2-(2-Furylmethyl­amino­meth­yl)-4-sulfanylphenol

Abstract

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,

• a = 5.5778 (12) Å

• b = 13.589 (3) Å

• c = 14.943 (3) Å

• V = 1132.6 (4) ų

• 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[F ² > 2σ(F ²)] = 0.058

• wR(F ²) = 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)

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

The N-bound H atom was located in a difference map and its position was freely refined. The other H atoms were positioned geometrically (C—H = 0.93–0.97Å, O—H = 0.82Å, S—H = 1.20Å) and refined as riding, with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl C).

Figures

Fig. 1.

The molecular structure of (I) showing 30% probability displacement ellipsoids.

Crystal data

C12H13NO2S	F(000) = 496
Mr = 235.29	Dx = 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

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

Refinement

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(Fo2) + (0.1031P)2 + 0.1612P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.166	(Δ/σ)max = 0.002
S = 1.06	Δρmax = 0.35 e Å−3
2216 reflections	Δρmin = −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	Flack parameter: 0.00 (17)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x+1/2, −y+2, z+1/2.