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The title compound, C9H11NO3S, has crystallographic mirror symmetry, occurs in the thio­carbamate form and is stabilized in an s-cisoid,s-transoid conformation with respect to the C-N-C group. There are two intramolecular hydrogen bonds, one between the H atom of the N-H group and the O atom of the furan ring, and the other between the H atom of the secondary carbon of the iso­propyl group and the S atom. The packing of the mol­ecules is assumed to be dictated by van der Waals interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100007514/na1477sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100007514/na1477Isup2.hkl
Contains datablock I

CCDC reference: 150405

Comment top

The chemistry of organic sulfur compounds, such as thiocarbamates and their S-alkylated products, has been investigated with increasing interest due to the biological activity of these compounds (Schröpl & Pohloudek-Fabini, 1968). In recent years, O-alkyl N-acylthiocarbamates have been proposed as intermediates for regio- and chemoselective deoxygenation for primary and secondary aliphatic alcohols (Oba & Nishiyama, 1994). Structural studies of O-alkyl N-benzoylthiocarbamate showed the C—N bonds to have partial double-bond character, thus giving rise to hindered rotation (Schröder et al., 1995). The present paper reports the crystal structure of O-isopropyl N-(2-furoyl)thiocarbamate, (I), in order to provide a better understanding of the above-mentioned properties.

The title compound crystallizes in the thiocarbamate form. A view of the molecule with the atom-numbering scheme is shown in Fig. 1. The asymmetry of the C3—C4—C5 and O1—C4—C5 angles [131.8 (5) and 118.9 (4)°, respectively] is probably caused by repulsion in the C3—H3···O2 system [C3···O2 = 3.006 (6) and H3···O2 = 2.96 Å] and attraction in the N—H···O1 system (see Table 2). The molecule is stabilized in the s-cisoid,s-transoid conformation with respect to the C5—N1—C6 group. The bond distance C6—O3 indiactes double-bond character, while the C5—N1 and C6—N1 distances indicate Csp2—Nsp2 single-bond character. This indicates that there is ππ conjugation along S1—C6—O3, but not along O2—C5—N1 and N1—C6—S1 as reported for O-alkyl N-benzoylthiocarbamate (Schröder et al., 1995).

There are two intramolecular hydrogen bonds, one between the N—H group and the O atom of the furan ring, and the other between the H atom of the secondary carbon of the isopropyl group and the S atom. The packing of the molecules is assumed to be dictated by short contacts and van der Waals interactions.

Experimental top

The title compound was synthesized by the reaction of furoyl isothiocyanate with isopropyl alcohol using acetone as solvent (Schröder et al., 1995). Recrystallization from methanol gave crystals suitable for X-ray analysis.

Refinement top

H atoms were calculated geometrically and included in the refinement, but were restrained to ride on their parent atoms. The isotropic displacement parameters of the H atoms were fixed to 1.3Ueq of their parent atoms.

Computing details top

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Bergerhoff, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick 1997) and PARST (Nardelli, 1983, 1995).

Figures top
[Figure 1] Fig. 1. Plot of (I) showing the atomic numbering scheme. Displacement ellipsoids are drawn at 50% probability level for non-H atoms. [Symmetry code: (i) x, 1/2 − y, z.]
O-Isopropyl N-(2-furoyl)thiocarbamate top
Crystal data top
C9H11NO3SF(000) = 224
Mr = 213.25Dx = 1.331 Mg m3
Monoclinic, P21/mMo Kα radiation, λ = 0.71073 Å
a = 7.679 (4) ÅCell parameters from 25 reflections
b = 7.004 (5) Åθ = 10–15°
c = 10.372 (5) ŵ = 0.29 mm1
β = 107.43 (4)°T = 293 K
V = 532.2 (5) Å3Prism, colourless
Z = 20.6 × 0.2 × 0.1 mm
Data collection top
Stoe Stadi-4 four-circle
diffractometer
Rint = 0.058
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.1°
Graphite monochromatorh = 29
ω scansk = 28
1980 measured reflectionsl = 1212
1019 independent reflections2 standard reflections every 60 min
457 reflections with I > 2σ(I) intensity decay: <2.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H-atom parameters constrained
wR(F2) = 0.134 w = 1/[σ2(Fo2) + (0.0545P)2 + 0.0084P]
where P = (Fo2 + 2Fc2)/3
S = 0.98(Δ/σ)max < 0.001
1019 reflectionsΔρmax = 0.19 e Å3
84 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.038 (7)
Crystal data top
C9H11NO3SV = 532.2 (5) Å3
Mr = 213.25Z = 2
Monoclinic, P21/mMo Kα radiation
a = 7.679 (4) ŵ = 0.29 mm1
b = 7.004 (5) ÅT = 293 K
c = 10.372 (5) Å0.6 × 0.2 × 0.1 mm
β = 107.43 (4)°
Data collection top
Stoe Stadi-4 four-circle
diffractometer
Rint = 0.058
1980 measured reflections2 standard reflections every 60 min
1019 independent reflections intensity decay: <2.0%
457 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.134H-atom parameters constrained
S = 0.98Δρmax = 0.19 e Å3
1019 reflectionsΔρmin = 0.19 e Å3
84 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
xyzUiso*/Ueq
S10.3128 (2)0.25000.91368 (13)0.0848 (8)
O10.1571 (5)0.25000.4904 (3)0.0656 (13)
O20.2914 (5)0.25000.4666 (3)0.0947 (19)
O30.4864 (5)0.25000.7292 (3)0.0827 (17)
N10.1849 (5)0.25000.6505 (4)0.0590 (15)
H10.08300.25000.66900.071*
C10.3197 (7)0.25000.3881 (6)0.076 (2)
H1A0.43450.25000.40110.091*
C20.2903 (7)0.25000.2686 (6)0.070 (2)
H20.37840.25000.18440.084*
C30.1005 (7)0.25000.2938 (5)0.0659 (19)
H30.03870.25000.22910.079*
C40.0237 (7)0.25000.4294 (5)0.0551 (18)
C50.1670 (8)0.25000.5134 (5)0.0588 (18)
C60.3373 (7)0.25000.7623 (5)0.0537 (18)
C70.6648 (7)0.25000.8351 (6)0.096 (3)
H70.64990.25000.92570.116*
C80.7613 (6)0.4272 (9)0.8109 (5)0.123 (3)
H8A0.76470.42850.71920.185*
H8B0.88370.42830.87120.185*
H8C0.69720.53800.82710.185*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0516 (10)0.155 (2)0.0464 (8)0.0000.0131 (7)0.000
O10.035 (2)0.107 (4)0.053 (2)0.0000.0114 (19)0.000
O20.036 (2)0.199 (6)0.050 (2)0.0000.0134 (19)0.000
O30.033 (2)0.167 (5)0.0436 (19)0.0000.0048 (17)0.000
N10.030 (2)0.100 (5)0.045 (2)0.0000.008 (2)0.000
C10.032 (3)0.113 (7)0.075 (4)0.0000.006 (3)0.000
C20.045 (4)0.096 (7)0.056 (3)0.0000.005 (3)0.000
C30.044 (4)0.100 (6)0.051 (3)0.0000.010 (3)0.000
C40.034 (3)0.087 (6)0.044 (3)0.0000.010 (2)0.000
C50.047 (4)0.082 (6)0.048 (3)0.0000.016 (3)0.000
C60.035 (3)0.071 (6)0.054 (3)0.0000.012 (3)0.000
C70.034 (4)0.202 (11)0.052 (3)0.0000.011 (3)0.000
C80.055 (3)0.152 (7)0.140 (5)0.004 (4)0.007 (3)0.056 (5)
Geometric parameters (Å, º) top
S1—C61.636 (5)C2—C31.402 (7)
O1—C41.356 (6)C2—H20.93
O1—C11.375 (6)C3—C41.352 (7)
O2—C51.194 (6)C3—H30.93
O3—C61.290 (6)C4—C51.463 (7)
O3—C71.477 (6)C7—C8i1.505 (6)
N1—C61.379 (6)C7—C81.505 (6)
N1—C51.387 (6)C7—H70.9800
N1—H10.86C8—H8A0.96
C1—C21.326 (7)C8—H8B0.96
C1—H1A0.93C8—H8C0.96
C4—O1—C1106.2 (4)O2—C5—C4122.5 (5)
C6—O3—C7120.1 (4)N1—C5—C4112.6 (5)
C6—N1—C5131.4 (4)O3—C6—N1111.9 (4)
C6—N1—H1114.3O3—C6—S1128.4 (4)
C5—N1—H1114.3N1—C6—S1119.7 (4)
C2—C1—O1110.6 (5)O3—C7—C8i105.6 (3)
C2—C1—H1A124.7O3—C7—C8105.6 (3)
O1—C1—H1A124.7C8i—C7—C8111.1 (6)
C1—C2—C3106.5 (5)O3—C7—H7111.4
C1—C2—H2126.7C8i—C7—H7111.4
C3—C2—H2126.7C8—C7—H7111.4
C4—C3—C2107.4 (5)C7—C8—H8A109.5
C4—C3—H3126.3C7—C8—H8B109.5
C2—C3—H3126.3H8A—C8—H8B109.5
C3—C4—O1109.3 (4)C7—C8—H8C109.5
C3—C4—C5131.8 (5)H8A—C8—H8C109.5
O1—C4—C5118.9 (4)H8B—C8—H8C109.5
O2—C5—N1124.8 (5)
C4—O1—C1—C20O1—C4—C5—O2180
O1—C1—C2—C30C3—C4—C5—N1180
C1—C2—C3—C40O1—C4—C5—N10
C2—C3—C4—O10C7—O3—C6—N1180
C2—C3—C4—C5180C7—O3—C6—S10
C1—O1—C4—C30C5—N1—C6—O30
C1—O1—C4—C5180C5—N1—C6—S1180
C6—N1—C5—O20C6—O3—C7—C8i121.1 (3)
C6—N1—C5—C4180C6—O3—C7—C8121.1 (3)
C3—C4—C5—O20
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.192.654 (6)114
C1—H1A···O2ii0.932.403.322 (7)172
C7—H7···S10.982.553.048 (7)111
Symmetry code: (ii) x1, y, z.

Experimental details

Crystal data
Chemical formulaC9H11NO3S
Mr213.25
Crystal system, space groupMonoclinic, P21/m
Temperature (K)293
a, b, c (Å)7.679 (4), 7.004 (5), 10.372 (5)
β (°) 107.43 (4)
V3)532.2 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.6 × 0.2 × 0.1
Data collection
DiffractometerStoe Stadi-4 four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1980, 1019, 457
Rint0.058
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.134, 0.98
No. of reflections1019
No. of parameters84
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.19

Computer programs: DIF4 (Stoe & Cie, 1992), DIF4, REDU4 (Stoe & Cie, 1992), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Bergerhoff, 1996), SHELXL97 (Sheldrick 1997) and PARST (Nardelli, 1983, 1995).

Selected geometric parameters (Å, º) top
S1—C61.636 (5)O3—C61.290 (6)
O1—C41.356 (6)O3—C71.477 (6)
O1—C11.375 (6)N1—C61.379 (6)
O2—C51.194 (6)N1—C51.387 (6)
C6—O3—C7120.1 (4)N1—C5—C4112.6 (5)
C6—N1—C5131.4 (4)O3—C6—N1111.9 (4)
O2—C5—N1124.8 (5)O3—C6—S1128.4 (4)
O2—C5—C4122.5 (5)N1—C6—S1119.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.192.654 (6)114
C1—H1A···O2i0.932.403.322 (7)172
C7—H7···S10.982.553.048 (7)111
Symmetry code: (i) x1, y, z.
 

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