2-(2-Furylmethyl­amino­meth­yl)-4-sulfanylphenol

Chen, W.; Liu, L.; Xu, D.; Zeng, Q.-F.

doi:10.1107/S1600536809032401

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2204

doi:10.1107/S1600536809032401

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2-(2-Furylmethylaminomethyl)-4-sulfanylphenol

Wu Chen,^a Lian Liu,^a Di Xu ^a and Qing-Fu Zeng ^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: qfzeng@wuse.edu.cn

(Received 14 August 2009; accepted 15 August 2009; online 22 August 2009)

In the title compound, C₁₂H₁₃NO₂S, the dihedral angle between the furan and benzene rings is 62.2 (2)° and an intramolecular O—H⋯N hydrogen bond is formed. In the crystal, molecules are linked by weak intermolecular N—H⋯S hydrogen bonds.

Related literature

For background, see: Shi et al. (2007 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₃NO₂S
M_r = 235.29
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.5778 (12) Å
b = 13.589 (3) Å
c = 14.943 (3) Å
V = 1132.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.10 mm

Data collection

Enraf–Nonius CAD4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.924, T_max = 0.974
2528 measured reflections
2216 independent reflections
1811 reflections with I > 2σ(I)
R_int = 0.034
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.166
S = 1.06
2216 reflections
150 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.46 e Å⁻³
Absolute structure: Flack (1983 ), 900 Friedel pairs
Flack parameter: 0.00 (17)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯N1	0.82	2.04	2.692 (5)	136
N1—H1C⋯S1ⁱ	0.93 (5)	2.90 (4)	3.605 (3)	134 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ .

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/S1600536809032401/hb5047sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032401/hb5047Isup2.hkl

checkCIF report

Comment top

There has been much research interest in Schiff base compounds due to their biological activities (Shi et al., 2007). In this work, we report here the crystal structure of the title compound, (I). In (I), all bond lengths are within normal ranges (Allen et al., 1987) (Fig. 1). There are an intramolecular O-H···N hydrogen bond and an intermolecular N-H···S hydrogen bond in (I).

Related literature top

For background, see: Shi et al. (2007). For reference structural data, see: Allen et al. (1987).

Experimental top

A mixture of 2-hydroxy-5-mercaptobenzaldehyde (154 mg, 1 mmol) and furan-2-ylmethanamine (97 mg, 1 mmol) were stirred in methanol (10 ml) for 2 h. Then NaBH₄ (76 mg, 2 mmol) was added to the reaction solution slowly, and stirred at room temperature for 2 h. The mixture was evaporated under vacuum, and dissolved in dichloromethane (5 ml). The solution was washed with saturated NaCl solution and water, respectively, dried over anhydrous sodium sulfate, and evaporated. Purification by silica gel afforded pure product. Colourless blocks of (I) were obtained by recrystallization of the pure product in methanol.

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 30% probability displacement ellipsoids.

2-(2-Furylmethylaminomethyl)-4-sulfanylphenol top

Crystal data top

C₁₂H₁₃NO₂S	F(000) = 496
M_r = 235.29	D_x = 1.380 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 5.5778 (12) Å	θ = 9–12°
b = 13.589 (3) Å	µ = 0.27 mm⁻¹
c = 14.943 (3) Å	T = 293 K
V = 1132.6 (4) Å³	Block, colorless
Z = 4	0.30 × 0.30 × 0.10 mm

Data collection top

Enraf–Nonius CAD4 diffractometer	1811 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
ω/2θ scans	h = −6→0
Absorption correction: ψ scan (North et al., 1968)	k = −16→16
T_min = 0.924, T_max = 0.974	l = −18→0
2528 measured reflections	3 standard reflections every 200 reflections
2216 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.058	w = 1/[σ²(F_o²) + (0.1031P)² + 0.1612P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.166	(Δ/σ)_max = 0.002
S = 1.06	Δρ_max = 0.35 e Å⁻³
2216 reflections	Δρ_min = −0.46 e Å⁻³
150 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.058 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 900 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (17)

Crystal data top

C₁₂H₁₃NO₂S	V = 1132.6 (4) Å³
M_r = 235.29	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 5.5778 (12) Å	µ = 0.27 mm⁻¹
b = 13.589 (3) Å	T = 293 K
c = 14.943 (3) Å	0.30 × 0.30 × 0.10 mm

Data collection top

Enraf–Nonius CAD4 diffractometer	1811 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.034
T_min = 0.924, T_max = 0.974	3 standard reflections every 200 reflections
2528 measured reflections	intensity decay: 1%
2216 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.166	Δρ_max = 0.35 e Å⁻³
S = 1.06	Δρ_min = −0.46 e Å⁻³
2216 reflections	Absolute structure: Flack (1983), 900 Friedel pairs
150 parameters	Absolute structure parameter: 0.00 (17)
0 restraints

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
C1	−0.2480 (7)	0.7259 (3)	0.4206 (3)	0.0591 (10)
H1	−0.3948	0.7288	0.4501	0.071*
C2	−0.1233 (8)	0.6441 (3)	0.4068 (3)	0.0581 (9)
H2	−0.1659	0.5807	0.4239	0.070*
C3	0.0881 (8)	0.6728 (3)	0.3607 (3)	0.0564 (10)
H3	0.2108	0.6312	0.3420	0.068*
C4	0.0791 (6)	0.7696 (3)	0.3490 (2)	0.0480 (8)
C5	0.2431 (8)	0.8424 (3)	0.3079 (3)	0.0600 (10)
H5A	0.2795	0.8933	0.3512	0.072*
H5B	0.3923	0.8100	0.2920	0.072*
C6	0.1385 (8)	0.8197 (2)	0.1507 (2)	0.0526 (9)
H6A	0.0551	0.7597	0.1671	0.063*
H6B	0.3023	0.8025	0.1354	0.063*
C7	0.0183 (6)	0.8652 (2)	0.0710 (2)	0.0422 (8)
C8	0.1130 (6)	0.8552 (2)	−0.0141 (2)	0.0449 (8)
H8	0.2558	0.8209	−0.0219	0.054*
C9	−0.0009 (7)	0.8953 (3)	−0.0874 (3)	0.0481 (8)
C10	−0.2099 (8)	0.9468 (3)	−0.0782 (3)	0.0591 (10)
H10	−0.2856	0.9737	−0.1280	0.071*
C11	−0.3069 (7)	0.9583 (3)	0.0062 (3)	0.0613 (11)
H11	−0.4480	0.9939	0.0134	0.074*
C12	−0.1958 (6)	0.9172 (3)	0.0804 (3)	0.0502 (9)
H1C	0.230 (9)	0.942 (3)	0.212 (3)	0.060*
N1	0.1391 (7)	0.8878 (2)	0.2275 (2)	0.0550 (8)
O1	−0.1310 (6)	0.8050 (2)	0.38570 (18)	0.0632 (8)
O2	−0.2984 (5)	0.9310 (2)	0.1623 (2)	0.0696 (8)
H2A	−0.2170	0.9038	0.2007	0.104*
S1	0.1282 (2)	0.88051 (8)	−0.19340 (6)	0.0635 (4)
H1A	0.3423	0.8770	−0.1863	0.095*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.041 (2)	0.091 (3)	0.0460 (19)	0.001 (2)	0.0025 (17)	0.011 (2)
C2	0.052 (2)	0.063 (2)	0.059 (2)	−0.006 (2)	0.005 (2)	0.0063 (17)
C3	0.053 (2)	0.058 (2)	0.057 (2)	0.0042 (18)	0.010 (2)	−0.0024 (18)
C4	0.0402 (19)	0.062 (2)	0.0419 (17)	0.0025 (16)	−0.0010 (15)	−0.0007 (16)
C5	0.058 (2)	0.068 (2)	0.054 (2)	−0.015 (2)	−0.007 (2)	0.0067 (19)
C6	0.055 (2)	0.0490 (18)	0.054 (2)	0.0003 (19)	0.002 (2)	0.0033 (16)
C7	0.0361 (17)	0.0396 (16)	0.0508 (19)	−0.0041 (15)	−0.0016 (15)	−0.0001 (14)
C8	0.0382 (17)	0.0426 (16)	0.0540 (19)	0.0009 (15)	0.0022 (17)	−0.0009 (14)
C9	0.047 (2)	0.0470 (18)	0.0501 (19)	−0.0058 (17)	−0.0034 (17)	0.0017 (15)
C10	0.054 (2)	0.057 (2)	0.066 (2)	0.0046 (19)	−0.017 (2)	0.0031 (19)
C11	0.041 (2)	0.060 (2)	0.083 (3)	0.0110 (17)	−0.007 (2)	−0.002 (2)
C12	0.0385 (19)	0.0486 (18)	0.064 (2)	−0.0037 (15)	0.0074 (17)	−0.0040 (17)
N1	0.064 (2)	0.0487 (16)	0.0518 (16)	−0.0126 (18)	−0.0062 (16)	0.0024 (14)
O1	0.0598 (17)	0.0678 (16)	0.0619 (16)	0.0180 (15)	0.0025 (15)	0.0038 (12)
O2	0.0543 (17)	0.0815 (18)	0.0731 (19)	0.0024 (15)	0.0224 (15)	−0.0063 (15)
S1	0.0710 (7)	0.0711 (7)	0.0486 (5)	−0.0030 (6)	0.0064 (5)	0.0029 (4)

Geometric parameters (Å, º) top

C1—C2	1.328 (6)	C6—H6B	0.9700
C1—O1	1.361 (5)	C7—C8	1.383 (5)
C1—H1	0.9300	C7—C12	1.394 (5)
C2—C3	1.420 (6)	C8—C9	1.379 (5)
C2—H2	0.9300	C8—H8	0.9300
C3—C4	1.327 (5)	C9—C10	1.366 (6)
C3—H3	0.9300	C9—S1	1.752 (4)
C4—O1	1.381 (5)	C10—C11	1.382 (6)
C4—C5	1.481 (5)	C10—H10	0.9300
C5—N1	1.470 (5)	C11—C12	1.388 (6)
C5—H5A	0.9700	C11—H11	0.9300
C5—H5B	0.9700	C12—O2	1.365 (5)
C6—N1	1.473 (5)	N1—H1C	0.93 (5)
C6—C7	1.501 (5)	O2—H2A	0.8200
C6—H6A	0.9700	S1—H1A	1.2000

C2—C1—O1	110.5 (3)	C8—C7—C12	118.0 (3)
C2—C1—H1	124.8	C8—C7—C6	121.2 (3)
O1—C1—H1	124.8	C12—C7—C6	120.7 (3)
C1—C2—C3	106.3 (4)	C9—C8—C7	121.0 (3)
C1—C2—H2	126.8	C9—C8—H8	119.5
C3—C2—H2	126.8	C7—C8—H8	119.5
C4—C3—C2	107.7 (4)	C10—C9—C8	121.1 (4)
C4—C3—H3	126.1	C10—C9—S1	120.0 (3)
C2—C3—H3	126.1	C8—C9—S1	118.9 (3)
C3—C4—O1	108.9 (3)	C9—C10—C11	118.9 (4)
C3—C4—C5	133.9 (4)	C9—C10—H10	120.6
O1—C4—C5	117.2 (3)	C11—C10—H10	120.6
N1—C5—C4	112.1 (3)	C10—C11—C12	120.6 (4)
N1—C5—H5A	109.2	C10—C11—H11	119.7
C4—C5—H5A	109.2	C12—C11—H11	119.7
N1—C5—H5B	109.2	O2—C12—C11	118.3 (3)
C4—C5—H5B	109.2	O2—C12—C7	121.3 (4)
H5A—C5—H5B	107.9	C11—C12—C7	120.4 (4)
N1—C6—C7	111.1 (3)	C5—N1—C6	111.9 (3)
N1—C6—H6A	109.4	C5—N1—H1C	109 (3)
C7—C6—H6A	109.4	C6—N1—H1C	108 (2)
N1—C6—H6B	109.4	C1—O1—C4	106.5 (3)
C7—C6—H6B	109.4	C12—O2—H2A	109.5
H6A—C6—H6B	108.0	C9—S1—H1A	109.5

O1—C1—C2—C3	0.5 (5)	S1—C9—C10—C11	−179.4 (3)
C1—C2—C3—C4	−0.2 (5)	C9—C10—C11—C12	−0.8 (6)
C2—C3—C4—O1	−0.1 (4)	C10—C11—C12—O2	179.7 (4)
C2—C3—C4—C5	178.8 (4)	C10—C11—C12—C7	1.3 (6)
C3—C4—C5—N1	114.6 (5)	C8—C7—C12—O2	−179.2 (3)
O1—C4—C5—N1	−66.5 (4)	C6—C7—C12—O2	2.2 (5)
N1—C6—C7—C8	137.6 (3)	C8—C7—C12—C11	−0.8 (5)
N1—C6—C7—C12	−43.8 (5)	C6—C7—C12—C11	−179.4 (3)
C12—C7—C8—C9	−0.1 (5)	C4—C5—N1—C6	−73.9 (4)
C6—C7—C8—C9	178.6 (3)	C7—C6—N1—C5	176.6 (3)
C7—C8—C9—C10	0.5 (5)	C2—C1—O1—C4	−0.6 (4)
C7—C8—C9—S1	179.8 (3)	C3—C4—O1—C1	0.4 (4)
C8—C9—C10—C11	0.0 (6)	C5—C4—O1—C1	−178.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···N1	0.82	2.04	2.692 (5)	136
N1—H1C···S1ⁱ	0.93 (5)	2.90 (4)	3.605 (3)	134 (3)

Symmetry code: (i) −x+1/2, −y+2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₂S
M_r	235.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	5.5778 (12), 13.589 (3), 14.943 (3)
V (Å³)	1132.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.27
Crystal size (mm)	0.30 × 0.30 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.924, 0.974
No. of measured, independent and observed [I > 2σ(I)] reflections	2528, 2216, 1811
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.166, 1.06
No. of reflections	2216
No. of parameters	150
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.46
Absolute structure	Flack (1983), 900 Friedel pairs
Absolute structure parameter	0.00 (17)

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
O2—H2A···N1	0.82	2.04	2.692 (5)	136
N1—H1C···S1ⁱ	0.93 (5)	2.90 (4)	3.605 (3)	134 (3)

Symmetry code: (i) −x+1/2, −y+2, z+1/2.

Acknowledgements

The project was supported by the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, Educational Commission of Hubei Province (D20091703) and the Natural Science Foundation of Hubei Province (2008CDB038).

References

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