Ethyl 3-({[(4-methyl­phen­yl)carbamo­yl]meth­yl}sulfan­yl)-5,6-di­phenyl­pyridazine-4-carboxyl­ate

Mague, J.T.; Mohamed, S.K.; Akkurt, M.; Bakhite, E.A.; Albayati, M.R.

doi:10.1107/S241431461600479X

organic compounds

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ISSN: 2414-3146

Volume 1| Part 3| March 2016| x160479

doi:10.1107/S241431461600479X

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Ethyl 3-({[(4-methylphenyl)carbamoyl]methyl}sulfanyl)-5,6-diphenylpyridazine-4-carboxylate

Joel T. Mague,^a Shaaban K. Mohamed,^b,^c Mehmet Akkurt,^d Etify A. Bakhite ^e and Mustafa R. Albayati ^f ^*

^aDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^bChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^cChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^dDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, ^eChemistry Department, Faculty of Science, Assiut University, 71516 Assiut, Egypt, and ^fKirkuk University, College of Science, Department of Chemistry, Kirkuk, Iraq
^*Correspondence e-mail: shaabankamel@yahoo.com

Edited by D.-J. Xu, Zhejiang University (Yuquan Campus), China (Received 11 March 2016; accepted 21 March 2016; online 31 March 2016)

The packing in the crystal of the title molecule, C₂₈H₂₅N₃O₃S, is aided by intermolecular N—H⋯O and C—H⋯O hydrogen bonds. In the crystal, the ethyl group of the ester is disordered over two sets of sites with refined occupancies of 0.760 (8) and 0.240 (8).

Keywords: crystal structure; diphenylpyridazine; mercaptopyridazine.

CCDC reference: 1469872

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Chemical scheme

Structure description

The broad spectrum of biological activities associated with many pyridazine derivatives are well known. Some of them are reported to exhibit antiviral, anticancer, antituberculosis and antimicrobial activity (Butnariu & Mangalagiu, 2009 ). Others reported to possess promising pharmacological activity for use as anti-hypertensive, cardiotonic and antinociceptive agents as well as coagulants (Alonazy et al., 2009 ). As part of our studies in this area, we undertook the synthesis of the title compound (Fig. 1) and determine its crystal structure.

Figure 1
The title molecule with the labeling scheme and 50% probability ellipsoids.

The phenyl rings C17–C22 and C23–C28 make dihedral angles of 77.09 (11) and 45.86 (12)°, respectively, with the pyridazine ring. All geometric parameters are within normal ranges.

In the crystal, molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds (Table 1, Fig. 2 and Fig. 3). No π–π stacking interactions are observed but C—H⋯π interactions help to consolidate the packing (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2 and Cg4 are the centroids of the pyridazine (N1/N2/C1–C4), 4-methylphenyl (C7–C12) and phenyl (C23–C28) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.87	2.21	3.073 (3)	174
C5—H5B⋯O2ⁱ	0.99	2.36	3.220 (4)	144
C11—H11⋯O2ⁱⁱ	0.95	2.43	3.263 (4)	146
C20—H20⋯Cg4ⁱⁱⁱ	0.95	2.61	3.495 (3)	155
C26—H26⋯Cg1^iv	0.95	2.80	3.556 (3)	137
C28—H28⋯Cg2^v	0.95	2.66	3.484 (3)	146
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x-1, -y+1, z+{\script{1\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) $[x, -y+1, z-{\script{1\over 2}}]$ .

Figure 2
Packing viewed down the a axis with N—H⋯O and C—H⋯O hydrogen bonds shown, respectively, as blue and orange dotted lines.

Figure 3
Packing viewed down the c axis with N—H⋯O and C—H⋯O hydrogen bonds shown, respectively, as blue and orange dotted lines.

Synthesis and crystallization

A mixture of ethyl 2,3-dihydro-5,6-diphenyl-3-thioxopyridazine-4-carboxylate (1.68 g, 5 mmol), sodium acetate trihydrate (0.68 g, 5 mmol) and chloro-N-(4-methyl-phenyl)acetamide (0.92 g, 5 mmol) in ethanol (30 ml) was heated under reflux for 2 h. The product which separated on cooling was collected and recrystallized from ethanol to give colorless crystals of the title compound. Yield: 2.10 g (87%), m.p. 433–434 K. IR (KBr) ν = 3300 (NH), 1720 (C=O, ester), 1670 (C=O, carbamoyl), ¹H NMR (CDCl₃): δ 9.0 (s, 1H, NH), 6.9–7.6 (m, 14H, Ar—H), 4.1–4.4 (q, 2H, OCH₂), 4.0 (s, 2H, SCH₂), 2.2 (s, 3H, CH₃), 1.0–1.3 (t, 3H, CH₃ of ester). Elemental analysis calculated for C₂₈H₂₅N₃O₃S (%): C, 69.54; H, 5.21; N, 8.69; S, 6.63. Found (%): C, 69.19; H, 5.14; N, 8.61; S, 6.70.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The ethoxy group of the ester is disordered over two sets of sites with an occupancy ratio of 0.760 (8):0.240 (8) and these were modeled with restraints that their geometries be comparable. In the disorder model, atoms O3 and O3A were kept in the same position using EXYZ and EADP commands.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₈H₂₅N₃O₃S
M_r	483.57
Crystal system, space group	Monoclinic, Cc
Temperature (K)	150
a, b, c (Å)	10.2254 (3), 26.6695 (9), 9.9210 (3)
β (°)	110.718 (1)
V (Å³)	2530.56 (14)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	1.41
Crystal size (mm)	0.19 × 0.19 × 0.10

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.81, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	13580, 3992, 3898
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.04
No. of reflections	3992
No. of parameters	326
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.15
Absolute structure	Flack (1983 ), 1791 Friedel pairs
Absolute structure parameter	0.032 (17)
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1469872

Crystal structure: contains datablocks global, I. DOI: 10.1107/S241431461600479X/xu4003sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461600479X/xu4003Isup2.hkl

Supporting information file. DOI: 10.1107/S241431461600479X/xu4003Isup3.cml

checkCIF report

Experimental top

A mixture of ethyl 2,3-dihydro-5,6-diphenyl-3-thioxopyridazine-4-carboxylate (1.68 g, 5 mmol), sodium acetate trihydrate (0.68 g, 5 mmol) and chloro-N-(4-methyl-phenyl)acetamide (0.92 g, 5 mmol) in ethanol (30 ml) was heated under reflux for 2 h. The product which separated on cooling was collected and recrystallized from ethanol to give colorless crystals of the title compound. Yield: 2.10 g (87%), m.p. 433–434 K. IR (KBr) ν = 3300 (NH), 1720 (C═O, ester), 1670 (C═O, carbamoyl), ¹H NMR (CDCl₃): δ 9.0 (s, 1H, NH), 6.9–7.6 (m, 14H, Ar—H), 4.1–4.4 (q, 2H, OCH₂), 4.0 (s, 2H, SCH₂), 2.2 (s, 3H, CH₃), 1.0–1.3 (t, 3H, CH₃ of ester). Elemental analysis calculated for C₂₈H₂₅N₃O₃S (%): C, 69.54; H, 5.21; N, 8.69; S, 6.63. Found (%): C, 69.19; H, 5.14; N, 8.61; S, 6.70.

Structure description top

The broad spectrum of biological activities associated with many pyridazine derivatives are well known. Some of them are reported to exhibit antiviral, anticancer, antituberculosis and antimicrobial activity (Butnariu & Mangalagiu, 2009). Others reported to possess promising pharmacological activity for use as anti-hypertensive, cardiotonic and antinociceptive agents as well as coagulants (Alonazy et al., 2009). In view of the above findings, we undertook the synthesis of the title compound (Fig. 1) and determine its crystal structure.

The phenyl rings C17–C22 and C23–C28 make dihedral angles of 77.09 (11) and 45.86 (12)°, respectively, with the pyridazine ring. All geometric parameters are within normal ranges.

In the crystal, molecules are linked by N—H···O and C—H···O hydrogen bonds (Table 1, Fig. 2 and Fig. 3). No π–π stacking interactions are observed but C—H···π interactions help to stabilize the crystal structure (Table 1).

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The title molecule with the labeling scheme and 50% probability ellipsoids.
	Fig. 2. Packing viewed down the a axis with N—H···O and C—H···O hydrogen bonds shown, respectively, as blue and orange dotted lines.
	Fig. 3. Packing viewed down the c axis with N—H···O and C—H···O hydrogen bonds shown, respectively, as blue and orange dotted lines.

Ethyl 3-({[(4-methylphenyl)carbamoyl]methyl}sulfanyl)-5,6-diphenylpyridazine-4-carboxylate top

Crystal data top

C₂₈H₂₅N₃O₃S	F(000) = 1016
M_r = 483.57	D_x = 1.269 Mg m⁻³
Monoclinic, Cc	Cu Kα radiation, λ = 1.54178 Å
a = 10.2254 (3) Å	Cell parameters from 9986 reflections
b = 26.6695 (9) Å	θ = 3.3–66.2°
c = 9.9210 (3) Å	µ = 1.41 mm⁻¹
β = 110.718 (1)°	T = 150 K
V = 2530.56 (14) Å³	Plate, colourless
Z = 4	0.19 × 0.19 × 0.10 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3992 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3898 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.029
Detector resolution: 10.4167 pixels mm^-1	θ_max = 66.2°, θ_min = 3.3°
ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −31→31
T_min = 0.81, T_max = 0.88	l = −11→11
13580 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0428P)² + 0.5908P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.071	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.30 e Å⁻³
3992 reflections	Δρ_min = −0.15 e Å⁻³
326 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.00168 (17)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1791 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.032 (17)

Crystal data top

C₂₈H₂₅N₃O₃S	V = 2530.56 (14) Å³
M_r = 483.57	Z = 4
Monoclinic, Cc	Cu Kα radiation
a = 10.2254 (3) Å	µ = 1.41 mm⁻¹
b = 26.6695 (9) Å	T = 150 K
c = 9.9210 (3) Å	0.19 × 0.19 × 0.10 mm
β = 110.718 (1)°

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	3992 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2016)	3898 reflections with I > 2σ(I)
T_min = 0.81, T_max = 0.88	R_int = 0.029
13580 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.071	Δρ_max = 0.30 e Å⁻³
S = 1.04	Δρ_min = −0.15 e Å⁻³
3992 reflections	Absolute structure: Flack (1983), 1791 Friedel pairs
326 parameters	Absolute structure parameter: 0.032 (17)
6 restraints

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.74550 (6)	0.46021 (2)	0.76373 (6)	0.03062 (16)
O1	0.48527 (18)	0.52387 (7)	0.63741 (18)	0.0330 (4)
O2	0.8388 (2)	0.41894 (9)	0.4697 (3)	0.0524 (6)
N1	0.5118 (2)	0.40599 (7)	0.6734 (2)	0.0279 (4)
N2	0.4255 (2)	0.37053 (7)	0.5934 (2)	0.0267 (4)
N3	0.4189 (2)	0.52041 (8)	0.8345 (2)	0.0306 (5)
H3	0.4400	0.5057	0.9177	0.037*
C1	0.6375 (2)	0.41215 (8)	0.6639 (2)	0.0242 (5)
C2	0.6853 (3)	0.38241 (9)	0.5729 (2)	0.0249 (5)
C3	0.5952 (2)	0.34723 (9)	0.4866 (2)	0.0246 (5)
C4	0.4638 (2)	0.34225 (9)	0.5020 (2)	0.0255 (5)
C5	0.6394 (3)	0.48489 (9)	0.8579 (3)	0.0291 (5)
H5A	0.6128	0.4571	0.9090	0.035*
H5B	0.6960	0.5089	0.9315	0.035*
C6	0.5068 (3)	0.51128 (8)	0.7625 (3)	0.0272 (5)
C7	0.2813 (2)	0.54069 (9)	0.7795 (3)	0.0292 (6)
C8	0.2266 (3)	0.56605 (9)	0.6500 (3)	0.0336 (6)
H8	0.2820	0.5716	0.5921	0.040*
C9	0.0888 (3)	0.58348 (10)	0.6052 (3)	0.0358 (6)
H9	0.0513	0.6006	0.5157	0.043*
C10	0.0053 (3)	0.57657 (10)	0.6875 (3)	0.0339 (6)
C11	0.0634 (3)	0.55100 (10)	0.8176 (3)	0.0365 (6)
H11	0.0080	0.5454	0.8755	0.044*
C12	0.1995 (3)	0.53361 (9)	0.8645 (3)	0.0326 (6)
H12	0.2373	0.5168	0.9546	0.039*
C13	−0.1412 (3)	0.59740 (11)	0.6421 (3)	0.0434 (7)
H13A	−0.2041	0.5718	0.6556	0.065*
H13B	−0.1725	0.6071	0.5403	0.065*
H13C	−0.1419	0.6268	0.7009	0.065*
C14	0.8249 (3)	0.39184 (9)	0.5604 (3)	0.0273 (5)
O3_a	0.92581 (19)	0.36604 (8)	0.6547 (2)	0.0412 (5)	0.760 (8)
C15_a	1.0650 (10)	0.3697 (8)	0.6450 (15)	0.0487 (9)	0.760 (8)
H15A_a	1.0557	0.3696	0.5422	0.058*	0.760 (8)
H15B_a	1.1205	0.3399	0.6914	0.058*	0.760 (8)
C16_a	1.1403 (5)	0.4156 (2)	0.7147 (5)	0.0548 (14)	0.760 (8)
H16A_a	1.2322	0.4165	0.7047	0.082*	0.760 (8)
H16B_a	1.1522	0.4154	0.8172	0.082*	0.760 (8)
H16C_a	1.0863	0.4452	0.6684	0.082*	0.760 (8)
O3A_b	0.92581 (19)	0.36604 (8)	0.6547 (2)	0.0412 (5)	0.240 (8)
C15A_b	1.064 (3)	0.368 (3)	0.635 (4)	0.0487 (9)	0.240 (8)
H15C_b	1.0904	0.3341	0.6120	0.058*	0.240 (8)
H15D_b	1.0594	0.3908	0.5548	0.058*	0.240 (8)
C16A_b	1.1697 (16)	0.3864 (8)	0.7724 (17)	0.0548 (14)	0.240 (8)
H16D_b	1.2616	0.3881	0.7625	0.082*	0.240 (8)
H16E_b	1.1741	0.3634	0.8508	0.082*	0.240 (8)
H16F_b	1.1428	0.4199	0.7941	0.082*	0.240 (8)
C17	0.6349 (3)	0.31765 (9)	0.3795 (3)	0.0285 (5)
C18	0.7382 (3)	0.28145 (10)	0.4234 (3)	0.0365 (6)
H18	0.7855	0.2752	0.5232	0.044*
C19	0.7725 (3)	0.25428 (12)	0.3210 (4)	0.0445 (7)
H19	0.8421	0.2289	0.3508	0.053*
C20	0.7055 (3)	0.26401 (12)	0.1760 (3)	0.0466 (8)
H20	0.7293	0.2454	0.1063	0.056*
C21	0.6050 (3)	0.30046 (13)	0.1328 (3)	0.0459 (7)
H21	0.5603	0.3075	0.0330	0.055*
C22	0.5680 (3)	0.32730 (11)	0.2339 (3)	0.0391 (6)
H22	0.4970	0.3522	0.2034	0.047*
C23	0.3571 (3)	0.30472 (9)	0.4227 (2)	0.0267 (5)
C24	0.3919 (3)	0.25438 (10)	0.4137 (3)	0.0315 (5)
H24	0.4869	0.2440	0.4522	0.038*
C25	0.2879 (3)	0.21976 (10)	0.3485 (3)	0.0380 (6)
H25	0.3116	0.1855	0.3436	0.046*
C26	0.1498 (3)	0.23462 (11)	0.2908 (3)	0.0414 (7)
H26	0.0789	0.2106	0.2468	0.050*
C27	0.1147 (3)	0.28431 (11)	0.2969 (3)	0.0392 (6)
H27	0.0199	0.2946	0.2555	0.047*
C28	0.2182 (3)	0.31937 (10)	0.3637 (3)	0.0319 (5)
H28	0.1937	0.3535	0.3689	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0250 (3)	0.0342 (3)	0.0338 (3)	−0.0036 (3)	0.0117 (2)	−0.0090 (2)
O1	0.0343 (10)	0.0380 (9)	0.0290 (9)	0.0020 (8)	0.0142 (7)	0.0001 (7)
O2	0.0378 (12)	0.0637 (13)	0.0644 (14)	0.0072 (10)	0.0289 (10)	0.0290 (11)
N1	0.0260 (11)	0.0286 (10)	0.0308 (10)	−0.0014 (8)	0.0123 (8)	−0.0026 (8)
N2	0.0257 (11)	0.0271 (10)	0.0286 (10)	−0.0012 (8)	0.0113 (8)	−0.0025 (8)
N3	0.0303 (12)	0.0351 (11)	0.0273 (10)	0.0063 (9)	0.0115 (9)	0.0015 (8)
C1	0.0235 (12)	0.0254 (12)	0.0242 (11)	0.0005 (9)	0.0090 (9)	−0.0008 (9)
C2	0.0266 (12)	0.0254 (11)	0.0237 (11)	0.0024 (9)	0.0099 (9)	0.0031 (9)
C3	0.0257 (12)	0.0254 (11)	0.0240 (11)	0.0035 (9)	0.0105 (9)	0.0023 (9)
C4	0.0272 (13)	0.0261 (11)	0.0246 (11)	0.0028 (9)	0.0109 (9)	0.0043 (9)
C5	0.0287 (13)	0.0333 (13)	0.0265 (12)	0.0007 (10)	0.0111 (10)	−0.0088 (10)
C6	0.0285 (13)	0.0261 (12)	0.0271 (13)	−0.0027 (10)	0.0098 (9)	−0.0063 (10)
C7	0.0291 (15)	0.0275 (11)	0.0314 (13)	0.0015 (10)	0.0113 (11)	−0.0063 (9)
C8	0.0349 (15)	0.0375 (13)	0.0295 (13)	0.0028 (11)	0.0127 (10)	−0.0018 (10)
C9	0.0350 (15)	0.0402 (15)	0.0290 (13)	0.0062 (11)	0.0076 (11)	−0.0020 (10)
C10	0.0293 (14)	0.0333 (13)	0.0376 (14)	0.0013 (11)	0.0100 (10)	−0.0107 (11)
C11	0.0352 (15)	0.0376 (14)	0.0408 (14)	−0.0017 (12)	0.0186 (12)	−0.0071 (11)
C12	0.0341 (15)	0.0341 (13)	0.0317 (13)	0.0025 (11)	0.0142 (11)	−0.0005 (10)
C13	0.0308 (15)	0.0493 (16)	0.0464 (16)	0.0056 (12)	0.0091 (12)	−0.0076 (13)
C14	0.0275 (13)	0.0271 (12)	0.0293 (12)	0.0015 (10)	0.0124 (10)	−0.0020 (10)
O3_a	0.0258 (10)	0.0542 (12)	0.0453 (11)	0.0064 (8)	0.0147 (8)	0.0137 (9)
C15_a	0.0270 (15)	0.061 (2)	0.062 (3)	0.0052 (14)	0.0203 (15)	0.0056 (18)
C16_a	0.037 (2)	0.088 (4)	0.043 (3)	−0.019 (2)	0.0196 (19)	−0.015 (2)
O3A_b	0.0258 (10)	0.0542 (12)	0.0453 (11)	0.0064 (8)	0.0147 (8)	0.0137 (9)
C15A_b	0.0270 (15)	0.061 (2)	0.062 (3)	0.0052 (14)	0.0203 (15)	0.0056 (18)
C16A_b	0.037 (2)	0.088 (4)	0.043 (3)	−0.019 (2)	0.0196 (19)	−0.015 (2)
C17	0.0275 (12)	0.0308 (12)	0.0312 (12)	−0.0044 (10)	0.0155 (10)	−0.0072 (10)
C18	0.0347 (15)	0.0396 (14)	0.0382 (14)	0.0010 (12)	0.0168 (11)	−0.0071 (11)
C19	0.0386 (16)	0.0438 (16)	0.0581 (18)	0.0013 (13)	0.0258 (14)	−0.0138 (13)
C20	0.0488 (18)	0.0528 (17)	0.0504 (18)	−0.0160 (15)	0.0326 (15)	−0.0261 (14)
C21	0.0483 (18)	0.0602 (19)	0.0327 (14)	−0.0096 (15)	0.0188 (12)	−0.0128 (13)
C22	0.0397 (16)	0.0488 (16)	0.0315 (14)	−0.0035 (12)	0.0161 (11)	−0.0059 (12)
C23	0.0282 (13)	0.0312 (12)	0.0237 (11)	−0.0037 (10)	0.0127 (9)	−0.0001 (9)
C24	0.0345 (14)	0.0318 (13)	0.0315 (13)	−0.0021 (11)	0.0158 (11)	−0.0042 (10)
C25	0.0489 (17)	0.0328 (14)	0.0374 (14)	−0.0093 (12)	0.0217 (13)	−0.0110 (11)
C26	0.0442 (17)	0.0499 (17)	0.0316 (13)	−0.0202 (14)	0.0151 (11)	−0.0118 (12)
C27	0.0307 (14)	0.0535 (17)	0.0315 (13)	−0.0067 (12)	0.0087 (11)	−0.0001 (12)
C28	0.0311 (14)	0.0373 (13)	0.0279 (12)	−0.0020 (11)	0.0112 (10)	0.0024 (10)

Geometric parameters (Å, º) top

S1—C1	1.752 (2)	C15_a—C16_a	1.481 (15)
S1—C5	1.789 (2)	C15_a—H15A_a	0.9900
O1—C6	1.228 (3)	C15_a—H15B_a	0.9900
O2—C14	1.201 (3)	C16_a—H16A_a	0.9800
N1—C1	1.332 (3)	C16_a—H16B_a	0.9800
N1—N2	1.344 (3)	C16_a—H16C_a	0.9800
N2—C4	1.341 (3)	C15A_b—C16A_b	1.49 (3)
N3—C6	1.354 (3)	C15A_b—H15C_b	0.9900
N3—C7	1.423 (3)	C15A_b—H15D_b	0.9900
N3—H3	0.8702	C16A_b—H16D_b	0.9800
C1—C2	1.412 (3)	C16A_b—H16E_b	0.9800
C2—C3	1.380 (3)	C16A_b—H16F_b	0.9800
C2—C14	1.497 (3)	C17—C18	1.382 (4)
C3—C4	1.411 (3)	C17—C22	1.386 (4)
C3—C17	1.491 (3)	C18—C19	1.390 (4)
C4—C23	1.484 (3)	C18—H18	0.9500
C5—C6	1.523 (3)	C19—C20	1.382 (5)
C5—H5A	0.9900	C19—H19	0.9500
C5—H5B	0.9900	C20—C21	1.369 (5)
C7—C8	1.383 (4)	C20—H20	0.9500
C7—C12	1.395 (4)	C21—C22	1.390 (4)
C8—C9	1.398 (4)	C21—H21	0.9500
C8—H8	0.9500	C22—H22	0.9500
C9—C10	1.387 (4)	C23—C28	1.387 (4)
C9—H9	0.9500	C23—C24	1.400 (4)
C10—C11	1.394 (4)	C24—C25	1.384 (4)
C10—C13	1.509 (4)	C24—H24	0.9500
C11—C12	1.382 (4)	C25—C26	1.381 (4)
C11—H11	0.9500	C25—H25	0.9500
C12—H12	0.9500	C26—C27	1.380 (5)
C13—H13A	0.9800	C26—H26	0.9500
C13—H13B	0.9800	C27—C28	1.392 (4)
C13—H13C	0.9800	C27—H27	0.9500
C14—O3_a	1.316 (3)	C28—H28	0.9500
O3_a—C15_a	1.463 (9)

C1—S1—C5	100.79 (11)	O3_a—C15_a—H15A_a	109.1
C1—N1—N2	119.57 (19)	C16_a—C15_a—H15A_a	109.1
C4—N2—N1	120.5 (2)	O3_a—C15_a—H15B_a	109.1
C6—N3—C7	128.1 (2)	C16_a—C15_a—H15B_a	109.1
C6—N3—H3	115.5	H15A_a—C15_a—H15B_a	107.9
C7—N3—H3	114.5	C15_a—C16_a—H16A_a	109.5
N1—C1—C2	122.5 (2)	C15_a—C16_a—H16B_a	109.5
N1—C1—S1	118.76 (17)	H16A_a—C16_a—H16B_a	109.5
C2—C1—S1	118.76 (18)	C15_a—C16_a—H16C_a	109.5
C3—C2—C1	118.2 (2)	H16A_a—C16_a—H16C_a	109.5
C3—C2—C14	120.6 (2)	H16B_a—C16_a—H16C_a	109.5
C1—C2—C14	120.9 (2)	C16A_b—C15A_b—H15C_b	110.2
C2—C3—C4	116.7 (2)	C16A_b—C15A_b—H15D_b	110.2
C2—C3—C17	120.8 (2)	H15C_b—C15A_b—H15D_b	108.5
C4—C3—C17	122.5 (2)	C15A_b—C16A_b—H16D_b	109.5
N2—C4—C3	122.5 (2)	C15A_b—C16A_b—H16E_b	109.5
N2—C4—C23	113.7 (2)	H16D_b—C16A_b—H16E_b	109.5
C3—C4—C23	123.8 (2)	C15A_b—C16A_b—H16F_b	109.5
C6—C5—S1	114.61 (17)	H16D_b—C16A_b—H16F_b	109.5
C6—C5—H5A	108.6	H16E_b—C16A_b—H16F_b	109.5
S1—C5—H5A	108.6	C18—C17—C22	119.9 (2)
C6—C5—H5B	108.6	C18—C17—C3	121.0 (2)
S1—C5—H5B	108.6	C22—C17—C3	119.1 (2)
H5A—C5—H5B	107.6	C17—C18—C19	119.7 (3)
O1—C6—N3	124.7 (2)	C17—C18—H18	120.2
O1—C6—C5	123.8 (2)	C19—C18—H18	120.2
N3—C6—C5	111.5 (2)	C20—C19—C18	120.2 (3)
C8—C7—C12	119.7 (2)	C20—C19—H19	119.9
C8—C7—N3	124.2 (2)	C18—C19—H19	119.9
C12—C7—N3	116.1 (2)	C21—C20—C19	120.0 (3)
C7—C8—C9	119.2 (2)	C21—C20—H20	120.0
C7—C8—H8	120.4	C19—C20—H20	120.0
C9—C8—H8	120.4	C20—C21—C22	120.4 (3)
C10—C9—C8	122.0 (2)	C20—C21—H21	119.8
C10—C9—H9	119.0	C22—C21—H21	119.8
C8—C9—H9	119.0	C17—C22—C21	119.7 (3)
C9—C10—C11	117.5 (2)	C17—C22—H22	120.1
C9—C10—C13	121.9 (3)	C21—C22—H22	120.1
C11—C10—C13	120.6 (3)	C28—C23—C24	119.3 (2)
C12—C11—C10	121.6 (3)	C28—C23—C4	119.0 (2)
C12—C11—H11	119.2	C24—C23—C4	121.7 (2)
C10—C11—H11	119.2	C25—C24—C23	119.9 (2)
C11—C12—C7	119.9 (2)	C25—C24—H24	120.0
C11—C12—H12	120.0	C23—C24—H24	120.0
C7—C12—H12	120.0	C26—C25—C24	120.4 (3)
C10—C13—H13A	109.5	C26—C25—H25	119.8
C10—C13—H13B	109.5	C24—C25—H25	119.8
H13A—C13—H13B	109.5	C27—C26—C25	120.1 (3)
C10—C13—H13C	109.5	C27—C26—H26	120.0
H13A—C13—H13C	109.5	C25—C26—H26	120.0
H13B—C13—H13C	109.5	C26—C27—C28	120.0 (3)
O2—C14—O3_a	125.2 (2)	C26—C27—H27	120.0
O2—C14—C2	122.2 (2)	C28—C27—H27	120.0
O3_a—C14—C2	112.6 (2)	C23—C28—C27	120.3 (3)
C14—O3_a—C15_a	117.0 (9)	C23—C28—H28	119.9
O3_a—C15_a—C16_a	112.4 (10)	C27—C28—H28	119.9

C1—N1—N2—C4	−1.6 (3)	C8—C7—C12—C11	1.4 (4)
N2—N1—C1—C2	−0.5 (3)	N3—C7—C12—C11	−178.4 (2)
N2—N1—C1—S1	177.52 (16)	C3—C2—C14—O2	82.4 (3)
C5—S1—C1—N1	2.3 (2)	C1—C2—C14—O2	−92.1 (3)
C5—S1—C1—C2	−179.63 (18)	C3—C2—C14—O3_a	−95.3 (3)
N1—C1—C2—C3	2.8 (3)	C1—C2—C14—O3_a	90.2 (3)
S1—C1—C2—C3	−175.15 (17)	O2—C14—O3_a—C15_a	−2.0 (7)
N1—C1—C2—C14	177.4 (2)	C2—C14—O3_a—C15_a	175.7 (6)
S1—C1—C2—C14	−0.6 (3)	C14—O3_a—C15_a—C16_a	81.2 (11)
C1—C2—C3—C4	−3.0 (3)	C2—C3—C17—C18	70.0 (3)
C14—C2—C3—C4	−177.6 (2)	C4—C3—C17—C18	−112.2 (3)
C1—C2—C3—C17	174.9 (2)	C2—C3—C17—C22	−109.2 (3)
C14—C2—C3—C17	0.3 (3)	C4—C3—C17—C22	68.6 (3)
N1—N2—C4—C3	1.3 (3)	C22—C17—C18—C19	−1.2 (4)
N1—N2—C4—C23	179.63 (19)	C3—C17—C18—C19	179.7 (3)
C2—C3—C4—N2	1.1 (3)	C17—C18—C19—C20	1.2 (4)
C17—C3—C4—N2	−176.7 (2)	C18—C19—C20—C21	−0.1 (5)
C2—C3—C4—C23	−177.1 (2)	C19—C20—C21—C22	−1.1 (5)
C17—C3—C4—C23	5.1 (3)	C18—C17—C22—C21	0.0 (4)
C1—S1—C5—C6	−67.9 (2)	C3—C17—C22—C21	179.2 (2)
C7—N3—C6—O1	7.3 (4)	C20—C21—C22—C17	1.1 (4)
C7—N3—C6—C5	−174.7 (2)	N2—C4—C23—C28	44.8 (3)
S1—C5—C6—O1	−13.9 (3)	C3—C4—C23—C28	−136.9 (2)
S1—C5—C6—N3	168.15 (17)	N2—C4—C23—C24	−131.2 (2)
C6—N3—C7—C8	−16.8 (4)	C3—C4—C23—C24	47.1 (3)
C6—N3—C7—C12	162.9 (2)	C28—C23—C24—C25	−1.1 (4)
C12—C7—C8—C9	−1.1 (4)	C4—C23—C24—C25	174.9 (2)
N3—C7—C8—C9	178.7 (2)	C23—C24—C25—C26	0.8 (4)
C7—C8—C9—C10	0.6 (4)	C24—C25—C26—C27	0.4 (4)
C8—C9—C10—C11	−0.5 (4)	C25—C26—C27—C28	−1.2 (4)
C8—C9—C10—C13	177.3 (2)	C24—C23—C28—C27	0.3 (4)
C9—C10—C11—C12	0.8 (4)	C4—C23—C28—C27	−175.9 (2)
C13—C10—C11—C12	−177.0 (2)	C26—C27—C28—C23	0.9 (4)
C10—C11—C12—C7	−1.2 (4)

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg4 are the centroids of the pyridazine (N1/N2/C1–C4), 4-methylphenyl (C7–C12) and phenyl (C23–C28) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.87	2.21	3.073 (3)	174
C5—H5B···O2ⁱ	0.99	2.36	3.220 (4)	144
C11—H11···O2ⁱⁱ	0.95	2.43	3.263 (4)	146
C20—H20···Cg4ⁱⁱⁱ	0.95	2.61	3.495 (3)	155
C26—H26···Cg1^iv	0.95	2.80	3.556 (3)	137
C28—H28···Cg2^v	0.95	2.66	3.484 (3)	146

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2 and Cg4 are the centroids of the pyridazine (N1/N2/C1–C4), 4-methylphenyl (C7–C12) and phenyl (C23–C28) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.87	2.21	3.073 (3)	174
C5—H5B···O2ⁱ	0.99	2.36	3.220 (4)	144
C11—H11···O2ⁱⁱ	0.95	2.43	3.263 (4)	146
C20—H20···Cg4ⁱⁱⁱ	0.95	2.61	3.495 (3)	155
C26—H26···Cg1^iv	0.95	2.80	3.556 (3)	137
C28—H28···Cg2^v	0.95	2.66	3.484 (3)	146

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

Experimental details

Crystal data
Chemical formula	C₂₈H₂₅N₃O₃S
M_r	483.57
Crystal system, space group	Monoclinic, Cc
Temperature (K)	150
a, b, c (Å)	10.2254 (3), 26.6695 (9), 9.9210 (3)
β (°)	110.718 (1)
V (Å³)	2530.56 (14)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	1.41
Crystal size (mm)	0.19 × 0.19 × 0.10

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.81, 0.88
No. of measured, independent and observed [I > 2σ(I)] reflections	13580, 3992, 3898
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.071, 1.04
No. of reflections	3992
No. of parameters	326
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.15
Absolute structure	Flack (1983), 1791 Friedel pairs
Absolute structure parameter	0.032 (17)

Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b), DIAMOND (Brandenburg & Putz, 2012), SHELXTL (Sheldrick, 2008).

Acknowledgements

The support of NSF–MRI Grant No.1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

Alonazy, H. S., AL-Hazimi, H. M. A. & Korraa, M. M. S. (2009). Arab. J. Chem. 2, 101–108. CrossRef CAS Google Scholar
Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Butnariu, R. M. & Mangalagiu, I. I. (2009). Bioorg. Med. Chem. 17, 2823–2829. CrossRef PubMed CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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Volume 1| Part 3| March 2016| x160479

doi:10.1107/S241431461600479X

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

Ethyl 3-({[(4-methyl­phen­yl)carbamo­yl]meth­yl}sulfan­yl)-5,6-di­phenyl­pyridazine-4-carboxyl­ate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

Ethyl 3-({[(4-methylphenyl)carbamoyl]methyl}sulfanyl)-5,6-diphenylpyridazine-4-carboxylate