Ethyl 13-(4-chloro­phen­yl)-11-methyl-6-oxo-5-phenyl-8-thia-3,4,5,10-tetra­aza­tri­cyclo­[7.4.0.02,7]trideca-1(9),2(7),3,10,12-penta­ene-12-carboxyl­ate

Al-Taifi, E.A.; Mague, J.T.; Mohamed, S.K.; Akkurt, M.; Bakhite, E.A.

doi:10.1107/S241431461600701X

organic compounds

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ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160701

doi:10.1107/S241431461600701X

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Ethyl 13-(4-chlorophenyl)-11-methyl-6-oxo-5-phenyl-8-thia-3,4,5,10-tetraazatricyclo[7.4.0.0^2,7]trideca-1(9),2(7),3,10,12-pentaene-12-carboxylate

Elham A. Al-Taifi,^a Joel T. Mague,^b Shaaban K. Mohamed,^c,^d ^* Mehmet Akkurt ^e and Etify A. Bakhite ^f

^aChemistry Department, Faculty of Science, Sana'a University, Sana'a, Yemen, ^bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA, ^cChemistry and Environmental Division, Manchester Metropolitan University, Manchester M1 5GD, England, ^dChemistry Department, Faculty of Science, Minia University, 61519 El-Minia, Egypt, ^eDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, and ^fChemistry Department, Faculty of Science, Assiut University, Assiut 71516, Egypt
^*Correspondence e-mail: s.mohamed@mmu.ac.uk

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 15 April 2016; accepted 25 April 2016; online 4 May 2016)

In the title molecule, C₂₄H₁₇ClN₄O₃S, the central tricyclic moiety is twisted slightly, as indicated by the dihedral angles of 4.86 (5) and 0.97 (6)°, respectively, between the five-membered ring and the C₃N₃ and pyridyl rings. Additionally, the chlorobenzene ring makes a dihedral angle of 65.80 (5)° with the pyridyl ring. Weak C—H⋯O, C—Cl⋯N [3.0239 (13) Å] and π–π stacking interactions [inter-centroid distance between thienyl rings = 3.6994 (8) Å, and between thienyl and pyridyl rings = 3.7074 (8) Å] contribute to the molecular packing. The ethyl group in the ester moiety is disordered over two sets of sites, with the major component having an occupancy of 0.567 (11).

Keywords: crystal structure; thienopyridines; pyridothienotriazinones.

CCDC reference: 1476505

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Chemical scheme

Structure description

Among heterocyclic systems, thienopyridines attract considerable attention due to their various biological activities and pharmaceutical properties (Litvinov et al., 2005 ; Mohamed et al., 2007 ; Bakhite, 2003 ). Thienopyridines have been reported to be anti-malarial (Görlitzer et al., 2004 ), anti-platelet (Girija et al., 2011 ) and anti-microbial agents. As part of our studies in this area, we report here the synthesis and the crystal structure of the title compound (Fig. 1).

Figure 1
Perspective view of the title molecule with labelling scheme and 50% probability ellipsoids.

The central tricyclic moiety is twisted slightly, as indicated by the dihedral angles of 4.86 (5) and 0.97 (6)°, respectively, between the five-membered ring and the C₃N₃ and pyridyl rings. Additionally, the 4-chlorobenzene ring makes a dihedral angle of 65.80 (5)° with the pyridyl ring.

In the crystal, weak C8—H8A⋯O1ⁱ hydrogen bonds (Table 1) form chains parallel to (100). Intercalation of adjacent chains is aided by slipped π–π stacking interactions between centrosymmetrically related thienyl rings [inter-centroid distance = 3.6994 (8) Å; −x, −y, 1 − z] and the between thienyl and pyridyl rings [inter-centroid distance = 3.7074 (8) Å; −x, 1 − y, 1 − z]. In the latter interaction, the dihedral angle between the planes is 0.97 (7)°. This intercalation forms sheets which are associated through Cl1—N1(−1 + x, y, z) interactions with Cl⋯N distances of 3.024 (1) Å. This is 0.28 Å less than the sum of the corresponding van der Waals radii and is thus considered to be an attractive interaction. The ethyl group of the ester is disordered over two sets of sites by a rotation of approximately 13° about the C7—O3 bond.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O2ⁱ	0.99	2.42	3.339 (7)	154
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Synthesis and crystallization

The title compound was synthesized according to our reported method (Mohamed et al., 2007). Single crystals of the title compound were obtained by recrystallization from an ethanol solution to afford colourless plates suitable for X-ray diffraction. Yield (81%); M.p. 453–454 K. IR: 1720 (C=O, ester), 1660 (C=O, triazinone) cm^{-1. 1}H NMR (CDCl₃): δ = 7.1–7.6 (m, 9H, ArH), 4.1 (q, 2H, OCH₂), 2.7 (s, 3H, CH₃ at C-7), 1.1 (t, 3H, CH₃ of ester group).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.The ethyl group in the ester moiety is disordered over two sets of sites in approximately equal amounts; major component = 0.567 (11). The two components of the disorder were refined with restraints so that their geometries are comparable.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₄H₁₇ClN₄O₃S
M_r	476.92
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	11.8562 (3), 7.1984 (2), 25.4331 (5)
β (°)	101.045 (1)
V (Å³)	2130.40 (9)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	2.81
Crystal size (mm)	0.22 × 0.17 × 0.06

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.73, 0.85
No. of measured, independent and observed [I > 2σ(I)] reflections	15584, 4116, 3824
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.02
No. of reflections	4116
No. of parameters	309
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXTL (Sheldrick, 2008 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and DIAMOND (Brandenburg & Putz, 2012 ).

Structural data

CCDC reference: 1476505

Crystal structure: contains datablocks global, I. DOI: 10.1107/S241431461600701X/tk4011sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S241431461600701X/tk4011Isup2.hkl

Supporting information file. DOI: 10.1107/S241431461600701X/tk4011Isup3.cml

checkCIF report

Experimental top

The title compound was synthesized according to our reported method (Mohamed et al., 2007). Pure crystals of the title compound were obtained by recrystallization from ethanol to afford colourless plates suitable for X-ray diffraction. Yield (81%); M.p. 453–454 K. IR: 1720 (C═O, ester), 1660 (C═O, triazinone) cm^{-1. 1}H NMR (CDCl₃): δ = 7.1–7.6 (m, 9H, ArH), 4.1 (q, 2H, OCH₂), 2.7 (s, 3H, CH₃ at C-7), 1.1 (t, 3H, CH₃ of ester group).

Structure description top

Among heterocyclic systems, thienopyridines attract considerable attention due to their various biological activities and pharmaceutical properties (Litvinov et al., 2005; Mohamed et al., 2007; Bakhite, 2003). Thienopyridines have been reported to be anti-malarial (Görlitzer et al., 2004), anti-platelet (Girija et al., 2011) and anti-microbial agents. In this context we report here the synthesis and the crystal structure of the title compound (Fig. 1).

In the crystal, weak C8—H8A···O1ⁱ hydrogen bonds (Table 1) form chains approximately parallel to (100). Intercalation of adjacent chains is aided by slipped π–π stacking interactions between centrosymmetrically related thienyl rings [inter-centroid distance = 3.6994 (8) Å; -x, -y, 1 - z] and the between thienyl and pyridyl rings [inter-centroid distance = 3.7074 (8) Å; -x, 1 - y, 1 - z]. In the latter interaction, the dihedral angle between the planes is 0.97 (7)°. This intercalation forms sheets which are associated through Cl1—N1(-1 + x, y, z) interactions with Cl···N distances of 3.024 (1) Å. This is 0.28 Å less than the sum of the corresponding van der Waals radii and is thus considered to be an attractive interaction. The ethyl group of the ester is disordered over two sets of sites by a rotation of approximately 13° about the C7—O3 bond.

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. Perspective view of the title molecule with labelling scheme and 50% probability ellipsoids.

Ethyl 13-(4-chlorophenyl)-11-methyl-6-oxo-5-phenyl-8-thia-3,4,5,10-tetraazatricyclo[7.4.0.0^2,7]trideca-1(9),2(7),3,10,12-pentaene-12-carboxylate top

Crystal data top

C₂₄H₁₇ClN₄O₃S	F(000) = 984
M_r = 476.92	D_x = 1.487 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54178 Å
a = 11.8562 (3) Å	Cell parameters from 9972 reflections
b = 7.1984 (2) Å	θ = 3.5–72.3°
c = 25.4331 (5) Å	µ = 2.81 mm⁻¹
β = 101.045 (1)°	T = 150 K
V = 2130.40 (9) Å³	Tablet, colourless
Z = 4	0.22 × 0.17 × 0.06 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4116 independent reflections
Radiation source: INCOATEC IµS micro–focus source	3824 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.4°, θ_min = 3.5°
ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −8→8
T_min = 0.73, T_max = 0.85	l = −30→31
15584 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H-atom parameters constrained
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.0445P)² + 1.0088P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
4116 reflections	Δρ_max = 0.27 e Å⁻³
309 parameters	Δρ_min = −0.25 e Å⁻³
2 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015a), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00183 (15)

Crystal data top

C₂₄H₁₇ClN₄O₃S	V = 2130.40 (9) Å³
M_r = 476.92	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 11.8562 (3) Å	µ = 2.81 mm⁻¹
b = 7.1984 (2) Å	T = 150 K
c = 25.4331 (5) Å	0.22 × 0.17 × 0.06 mm
β = 101.045 (1)°

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	4116 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2016)	3824 reflections with I > 2σ(I)
T_min = 0.73, T_max = 0.85	R_int = 0.027
15584 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	2 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.02	Δρ_max = 0.27 e Å⁻³
4116 reflections	Δρ_min = −0.25 e Å⁻³
309 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) and included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. The ethyl group in the ester moiety is disordered over two sites in approximately equal amounts. The two components of the disorder were refined with restraints that their geometries be comparable.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.71998 (3)	0.29217 (6)	0.56218 (2)	0.02941 (11)
S1	−0.07638 (3)	0.19406 (5)	0.46290 (2)	0.02105 (11)
O1	−0.05465 (9)	0.03663 (16)	0.34942 (4)	0.0281 (2)
O2	0.29995 (10)	0.35512 (17)	0.69010 (5)	0.0377 (3)
O3	0.25376 (10)	0.63799 (16)	0.65508 (4)	0.0341 (3)
N1	−0.02471 (10)	0.31809 (17)	0.56408 (5)	0.0214 (3)
N2	0.24293 (10)	0.21959 (17)	0.44231 (5)	0.0218 (3)
N3	0.23889 (10)	0.17642 (18)	0.39328 (5)	0.0233 (3)
N4	0.13775 (10)	0.11843 (17)	0.36123 (5)	0.0215 (3)
C1	0.05229 (12)	0.3755 (2)	0.60634 (5)	0.0212 (3)
C2	0.17099 (11)	0.3855 (2)	0.60556 (5)	0.0201 (3)
C3	0.21389 (11)	0.33098 (19)	0.56076 (5)	0.0189 (3)
C4	0.13238 (11)	0.27512 (19)	0.51566 (5)	0.0185 (3)
C5	0.01653 (11)	0.27172 (19)	0.52070 (5)	0.0194 (3)
C6	0.00673 (13)	0.4217 (2)	0.65600 (6)	0.0275 (3)
H6A	−0.0765	0.4408	0.6466	0.041*
H6B	0.0436	0.5354	0.6721	0.041*
H6C	0.0234	0.3192	0.6816	0.041*
C7	0.24994 (11)	0.4536 (2)	0.65525 (5)	0.0227 (3)
C8	0.3101 (7)	0.7424 (11)	0.70277 (19)	0.0316 (14)	0.567 (11)
H8A	0.2540	0.7684	0.7261	0.038*	0.567 (11)
H8B	0.3736	0.6680	0.7234	0.038*	0.567 (11)
C9	0.3541 (7)	0.9138 (10)	0.6860 (3)	0.0541 (14)	0.567 (11)
H9A	0.4033	0.8878	0.6600	0.081*	0.567 (11)
H9B	0.3990	0.9775	0.7171	0.081*	0.567 (11)
H9C	0.2899	0.9932	0.6693	0.081*	0.567 (11)
C8A	0.3320 (9)	0.7159 (15)	0.7019 (3)	0.0316 (14)	0.433 (11)
H8C	0.2872	0.7612	0.7284	0.038*	0.433 (11)
H8D	0.3854	0.6184	0.7192	0.038*	0.433 (11)
C9A	0.3961 (9)	0.8666 (14)	0.6850 (4)	0.0541 (14)	0.433 (11)
H9D	0.4612	0.8170	0.6708	0.081*	0.433 (11)
H9E	0.4245	0.9478	0.7156	0.081*	0.433 (11)
H9F	0.3461	0.9380	0.6570	0.081*	0.433 (11)
C10	0.33982 (11)	0.3247 (2)	0.56127 (5)	0.0197 (3)
C11	0.40585 (12)	0.4854 (2)	0.56597 (5)	0.0215 (3)
H11	0.3707	0.6024	0.5691	0.026*
C12	0.52335 (12)	0.4761 (2)	0.56616 (6)	0.0242 (3)
H12	0.5684	0.5860	0.5689	0.029*
C13	0.57320 (12)	0.3046 (2)	0.56232 (5)	0.0231 (3)
C14	0.50944 (12)	0.1421 (2)	0.55833 (6)	0.0259 (3)
H14	0.5454	0.0250	0.5564	0.031*
C15	0.39210 (12)	0.1534 (2)	0.55720 (6)	0.0245 (3)
H15	0.3471	0.0434	0.5536	0.029*
C16	0.14303 (11)	0.21819 (19)	0.46256 (5)	0.0190 (3)
C17	0.03916 (12)	0.1688 (2)	0.43152 (5)	0.0200 (3)
C18	0.03111 (12)	0.1005 (2)	0.37788 (5)	0.0214 (3)
C19	0.15161 (13)	0.0795 (2)	0.30702 (6)	0.0241 (3)
C20	0.06189 (13)	0.1114 (2)	0.26393 (6)	0.0286 (3)
H20	−0.0113	0.1500	0.2698	0.034*
C21	0.08119 (15)	0.0859 (3)	0.21222 (6)	0.0343 (4)
H21	0.0203	0.1059	0.1826	0.041*
C22	0.18800 (15)	0.0317 (2)	0.20337 (6)	0.0359 (4)
H22	0.2007	0.0160	0.1679	0.043*
C23	0.27619 (15)	0.0005 (3)	0.24668 (6)	0.0352 (4)
H23	0.3497	−0.0359	0.2407	0.042*
C24	0.25848 (14)	0.0218 (2)	0.29868 (6)	0.0303 (3)
H24	0.3188	−0.0028	0.3283	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01424 (17)	0.0434 (2)	0.0316 (2)	0.00137 (14)	0.00669 (13)	0.00109 (15)
S1	0.01390 (17)	0.02804 (19)	0.02085 (18)	−0.00149 (12)	0.00243 (12)	0.00103 (13)
O1	0.0230 (5)	0.0360 (6)	0.0239 (5)	−0.0074 (4)	0.0006 (4)	−0.0033 (4)
O2	0.0383 (6)	0.0409 (7)	0.0284 (6)	−0.0021 (5)	−0.0077 (5)	0.0051 (5)
O3	0.0440 (7)	0.0310 (6)	0.0232 (5)	−0.0001 (5)	−0.0040 (5)	−0.0060 (5)
N1	0.0167 (5)	0.0269 (6)	0.0214 (6)	0.0013 (5)	0.0058 (4)	0.0016 (5)
N2	0.0185 (6)	0.0290 (6)	0.0186 (6)	−0.0021 (5)	0.0055 (4)	−0.0012 (5)
N3	0.0188 (6)	0.0308 (6)	0.0204 (6)	−0.0025 (5)	0.0037 (4)	−0.0014 (5)
N4	0.0193 (6)	0.0267 (6)	0.0184 (6)	−0.0013 (5)	0.0032 (4)	−0.0008 (5)
C1	0.0190 (6)	0.0244 (7)	0.0213 (7)	0.0021 (5)	0.0062 (5)	0.0022 (6)
C2	0.0181 (6)	0.0237 (7)	0.0187 (6)	0.0019 (5)	0.0040 (5)	0.0014 (5)
C3	0.0169 (6)	0.0214 (7)	0.0186 (6)	0.0004 (5)	0.0040 (5)	0.0024 (5)
C4	0.0155 (6)	0.0206 (7)	0.0196 (6)	0.0006 (5)	0.0042 (5)	0.0027 (5)
C5	0.0160 (6)	0.0213 (7)	0.0205 (6)	0.0003 (5)	0.0025 (5)	0.0024 (5)
C6	0.0227 (7)	0.0383 (8)	0.0235 (7)	0.0017 (6)	0.0094 (6)	−0.0028 (6)
C7	0.0182 (6)	0.0325 (8)	0.0185 (6)	−0.0001 (6)	0.0062 (5)	−0.0006 (6)
C8	0.034 (3)	0.034 (2)	0.0244 (8)	0.006 (2)	0.0007 (11)	−0.0152 (9)
C9	0.057 (4)	0.047 (3)	0.0479 (14)	−0.013 (2)	−0.016 (3)	−0.001 (2)
C8A	0.034 (3)	0.034 (2)	0.0244 (8)	0.006 (2)	0.0007 (11)	−0.0152 (9)
C9A	0.057 (4)	0.047 (3)	0.0479 (14)	−0.013 (2)	−0.016 (3)	−0.001 (2)
C10	0.0157 (6)	0.0288 (7)	0.0149 (6)	0.0001 (5)	0.0037 (5)	0.0001 (5)
C11	0.0190 (6)	0.0261 (7)	0.0198 (6)	0.0005 (5)	0.0046 (5)	0.0000 (5)
C12	0.0190 (7)	0.0310 (8)	0.0228 (7)	−0.0046 (6)	0.0040 (5)	0.0004 (6)
C13	0.0149 (6)	0.0368 (8)	0.0179 (6)	0.0001 (6)	0.0038 (5)	0.0009 (6)
C14	0.0204 (7)	0.0296 (8)	0.0276 (7)	0.0037 (6)	0.0042 (5)	−0.0022 (6)
C15	0.0191 (7)	0.0265 (7)	0.0277 (7)	−0.0015 (6)	0.0041 (5)	−0.0026 (6)
C16	0.0171 (6)	0.0205 (7)	0.0194 (6)	−0.0012 (5)	0.0035 (5)	0.0018 (5)
C17	0.0181 (6)	0.0218 (7)	0.0200 (7)	−0.0016 (5)	0.0032 (5)	0.0020 (5)
C18	0.0210 (7)	0.0222 (7)	0.0207 (7)	−0.0012 (6)	0.0029 (5)	0.0019 (5)
C19	0.0287 (7)	0.0246 (7)	0.0194 (7)	−0.0010 (6)	0.0057 (5)	−0.0013 (6)
C20	0.0269 (7)	0.0347 (8)	0.0237 (7)	−0.0028 (6)	0.0036 (6)	−0.0027 (6)
C21	0.0357 (8)	0.0444 (10)	0.0213 (7)	−0.0037 (8)	0.0019 (6)	−0.0030 (7)
C22	0.0452 (9)	0.0420 (10)	0.0214 (7)	0.0009 (8)	0.0091 (7)	−0.0058 (7)
C23	0.0385 (9)	0.0406 (9)	0.0287 (8)	0.0103 (7)	0.0115 (7)	−0.0035 (7)
C24	0.0333 (8)	0.0337 (8)	0.0240 (7)	0.0079 (7)	0.0059 (6)	−0.0004 (6)

Geometric parameters (Å, º) top

Cl1—C13	1.7433 (14)	C9—H9C	0.9800
S1—C17	1.7222 (14)	C8A—C9A	1.436 (4)
S1—C5	1.7511 (14)	C8A—H8C	0.9900
O1—C18	1.2196 (17)	C8A—H8D	0.9900
O2—C7	1.1989 (18)	C9A—H9D	0.9800
O3—C7	1.3284 (19)	C9A—H9E	0.9800
O3—C8A	1.473 (3)	C9A—H9F	0.9800
O3—C8	1.473 (3)	C10—C11	1.389 (2)
N1—C5	1.3320 (18)	C10—C15	1.393 (2)
N1—C1	1.3355 (18)	C11—C12	1.3939 (19)
N2—N3	1.2771 (17)	C11—H11	0.9500
N2—C16	1.3792 (17)	C12—C13	1.380 (2)
N3—N4	1.3792 (16)	C12—H12	0.9500
N4—C18	1.4140 (18)	C13—C14	1.386 (2)
N4—C19	1.4470 (17)	C14—C15	1.388 (2)
C1—C2	1.4131 (18)	C14—H14	0.9500
C1—C6	1.5028 (18)	C15—H15	0.9500
C2—C3	1.3902 (18)	C16—C17	1.3760 (19)
C2—C7	1.5035 (19)	C17—C18	1.4360 (19)
C3—C4	1.4094 (19)	C19—C24	1.388 (2)
C3—C10	1.4914 (18)	C19—C20	1.392 (2)
C4—C5	1.4040 (18)	C20—C21	1.389 (2)
C4—C16	1.4399 (18)	C20—H20	0.9500
C6—H6A	0.9800	C21—C22	1.384 (2)
C6—H6B	0.9800	C21—H21	0.9500
C6—H6C	0.9800	C22—C23	1.384 (2)
C8—C9	1.436 (3)	C22—H22	0.9500
C8—H8A	0.9900	C23—C24	1.387 (2)
C8—H8B	0.9900	C23—H23	0.9500
C9—H9A	0.9800	C24—H24	0.9500
C9—H9B	0.9800

C17—S1—C5	89.68 (7)	C8A—C9A—H9D	109.5
C7—O3—C8A	113.2 (5)	C8A—C9A—H9E	109.5
C7—O3—C8	121.2 (3)	H9D—C9A—H9E	109.5
C5—N1—C1	116.19 (12)	C8A—C9A—H9F	109.5
N3—N2—C16	119.25 (12)	H9D—C9A—H9F	109.5
N2—N3—N4	121.09 (11)	H9E—C9A—H9F	109.5
N3—N4—C18	125.22 (11)	C11—C10—C15	119.49 (12)
N3—N4—C19	112.15 (11)	C11—C10—C3	121.48 (13)
C18—N4—C19	122.62 (11)	C15—C10—C3	119.03 (13)
N1—C1—C2	122.24 (12)	C10—C11—C12	120.44 (13)
N1—C1—C6	116.39 (12)	C10—C11—H11	119.8
C2—C1—C6	121.32 (13)	C12—C11—H11	119.8
C3—C2—C1	121.26 (13)	C13—C12—C11	118.95 (13)
C3—C2—C7	120.95 (12)	C13—C12—H12	120.5
C1—C2—C7	117.78 (12)	C11—C12—H12	120.5
C2—C3—C4	116.48 (12)	C12—C13—C14	121.68 (13)
C2—C3—C10	121.63 (12)	C12—C13—Cl1	119.16 (11)
C4—C3—C10	121.84 (12)	C14—C13—Cl1	119.16 (11)
C5—C4—C3	117.45 (12)	C13—C14—C15	118.82 (14)
C5—C4—C16	110.11 (12)	C13—C14—H14	120.6
C3—C4—C16	132.44 (12)	C15—C14—H14	120.6
N1—C5—C4	126.30 (13)	C14—C15—C10	120.60 (14)
N1—C5—S1	120.24 (10)	C14—C15—H15	119.7
C4—C5—S1	113.45 (10)	C10—C15—H15	119.7
C1—C6—H6A	109.5	C17—C16—N2	121.72 (13)
C1—C6—H6B	109.5	C17—C16—C4	112.46 (12)
H6A—C6—H6B	109.5	N2—C16—C4	125.74 (12)
C1—C6—H6C	109.5	C16—C17—C18	121.52 (12)
H6A—C6—H6C	109.5	C16—C17—S1	114.25 (11)
H6B—C6—H6C	109.5	C18—C17—S1	124.22 (10)
O2—C7—O3	125.50 (14)	O1—C18—N4	123.25 (13)
O2—C7—C2	124.66 (14)	O1—C18—C17	126.09 (13)
O3—C7—C2	109.83 (12)	N4—C18—C17	110.66 (12)
C9—C8—O3	109.1 (5)	C24—C19—C20	120.75 (13)
C9—C8—H8A	109.9	C24—C19—N4	118.50 (13)
O3—C8—H8A	109.9	C20—C19—N4	120.60 (13)
C9—C8—H8B	109.9	C21—C20—C19	118.92 (14)
O3—C8—H8B	109.9	C21—C20—H20	120.5
H8A—C8—H8B	108.3	C19—C20—H20	120.5
C8—C9—H9A	109.5	C22—C21—C20	120.86 (15)
C8—C9—H9B	109.5	C22—C21—H21	119.6
H9A—C9—H9B	109.5	C20—C21—H21	119.6
C8—C9—H9C	109.5	C23—C22—C21	119.44 (15)
H9A—C9—H9C	109.5	C23—C22—H22	120.3
H9B—C9—H9C	109.5	C21—C22—H22	120.3
C9A—C8A—O3	109.4 (7)	C22—C23—C24	120.78 (15)
C9A—C8A—H8C	109.8	C22—C23—H23	119.6
O3—C8A—H8C	109.8	C24—C23—H23	119.6
C9A—C8A—H8D	109.8	C23—C24—C19	119.23 (15)
O3—C8A—H8D	109.8	C23—C24—H24	120.4
H8C—C8A—H8D	108.2	C19—C24—H24	120.4

C16—N2—N3—N4	−3.7 (2)	C10—C11—C12—C13	−0.9 (2)
N2—N3—N4—C18	0.0 (2)	C11—C12—C13—C14	0.0 (2)
N2—N3—N4—C19	179.04 (13)	C11—C12—C13—Cl1	179.67 (10)
C5—N1—C1—C2	−0.5 (2)	C12—C13—C14—C15	1.2 (2)
C5—N1—C1—C6	−177.96 (13)	Cl1—C13—C14—C15	−178.50 (11)
N1—C1—C2—C3	−1.6 (2)	C13—C14—C15—C10	−1.5 (2)
C6—C1—C2—C3	175.69 (14)	C11—C10—C15—C14	0.6 (2)
N1—C1—C2—C7	179.53 (13)	C3—C10—C15—C14	−179.04 (13)
C6—C1—C2—C7	−3.1 (2)	N3—N2—C16—C17	1.0 (2)
C1—C2—C3—C4	3.2 (2)	N3—N2—C16—C4	−175.58 (13)
C7—C2—C3—C4	−178.00 (13)	C5—C4—C16—C17	−2.35 (17)
C1—C2—C3—C10	−174.38 (13)	C3—C4—C16—C17	177.86 (15)
C7—C2—C3—C10	4.4 (2)	C5—C4—C16—N2	174.47 (13)
C2—C3—C4—C5	−2.70 (19)	C3—C4—C16—N2	−5.3 (2)
C10—C3—C4—C5	174.87 (12)	N2—C16—C17—C18	5.6 (2)
C2—C3—C4—C16	177.08 (14)	C4—C16—C17—C18	−177.44 (13)
C10—C3—C4—C16	−5.3 (2)	N2—C16—C17—S1	−175.10 (11)
C1—N1—C5—C4	1.0 (2)	C4—C16—C17—S1	1.87 (16)
C1—N1—C5—S1	179.90 (10)	C5—S1—C17—C16	−0.66 (12)
C3—C4—C5—N1	0.7 (2)	C5—S1—C17—C18	178.62 (13)
C16—C4—C5—N1	−179.14 (13)	N3—N4—C18—O1	−174.77 (14)
C3—C4—C5—S1	−178.30 (10)	C19—N4—C18—O1	6.3 (2)
C16—C4—C5—S1	1.87 (15)	N3—N4—C18—C17	5.79 (19)
C17—S1—C5—N1	−179.80 (12)	C19—N4—C18—C17	−173.12 (13)
C17—S1—C5—C4	−0.75 (11)	C16—C17—C18—O1	172.31 (14)
C8A—O3—C7—O2	2.9 (6)	S1—C17—C18—O1	−6.9 (2)
C8—O3—C7—O2	−8.4 (4)	C16—C17—C18—N4	−8.27 (19)
C8A—O3—C7—C2	−178.4 (5)	S1—C17—C18—N4	172.50 (10)
C8—O3—C7—C2	170.3 (4)	N3—N4—C19—C24	28.53 (19)
C3—C2—C7—O2	−85.10 (19)	C18—N4—C19—C24	−152.44 (14)
C1—C2—C7—O2	93.74 (18)	N3—N4—C19—C20	−147.19 (14)
C3—C2—C7—O3	96.17 (16)	C18—N4—C19—C20	31.8 (2)
C1—C2—C7—O3	−84.98 (16)	C24—C19—C20—C21	−0.5 (2)
C7—O3—C8—C9	150.7 (4)	N4—C19—C20—C21	175.14 (15)
C7—O3—C8A—C9A	138.1 (7)	C19—C20—C21—C22	−0.7 (3)
C2—C3—C10—C11	−66.39 (18)	C20—C21—C22—C23	0.8 (3)
C4—C3—C10—C11	116.16 (15)	C21—C22—C23—C24	0.4 (3)
C2—C3—C10—C15	113.26 (16)	C22—C23—C24—C19	−1.6 (3)
C4—C3—C10—C15	−64.19 (18)	C20—C19—C24—C23	1.6 (2)
C15—C10—C11—C12	0.6 (2)	N4—C19—C24—C23	−174.09 (15)
C3—C10—C11—C12	−179.78 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ⁱ	0.99	2.42	3.339 (7)	154

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···O2ⁱ	0.99	2.42	3.339 (7)	154

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

Experimental details

Crystal data
Chemical formula	C₂₄H₁₇ClN₄O₃S
M_r	476.92
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	11.8562 (3), 7.1984 (2), 25.4331 (5)
β (°)	101.045 (1)
V (Å³)	2130.40 (9)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	2.81
Crystal size (mm)	0.22 × 0.17 × 0.06

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016)
T_min, T_max	0.73, 0.85
No. of measured, independent and observed [I > 2σ(I)] reflections	15584, 4116, 3824
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.02
No. of reflections	4116
No. of parameters	309
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25

Computer programs: APEX3 (Bruker, 2016), SAINT (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

Bakhite, E. A. (2003). Phosphorus Sulfur Silicon, 178, 929–992. Web of Science 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
Girija, D., Singh, B. D. & Komal, S. (2011). J. Drug Deliv. Therapeut. 1, 8–16. Google Scholar
Görlitzer, K., Meyer, H., Walter, R. D., Jomaa, H. & Wiesner, J. (2004). Pharmazie, 59, 506–512. Web of Science PubMed Google Scholar
Litvinov, V. P., Dotsenko, V. V. & Krivokolysko, S. G. (2005). Russ. Chem. Bull. 54, 864–904. Web of Science CrossRef CAS Google Scholar
Mohamed, O. S., Al-Taifi, E. A., El-Emary, T. I. & Bakhite, E. A.-G. (2007). Phosphorus Sulfur Silicon, 182, 1061–1082. Web of Science CrossRef CAS 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. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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IUCrDATA

ISSN: 2414-3146

Volume 1| Part 5| May 2016| x160701

doi:10.1107/S241431461600701X

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

Ethyl 13-(4-chloro­phen­yl)-11-methyl-6-oxo-5-phenyl-8-thia-3,4,5,10-tetra­aza­tri­cyclo­[7.4.0.02,7]trideca-1(9),2(7),3,10,12-penta­ene-12-carboxyl­ate

Structure description

Synthesis and crystallization

Refinement

Structural data

Acknowledgements

References

organic compounds

Ethyl 13-(4-chlorophenyl)-11-methyl-6-oxo-5-phenyl-8-thia-3,4,5,10-tetraazatricyclo[7.4.0.0^2,7]trideca-1(9),2(7),3,10,12-pentaene-12-carboxylate