Ethyl 4-hydr­oxy-2,6-diphenyl-5-(phenyl­sulfan­yl)pyridine-3-carboxyl­ate and ethyl 2,6-bis­(4-fluoro­phen­yl)-4-hydr­oxy-5-(4-methyl­phenyl­sulfan­yl)pyridine-3-carboxyl­ate: supra­molecular aggregation through C—H...O, C—H...F and C—H...π inter­actions

The title polysubstituted pyridines, ethyl 4-hydroxy-2,6-diphenyl-5-(phenylsulfanyl)pyridine-3-carboxylate, C₂₆H₂₁NO₃S, (I), and ethyl 2,6-bis(4-fluorophenyl)-4-hydroxy-5-(4-methylphenylsulfanyl)pyridine-3-carboxylate, C₂₇H₂₁F₂NO₃S, (II), adopt nearly planar structures. The crystal structure of (I) is stabilized by inter­molecular C—H...O and C—H...π inter­actions. The C—H...O hydrogen bonds generate rings of motifs R₂²(14) and R₂²(20). The crystal structure of (II) is stabilized by inter­molecular C—H...F and C—H...π inter­actions. The C—H...F bond generates a linear chain of motif C(14). In addition, in (I) and (II), intra­molecular O—H...O inter­actions generating a graph-set motif S(6) are found. No significant aryl–aryl or π–π inter­actions exist in these structures.

S1. Comment

Pyridines are of great interest because of the occurrence of their saturated and partially saturated derivatives in biologically active compounds and natural products such as NAD nucleotides, pyridoxol (vitamin B6) and pyridine alkaloids (Balasubramanian & Keay, 1996). Substituted pyridines have also found a number of applications, such as anticorrosion agents, insecticides and as potential drug substances (Keney, 1968; Goodhue, 1967; Cooke et al., 1998). In this context, the synthesis of polysubstituted pyridines has been an active research area for many years in our laboratory. The present work reports the X-ray crystallographic study of two such substituted pyridines, (I) and (II).

The molecular structures of (I) and (II) are shown in Fig. 1 and Fig. 2, respectively, and selected geometric parameters are given in Tables 1 and 3, respectively. In (I) and (II), the pyridine heterocycles are planar; the displacements of the atoms from their mean planes do not exceed 0.043 (2) Å. None of the substituted groups forming a plane is either coplanar with or orthogonal to the pyridine ring. The dihedral angles of the phenylsulfanyl group at C5, the ethoxycarbonyl group at C3 and the phenyl ring at C2 with the pyridine ring are 76.2, 37.8 and 43.7°, respectively, in (I), and 83.6 (1), 46.4 (1) and 39.2 (1)°, respectively, in (II). The phenylsulfanyl group is cis to the phenyl ring at C6, with dihedral angles of 62.6 (1)° in (I) and 70.5 (2)° in (II). The C5—S1 bond [1.769 Å in (I) and 1.770 Å in (II)] is slightly shorter than the C51—S1 bond [1.782 Å in (I) and 1.778 Å in (II)], which may be due to the conjugation of atom S1 with the pyridine ring. Similarly, the C7—O3 bond [1.335 Å in (I) and 1.332 Å in (II)] is longer than the C7—O2 bond [1.222 Å in (I) and 1.203 Å in (II)] and considerably shorter than C8—O3 [1.462 Å in (I) and 1.468 Å in (II)], which demonstrates the conjugation of atom O3 with C7—O2.

The crystal structure of (I) is stabilized by weak C—H···O interactions. The C26—H26···O2 and C65—H65···O3 interactions form cyclic dimers, generating rings of graph-set motifs R₂²(14) and R₂²(20), respectively (Etter et al., 1990) (Table 2 and Fig. 3). The intramolecular hydrogen bond found between the hydroxyl and carboxylate moieties (O1—H1···O2) (Table 2 and Fig. 3) generates a graph-set motif S(6). Two weak C—H···π interactions, viz. C22—H22···Cg1ⁱ and C8—H8B···Cg2ⁱⁱ (Cg1 and Cg2 are the centroids of rings C51—C56 and C61—C66, respectively; symmetry codes are given in Table 2) are observed. No π–π interactions or significant aryl–aryl interactions are observed. The molecular packing in the unit cell is shown in Fig. 4.

The crystal structure of (II) is stabilized by a weak C—H···F interaction. This C57—H57C···F1 interaction (Table 4 and Fig. 5) forms a linear chain generating a graph-set motif C(14). The intramolecular hydrogen bond found between the hydroxyl and carboxylate moieties (O1—H1···O2) (Table 4 and Fig. 5) generates a graph-set motif S(6). The supramolecular aggregation is completed by the presence of a weak C—H···π interaction (Table 4; Cg1 is the centroid of the C51–C56 ring). The molecular packing in the unit cell is shown in Fig. 6. The geometry of the C—H···π interaction was obtained from PLATON (Spek, 2003)

Related literature

For related literature, see: Balasubramanian & Keay (1996); Cooke et al. (1998); Etter et al. (1990); Goodhue (1967); Keney (1968); Spek (2003).

S2. Experimental

The preparation of (I) was carried out as follows. To a solution of ethyl 4-hydroxy-2,6-diphenyl-5-(phenylsulfanyl)-1,2,5,6-tetrahydro-3-pyridine carboxylate (0.1 g, 0.2 mmol) in benzene (10 ml), dichlorodicyanobenzoquinone (0.105 g, 0.4 mmol) was added and the mixture was refluxed in a water bath for 30 min. The precipitated DDQ-H2 was filtered off and the filtrate evaporated under vaccum. The residue was recrystallized from ethanol to give the product, (I) (yield 0.072 g, 73%; m.p. 421–422 K).

The preparation of (II) was carried out as follows. To a solution of ethyl 2,6-bis(4-fluorophenyl)-4-hydroxy-5-[(4-methylphenyl)sulfanyl]-1,2,5,6-tetrahydro-3-pyridinecarboxylate (0.1 g, 0.2 mmol) in benzene (10 ml), dichlorodicyanobenzoquinone (0.094 g, 0.4 mmol) was added and the mixture was refluxed in a water bath for 30 min. The precipitated DDQ-H2 was filtered off and the filtrate evaporated under vaccum. The residue was recrystallized from ethanol to give the product, (II) (yield 0.071 g, 72%; m.p. 380–381 K).

S3. Refinement

H atoms were placed in calculated positions and allowed to ride on their carrier atoms, with C—H = 0.93–0.97 Å and O—H = 0.82 Å, and with U_iso(H) = 1.2U_eq(C) for CH₂ and CH groups, 1.5U_eq for CH₃ groups and 1.5U_eq(O)for OH groups.

Computing details

Data collection: SMART (Bruker, 2001) for (I); CAD-4 EXPRESS (Enraf–Nonius, 1994) for (II). Cell refinement: SAINT (Bruker, 2001) for (I); CAD-4 EXPRESS for (II). Data reduction: SAINT (Bruker, 2001) for (I); XCAD4 (Harms & Wocadlo, 1996) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II), showing 30% probability displacement ellipsoids and the atom-numbering scheme. H atoms are represented as small spheres of arbitrary radii.
	Fig. 3. A partial packing view, showing the intermolecular C—H···O hydrogen bonding (dashed lines) in compound (I). H atoms are shown as small spheres of arbitrary radii. H atoms not involved in hydrogen-bonding interactions have been omitted for clarity. [Symmetry codes: (i) -x, y - 1/2, 1/2 - z; (ii) -x, -y, -z; (iii) 1 - x, -y, 1 - z.]
	Fig. 4. The packing of the molecules of (I), showing the C—H··· π interactions (dashed lines) within the unit cell, viewed down the a axis. H atoms are shown as small spheres of arbitrary radii. H atoms not involved in hydrogen-bonding interactions have been omitted for clarity.
	Fig. 5. A partial packing view, showing the intermolecular C—H···F hydrogen bonding (dashed lines) in compound (II). H atoms are shown as small spheres of arbitrary radii. H atoms not involved in hydrogen-bonding interactions have been omitted for clarity. [Symmetry codes: (i) x - 1/2, -y + 3/2, z - 1/2.]
	Fig. 6. The packing of the molecules of (II), showing the C—H··· π interactions (dashed lines) within the unit cell, viewed down the b axis. H atoms are shown as small spheres of arbitrary radii. H atoms not involved in hydrogen-bonding interactions have been omitted for clarity.

(I) Ethyl 4-hydroxy-2,6-diphenyl-5-(phenylsulfanyl)pyridine-3-carboxylate

Crystal data

C26H21NO3S	F(000) = 896
Mr = 427.50	Dx = 1.325 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1024 reflections
a = 10.3728 (2) Å	θ = 2.1–28.3°
b = 17.1008 (4) Å	µ = 0.18 mm^−1
c = 12.9444 (3) Å	T = 105 K
β = 111.041 (1)°	Block, colourless
V = 2143.02 (8) Å^3	0.28 × 0.14 × 0.12 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5325 independent reflections
Radiation source: fine-focus sealed tube	4855 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.043
Detector resolution: 8 pixels mm^-1	θmax = 28.3°, θmin = 2.1°
ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −22→22
Tmin = 0.97, Tmax = 0.979	l = −17→17
32101 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.112	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0504P)^2 + 1.7947P] where P = (Fo^2 + 2Fc^2)/3
5325 reflections	(Δ/σ)max = 0.001
280 parameters	Δρmax = 0.84 e Å^−3
1 restraint	Δρmin = −0.78 e Å^−3

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
S1	0.53613 (3)	0.111038 (19)	0.24647 (3)	0.01821 (10)
O3	−0.04370 (10)	−0.00306 (6)	0.22688 (8)	0.0178 (2)
O2	−0.03086 (10)	0.06894 (6)	0.08528 (8)	0.0208 (2)
N1	0.35713 (11)	−0.08449 (6)	0.30626 (9)	0.0151 (2)
C4	0.26934 (14)	0.06118 (7)	0.20182 (10)	0.0152 (2)
C5	0.41167 (13)	0.04426 (8)	0.25795 (11)	0.0155 (2)
C2	0.22209 (13)	−0.06883 (7)	0.25484 (10)	0.0139 (2)
O1	0.23038 (13)	0.13075 (7)	0.14915 (11)	0.0320 (3)
H1	0.1458	0.1331	0.1226	0.048*
C6	0.44965 (13)	−0.02807 (8)	0.31048 (11)	0.0148 (2)
C7	0.02297 (13)	0.02565 (7)	0.16414 (11)	0.0150 (2)
C21	0.13040 (13)	−0.13751 (7)	0.24604 (11)	0.0147 (2)
C3	0.17215 (13)	0.00395 (7)	0.20649 (10)	0.0140 (2)
C52	0.46664 (15)	0.18705 (9)	0.41216 (12)	0.0223 (3)
H52	0.4067	0.1461	0.4099	0.027*
C61	0.59700 (13)	−0.05049 (8)	0.36987 (11)	0.0168 (3)
C51	0.54401 (14)	0.18656 (8)	0.34340 (11)	0.0167 (2)
C55	0.64774 (16)	0.30974 (9)	0.42023 (12)	0.0239 (3)
H55	0.7086	0.3504	0.4234	0.029*
C22	0.15448 (14)	−0.18766 (8)	0.33627 (11)	0.0187 (3)
H22	0.2240	−0.1763	0.4035	0.022*
C26	0.02641 (15)	−0.15553 (8)	0.14508 (11)	0.0194 (3)
H26	0.0098	−0.1224	0.0847	0.023*
C62	0.64739 (15)	−0.11835 (8)	0.33759 (13)	0.0214 (3)
H62	0.5887	−0.1495	0.2815	0.026*
C66	0.68497 (15)	−0.00516 (9)	0.45660 (12)	0.0223 (3)
H66	0.6519	0.0398	0.4790	0.027*
C63	0.78557 (16)	−0.13937 (9)	0.38927 (15)	0.0279 (3)
H63	0.8195	−0.1837	0.3662	0.033*
C56	0.63519 (15)	0.24782 (8)	0.34790 (12)	0.0211 (3)
H56	0.6873	0.2471	0.3025	0.025*
C23	0.07422 (16)	−0.25479 (9)	0.32540 (13)	0.0232 (3)
H23	0.0895	−0.2877	0.3858	0.028*
C9	−0.28237 (16)	−0.02996 (11)	0.10367 (15)	0.0313 (3)
H9A	−0.3764	−0.0138	0.0865	0.047*
H9B	−0.2729	−0.0840	0.1253	0.047*
H9C	−0.2574	−0.0235	0.0396	0.047*
C8	−0.18861 (14)	0.01925 (9)	0.19726 (12)	0.0209 (3)
H8A	−0.1996	0.0739	0.1756	0.025*
H8B	−0.2152	0.0133	0.2614	0.025*
C25	−0.05231 (16)	−0.22294 (9)	0.13464 (12)	0.0244 (3)
H25	−0.1211	−0.2348	0.0672	0.029*
C54	0.56959 (17)	0.31116 (9)	0.48794 (12)	0.0247 (3)
H54	0.5770	0.3531	0.5355	0.030*
C53	0.48040 (17)	0.24970 (9)	0.48418 (13)	0.0262 (3)
H53	0.4293	0.2504	0.5303	0.031*
C24	−0.02860 (16)	−0.27258 (9)	0.22460 (13)	0.0245 (3)
H24	−0.0814	−0.3176	0.2174	0.029*
C64	0.87261 (16)	−0.09418 (10)	0.47512 (14)	0.0301 (3)
H64	0.9646	−0.1085	0.5097	0.036*
C65	0.82238 (16)	−0.02752 (10)	0.50947 (13)	0.0277 (3)
H65	0.8805	0.0022	0.5678	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01923 (17)	0.01681 (17)	0.02316 (17)	−0.00354 (12)	0.01313 (13)	−0.00145 (12)
O3	0.0130 (4)	0.0218 (5)	0.0196 (4)	0.0026 (3)	0.0071 (4)	0.0037 (4)
O2	0.0196 (5)	0.0209 (5)	0.0213 (5)	0.0040 (4)	0.0068 (4)	0.0060 (4)
N1	0.0146 (5)	0.0142 (5)	0.0171 (5)	0.0002 (4)	0.0062 (4)	0.0006 (4)
C4	0.0180 (6)	0.0137 (6)	0.0158 (6)	−0.0003 (5)	0.0082 (5)	−0.0012 (4)
C5	0.0160 (6)	0.0152 (6)	0.0177 (6)	−0.0022 (5)	0.0088 (5)	−0.0010 (5)
C2	0.0146 (6)	0.0142 (6)	0.0141 (5)	−0.0001 (4)	0.0065 (4)	−0.0003 (4)
O1	0.0310 (6)	0.0260 (6)	0.0392 (7)	0.0017 (5)	0.0129 (5)	0.0063 (5)
C6	0.0149 (6)	0.0160 (6)	0.0151 (5)	−0.0004 (5)	0.0074 (5)	−0.0012 (4)
C7	0.0161 (6)	0.0128 (6)	0.0165 (6)	0.0000 (4)	0.0063 (5)	−0.0015 (4)
C21	0.0138 (5)	0.0123 (5)	0.0188 (6)	0.0008 (4)	0.0070 (5)	−0.0001 (4)
C3	0.0146 (6)	0.0137 (6)	0.0146 (6)	0.0005 (4)	0.0062 (5)	−0.0002 (4)
C52	0.0221 (7)	0.0219 (7)	0.0269 (7)	−0.0051 (5)	0.0136 (6)	−0.0031 (5)
C61	0.0143 (6)	0.0193 (6)	0.0172 (6)	−0.0011 (5)	0.0062 (5)	0.0034 (5)
C51	0.0160 (6)	0.0158 (6)	0.0180 (6)	0.0005 (5)	0.0057 (5)	0.0017 (5)
C55	0.0279 (7)	0.0190 (7)	0.0231 (7)	−0.0071 (5)	0.0070 (6)	0.0010 (5)
C22	0.0171 (6)	0.0175 (6)	0.0198 (6)	−0.0006 (5)	0.0045 (5)	0.0029 (5)
C26	0.0222 (6)	0.0172 (6)	0.0176 (6)	−0.0018 (5)	0.0056 (5)	0.0008 (5)
C62	0.0174 (6)	0.0187 (6)	0.0271 (7)	0.0001 (5)	0.0068 (5)	0.0024 (5)
C66	0.0203 (7)	0.0279 (7)	0.0187 (6)	−0.0034 (5)	0.0072 (5)	−0.0002 (5)
C63	0.0206 (7)	0.0231 (7)	0.0398 (9)	0.0060 (6)	0.0107 (6)	0.0087 (6)
C56	0.0230 (7)	0.0206 (7)	0.0218 (6)	−0.0043 (5)	0.0105 (5)	0.0013 (5)
C23	0.0247 (7)	0.0184 (6)	0.0260 (7)	−0.0024 (5)	0.0085 (6)	0.0059 (5)
C9	0.0184 (7)	0.0366 (9)	0.0355 (9)	−0.0019 (6)	0.0053 (6)	−0.0044 (7)
C8	0.0134 (6)	0.0248 (7)	0.0251 (7)	0.0033 (5)	0.0077 (5)	0.0019 (5)
C25	0.0261 (7)	0.0211 (7)	0.0219 (7)	−0.0067 (6)	0.0039 (6)	−0.0025 (5)
C54	0.0302 (8)	0.0203 (7)	0.0216 (7)	−0.0007 (6)	0.0070 (6)	−0.0031 (5)
C53	0.0278 (7)	0.0279 (8)	0.0273 (7)	−0.0020 (6)	0.0153 (6)	−0.0048 (6)
C24	0.0255 (7)	0.0173 (6)	0.0297 (7)	−0.0072 (5)	0.0087 (6)	0.0003 (5)
C64	0.0157 (6)	0.0372 (9)	0.0338 (8)	0.0016 (6)	0.0044 (6)	0.0146 (7)
C65	0.0200 (7)	0.0390 (9)	0.0199 (7)	−0.0077 (6)	0.0022 (5)	0.0045 (6)

Geometric parameters (Å, º)

S1—C5	1.7693 (13)	C22—H22	0.9300
S1—C51	1.7819 (14)	C26—C25	1.3909 (19)
O3—C7	1.3350 (16)	C26—H26	0.9300
O3—C8	1.4622 (16)	C62—C63	1.394 (2)
O2—C7	1.2216 (16)	C62—H62	0.9300
N1—C2	1.3444 (16)	C66—C65	1.395 (2)
N1—C6	1.3480 (17)	C66—H66	0.9300
C4—O1	1.3586 (17)	C63—C64	1.388 (2)
C4—C5	1.4216 (18)	C63—H63	0.9300
C4—C3	1.4218 (17)	C56—H56	0.9300
C5—C6	1.3984 (18)	C23—C24	1.390 (2)
C2—C3	1.4059 (17)	C23—H23	0.9300
C2—C21	1.4896 (17)	C9—C8	1.509 (2)
O1—H1	0.8200	C9—H9A	0.9600
C6—C61	1.4935 (18)	C9—H9B	0.9600
C7—C3	1.4911 (17)	C9—H9C	0.9600
C21—C22	1.3973 (18)	C8—H8A	0.9700
C21—C26	1.3979 (18)	C8—H8B	0.9700
C52—C53	1.393 (2)	C25—C24	1.390 (2)
C52—C51	1.3963 (19)	C25—H25	0.9300
C52—H52	0.9300	C54—C53	1.390 (2)
C61—C62	1.397 (2)	C54—H54	0.9300
C61—C66	1.3994 (19)	C53—H53	0.9300
C51—C56	1.3985 (19)	C24—H24	0.9300
C55—C56	1.388 (2)	C64—C65	1.391 (3)
C55—C54	1.391 (2)	C64—H64	0.9300
C55—H55	0.9300	C65—H65	0.9300
C22—C23	1.3951 (19)
C5—S1—C51	105.01 (6)	C63—C62—H62	120.0
C7—O3—C8	116.93 (10)	C61—C62—H62	120.0
C2—N1—C6	118.53 (11)	C65—C66—C61	119.93 (14)
O1—C4—C5	120.13 (12)	C65—C66—H66	120.0
O1—C4—C3	122.44 (12)	C61—C66—H66	120.0
C5—C4—C3	117.41 (12)	C64—C63—C62	120.12 (15)
C6—C5—C4	119.21 (12)	C64—C63—H63	119.9
C6—C5—S1	121.68 (10)	C62—C63—H63	119.9
C4—C5—S1	118.75 (10)	C55—C56—C51	119.85 (13)
N1—C2—C3	123.27 (12)	C55—C56—H56	120.1
N1—C2—C21	113.82 (11)	C51—C56—H56	120.1
C3—C2—C21	122.75 (11)	C24—C23—C22	120.24 (13)
C4—O1—H1	109.5	C24—C23—H23	119.9
N1—C6—C5	122.77 (12)	C22—C23—H23	119.9
N1—C6—C61	114.79 (11)	C8—C9—H9A	109.5
C5—C6—C61	122.34 (12)	C8—C9—H9B	109.5
O2—C7—O3	123.36 (12)	H9A—C9—H9B	109.5
O2—C7—C3	124.10 (12)	C8—C9—H9C	109.5
O3—C7—C3	112.38 (11)	H9A—C9—H9C	109.5
C22—C21—C26	119.50 (12)	H9B—C9—H9C	109.5
C22—C21—C2	120.16 (12)	O3—C8—C9	111.76 (12)
C26—C21—C2	120.16 (12)	O3—C8—H8A	109.3
C2—C3—C4	118.35 (12)	C9—C8—H8A	109.3
C2—C3—C7	123.49 (11)	O3—C8—H8B	109.3
C4—C3—C7	118.11 (11)	C9—C8—H8B	109.3
C53—C52—C51	119.13 (13)	H8A—C8—H8B	107.9
C53—C52—H52	120.4	C24—C25—C26	120.24 (13)
C51—C52—H52	120.4	C24—C25—H25	119.9
C62—C61—C66	119.60 (13)	C26—C25—H25	119.9
C62—C61—C6	118.88 (12)	C53—C54—C55	119.73 (14)
C66—C61—C6	121.52 (12)	C53—C54—H54	120.1
C52—C51—C56	120.26 (13)	C55—C54—H54	120.1
C52—C51—S1	124.17 (11)	C54—C53—C52	120.80 (14)
C56—C51—S1	115.57 (10)	C54—C53—H53	119.6
C56—C55—C54	120.22 (13)	C52—C53—H53	119.6
C56—C55—H55	119.9	C25—C24—C23	119.87 (13)
C54—C55—H55	119.9	C25—C24—H24	120.1
C23—C22—C21	119.97 (13)	C23—C24—H24	120.1
C23—C22—H22	120.0	C63—C64—C65	120.10 (14)
C21—C22—H22	120.0	C63—C64—H64	119.9
C25—C26—C21	120.17 (13)	C65—C64—H64	119.9
C25—C26—H26	119.9	C64—C65—C66	120.12 (15)
C21—C26—H26	119.9	C64—C65—H65	119.9
C63—C62—C61	120.10 (14)	C66—C65—H65	119.9
O1—C4—C5—C6	−179.22 (12)	N1—C6—C61—C62	53.60 (17)
C3—C4—C5—C6	2.66 (18)	C5—C6—C61—C62	−122.86 (14)
O1—C4—C5—S1	−6.01 (17)	N1—C6—C61—C66	−126.42 (14)
C3—C4—C5—S1	175.87 (9)	C5—C6—C61—C66	57.13 (18)
C51—S1—C5—C6	−106.18 (11)	C53—C52—C51—C56	0.7 (2)
C51—S1—C5—C4	80.79 (11)	C53—C52—C51—S1	−179.42 (12)
C6—N1—C2—C3	−0.96 (19)	C5—S1—C51—C52	1.27 (14)
C6—N1—C2—C21	174.60 (11)	C5—S1—C51—C56	−178.87 (11)
C2—N1—C6—C5	−3.98 (19)	C26—C21—C22—C23	−0.5 (2)
C2—N1—C6—C61	179.58 (11)	C2—C21—C22—C23	−175.69 (13)
C4—C5—C6—N1	3.05 (19)	C22—C21—C26—C25	−0.1 (2)
S1—C5—C6—N1	−169.95 (10)	C2—C21—C26—C25	175.10 (13)
C4—C5—C6—C61	179.23 (12)	C66—C61—C62—C63	−2.0 (2)
S1—C5—C6—C61	6.23 (18)	C6—C61—C62—C63	178.01 (13)
C8—O3—C7—O2	0.29 (19)	C62—C61—C66—C65	0.6 (2)
C8—O3—C7—C3	175.85 (11)	C6—C61—C66—C65	−179.39 (13)
N1—C2—C21—C22	42.75 (17)	C61—C62—C63—C64	1.9 (2)
C3—C2—C21—C22	−141.67 (13)	C54—C55—C56—C51	−0.2 (2)
N1—C2—C21—C26	−132.38 (13)	C52—C51—C56—C55	−0.7 (2)
C3—C2—C21—C26	43.20 (18)	S1—C51—C56—C55	179.47 (11)
N1—C2—C3—C4	6.59 (19)	C21—C22—C23—C24	0.9 (2)
C21—C2—C3—C4	−168.58 (11)	C7—O3—C8—C9	81.25 (15)
N1—C2—C3—C7	−170.70 (12)	C21—C26—C25—C24	0.3 (2)
C21—C2—C3—C7	14.13 (19)	C56—C55—C54—C53	1.0 (2)
O1—C4—C3—C2	174.79 (12)	C55—C54—C53—C52	−0.9 (2)
C5—C4—C3—C2	−7.13 (18)	C51—C52—C53—C54	0.1 (2)
O1—C4—C3—C7	−7.77 (18)	C26—C25—C24—C23	0.0 (2)
C5—C4—C3—C7	170.30 (11)	C22—C23—C24—C25	−0.6 (2)
O2—C7—C3—C2	−147.73 (14)	C62—C63—C64—C65	−0.4 (2)
O3—C7—C3—C2	36.75 (17)	C63—C64—C65—C66	−1.0 (2)
O2—C7—C3—C4	34.98 (19)	C61—C66—C65—C64	0.9 (2)
O3—C7—C3—C4	−140.54 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.04	2.7450 (16)	144
C23—H23···O2^i	0.93	2.59	3.3168 (18)	136
C26—H26···O2^ii	0.93	2.46	3.3446 (17)	158
C65—H65···O3^iii	0.93	2.59	3.4008 (18)	146
C22—H22···Cg1^iii	0.93	2.89	3.6647 (15)	142
C8—H8B···Cg2^iv	0.97	2.75	3.6458 (16)	154

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x, −y, −z; (iii) −x+1, −y, −z+1; (iv) x+1, y, z.

(II) ethyl 2,6-bis(4-fluorophenyl)-4-hydroxy-5-(4-methylphenylsulfanyl)pyridine-3- carboxylate

Crystal data

C27H21F2NO3S	F(000) = 992
Mr = 477.52	Dx = 1.357 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 12.092 (1) Å	θ = 2.1–25°
b = 10.489 (1) Å	µ = 0.18 mm^−1
c = 18.496 (2) Å	T = 293 K
β = 94.78 (1)°	Block, colourless
V = 2337.7 (4) Å^3	0.18 × 0.16 × 0.12 mm
Z = 4

Data collection

Nonius MACH3 four-circle diffractometer	2764 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 25.0°, θmin = 2.1°
ω scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = −1→12
Tmin = 0.992, Tmax = 0.995	l = −21→21
4815 measured reflections	3 standard reflections every 60 min
4099 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0654P)^2 + 0.8462P] where P = (Fo^2 + 2Fc^2)/3
4097 reflections	(Δ/σ)max = 0.011
310 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

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
S1	0.69276 (6)	0.63200 (6)	0.45788 (4)	0.0499 (2)
F1	1.08865 (15)	0.96844 (16)	0.58697 (11)	0.0812 (6)
F2	0.95802 (16)	−0.01595 (18)	0.83625 (9)	0.0817 (6)
N1	0.86681 (16)	0.43305 (18)	0.61503 (10)	0.0400 (5)
O1	0.59470 (19)	0.3728 (2)	0.46464 (13)	0.0836 (7)
H1	0.5591	0.3108	0.4766	0.125*
O2	0.57232 (17)	0.14879 (19)	0.54263 (16)	0.0892 (8)
O3	0.74442 (15)	0.07179 (15)	0.55407 (10)	0.0515 (4)
C2	0.81170 (19)	0.3213 (2)	0.61398 (12)	0.0384 (5)
C3	0.72390 (19)	0.2931 (2)	0.56223 (13)	0.0417 (6)
C4	0.68499 (19)	0.3899 (2)	0.51355 (13)	0.0428 (6)
C5	0.7451 (2)	0.5055 (2)	0.51411 (12)	0.0409 (5)
C6	0.83688 (19)	0.5205 (2)	0.56465 (12)	0.0378 (5)
C7	0.6708 (2)	0.1651 (2)	0.55316 (15)	0.0508 (6)
C8	0.7021 (3)	−0.0583 (2)	0.54160 (17)	0.0632 (8)
H8A	0.7596	−0.1105	0.5230	0.076*
H8B	0.6395	−0.0562	0.5053	0.076*
C9	0.6671 (3)	−0.1159 (3)	0.60874 (19)	0.0764 (9)
H9A	0.7273	−0.1121	0.6460	0.115*
H9B	0.6467	−0.2033	0.5997	0.115*
H9C	0.6046	−0.0700	0.6242	0.115*
C21	0.8496 (2)	0.2321 (2)	0.67337 (12)	0.0406 (5)
C22	0.9622 (2)	0.2186 (2)	0.69426 (14)	0.0504 (6)
H22	1.0135	0.2665	0.6711	0.060*
C23	0.9993 (2)	0.1350 (3)	0.74914 (15)	0.0594 (7)
H23	1.0746	0.1255	0.7627	0.071*
C24	0.9219 (3)	0.0670 (3)	0.78258 (13)	0.0558 (7)
C25	0.8109 (2)	0.0782 (3)	0.76490 (14)	0.0559 (7)
H25	0.7604	0.0308	0.7890	0.067*
C26	0.7751 (2)	0.1618 (2)	0.71021 (13)	0.0515 (6)
H26	0.6994	0.1711	0.6978	0.062*
C51	0.7413 (2)	0.5993 (2)	0.37167 (14)	0.0459 (6)
C52	0.7051 (3)	0.6812 (3)	0.31585 (16)	0.0638 (8)
H52	0.6557	0.7464	0.3243	0.077*
C53	0.7421 (3)	0.6664 (3)	0.24784 (17)	0.0693 (8)
H53	0.7170	0.7222	0.2110	0.083*
C54	0.8155 (2)	0.5708 (3)	0.23299 (15)	0.0605 (7)
C55	0.8507 (2)	0.4909 (3)	0.28892 (15)	0.0578 (7)
H55	0.9003	0.4260	0.2804	0.069*
C56	0.8147 (2)	0.5037 (2)	0.35770 (14)	0.0525 (6)
H56	0.8400	0.4477	0.3944	0.063*
C57	0.8556 (3)	0.5580 (4)	0.15784 (17)	0.0901 (11)
H57A	0.9010	0.4832	0.1560	0.135*
H57B	0.8983	0.6319	0.1473	0.135*
H57C	0.7929	0.5508	0.1227	0.135*
C61	0.90526 (19)	0.6398 (2)	0.56882 (13)	0.0394 (5)
C62	0.9225 (2)	0.7023 (2)	0.63465 (14)	0.0509 (6)
H62	0.8923	0.6689	0.6752	0.061*
C63	0.9842 (2)	0.8139 (3)	0.64111 (16)	0.0588 (7)
H63	0.9947	0.8566	0.6852	0.071*
C64	1.0288 (2)	0.8590 (2)	0.58089 (17)	0.0556 (7)
C65	1.0169 (2)	0.7993 (3)	0.51554 (15)	0.0541 (7)
H65	1.0501	0.8316	0.4759	0.065*
C66	0.9536 (2)	0.6888 (2)	0.50955 (14)	0.0463 (6)
H66	0.9437	0.6471	0.4651	0.056*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0554 (4)	0.0366 (3)	0.0570 (4)	0.0085 (3)	0.0009 (3)	0.0011 (3)
F1	0.0786 (12)	0.0498 (10)	0.1151 (15)	−0.0265 (9)	0.0062 (10)	−0.0027 (9)
F2	0.0986 (14)	0.0750 (12)	0.0688 (11)	−0.0021 (10)	−0.0099 (10)	0.0303 (9)
N1	0.0436 (11)	0.0365 (10)	0.0406 (11)	−0.0033 (9)	0.0074 (8)	−0.0032 (9)
O1	0.0730 (15)	0.0713 (15)	0.1023 (18)	−0.0107 (12)	−0.0170 (13)	−0.0001 (13)
O2	0.0464 (12)	0.0508 (12)	0.166 (2)	−0.0123 (10)	−0.0206 (13)	0.0153 (13)
O3	0.0536 (11)	0.0336 (9)	0.0675 (12)	−0.0044 (8)	0.0065 (8)	−0.0055 (8)
C2	0.0389 (13)	0.0343 (12)	0.0432 (13)	−0.0011 (10)	0.0095 (10)	−0.0022 (10)
C3	0.0387 (13)	0.0353 (12)	0.0512 (14)	−0.0030 (10)	0.0054 (11)	−0.0026 (11)
C4	0.0387 (13)	0.0409 (14)	0.0483 (14)	0.0004 (10)	−0.0006 (11)	−0.0046 (11)
C5	0.0436 (13)	0.0351 (12)	0.0438 (13)	0.0010 (10)	0.0032 (10)	−0.0016 (10)
C6	0.0429 (13)	0.0330 (12)	0.0388 (12)	0.0006 (10)	0.0105 (10)	−0.0032 (10)
C7	0.0494 (16)	0.0400 (14)	0.0619 (17)	−0.0049 (12)	−0.0025 (12)	0.0064 (12)
C8	0.074 (2)	0.0335 (14)	0.082 (2)	−0.0104 (13)	0.0028 (16)	−0.0039 (13)
C9	0.076 (2)	0.0472 (17)	0.108 (3)	−0.0061 (15)	0.0181 (19)	0.0077 (17)
C21	0.0476 (14)	0.0348 (12)	0.0398 (12)	−0.0032 (10)	0.0067 (10)	−0.0060 (10)
C22	0.0498 (15)	0.0475 (14)	0.0529 (15)	−0.0121 (12)	−0.0014 (12)	0.0063 (12)
C23	0.0533 (16)	0.0584 (16)	0.0640 (17)	−0.0048 (14)	−0.0097 (13)	0.0095 (14)
C24	0.077 (2)	0.0460 (15)	0.0428 (14)	−0.0009 (14)	−0.0026 (13)	0.0066 (12)
C25	0.0662 (19)	0.0534 (15)	0.0503 (15)	−0.0020 (14)	0.0177 (13)	0.0104 (13)
C26	0.0512 (15)	0.0554 (16)	0.0494 (15)	0.0022 (13)	0.0132 (12)	0.0058 (12)
C51	0.0454 (14)	0.0402 (13)	0.0505 (14)	−0.0035 (11)	−0.0059 (11)	0.0017 (11)
C52	0.0641 (18)	0.0580 (17)	0.0684 (19)	0.0127 (15)	0.0009 (15)	0.0128 (15)
C53	0.073 (2)	0.077 (2)	0.0564 (18)	0.0022 (17)	−0.0029 (15)	0.0220 (15)
C54	0.0522 (16)	0.0721 (19)	0.0569 (17)	−0.0122 (15)	0.0026 (13)	0.0020 (15)
C55	0.0550 (16)	0.0576 (17)	0.0599 (17)	0.0016 (14)	−0.0008 (13)	−0.0040 (14)
C56	0.0593 (16)	0.0424 (14)	0.0542 (15)	0.0051 (12)	−0.0055 (12)	0.0016 (12)
C57	0.087 (2)	0.120 (3)	0.065 (2)	−0.003 (2)	0.0163 (18)	0.010 (2)
C61	0.0370 (12)	0.0327 (12)	0.0487 (13)	0.0013 (10)	0.0040 (10)	−0.0023 (10)
C62	0.0533 (15)	0.0480 (15)	0.0519 (15)	−0.0085 (12)	0.0085 (12)	−0.0043 (12)
C63	0.0610 (17)	0.0513 (16)	0.0635 (18)	−0.0106 (14)	0.0016 (14)	−0.0172 (14)
C64	0.0476 (15)	0.0361 (13)	0.083 (2)	−0.0083 (12)	0.0029 (14)	0.0009 (14)
C65	0.0520 (16)	0.0463 (15)	0.0653 (18)	−0.0035 (12)	0.0129 (13)	0.0085 (13)
C66	0.0489 (14)	0.0415 (13)	0.0494 (14)	−0.0018 (11)	0.0087 (11)	−0.0012 (11)

Geometric parameters (Å, º)

S1—C5	1.770 (2)	C24—C25	1.360 (4)
S1—C51	1.778 (3)	C25—C26	1.380 (4)
F1—C64	1.356 (3)	C25—H25	0.9300
F2—C24	1.364 (3)	C26—H26	0.9300
N1—C6	1.336 (3)	C51—C56	1.378 (4)
N1—C2	1.347 (3)	C51—C52	1.386 (4)
O1—C4	1.371 (3)	C51—CG1	1.397 (3)
O1—H1	0.8200	C52—C53	1.379 (4)
O2—C7	1.203 (3)	C52—H52	0.9300
O3—C7	1.322 (3)	C53—C54	1.382 (4)
O3—C8	1.468 (3)	C53—H53	0.9300
C2—C3	1.401 (3)	C54—C55	1.371 (4)
C2—C21	1.486 (3)	C54—CG1	1.405 (3)
C3—C4	1.411 (3)	C54—C57	1.516 (4)
C3—C7	1.492 (3)	C55—C56	1.385 (4)
C4—C5	1.413 (3)	C55—H55	0.9300
C5—C6	1.399 (3)	C56—H56	0.9300
C6—C61	1.499 (3)	C57—H57A	0.9600
C8—C9	1.475 (4)	C57—H57B	0.9600
C8—H8A	0.9700	C57—H57C	0.9600
C8—H8B	0.9700	C61—C62	1.383 (3)
C9—H9A	0.9600	C61—C66	1.384 (3)
C9—H9B	0.9600	C62—C63	1.387 (4)
C9—H9C	0.9600	C62—H62	0.9300
C21—C26	1.387 (3)	C63—C64	1.363 (4)
C21—C22	1.391 (3)	C63—H63	0.9300
C22—C23	1.388 (4)	C64—C65	1.358 (4)
C22—H22	0.9300	C65—C66	1.388 (4)
C23—C24	1.364 (4)	C65—H65	0.9300
C23—H23	0.9300	C66—H66	0.9300
C5—S1—C51	104.69 (11)	C21—C26—H26	119.3
C6—N1—C2	118.8 (2)	C56—C51—C52	118.7 (3)
C4—O1—H1	109.5	C56—C51—CG1	59.50 (16)
C7—O3—C8	117.4 (2)	C52—C51—CG1	59.19 (17)
N1—C2—C3	122.6 (2)	C56—C51—S1	125.1 (2)
N1—C2—C21	114.5 (2)	C52—C51—S1	116.2 (2)
C3—C2—C21	122.8 (2)	CG1—C51—S1	174.78 (18)
C2—C3—C4	118.5 (2)	C53—C52—C51	120.2 (3)
C2—C3—C7	124.1 (2)	C53—C52—H52	119.9
C4—C3—C7	117.3 (2)	C51—C52—H52	119.9
O1—C4—C3	122.1 (2)	C52—C53—C54	121.7 (3)
O1—C4—C5	119.9 (2)	C52—C53—H53	119.1
C3—C4—C5	117.9 (2)	C54—C53—H53	119.1
C6—C5—C4	118.7 (2)	C55—C54—C53	117.2 (3)
C6—C5—S1	122.22 (18)	C55—C54—CG1	58.63 (17)
C4—C5—S1	118.73 (18)	C53—C54—CG1	58.61 (18)
N1—C6—C5	122.9 (2)	C55—C54—C57	122.3 (3)
N1—C6—C61	114.9 (2)	C53—C54—C57	120.4 (3)
C5—C6—C61	122.1 (2)	CG1—C54—C57	178.8 (3)
O2—C7—O3	123.6 (2)	C54—C55—C56	122.1 (3)
O2—C7—C3	123.8 (2)	C54—C55—H55	118.9
O3—C7—C3	112.5 (2)	C56—C55—H55	118.9
O3—C8—C9	111.7 (2)	C51—C56—C55	120.0 (2)
O3—C8—H8A	109.3	C51—C56—H56	120.0
C9—C8—H8A	109.3	C55—C56—H56	120.0
O3—C8—H8B	109.3	C54—C57—H57A	109.5
C9—C8—H8B	109.3	C54—C57—H57B	109.5
H8A—C8—H8B	107.9	H57A—C57—H57B	109.5
C8—C9—H9A	109.5	C54—C57—H57C	109.5
C8—C9—H9B	109.5	H57A—C57—H57C	109.5
H9A—C9—H9B	109.5	H57B—C57—H57C	109.5
C8—C9—H9C	109.5	C62—C61—C66	118.6 (2)
H9A—C9—H9C	109.5	C62—C61—C6	118.9 (2)
H9B—C9—H9C	109.5	C66—C61—C6	122.5 (2)
C26—C21—C22	118.1 (2)	C61—C62—C63	121.1 (2)
C26—C21—C2	121.7 (2)	C61—C62—H62	119.5
C22—C21—C2	120.3 (2)	C63—C62—H62	119.5
C23—C22—C21	121.1 (2)	C64—C63—C62	118.0 (3)
C23—C22—H22	119.5	C64—C63—H63	121.0
C21—C22—H22	119.5	C62—C63—H63	121.0
C24—C23—C22	118.0 (3)	F1—C64—C65	118.7 (3)
C24—C23—H23	121.0	F1—C64—C63	118.1 (3)
C22—C23—H23	121.0	C65—C64—C63	123.2 (2)
C25—C24—C23	123.1 (3)	C64—C65—C66	118.3 (2)
C25—C24—F2	118.7 (3)	C64—C65—H65	120.9
C23—C24—F2	118.2 (3)	C66—C65—H65	120.9
C24—C25—C26	118.3 (2)	C61—C66—C65	120.9 (2)
C24—C25—H25	120.9	C61—C66—H66	119.6
C26—C25—H25	120.9	C65—C66—H66	119.6
C25—C26—C21	121.4 (3)	C51—CG1—C54	179.74 (18)
C25—C26—H26	119.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	2.09	2.782 (3)	142
C57—H57C···F1^i	0.96	2.51	3.393 (4)	153
C22—H22···Cg1^ii	0.93	2.97	3.749 (3)	143

Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+2, −y+1, −z+1.