Electron density study of 2H-chromene-2-thione

Munshi, P.; Guru Row, T.N.

doi:10.1107/S0108768102018712

Electron density study of 2H-chromene-2-thione

The charge-density distribution in 2H-chromene-2-thione (2-thiocoumarin), C₉H₆OS, has been determined from X-ray diffraction data measured at 90 K using a CCD detector, to a resolution of sinθ/λ < 1.08 Å⁻¹. A multipolar-atom density model was fitted against 6908 reflections with I > 2σ(I) [R(F) = 0.021, wR(F) = 0.022, goodness of fit = 1.81] in order to generate the difference Fourier maps. The topological properties of the molecular electron density in terms of the bond critical points and the evaluation of the dipole moment show that the molecular dipole moment in the crystal is higher than the corresponding value derived from theoretical calculations.

Keywords: experimental electron density; 2H-chromene-2-thione; multipole model.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S0108768102018712/lc0053sup1.cif Contains datablock THIO2
	Structure factor file (CIF format) https://doi.org/10.1107/S0108768102018712/lc0053sup2.hkl Contains datablock ppm290
	Portable Document Format (PDF) file https://doi.org/10.1107/S0108768102018712/lc0053sup3.pdf Multipole population coefficients

CCDC reference: 201622

Comment top

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Experimental top

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Computing details top

Data collection: Bruker SMART; cell refinement: Bruker SMART; data reduction: Bruker SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: Koritsanszky et al., (1999); molecular graphics: Koritsanszky et al., (1999); software used to prepare material for publication: Koritsanszky et al., (1999).

Figures top

2H-chromene-2-thione top

Crystal data top

C₉H₆OS	D_x = 1.481 Mg m⁻³
M_r = 162.21	Melting point: 371 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9651 reflections
a = 4.0515 (2) Å	θ = 2.3–50.1°
b = 10.1749 (7) Å	µ = 0.37 mm⁻¹
c = 17.6519 (9) Å	T = 90 K
V = 727.67 (7) Å³	Prism, yellow
Z = 4	0.60 × 0.37 × 0.10 mm
F(000) = 336

Data collection top

CCD area detector Bruker Axs SMART APEX diffractometer	6908 reflections with I > 2σ(I)
ϕ and ω scans	R_int = 0.038
Absorption correction: empirical (using intensity measurements) R.H. Blessing, Acta Cryst. (1995), A51, 33-38	θ_max = 50.1°, θ_min = 2.3°
T_min = 0.809, T_max = 0.964	h = 0→8
7608 measured reflections	k = 0→21
7608 independent reflections	l = −37→37

Refinement top

Refinement on F	All H-atom parameters refined
Least-squares matrix: full	w = 1/[σ²(F_o²)]
R[F² > 2σ(F²)] = 0.022	(Δ/σ)_max = 0.002
wR(F²) = 0.022	Δρ_max = 0.20 e Å⁻³
S = 1.81	Δρ_min = −0.28 e Å⁻³
7608 reflections	Absolute structure: Flack H.D. (1983), Acta Cryst. A39, 876-881
318 parameters	Absolute structure parameter: −0.01 (3)
0 restraints

Crystal data top

C₉H₆OS	V = 727.67 (7) Å³
M_r = 162.21	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.0515 (2) Å	µ = 0.37 mm⁻¹
b = 10.1749 (7) Å	T = 90 K
c = 17.6519 (9) Å	0.60 × 0.37 × 0.10 mm

Data collection top

CCD area detector Bruker Axs SMART APEX diffractometer	7608 independent reflections
Absorption correction: empirical (using intensity measurements) R.H. Blessing, Acta Cryst. (1995), A51, 33-38	6908 reflections with I > 2σ(I)
T_min = 0.809, T_max = 0.964	R_int = 0.038
7608 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	All H-atom parameters refined
wR(F²) = 0.022	Δρ_max = 0.20 e Å⁻³
S = 1.81	Δρ_min = −0.28 e Å⁻³
7608 reflections	Absolute structure: Flack H.D. (1983), Acta Cryst. A39, 876-881
318 parameters	Absolute structure parameter: −0.01 (3)
0 restraints

Special details top

Experimental. Crystal to Detector distance was 6.03 cm, ω range is 0.3 ° and exposure time was 15 s, 30 s and 45 s in three batches respectively.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S(1)	0.51603 (3)	0.94025 (1)	0.83667 (1)	0.016
O(1)	0.23422 (13)	1.01214 (4)	0.71198 (3)	0.013
C(8)	0.05056 (10)	0.99619 (4)	0.64708 (2)	0.012
C(3)	0.03656 (11)	0.76104 (4)	0.66970 (2)	0.014
C(9)	−0.06119 (10)	0.87198 (4)	0.62490 (2)	0.013
C(2)	0.22833 (12)	0.77913 (4)	0.73200 (2)	0.014
C(4)	−0.25394 (11)	0.86232 (5)	0.55854 (3)	0.016
C(1)	0.31873 (10)	0.90866 (4)	0.75672 (2)	0.012
C(7)	−0.01552 (12)	1.10918 (4)	0.60496 (2)	0.015
C(6)	−0.20365 (13)	1.09660 (5)	0.53942 (3)	0.017
C(5)	−0.32431 (12)	0.97352 (5)	0.51619 (3)	0.018
H(3)	−0.02857	0.66100	0.65575	0.038 (4)
H(7)	0.08128	1.20440	0.62037	0.046 (4)
H(4)	−0.36004	0.76764	0.54542	0.069 (5)
H(5)	−0.49509	0.96935	0.46927	0.046 (5)
H(6)	−0.26079	1.18565	0.50882	0.042 (4)
H(2)	0.32209	0.69667	0.76395	0.031 (4)
DUM0	0.00000	0.00000	0.00000	0.000	0.0000

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S(1)	0.01815 (5)	0.01430 (4)	0.01659 (4)	−0.00002 (3)	−0.00450 (3)	−0.00010 (3)
O(1)	0.0157 (1)	0.0100 (1)	0.0139 (1)	−0.0010 (1)	−0.0007 (1)	0.0002 (1)
C(8)	0.0125 (1)	0.0107 (1)	0.0126 (1)	−0.0002 (1)	0.0015 (1)	0.0000 (1)
C(3)	0.0169 (1)	0.0105 (1)	0.0155 (1)	−0.0019 (1)	0.0014 (1)	−0.0014 (1)
C(9)	0.0126 (1)	0.0121 (1)	0.0131 (1)	−0.0010 (1)	0.0019 (1)	−0.0013 (1)
C(2)	0.0175 (2)	0.0101 (1)	0.0153 (1)	−0.0005 (1)	0.0007 (1)	0.0006 (1)
C(4)	0.0145 (1)	0.0182 (2)	0.0144 (1)	−0.0013 (1)	0.0009 (1)	−0.0030 (1)
C(1)	0.0129 (1)	0.0109 (1)	0.0134 (1)	−0.0003 (1)	0.0003 (1)	0.0000 (1)
C(7)	0.0167 (1)	0.0130 (1)	0.0146 (1)	0.0007 (1)	0.0013 (1)	0.0016 (1)
C(6)	0.0180 (2)	0.0193 (2)	0.0147 (2)	0.0019 (1)	0.0007 (1)	0.0029 (1)
C(5)	0.0165 (2)	0.0231 (2)	0.0137 (1)	0.0001 (2)	0.0000 (1)	−0.0002 (1)

Geometric parameters (Å, º) top

S(1)—C(1)	1.6534 (4)	C(2)—C(1)	1.4358 (6)
O(1)—C(8)	1.3757 (6)	C(2)—H(2)	1.0800
O(1)—C(1)	1.3601 (6)	C(4)—C(5)	1.3858 (7)
C(8)—C(9)	1.3984 (5)	C(4)—H(4)	1.0800
C(8)—C(7)	1.3951 (5)	C(7)—C(6)	1.3913 (7)
C(3)—C(9)	1.4341 (6)	C(7)—H(7)	1.0800
C(3)—C(2)	1.3590 (6)	C(6)—C(5)	1.4054 (7)
C(3)—H(3)	1.0800	C(6)—H(6)	1.0800
C(9)—C(4)	1.4112 (6)	C(5)—H(5)	1.0800

C(8)—O(1)—C(1)	121.90 (4)	C(9)—C(4)—H(4)	117.41
O(1)—C(8)—C(9)	120.99 (4)	C(5)—C(4)—H(4)	122.06
O(1)—C(8)—C(7)	116.77 (4)	S(1)—C(1)—O(1)	117.83 (3)
C(9)—C(8)—C(7)	122.24 (4)	S(1)—C(1)—C(2)	124.14 (3)
C(9)—C(3)—C(2)	119.84 (4)	O(1)—C(1)—C(2)	118.03 (4)
C(9)—C(3)—H(3)	123.28	C(8)—C(7)—C(6)	118.19 (4)
C(2)—C(3)—H(3)	116.86	C(8)—C(7)—H(7)	122.36
C(8)—C(9)—C(3)	117.88 (4)	C(6)—C(7)—H(7)	119.41
C(8)—C(9)—C(4)	118.33 (4)	C(7)—C(6)—C(5)	121.01 (4)
C(3)—C(9)—C(4)	123.76 (4)	C(7)—C(6)—H(6)	117.13
C(3)—C(2)—C(1)	121.07 (4)	C(5)—C(6)—H(6)	121.81
C(3)—C(2)—H(2)	121.23	C(4)—C(5)—C(6)	119.90 (5)
C(1)—C(2)—H(2)	117.69	C(4)—C(5)—H(5)	120.89
C(9)—C(4)—C(5)	120.31 (4)	C(6)—C(5)—H(5)	118.79

C(8)—O(1)—C(1)—S(1)	−175.5 (1)	C(8)—C(9)—C(4)—C(5)	1.1 (1)
C(1)—O(1)—C(8)—C(9)	0.9 (1)	C(8)—C(9)—C(4)—H(4)	−173.6
C(8)—O(1)—C(1)—C(2)	3.8 (1)	C(3)—C(9)—C(4)—C(5)	−176.7 (1)
C(1)—O(1)—C(8)—C(7)	−178.8 (1)	C(3)—C(9)—C(4)—H(4)	8.6
O(1)—C(8)—C(9)—C(3)	−3.3 (1)	C(3)—C(2)—C(1)—S(1)	173.1 (1)
O(1)—C(8)—C(9)—C(4)	178.8 (1)	C(3)—C(2)—C(1)—O(1)	−6.3 (1)
O(1)—C(8)—C(7)—C(6)	−179.3 (1)	H(2)—C(2)—C(1)—S(1)	−8.1
O(1)—C(8)—C(7)—H(7)	3.0	H(2)—C(2)—C(1)—O(1)	172.5
C(7)—C(8)—C(9)—C(3)	176.4 (1)	C(9)—C(4)—C(5)—C(6)	−0.1 (1)
C(7)—C(8)—C(9)—C(4)	−1.6 (1)	C(9)—C(4)—C(5)—H(5)	−172.6
C(9)—C(8)—C(7)—C(6)	1.0 (1)	H(4)—C(4)—C(5)—C(6)	174.4
C(9)—C(8)—C(7)—H(7)	−176.7	H(4)—C(4)—C(5)—H(5)	1.9
C(2)—C(3)—C(9)—C(8)	0.8 (1)	C(8)—C(7)—C(6)—C(5)	0.0 (1)
C(2)—C(3)—C(9)—C(4)	178.6 (1)	C(8)—C(7)—C(6)—H(6)	177.5
C(9)—C(3)—C(2)—C(1)	3.9 (1)	H(7)—C(7)—C(6)—C(5)	177.8
C(9)—C(3)—C(2)—H(2)	−174.8	H(7)—C(7)—C(6)—H(6)	−4.7
H(3)—C(3)—C(9)—C(8)	−177.3	C(7)—C(6)—C(5)—C(4)	−0.5 (1)
H(3)—C(3)—C(9)—C(4)	0.5	C(7)—C(6)—C(5)—H(5)	172.2
H(3)—C(3)—C(2)—C(1)	−177.8	H(6)—C(6)—C(5)—C(4)	−177.9
H(3)—C(3)—C(2)—H(2)	3.4	H(6)—C(6)—C(5)—H(5)	−5.2

Experimental details

Crystal data
Chemical formula	C₉H₆OS
M_r	162.21
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	90
a, b, c (Å)	4.0515 (2), 10.1749 (7), 17.6519 (9)
V (Å³)	727.67 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.37
Crystal size (mm)	0.60 × 0.37 × 0.10

Data collection
Diffractometer	CCD area detector Bruker Axs SMART APEX diffractometer
Absorption correction	Empirical (using intensity measurements) R.H. Blessing, Acta Cryst. (1995), A51, 33-38
T_min, T_max	0.809, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	7608, 7608, 6908
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	1.080

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.022, 1.81
No. of reflections	7608
No. of parameters	318
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.28
Absolute structure	Flack H.D. (1983), Acta Cryst. A39, 876-881
Absolute structure parameter	−0.01 (3)

Computer programs: Bruker SMART, Bruker SAINT, SHELXS97 (Sheldrick, 1997), Koritsanszky et al., (1999).

Selected geometric parameters (Å, º) top

S(1)—C(1)	1.6534 (4)	C(2)—C(1)	1.4358 (6)
O(1)—C(8)	1.3757 (6)	C(2)—H(2)	1.0800
O(1)—C(1)	1.3601 (6)	C(4)—C(5)	1.3858 (7)
C(8)—C(9)	1.3984 (5)	C(4)—H(4)	1.0800
C(8)—C(7)	1.3951 (5)	C(7)—C(6)	1.3913 (7)
C(3)—C(9)	1.4341 (6)	C(7)—H(7)	1.0800
C(3)—C(2)	1.3590 (6)	C(6)—C(5)	1.4054 (7)
C(3)—H(3)	1.0800	C(6)—H(6)	1.0800
C(9)—C(4)	1.4112 (6)	C(5)—H(5)	1.0800

C(8)—O(1)—C(1)	121.90 (4)	C(9)—C(4)—H(4)	117.41
O(1)—C(8)—C(9)	120.99 (4)	C(5)—C(4)—H(4)	122.06
O(1)—C(8)—C(7)	116.77 (4)	S(1)—C(1)—O(1)	117.83 (3)
C(9)—C(8)—C(7)	122.24 (4)	S(1)—C(1)—C(2)	124.14 (3)
C(9)—C(3)—C(2)	119.84 (4)	O(1)—C(1)—C(2)	118.03 (4)
C(9)—C(3)—H(3)	123.28	C(8)—C(7)—C(6)	118.19 (4)
C(2)—C(3)—H(3)	116.86	C(8)—C(7)—H(7)	122.36
C(8)—C(9)—C(3)	117.88 (4)	C(6)—C(7)—H(7)	119.41
C(8)—C(9)—C(4)	118.33 (4)	C(7)—C(6)—C(5)	121.01 (4)
C(3)—C(9)—C(4)	123.76 (4)	C(7)—C(6)—H(6)	117.13
C(3)—C(2)—C(1)	121.07 (4)	C(5)—C(6)—H(6)	121.81
C(3)—C(2)—H(2)	121.23	C(4)—C(5)—C(6)	119.90 (5)
C(1)—C(2)—H(2)	117.69	C(4)—C(5)—H(5)	120.89
C(9)—C(4)—C(5)	120.31 (4)	C(6)—C(5)—H(5)	118.79

C(8)—O(1)—C(1)—S(1)	−175.5 (1)	C(8)—C(9)—C(4)—C(5)	1.1 (1)
C(1)—O(1)—C(8)—C(9)	0.9 (1)	C(8)—C(9)—C(4)—H(4)	−173.6
C(8)—O(1)—C(1)—C(2)	3.8 (1)	C(3)—C(9)—C(4)—C(5)	−176.7 (1)
C(1)—O(1)—C(8)—C(7)	−178.8 (1)	C(3)—C(9)—C(4)—H(4)	8.6
O(1)—C(8)—C(9)—C(3)	−3.3 (1)	C(3)—C(2)—C(1)—S(1)	173.1 (1)
O(1)—C(8)—C(9)—C(4)	178.8 (1)	C(3)—C(2)—C(1)—O(1)	−6.3 (1)
O(1)—C(8)—C(7)—C(6)	−179.3 (1)	H(2)—C(2)—C(1)—S(1)	−8.1
O(1)—C(8)—C(7)—H(7)	3.0	H(2)—C(2)—C(1)—O(1)	172.5
C(7)—C(8)—C(9)—C(3)	176.4 (1)	C(9)—C(4)—C(5)—C(6)	−0.1 (1)
C(7)—C(8)—C(9)—C(4)	−1.6 (1)	C(9)—C(4)—C(5)—H(5)	−172.6
C(9)—C(8)—C(7)—C(6)	1.0 (1)	H(4)—C(4)—C(5)—C(6)	174.4
C(9)—C(8)—C(7)—H(7)	−176.7	H(4)—C(4)—C(5)—H(5)	1.9
C(2)—C(3)—C(9)—C(8)	0.8 (1)	C(8)—C(7)—C(6)—C(5)	0.0 (1)
C(2)—C(3)—C(9)—C(4)	178.6 (1)	C(8)—C(7)—C(6)—H(6)	177.5
C(9)—C(3)—C(2)—C(1)	3.9 (1)	H(7)—C(7)—C(6)—C(5)	177.8
C(9)—C(3)—C(2)—H(2)	−174.8	H(7)—C(7)—C(6)—H(6)	−4.7
H(3)—C(3)—C(9)—C(8)	−177.3	C(7)—C(6)—C(5)—C(4)	−0.5 (1)
H(3)—C(3)—C(9)—C(4)	0.5	C(7)—C(6)—C(5)—H(5)	172.2
H(3)—C(3)—C(2)—C(1)	−177.8	H(6)—C(6)—C(5)—C(4)	−177.9
H(3)—C(3)—C(2)—H(2)	3.4	H(6)—C(6)—C(5)—H(5)	−5.2

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