Crystal structure of ethyl 4-(2-fluoro­phen­yl)-6-methyl-2-sulfanyl­idene-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate

Krishnamurthy, M.S.; Begum, N.S.

doi:10.1107/S2056989015015145

organic compounds

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ISSN: 2056-9890

Volume 71| Part 10| October 2015| Pages o699-o700

doi:10.1107/S2056989015015145

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Crystal structure of ethyl 4-(2-fluorophenyl)-6-methyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylate

M. S. Krishnamurthy ^a and Noor Shahina Begum ^a ^*

^aDepartment of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore 560 001, Karnataka, India
^*Correspondence e-mail: noorsb@rediffmail.com

Edited by A. J. Lough, University of Toronto, Canada (Received 8 August 2015; accepted 14 August 2015; online 12 September 2015)

The title compound, C₁₄H₁₅FN₂O₂S, crystallizes with two molecules in the asymmetric unit. In each molecule, the pyrimidine ring adopts a sofa conformation with the sp³-hybridized C atom forming the flap and the fluoro-substituted ring in an axial position. In the crystal, molecules are linked via N—H⋯S hydrogen bonds, forming chains of R₂²(8) rings along [100]. In one independent molecule, an intramolecular C—H⋯O hydrogen bond is observed.

Keywords: crystal structure; ester; pyrimidine; hydrogen bonding; 3,4-dihydropyrimidin-2(1H)-one; therapeutic properties; pharmacological properties.

CCDC reference: 1418668

1. Related literature

For the therapeutic and pharmacological properties of 3,4-dihydropyrimidin-2(1H)-ones, see: Kappe (2000 ); Hurst & Hull (1961 ); Mayer et al. (1999 ); Atwal et al. (1991 ). For their applications in calcium-channel modulators, see: Kappe (1998 ); Jauk et al. (2000 ); Krishnamurthy & Begum (2015 ). For the bioactivity of organo–fluorine compounds, see: Hermann et al. (2003 ); Ulrich (2004 ). For examples of fluorine-directed crystal packing, see: Prasanna & Guru Row (2001 ). For related structures, see: Qin et al. (2006 ); Krishnamurthy & Begum (2015). For hydrogen-bond graph-set notation, see: Bernstein et al. (1995 ).

2. Experimental

2.1. Crystal data

C₁₄H₁₅FN₂O₂S
M_r = 294.34
Triclinic, $[P \overline 1]$
a = 8.9298 (6) Å
b = 11.5870 (8) Å
c = 15.7459 (11) Å
α = 100.940 (2)°
β = 104.804 (2)°
γ = 98.153 (2)°
V = 1515.11 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.18 × 0.16 × 0.16 mm

2.2. Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.960, T_max = 0.965
17808 measured reflections
5328 independent reflections
3389 reflections with I > 2σ(I)
R_int = 0.039

2.3. Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.228
S = 0.98
5328 reflections
365 parameters
H-atom parameters constrained
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1′ⁱ	0.88	2.83	3.703 (4)	170
N1′—H1′⋯S1	0.88	2.84	3.711 (4)	171
N2—H2⋯S1′	0.88	2.52	3.337 (4)	155
N2′—H2′⋯S1ⁱⁱ	0.88	2.50	3.335 (5)	158
C1′—H1′1⋯O1′	0.98	2.14	2.861 (6)	129
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z.

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ), CAMERON (Watkin et al., 1996 ) and DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1418668

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015015145/lh5781sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015015145/lh5781Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015015145/lh5781Isup3.cml

checkCIF report

Comment top

The Biginelli reaction is a three-component condensation of ethyl acetoacetate, benzaldehyde and urea for the synthesis of 3,4-dihydropyrimidine-2(1H) -ones (abbreviated as DHPMs). DHPMs have recently emerged as important target molecules because of their therapeutic and pharmacological properties (Kappe, 2000), such as antiviral (Hurst & Hull, 1961), antimitotic (Mayer et al., 1999), anticarcinogenic and antihypertensive (Atwal et al., 1991). They are also noteworthy as calcium channel modulators (Kappe, 1998; Jauk et al., 2000). In addition, compounds that contain fluorine have special bioactivity, e.g. flumioxazin is a widely used herbicide (Hermann et al., 2003; Ulrich, 2004). Guru Row and co-workers have extensively studied the structural property of fluorine and they have presented several elegant examples of fluorine directed crystal packing (Prasanna & Guru Row, 2001). Herein, we report the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. There are two indpendent molecules in the asymmetric unit. The bond lengths and bond angles are in good agreement with the corresponding bond distances and angles reported in closely related structures (Qin et al., 2006; Krishnamurthy & Begum, 2015). In each molecule, the pyrimidine ring adopts a sofa conformation with the sp³ hybridized carbon atom [C4 and C4'] forming the flap and the fluoro-substituted ring in an axial position. The carbonyl group of the exocyclic ester at C5 and C5' adopts a cis orientation with respect to the C5═C6 and C5'═C6 double bond. The fluoro-substituted benzene ring adopts an syn periplanar conformation with respect to the C4—H4 and C4'—H4' bonds. In the crystal, molecules are linked via N—H···S hydrogen bonds forming chains of R₂²(8) rings (Bernstein et al., 1995) along [100] (Fig. 2). In one independent molecule an intramolecular C—H···O hydrogen bond is observed.

Related literature top

For the therapeutic and pharmacological properties of 3,4-dihydropyrimidin-2(1H)-ones, see: Kappe (2000); Hurst & Hull (1961); Mayer et al. (1999); Atwal et al., (1991). For their applications in calcium-channel modulators, see: Kappe (1998); Jauk et al. (2000); Krishnamurthy & Begum (2015). For the bioactivity of organo–fluorine compounds, see: Hermann et al. (2003); Ulrich (2004). For examples of fluorine-directed crystal packing, see: Prasanna & Guru Row (2001). For related structures, see: Qin et al. (2006); Krishnamurthy & Begum (2015). For hydrogen-bond graph-set notation, see: Bernstein et al. (1995).

Experimental top

The title compound was synthesized by the reaction of 2-fluorobenzaldehyde (1.24 g, 10 mmol), ethylacetoacetate (1.52 g, 12 mmol) and thiourea (1.14 g, 15 mmol) in 15 ml ethanol was refluxed for 6 h in the presence of concentrated hydrochloric acid as a catalyst. The reaction was monitored with TLC and the reaction medium was quenched in ice cold water. The precipitate obtained was filtered and dried. The compound was recrystallized from ethanol solvent by slow evaporation method, yielding colorless blocks suitable for X-ray diffraction studies (yield 76%; m.p. 485 K).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), CAMERON (Watkin et al., 1996) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

Ethyl 4-(2-fluorophenyl)-6-methyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylate top

Crystal data top

C₁₄H₁₅FN₂O₂S	Z = 4
M_r = 294.34	F(000) = 616
Triclinic, P1	D_x = 1.290 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9298 (6) Å	Cell parameters from 5328 reflections
b = 11.5870 (8) Å	θ = 2.4–25.0°
c = 15.7459 (11) Å	µ = 0.23 mm⁻¹
α = 100.940 (2)°	T = 100 K
β = 104.804 (2)°	Block, colourless
γ = 98.153 (2)°	0.18 × 0.16 × 0.16 mm
V = 1515.11 (18) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	5328 independent reflections
Radiation source: fine-focus sealed tube	3389 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −10→10
T_min = 0.960, T_max = 0.965	k = −13→13
17808 measured reflections	l = −18→18

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.228	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.1269P)² + 1.4728P] where P = (F_o² + 2F_c²)/3
5328 reflections	(Δ/σ)_max = 0.001
365 parameters	Δρ_max = 1.04 e Å⁻³
0 restraints	Δρ_min = −0.35 e Å⁻³

Crystal data top

C₁₄H₁₅FN₂O₂S	γ = 98.153 (2)°
M_r = 294.34	V = 1515.11 (18) Å³
Triclinic, P1	Z = 4
a = 8.9298 (6) Å	Mo Kα radiation
b = 11.5870 (8) Å	µ = 0.23 mm⁻¹
c = 15.7459 (11) Å	T = 100 K
α = 100.940 (2)°	0.18 × 0.16 × 0.16 mm
β = 104.804 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	5328 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	3389 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.965	R_int = 0.039
17808 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.228	H-atom parameters constrained
S = 0.98	Δρ_max = 1.04 e Å⁻³
5328 reflections	Δρ_min = −0.35 e Å⁻³
365 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.86288 (13)	0.90033 (10)	0.07601 (7)	0.0522 (3)
O1	0.6733 (4)	0.6314 (3)	−0.3693 (2)	0.0743 (10)
O2	0.4450 (4)	0.6240 (3)	−0.33627 (19)	0.0701 (10)
N1	0.8792 (4)	0.8058 (3)	−0.0880 (2)	0.0489 (9)
H1	0.9822	0.8229	−0.0631	0.059*
N2	0.6330 (4)	0.7993 (3)	−0.0734 (2)	0.0414 (8)
H2	0.5717	0.8312	−0.0439	0.050*
F1	0.2317 (4)	0.6093 (4)	−0.2084 (3)	0.1226 (14)
C1	0.9490 (6)	0.7543 (5)	−0.2257 (3)	0.0738 (15)
H1A	0.9492	0.6715	−0.2544	0.111*
H1B	1.0519	0.7900	−0.1810	0.111*
H1C	0.9294	0.8010	−0.2717	0.111*
C2	0.7856 (5)	0.8314 (3)	−0.0339 (3)	0.0412 (9)
C3	0.6001 (5)	0.6538 (4)	−0.3149 (3)	0.0499 (10)
C4	0.5536 (4)	0.7162 (3)	−0.1611 (2)	0.0382 (9)
H4	0.4611	0.7476	−0.1922	0.046*
C5	0.6672 (5)	0.7122 (3)	−0.2183 (3)	0.0415 (9)
C6	0.8224 (5)	0.7548 (4)	−0.1798 (3)	0.0460 (10)
C7	0.3610 (7)	0.5580 (6)	−0.4281 (3)	0.0891 (19)
H7A	0.3593	0.6128	−0.4694	0.107*
H7B	0.4162	0.4939	−0.4471	0.107*
C8	0.2083 (10)	0.5082 (10)	−0.4334 (5)	0.172 (5)
H8A	0.2091	0.4715	−0.3822	0.258*
H8B	0.1620	0.4467	−0.4901	0.258*
H8C	0.1453	0.5708	−0.4319	0.258*
C9	0.4933 (5)	0.5941 (4)	−0.1489 (3)	0.0455 (10)
C10	0.5973 (7)	0.5272 (4)	−0.1092 (3)	0.0641 (13)
H10	0.7080	0.5584	−0.0905	0.077*
C11	0.5406 (10)	0.4154 (5)	−0.0968 (4)	0.091 (2)
H11	0.6121	0.3698	−0.0706	0.109*
C12	0.3822 (15)	0.3718 (6)	−0.1225 (5)	0.121 (3)
H12	0.3439	0.2959	−0.1130	0.145*
C13	0.2769 (9)	0.4347 (7)	−0.1617 (5)	0.103 (2)
H13	0.1664	0.4031	−0.1807	0.123*
C14	0.3357 (6)	0.5445 (5)	−0.1726 (3)	0.0669 (13)
S1'	0.31495 (13)	0.84530 (11)	−0.00790 (7)	0.0544 (4)
O1'	0.6197 (5)	1.1437 (4)	0.4307 (3)	0.0940 (13)
O2'	0.3597 (4)	1.0906 (3)	0.4089 (2)	0.0683 (9)
N1'	0.5140 (4)	0.9516 (3)	0.1541 (2)	0.0490 (9)
H1'	0.5889	0.9363	0.1291	0.059*
N2'	0.2541 (4)	0.9254 (3)	0.1455 (2)	0.0463 (8)
H2'	0.1559	0.9156	0.1118	0.056*
F1'	0.0344 (4)	0.9094 (4)	0.3206 (3)	0.1074 (12)
C1'	0.7322 (5)	1.0702 (5)	0.2784 (3)	0.0692 (14)
H1'1	0.7651	1.0866	0.3446	0.104*
H1'2	0.7528	1.1453	0.2595	0.104*
H1'3	0.7921	1.0141	0.2544	0.104*
C2'	0.3619 (5)	0.9103 (3)	0.1028 (3)	0.0428 (9)
C3'	0.4889 (6)	1.0926 (4)	0.3814 (3)	0.0603 (12)
C4'	0.2823 (5)	0.9565 (4)	0.2428 (3)	0.0448 (10)
H4'	0.2094	1.0105	0.2567	0.054*
C5'	0.4504 (5)	1.0246 (3)	0.2879 (3)	0.0454 (10)
C6'	0.5595 (5)	1.0163 (4)	0.2430 (3)	0.0475 (10)
C7'	0.3799 (8)	1.1522 (5)	0.5011 (4)	0.0890 (18)
H7'1	0.4179	1.2393	0.5096	0.107*
H7'2	0.4591	1.1219	0.5431	0.107*
C8'	0.2281 (11)	1.1309 (9)	0.5198 (5)	0.144 (3)
H8'1	0.1539	1.1693	0.4828	0.217*
H8'2	0.2423	1.1647	0.5839	0.217*
H8'3	0.1862	1.0443	0.5052	0.217*
C9'	0.2458 (5)	0.8451 (4)	0.2768 (3)	0.0467 (10)
C10'	0.3336 (6)	0.7567 (4)	0.2711 (3)	0.0623 (13)
H10'	0.4194	0.7666	0.2460	0.075*
C11'	0.2998 (8)	0.6546 (5)	0.3007 (4)	0.0861 (18)
H11'	0.3602	0.5939	0.2946	0.103*
C12'	0.1789 (9)	0.6404 (6)	0.3392 (4)	0.091 (2)
H12'	0.1561	0.5704	0.3604	0.109*
C13'	0.0928 (8)	0.7260 (7)	0.3468 (4)	0.0926 (19)
H13'	0.0103	0.7176	0.3745	0.111*
C14'	0.1248 (6)	0.8256 (5)	0.3142 (3)	0.0675 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0422 (6)	0.0611 (7)	0.0453 (6)	0.0011 (5)	0.0124 (5)	0.0006 (5)
O1	0.076 (2)	0.100 (3)	0.0456 (18)	0.012 (2)	0.0265 (18)	0.0051 (17)
O2	0.053 (2)	0.103 (3)	0.0393 (17)	−0.0082 (18)	0.0078 (14)	0.0048 (16)
N1	0.0334 (18)	0.065 (2)	0.044 (2)	0.0023 (16)	0.0144 (15)	0.0047 (17)
N2	0.0351 (18)	0.0450 (18)	0.0419 (18)	0.0053 (15)	0.0147 (15)	0.0024 (15)
F1	0.057 (2)	0.161 (4)	0.132 (3)	−0.004 (2)	0.017 (2)	0.025 (3)
C1	0.057 (3)	0.099 (4)	0.063 (3)	−0.001 (3)	0.034 (3)	0.003 (3)
C2	0.039 (2)	0.037 (2)	0.047 (2)	0.0044 (17)	0.0133 (19)	0.0094 (18)
C3	0.057 (3)	0.049 (2)	0.045 (2)	0.005 (2)	0.016 (2)	0.017 (2)
C4	0.034 (2)	0.041 (2)	0.039 (2)	0.0074 (17)	0.0101 (17)	0.0083 (17)
C5	0.048 (2)	0.040 (2)	0.038 (2)	0.0046 (18)	0.0154 (18)	0.0136 (17)
C6	0.047 (2)	0.046 (2)	0.046 (2)	0.0057 (19)	0.020 (2)	0.0094 (19)
C7	0.076 (4)	0.117 (5)	0.044 (3)	−0.023 (3)	0.001 (3)	0.001 (3)
C8	0.102 (6)	0.268 (12)	0.072 (5)	−0.073 (7)	0.008 (4)	−0.030 (6)
C9	0.052 (2)	0.045 (2)	0.037 (2)	0.000 (2)	0.0194 (19)	0.0025 (18)
C10	0.097 (4)	0.047 (3)	0.059 (3)	0.016 (3)	0.037 (3)	0.016 (2)
C11	0.158 (7)	0.054 (3)	0.086 (4)	0.026 (4)	0.068 (4)	0.027 (3)
C12	0.216 (10)	0.057 (4)	0.095 (5)	−0.029 (5)	0.098 (6)	0.001 (4)
C13	0.107 (5)	0.087 (5)	0.096 (5)	−0.045 (4)	0.051 (4)	−0.003 (4)
C14	0.055 (3)	0.075 (3)	0.063 (3)	−0.008 (3)	0.022 (3)	0.006 (3)
S1'	0.0444 (6)	0.0736 (8)	0.0449 (6)	0.0117 (5)	0.0137 (5)	0.0122 (5)
O1'	0.076 (3)	0.107 (3)	0.067 (2)	−0.007 (2)	0.008 (2)	−0.017 (2)
O2'	0.077 (2)	0.071 (2)	0.0534 (19)	0.0092 (18)	0.0289 (17)	−0.0019 (16)
N1'	0.0341 (18)	0.062 (2)	0.049 (2)	0.0068 (16)	0.0149 (16)	0.0067 (17)
N2'	0.0359 (18)	0.066 (2)	0.0409 (19)	0.0151 (16)	0.0118 (15)	0.0167 (16)
F1'	0.083 (2)	0.135 (3)	0.138 (3)	0.034 (2)	0.074 (2)	0.047 (2)
C1'	0.042 (3)	0.084 (3)	0.070 (3)	−0.003 (2)	0.014 (2)	0.005 (3)
C2'	0.038 (2)	0.045 (2)	0.050 (2)	0.0109 (18)	0.0160 (19)	0.0165 (19)
C3'	0.069 (3)	0.050 (3)	0.060 (3)	0.010 (2)	0.018 (3)	0.011 (2)
C4'	0.041 (2)	0.051 (2)	0.046 (2)	0.0133 (19)	0.0185 (19)	0.0086 (19)
C5'	0.048 (2)	0.042 (2)	0.045 (2)	0.0080 (19)	0.012 (2)	0.0090 (18)
C6'	0.042 (2)	0.046 (2)	0.051 (3)	0.0055 (19)	0.012 (2)	0.010 (2)
C7'	0.134 (6)	0.077 (4)	0.057 (3)	0.021 (4)	0.039 (4)	0.004 (3)
C8'	0.153 (7)	0.189 (8)	0.105 (6)	0.029 (6)	0.092 (6)	−0.004 (5)
C9'	0.045 (2)	0.052 (2)	0.038 (2)	0.003 (2)	0.0100 (19)	0.0067 (19)
C10'	0.082 (3)	0.049 (3)	0.057 (3)	0.007 (2)	0.025 (3)	0.012 (2)
C11'	0.126 (5)	0.054 (3)	0.069 (4)	0.016 (3)	0.014 (4)	0.013 (3)
C12'	0.121 (5)	0.074 (4)	0.065 (4)	−0.022 (4)	0.022 (4)	0.024 (3)
C13'	0.094 (5)	0.102 (5)	0.083 (4)	−0.014 (4)	0.040 (4)	0.031 (4)
C14'	0.061 (3)	0.076 (3)	0.064 (3)	0.000 (3)	0.027 (3)	0.012 (3)

Geometric parameters (Å, º) top

S1—C2	1.679 (4)	S1'—C2'	1.679 (4)
O1—C3	1.216 (5)	O1'—C3'	1.218 (6)
O2—C3	1.316 (5)	O2'—C3'	1.330 (6)
O2—C7	1.450 (5)	O2'—C7'	1.443 (6)
N1—C2	1.360 (5)	N1'—C2'	1.354 (5)
N1—C6	1.382 (5)	N1'—C6'	1.383 (5)
N1—H1	0.8800	N1'—H1'	0.8800
N2—C2	1.311 (5)	N2'—C2'	1.321 (5)
N2—C4	1.463 (5)	N2'—C4'	1.452 (5)
N2—H2	0.8800	N2'—H2'	0.8800
F1—C14	1.355 (6)	F1'—C14'	1.354 (6)
C1—C6	1.490 (6)	C1'—C6'	1.496 (6)
C1—H1A	0.9800	C1'—H1'1	0.9800
C1—H1B	0.9800	C1'—H1'2	0.9800
C1—H1C	0.9800	C1'—H1'3	0.9800
C3—C5	1.469 (6)	C3'—C5'	1.459 (6)
C4—C9	1.506 (5)	C4'—C5'	1.512 (6)
C4—C5	1.518 (5)	C4'—C9'	1.513 (6)
C4—H4	1.0000	C4'—H4'	1.0000
C5—C6	1.340 (6)	C5'—C6'	1.346 (6)
C7—C8	1.378 (9)	C7'—C8'	1.456 (9)
C7—H7A	0.9900	C7'—H7'1	0.9900
C7—H7B	0.9900	C7'—H7'2	0.9900
C8—H8A	0.9800	C8'—H8'1	0.9800
C8—H8B	0.9800	C8'—H8'2	0.9800
C8—H8C	0.9800	C8'—H8'3	0.9800
C9—C14	1.368 (6)	C9'—C14'	1.368 (6)
C9—C10	1.394 (6)	C9'—C10'	1.378 (6)
C10—C11	1.391 (7)	C10'—C11'	1.375 (7)
C10—H10	0.9500	C10'—H10'	0.9500
C11—C12	1.359 (11)	C11'—C12'	1.371 (9)
C11—H11	0.9500	C11'—H11'	0.9500
C12—C13	1.366 (11)	C12'—C13'	1.345 (9)
C12—H12	0.9500	C12'—H12'	0.9500
C13—C14	1.365 (8)	C13'—C14'	1.373 (8)
C13—H13	0.9500	C13'—H13'	0.9500

C3—O2—C7	117.6 (4)	C3'—O2'—C7'	117.2 (4)
C2—N1—C6	124.0 (3)	C2'—N1'—C6'	124.3 (3)
C2—N1—H1	118.0	C2'—N1'—H1'	117.8
C6—N1—H1	118.0	C6'—N1'—H1'	117.8
C2—N2—C4	127.1 (3)	C2'—N2'—C4'	126.1 (3)
C2—N2—H2	116.5	C2'—N2'—H2'	117.0
C4—N2—H2	116.5	C4'—N2'—H2'	117.0
C6—C1—H1A	109.5	C6'—C1'—H1'1	109.5
C6—C1—H1B	109.5	C6'—C1'—H1'2	109.5
H1A—C1—H1B	109.5	H1'1—C1'—H1'2	109.5
C6—C1—H1C	109.5	C6'—C1'—H1'3	109.5
H1A—C1—H1C	109.5	H1'1—C1'—H1'3	109.5
H1B—C1—H1C	109.5	H1'2—C1'—H1'3	109.5
N2—C2—N1	115.6 (3)	N2'—C2'—N1'	115.6 (4)
N2—C2—S1	122.9 (3)	N2'—C2'—S1'	122.6 (3)
N1—C2—S1	121.5 (3)	N1'—C2'—S1'	121.8 (3)
O1—C3—O2	122.7 (4)	O1'—C3'—O2'	122.5 (5)
O1—C3—C5	126.7 (4)	O1'—C3'—C5'	126.7 (5)
O2—C3—C5	110.6 (4)	O2'—C3'—C5'	110.8 (4)
N2—C4—C9	110.5 (3)	N2'—C4'—C5'	109.6 (3)
N2—C4—C5	108.9 (3)	N2'—C4'—C9'	110.5 (3)
C9—C4—C5	112.3 (3)	C5'—C4'—C9'	112.3 (3)
N2—C4—H4	108.3	N2'—C4'—H4'	108.1
C9—C4—H4	108.3	C5'—C4'—H4'	108.1
C5—C4—H4	108.3	C9'—C4'—H4'	108.1
C6—C5—C3	122.6 (4)	C6'—C5'—C3'	122.6 (4)
C6—C5—C4	120.3 (3)	C6'—C5'—C4'	119.7 (4)
C3—C5—C4	117.0 (3)	C3'—C5'—C4'	117.7 (4)
C5—C6—N1	120.0 (4)	C5'—C6'—N1'	119.4 (4)
C5—C6—C1	126.9 (4)	C5'—C6'—C1'	127.2 (4)
N1—C6—C1	113.1 (4)	N1'—C6'—C1'	113.4 (4)
C8—C7—O2	110.1 (5)	O2'—C7'—C8'	108.5 (6)
C8—C7—H7A	109.6	O2'—C7'—H7'1	110.0
O2—C7—H7A	109.6	C8'—C7'—H7'1	110.0
C8—C7—H7B	109.6	O2'—C7'—H7'2	110.0
O2—C7—H7B	109.6	C8'—C7'—H7'2	110.0
H7A—C7—H7B	108.2	H7'1—C7'—H7'2	108.4
C7—C8—H8A	109.5	C7'—C8'—H8'1	109.5
C7—C8—H8B	109.5	C7'—C8'—H8'2	109.5
H8A—C8—H8B	109.5	H8'1—C8'—H8'2	109.5
C7—C8—H8C	109.5	C7'—C8'—H8'3	109.5
H8A—C8—H8C	109.5	H8'1—C8'—H8'3	109.5
H8B—C8—H8C	109.5	H8'2—C8'—H8'3	109.5
C14—C9—C10	116.4 (4)	C14'—C9'—C10'	116.2 (4)
C14—C9—C4	122.6 (4)	C14'—C9'—C4'	122.6 (4)
C10—C9—C4	120.9 (4)	C10'—C9'—C4'	121.2 (4)
C11—C10—C9	120.6 (6)	C11'—C10'—C9'	121.6 (5)
C11—C10—H10	119.7	C11'—C10'—H10'	119.2
C9—C10—H10	119.7	C9'—C10'—H10'	119.2
C12—C11—C10	119.6 (7)	C12'—C11'—C10'	119.9 (6)
C12—C11—H11	120.2	C12'—C11'—H11'	120.1
C10—C11—H11	120.2	C10'—C11'—H11'	120.1
C11—C12—C13	121.3 (6)	C13'—C12'—C11'	119.8 (5)
C11—C12—H12	119.3	C13'—C12'—H12'	120.1
C13—C12—H12	119.3	C11'—C12'—H12'	120.1
C14—C13—C12	117.8 (7)	C12'—C13'—C14'	119.5 (6)
C14—C13—H13	121.1	C12'—C13'—H13'	120.2
C12—C13—H13	121.1	C14'—C13'—H13'	120.2
F1—C14—C13	118.1 (6)	F1'—C14'—C9'	118.4 (4)
F1—C14—C9	117.7 (4)	F1'—C14'—C13'	118.6 (5)
C13—C14—C9	124.2 (6)	C9'—C14'—C13'	123.0 (6)

C4—N2—C2—N1	15.5 (6)	C4'—N2'—C2'—N1'	−14.4 (6)
C4—N2—C2—S1	−164.9 (3)	C4'—N2'—C2'—S1'	166.1 (3)
C6—N1—C2—N2	3.0 (6)	C6'—N1'—C2'—N2'	−6.2 (6)
C6—N1—C2—S1	−176.6 (3)	C6'—N1'—C2'—S1'	173.3 (3)
C7—O2—C3—O1	2.2 (7)	C7'—O2'—C3'—O1'	−0.1 (7)
C7—O2—C3—C5	−176.0 (4)	C7'—O2'—C3'—C5'	178.7 (4)
C2—N2—C4—C9	99.7 (4)	C2'—N2'—C4'—C5'	26.5 (5)
C2—N2—C4—C5	−24.1 (5)	C2'—N2'—C4'—C9'	−97.8 (4)
O1—C3—C5—C6	4.1 (7)	O1'—C3'—C5'—C6'	−3.7 (7)
O2—C3—C5—C6	−177.8 (4)	O2'—C3'—C5'—C6'	177.5 (4)
O1—C3—C5—C4	−172.3 (4)	O1'—C3'—C5'—C4'	173.1 (5)
O2—C3—C5—C4	5.9 (5)	O2'—C3'—C5'—C4'	−5.6 (5)
N2—C4—C5—C6	16.0 (5)	N2'—C4'—C5'—C6'	−20.0 (5)
C9—C4—C5—C6	−106.7 (4)	C9'—C4'—C5'—C6'	103.1 (4)
N2—C4—C5—C3	−167.6 (3)	N2'—C4'—C5'—C3'	163.0 (3)
C9—C4—C5—C3	69.7 (4)	C9'—C4'—C5'—C3'	−73.8 (5)
C3—C5—C6—N1	−178.2 (4)	C3'—C5'—C6'—N1'	−179.1 (4)
C4—C5—C6—N1	−2.0 (6)	C4'—C5'—C6'—N1'	4.1 (6)
C3—C5—C6—C1	1.9 (7)	C3'—C5'—C6'—C1'	1.1 (7)
C4—C5—C6—C1	178.1 (4)	C4'—C5'—C6'—C1'	−175.7 (4)
C2—N1—C6—C5	−9.2 (6)	C2'—N1'—C6'—C5'	10.9 (6)
C2—N1—C6—C1	170.7 (4)	C2'—N1'—C6'—C1'	−169.3 (4)
C3—O2—C7—C8	164.9 (7)	C3'—O2'—C7'—C8'	−175.2 (5)
N2—C4—C9—C14	114.6 (4)	N2'—C4'—C9'—C14'	−114.4 (4)
C5—C4—C9—C14	−123.6 (4)	C5'—C4'—C9'—C14'	123.0 (4)
N2—C4—C9—C10	−63.1 (5)	N2'—C4'—C9'—C10'	65.2 (5)
C5—C4—C9—C10	58.8 (5)	C5'—C4'—C9'—C10'	−57.5 (5)
C14—C9—C10—C11	1.1 (6)	C14'—C9'—C10'—C11'	0.5 (7)
C4—C9—C10—C11	179.0 (4)	C4'—C9'—C10'—C11'	−179.1 (4)
C9—C10—C11—C12	−0.9 (8)	C9'—C10'—C11'—C12'	−1.7 (8)
C10—C11—C12—C13	1.0 (10)	C10'—C11'—C12'—C13'	0.7 (9)
C11—C12—C13—C14	−1.4 (10)	C11'—C12'—C13'—C14'	1.4 (9)
C12—C13—C14—F1	−177.6 (6)	C10'—C9'—C14'—F1'	−179.5 (4)
C12—C13—C14—C9	1.7 (9)	C4'—C9'—C14'—F1'	0.1 (7)
C10—C9—C14—F1	177.8 (4)	C10'—C9'—C14'—C13'	1.7 (7)
C4—C9—C14—F1	0.0 (6)	C4'—C9'—C14'—C13'	−178.7 (5)
C10—C9—C14—C13	−1.6 (7)	C12'—C13'—C14'—F1'	178.5 (5)
C4—C9—C14—C13	−179.3 (5)	C12'—C13'—C14'—C9'	−2.7 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1′ⁱ	0.88	2.83	3.703 (4)	170
N1′—H1′···S1	0.88	2.84	3.711 (4)	171
N2—H2···S1′	0.88	2.52	3.337 (4)	155
N2′—H2′···S1ⁱⁱ	0.88	2.50	3.335 (5)	158
C1′—H1′1···O1′	0.98	2.14	2.861 (6)	129

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1'ⁱ	0.88	2.83	3.703 (4)	170
N1'—H1'···S1	0.88	2.84	3.711 (4)	171
N2—H2···S1'	0.88	2.52	3.337 (4)	155
N2'—H2'···S1ⁱⁱ	0.88	2.50	3.335 (5)	158
C1'—H1'1···O1'	0.98	2.14	2.861 (6)	129

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.

Acknowledgements

MSK thanks for the University Grants Commission (UGC), India, for the UGC–BSR Meritorious fellowship.

References

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Volume 71| Part 10| October 2015| Pages o699-o700

doi:10.1107/S2056989015015145

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of ethyl 4-(2-fluoro­phen­yl)-6-methyl-2-sulfanyl­­idene-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of ethyl 4-(2-fluorophenyl)-6-methyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidine-5-carboxylate