiation source: fine-focus sealed tube	1895 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
ω/2θ scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: ψ scan (North et al., 1968)	h = −7→7
T_min = 0.927, T_max = 0.940	k = −17→17
6838 measured reflections	l = −14→17

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.182	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	w = 1/[σ²(F_o²) + (0.1018P)² + 0.3741P] where P = (F_o² + 2F_c²)/3
2447 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.38 e Å⁻³
22 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₇H₁₀NO⁺·C₈H₇O₂S⁻	V = 1391.8 (19) Å³
M_r = 291.37	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.545 (5) Å	µ = 0.24 mm⁻¹
b = 14.792 (12) Å	T = 293 K
c = 14.868 (11) Å	0.32 × 0.28 × 0.26 mm
β = 104.78 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	2447 independent reflections
Absorption correction: ψ scan (North et al., 1968)	1895 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.940	R_int = 0.061
6838 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	22 restraints
wR(F²) = 0.182	H atoms treated by a mixture of independent and constrained refinement
S = 1.11	Δρ_max = 0.38 e Å⁻³
2447 reflections	Δρ_min = −0.45 e Å⁻³
191 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
S1	0.76277 (18)	0.46123 (6)	0.14786 (7)	0.0712 (4)
O1	1.3152 (3)	0.89080 (12)	−0.02444 (14)	0.0493 (5)
O2	1.0949 (3)	0.85420 (13)	0.06100 (13)	0.0495 (5)
C1	0.9143 (5)	0.53974 (18)	0.1055 (2)	0.0491 (7)
C2	0.8159 (5)	0.59649 (19)	0.0354 (2)	0.0511 (7)
H2	0.6711	0.5923	0.0096	0.061*
C3	0.9338 (5)	0.65976 (19)	0.0038 (2)	0.0482 (7)
H3A	0.8669	0.6986	−0.0438	0.058*
C4	1.1530 (5)	0.66758 (18)	0.04140 (18)	0.0425 (6)
C5	1.2476 (5)	0.60815 (19)	0.1105 (2)	0.0490 (7)
H5	1.3931	0.6105	0.1354	0.059*
C6	1.1284 (6)	0.54461 (19)	0.1435 (2)	0.0542 (8)
H6	1.1935	0.5055	0.1912	0.065*
C7	1.2790 (5)	0.73591 (19)	0.0050 (2)	0.0501 (7)
H7A	1.2629	0.7240	−0.0606	0.060*
H7B	1.4269	0.7273	0.0364	0.060*
C8	1.2232 (4)	0.83435 (18)	0.01580 (18)	0.0385 (6)
O3	0.6854 (4)	0.88722 (13)	0.17658 (14)	0.0603 (6)
H3B	0.7023	0.8765	0.1248	0.090*
N1	0.7229 (4)	0.56517 (17)	0.46681 (18)	0.0451 (6)
C9	0.6981 (5)	0.8088 (2)	0.22552 (19)	0.051
C10	0.5344 (5)	0.7868 (2)	0.2620 (2)	0.0560 (8)
H10	0.4183	0.8249	0.2547	0.067*
C11	0.5448 (5)	0.7067 (2)	0.3100 (2)	0.0494 (7)
H11	0.4338	0.6897	0.3348	0.059*
C12	0.7227 (4)	0.65084 (18)	0.32159 (17)	0.0423 (6)
C13	0.8840 (5)	0.6771 (2)	0.28458 (19)	0.0479 (7)
H13	1.0024	0.6402	0.2927	0.058*
C14	0.8762 (5)	0.7568 (2)	0.23553 (19)	0.0525 (7)
H14	0.9864	0.7744	0.2104	0.063*
C15	0.7290 (6)	0.5601 (2)	0.3675 (2)	0.0561 (8)
H15A	0.6097	0.5245	0.3334	0.067*
H15B	0.8570	0.5290	0.3637	0.067*
H1B	0.719 (5)	0.5117 (15)	0.4910 (19)	0.054 (9)*
H1C	0.851 (5)	0.585 (4)	0.496 (3)	0.13 (2)*
H1A	0.616 (4)	0.594 (2)	0.473 (3)	0.080 (13)*
H1D	0.719 (10)	0.455 (4)	0.229 (2)	0.18 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.1102 (8)	0.0416 (5)	0.0790 (6)	−0.0173 (5)	0.0555 (6)	−0.0050 (4)
O1	0.0561 (12)	0.0336 (11)	0.0632 (12)	−0.0046 (9)	0.0246 (10)	−0.0015 (9)
O2	0.0546 (12)	0.0400 (11)	0.0605 (12)	0.0055 (9)	0.0269 (10)	−0.0029 (9)
C1	0.074 (2)	0.0309 (15)	0.0500 (16)	−0.0040 (13)	0.0295 (15)	−0.0075 (12)
C2	0.0570 (18)	0.0426 (17)	0.0537 (16)	−0.0055 (13)	0.0144 (14)	−0.0068 (13)
C3	0.0542 (18)	0.0389 (16)	0.0494 (16)	0.0002 (13)	0.0092 (13)	0.0027 (12)
C4	0.0561 (17)	0.0292 (14)	0.0457 (14)	−0.0001 (12)	0.0192 (12)	−0.0055 (11)
C5	0.0552 (18)	0.0382 (15)	0.0513 (16)	0.0052 (13)	0.0097 (13)	−0.0038 (12)
C6	0.079 (2)	0.0376 (17)	0.0454 (15)	0.0083 (15)	0.0148 (15)	0.0061 (12)
C7	0.0582 (18)	0.0348 (15)	0.0645 (18)	0.0005 (13)	0.0290 (14)	−0.0042 (12)
C8	0.0390 (14)	0.0337 (14)	0.0422 (13)	−0.0005 (11)	0.0094 (11)	−0.0037 (11)
O3	0.0993 (17)	0.0344 (11)	0.0446 (11)	0.0015 (11)	0.0138 (11)	0.0139 (8)
N1	0.0511 (15)	0.0340 (13)	0.0545 (14)	−0.0007 (12)	0.0211 (12)	0.0041 (11)
C9	0.071	0.039	0.041	−0.002	0.011	0.000
C10	0.065 (2)	0.0479 (19)	0.0520 (16)	0.0133 (15)	0.0091 (14)	−0.0038 (14)
C11	0.0512 (17)	0.0486 (17)	0.0516 (16)	−0.0018 (14)	0.0192 (13)	−0.0057 (13)
C12	0.0546 (16)	0.0352 (14)	0.0374 (13)	−0.0009 (12)	0.0124 (12)	−0.0066 (11)
C13	0.0521 (17)	0.0464 (17)	0.0472 (15)	0.0062 (13)	0.0163 (13)	−0.0046 (12)
C14	0.0578 (18)	0.0570 (19)	0.0468 (15)	−0.0053 (15)	0.0208 (13)	−0.0036 (13)
C15	0.082 (2)	0.0366 (16)	0.0501 (16)	−0.0017 (15)	0.0187 (15)	−0.0030 (12)

Geometric parameters (Å, º) top

S1—C1	1.746 (3)	O3—H3B	0.8200
S1—H1D	1.31 (2)	N1—C15	1.490 (4)
O1—C8	1.266 (3)	N1—H1B	0.872 (18)
O2—C8	1.237 (3)	N1—H1C	0.89 (2)
C1—C2	1.365 (4)	N1—H1A	0.845 (19)
C1—C6	1.373 (5)	C9—C10	1.358 (5)
C2—C3	1.370 (4)	C9—C14	1.373 (5)
C2—H2	0.9300	C10—C11	1.376 (4)
C3—C4	1.405 (4)	C10—H10	0.9300
C3—H3A	0.9300	C11—C12	1.402 (4)
C4—C5	1.374 (4)	C11—H11	0.9300
C4—C7	1.491 (4)	C12—C13	1.366 (4)
C5—C6	1.389 (4)	C12—C15	1.501 (4)
C5—H5	0.9300	C13—C14	1.380 (4)
C6—H6	0.9300	C13—H13	0.9300
C7—C8	1.520 (4)	C14—H14	0.9300
C7—H7A	0.9700	C15—H15A	0.9700
C7—H7B	0.9700	C15—H15B	0.9700
O3—C9	1.361 (4)

C1—S1—H1D	131 (3)	C15—N1—H1C	104 (4)
C2—C1—C6	121.0 (3)	H1B—N1—H1C	102 (4)
C2—C1—S1	118.9 (3)	C15—N1—H1A	112 (3)
C6—C1—S1	120.0 (2)	H1B—N1—H1A	107 (3)
C1—C2—C3	119.0 (3)	H1C—N1—H1A	119 (5)
C1—C2—H2	120.5	C10—C9—O3	118.1 (3)
C3—C2—H2	120.5	C10—C9—C14	123.9 (3)
C2—C3—C4	121.8 (3)	O3—C9—C14	118.0 (3)
C2—C3—H3A	119.1	C9—C10—C11	118.3 (3)
C4—C3—H3A	119.1	C9—C10—H10	120.9
C5—C4—C3	117.7 (3)	C11—C10—H10	120.9
C5—C4—C7	121.3 (3)	C10—C11—C12	120.1 (3)
C3—C4—C7	121.0 (3)	C10—C11—H11	120.0
C4—C5—C6	120.7 (3)	C12—C11—H11	120.0
C4—C5—H5	119.6	C13—C12—C11	119.1 (3)
C6—C5—H5	119.6	C13—C12—C15	120.2 (3)
C1—C6—C5	119.8 (3)	C11—C12—C15	120.6 (3)
C1—C6—H6	120.1	C12—C13—C14	121.9 (3)
C5—C6—H6	120.1	C12—C13—H13	119.1
C4—C7—C8	116.2 (2)	C14—C13—H13	119.1
C4—C7—H7A	108.2	C9—C14—C13	116.8 (3)
C8—C7—H7A	108.2	C9—C14—H14	121.6
C4—C7—H7B	108.2	C13—C14—H14	121.6
C8—C7—H7B	108.2	N1—C15—C12	113.7 (2)
H7A—C7—H7B	107.4	N1—C15—H15A	108.8
O2—C8—O1	124.8 (2)	C12—C15—H15A	108.8
O2—C8—C7	120.0 (2)	N1—C15—H15B	108.8
O1—C8—C7	115.2 (2)	C12—C15—H15B	108.8
C9—O3—H3B	109.4	H15A—C15—H15B	107.7
C15—N1—H1B	112 (2)

C6—C1—C2—C3	−0.8 (4)	C4—C7—C8—O1	−172.5 (2)
S1—C1—C2—C3	178.3 (2)	O3—C9—C10—C11	178.8 (2)
C1—C2—C3—C4	0.2 (4)	C14—C9—C10—C11	−1.6 (5)
C2—C3—C4—C5	1.2 (4)	C9—C10—C11—C12	1.0 (4)
C2—C3—C4—C7	179.0 (3)	C10—C11—C12—C13	0.0 (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—C5	0.0 (4)	C15—C12—C13—C14	174.8 (3)
S1—C1—C6—C5	−179.0 (2)	C10—C9—C14—C13	1.1 (4)
C4—C5—C6—C1	1.3 (4)	O3—C9—C14—C13	−179.3 (2)
C5—C4—C7—C8	−119.7 (3)	C12—C13—C14—C9	0.0 (4)
C3—C4—C7—C8	62.5 (4)	C13—C12—C15—N1	120.6 (3)
C4—C7—C8—O2	7.1 (4)	C11—C12—C15—N1	−64.2 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.85 (2)	1.99 (2)	2.782 (4)	156 (4)
N1—H1C···O2ⁱⁱ	0.89 (2)	1.87 (2)	2.752 (4)	169 (5)
N1—H1B···O1ⁱⁱⁱ	0.87 (2)	1.89 (2)	2.749 (4)	171 (3)
O3—H3B···N1^iv	0.82	2.54	3.267 (4)	149
C6—H6···O3ⁱⁱⁱ	0.93	2.60	3.521 (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.

Experimental details

Crystal data
Chemical formula	C₇H₁₀NO⁺·C₈H₇O₂S⁻
M_r	291.37
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	6.545 (5), 14.792 (12), 14.868 (11)
β (°)	104.78 (4)
V (Å³)	1391.8 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.32 × 0.28 × 0.26

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.927, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	6838, 2447, 1895
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.182, 1.11
No. of reflections	2447
No. of parameters	191
No. of restraints	22
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.45

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), 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···O1ⁱ	0.845 (19)	1.99 (2)	2.782 (4)	156 (4)
N1—H1C···O2ⁱⁱ	0.89 (2)	1.87 (2)	2.752 (4)	169 (5)
N1—H1B···O1ⁱⁱⁱ	0.872 (18)	1.885 (19)	2.749 (4)	171 (3)
O3—H3B···N1^iv	0.82	2.54	3.267 (4)	149
C6—H6···O3ⁱⁱⁱ	0.93	2.60	3.521 (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

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

References

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