Crystal structure of ethyl 2-acetyl-3,7-dimethyl-5-(thio­phen-2-yl)-5H-thia­zolo[3,2-a]pyrimidine-6-carboxyl­ate

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

doi:10.1107/S2056989015010981

Crystal structure of ethyl 2-acetyl-3,7-dimethyl-5-(thiophen-2-yl)-5H-thiazolo[3,2-a]pyrimidine-6-carboxylate

N. L. Prasad, M. S. Krishnamurthy and N. S. Begum

In the title compound, C₁₇H₁₈N₂O₃S₂, the pyrimidine ring adopts a shallow sofa conformation, with the C atom bearing the axially-oriented thiophene ring as the flap [deviation = 0.439 (3) Å]. The plane of the thiophene ring lies almost normal to the pyrimidine ring, making a dihedral angle of 79.36 (19)°. In the crystal, pairs of very weak C—H

O hydrogen bonds link the molecules related by twofold rotation axes, forming R₂²(18) rings, which are in turn linked by another C—H

O interaction, forming chains of rings along [010]. In addition, weak C—H

π(thiophene) interactions link the chains into layers parallel to [001] and π–π interactions with a centroid–centroid distance of 3.772 (10) Å connect these layers into a three-dimensional network.

Keywords: crystal structure; fused pyrimidine derivative; hydrogen bonding; C—H

π interactions; π–π interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015010981/hb7433sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015010981/hb7433Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015010981/hb7433Isup3.cml Supplementary material

CCDC reference: 1405373

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.006 Å
R factor = 0.065
wR factor = 0.189
Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT222_ALERT_3_A Large Non-Solvent  H     Uiso(max)/Uiso(min) ...       10.0 Ratio

Author Response: This structure contains ester groups. The thermal parameters for one of the carbon atom 'C11' is very high. This was attempted to be modeled as disorder but the refinement was not successful.


Alert level C
PLAT220_ALERT_2_C Large Non-Solvent  C     Ueq(max)/Ueq(min) Range        3.2 Ratio
PLAT340_ALERT_3_C Low Bond Precision on  C-C Bonds ...............     0.0062 Ang.
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C10    -   C11    ...       1.43 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1C    ..  O1      ..       2.64 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H13    ..  O2      ..       2.63 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      8.660 Check
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.310 Check

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT072_ALERT_2_G SHELXL First  Parameter in WGHT Unusually Large.       0.11 Report
PLAT793_ALERT_4_G The Model has Chirality at C5      (Centro SPGR)          R Verify
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          33 %
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check

   1 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   7 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   6 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

Pyrimidine derivatives are important class of compounds which display number of pharmacological properties including antiviral, antitumour, antibacterial and antihypertensive effects (Atwal et al., 1991; Kappe et al., 1997). Pyrimidine has been subjected to a large variety of structural modifications in order to synthesize derivatives (Singh et al., 2011) with different biological properties, among which, thiazole ring fused to pyrimidine ring resulting in thiazolopyrimidine is found to be more active (Ozair et al., 2010; Hayam et al., 2010). Herein, we report the crystal structure of the title compound (1). The bond lengths and angles in the title compound are in good agreement with the corresponding bond distances and angles reported in closely related structures (Nagarajaiah et al., 2012; Prasad et al., 2014). The molecular structure of the compound C₁₇H₁₈N₂O₃S₂ is shown in Fig. 1. The thiophenyl ring at chiral carbon C5 is positioned axially and exactly bisects the pyrimidine ring with a dihedral angle of 82.973 (1)°. The thiazine and pyrimidine ring form a dihedral angle of 5.975 (1)°. In the central pyrimidine ring, the chiral carbon atom C6 is displaced by 0.3130 (4) Å and adopts a flattened sofa conformation. The exocyclic ester group at C6 adopts cis orientation with respect to C6=C7 double bond and the carboxyl group (C11/C10/O3/C16) is slightly deviating from the thiozolopyrimidine plane at -87.946 (6)°. The crystal structure is mainly stabilized by a variety of intermolecular C—H···O interactions. C1—H1C···O1 hydrogen bonds link the molecules related by twofold rotation axes, forming R²₂(18) loops, which are in turn linked by C13—H13···O2 interactions to form chains of rings along [010] (Table.1; Fig. 2). In addition, weak C—H···π (thiophene) interactions of the type C11—H11A···Cg link the chains into layers parallel to [001] and π–π interactions between inversion-related thiazolopyrimidine rings with a centroid—centroid distance of 3.772 (10) Å connect these layers into a three-dimensional network (Fig. 3).

Related literature top

For the biological activities of fused pyrimidine derivatives, see: Atwal et al. (1991); Kappe et al. (1997); Singh et al. (2011); Ozair et al. (2010); Hayam et al. (2010). For related structures, see: Prasad et al. (2014); Nagarajaiah et al. (2012).

Experimental top

A mixture of 6-methyl-4-thiophen-2-yl-2-thioxo-1,2,3,4-tetrahydro-pyrimidine-5- carboxylic acid ethyl ester (10 mmol) and 3-chloro-2,4-pentanedione (10 mmol) was refluxed in dry ethanol (20 mmol) for 12 h. The excess of solvent was distilled off and the solid hydrochloride salt that separated was collected by filtration, suspended in water and neutralized by aqueous sodium carbonate solution to yield the free base. The solution was filtered, the solid washed with water, dried and recrystallized from ethyl acetate to give the title compound (74% yield, mp 385 K). The compound was recrystallized by slow evaporation from 1:1 mixture of ethyl acetate and methanol, yielding pale- yellow blocks of the title compound.

Computing details top

Data collection: SMART (Bruker,1998); cell refinement: SAINT-Plus (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) and CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Unit-cell packing of the title compound showing C—H···O interactions as dotted lines. H atoms not involved in hydrogen bonding have been excluded.
	Fig. 3. Unit-cell packing depicting the C—H···π and π–π interactions with dotted lines.

Ethyl 2-acetyl-3,7-dimethyl-5-(thiophen-2-yl)-5H-thiazolo[3,2-a]pyrimidine-6-carboxylate top

Crystal data top

C₁₇H₁₈N₂O₃S₂	F(000) = 760
M_r = 362.45	D_x = 1.397 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3038 reflections
a = 7.8835 (10) Å	θ = 2.6–25.0°
b = 14.4041 (19) Å	µ = 0.33 mm⁻¹
c = 15.231 (2) Å	T = 100 K
β = 94.940 (4)°	Block, yellow
V = 1723.2 (4) Å³	0.18 × 0.16 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	3038 independent reflections
Radiation source: fine-focus sealed tube	1984 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→9
T_min = 0.944, T_max = 0.950	k = −17→17
12021 measured reflections	l = −17→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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.189	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.1059P)² + 1.4984P] where P = (F_o² + 2F_c²)/3
3038 reflections	(Δ/σ)_max < 0.001
221 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₁₇H₁₈N₂O₃S₂	V = 1723.2 (4) Å³
M_r = 362.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.8835 (10) Å	µ = 0.33 mm⁻¹
b = 14.4041 (19) Å	T = 100 K
c = 15.231 (2) Å	0.18 × 0.16 × 0.16 mm
β = 94.940 (4)°

Data collection top

Bruker SMART APEX CCD diffractometer	3038 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1984 reflections with I > 2σ(I)
T_min = 0.944, T_max = 0.950	R_int = 0.046
12021 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.189	H-atom parameters constrained
S = 1.00	Δρ_max = 0.51 e Å⁻³
3038 reflections	Δρ_min = −0.28 e Å⁻³
221 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	0.41155 (14)	0.67664 (8)	0.10428 (8)	0.0478 (4)
S2	0.86975 (15)	0.38590 (8)	0.30180 (7)	0.0514 (4)
N1	0.6122 (4)	0.5389 (2)	0.11268 (19)	0.0343 (8)
C6	0.5337 (5)	0.3792 (3)	0.1355 (2)	0.0384 (10)
O1	0.8379 (4)	0.7993 (2)	0.0552 (2)	0.0610 (9)
C9	0.4445 (5)	0.5583 (3)	0.1190 (2)	0.0378 (10)
N2	0.3249 (4)	0.5002 (3)	0.1340 (2)	0.0472 (9)
C3	0.7148 (5)	0.6131 (3)	0.0965 (2)	0.0345 (9)
C13	0.6889 (5)	0.5373 (3)	0.2994 (2)	0.0378 (10)
H13	0.6144	0.5869	0.2815	0.045*
O2	0.4904 (5)	0.2161 (2)	0.1141 (3)	0.0753 (11)
C2	0.6282 (5)	0.6938 (3)	0.0902 (3)	0.0386 (10)
C16	0.5843 (6)	0.2820 (3)	0.1255 (3)	0.0482 (11)
C17	0.9012 (5)	0.5964 (3)	0.0884 (3)	0.0521 (12)
H17A	0.9151	0.5420	0.0511	1.000*
H17B	0.9592	0.5855	0.1470	1.000*
H17C	0.9508	0.6509	0.0618	1.000*
C12	0.7368 (5)	0.4638 (3)	0.2456 (2)	0.0359 (9)
C7	0.3696 (6)	0.4072 (3)	0.1363 (3)	0.0434 (10)
C5	0.6754 (5)	0.4494 (3)	0.1488 (2)	0.0359 (9)
H5	0.7734	0.4286	0.1162	0.043*
C10	0.8235 (8)	0.1808 (3)	0.1127 (4)	0.0683 (15)
H10A	0.7431	0.1448	0.0724	0.082*
H10B	0.9319	0.1866	0.0849	0.082*
C14	0.7725 (6)	0.5240 (3)	0.3865 (3)	0.0499 (11)
H14	0.7602	0.5662	0.4335	0.060*
C4	0.6955 (6)	0.7881 (3)	0.0792 (3)	0.0447 (11)
C1	0.2188 (6)	0.3437 (3)	0.1387 (3)	0.0592 (13)
H1A	0.1198	0.3796	0.1538	1.000*
H1B	0.2444	0.2954	0.1832	1.000*
H1C	0.1940	0.3149	0.0808	1.000*
C8	0.5863 (7)	0.8697 (3)	0.0997 (4)	0.0686 (15)
H8A	0.5407	0.8599	0.1569	1.000*
H8B	0.4920	0.8758	0.0538	1.000*
H8C	0.6552	0.9264	0.1019	1.000*
C15	0.8682 (6)	0.4481 (3)	0.3959 (3)	0.0484 (11)
H15	0.9293	0.4306	0.4499	0.058*
O3	0.7530 (4)	0.2735 (2)	0.1262 (2)	0.0560 (8)
C11	0.8530 (10)	0.1323 (5)	0.1948 (4)	0.110 (3)
H11A	0.8940	0.0694	0.1839	0.166*
H11B	0.7466	0.1286	0.2235	0.166*
H11C	0.9387	0.1656	0.2332	0.166*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0422 (7)	0.0400 (7)	0.0619 (7)	0.0079 (5)	0.0093 (5)	0.0074 (5)
S2	0.0591 (8)	0.0471 (7)	0.0467 (7)	0.0086 (5)	−0.0026 (5)	0.0011 (5)
N1	0.0349 (19)	0.0318 (18)	0.0364 (18)	0.0033 (15)	0.0036 (14)	0.0039 (14)
C6	0.043 (2)	0.038 (2)	0.033 (2)	−0.0054 (19)	−0.0006 (17)	−0.0010 (17)
O1	0.061 (2)	0.047 (2)	0.075 (2)	−0.0107 (16)	0.0111 (18)	0.0040 (16)
C9	0.037 (2)	0.039 (2)	0.037 (2)	0.0067 (19)	0.0031 (17)	0.0017 (18)
N2	0.038 (2)	0.048 (2)	0.057 (2)	−0.0058 (18)	0.0122 (17)	−0.0046 (18)
C3	0.038 (2)	0.036 (2)	0.029 (2)	−0.0036 (19)	0.0006 (16)	0.0010 (16)
C13	0.048 (2)	0.035 (2)	0.030 (2)	−0.0105 (18)	−0.0020 (18)	−0.0038 (17)
O2	0.077 (3)	0.041 (2)	0.106 (3)	−0.0134 (19)	−0.006 (2)	−0.0007 (19)
C2	0.041 (2)	0.036 (2)	0.039 (2)	−0.0001 (18)	0.0054 (18)	0.0045 (18)
C16	0.062 (3)	0.036 (2)	0.045 (3)	−0.009 (2)	−0.005 (2)	−0.0013 (19)
C17	0.036 (2)	0.051 (3)	0.070 (3)	0.001 (2)	0.008 (2)	0.008 (2)
C12	0.036 (2)	0.031 (2)	0.040 (2)	0.0005 (17)	0.0011 (17)	0.0016 (17)
C7	0.051 (3)	0.039 (3)	0.041 (2)	−0.006 (2)	0.0069 (19)	0.0014 (18)
C5	0.042 (2)	0.032 (2)	0.034 (2)	0.0055 (18)	0.0034 (17)	−0.0009 (16)
C10	0.085 (4)	0.042 (3)	0.078 (4)	0.013 (3)	0.008 (3)	−0.014 (3)
C14	0.057 (3)	0.051 (3)	0.042 (2)	0.000 (2)	0.004 (2)	−0.009 (2)
C4	0.055 (3)	0.040 (2)	0.039 (2)	−0.004 (2)	0.003 (2)	0.0020 (19)
C1	0.051 (3)	0.057 (3)	0.070 (3)	−0.022 (2)	0.013 (2)	0.001 (2)
C8	0.087 (4)	0.038 (3)	0.083 (4)	0.008 (3)	0.019 (3)	−0.005 (2)
C15	0.052 (3)	0.054 (3)	0.038 (2)	−0.001 (2)	−0.0011 (19)	0.003 (2)
O3	0.060 (2)	0.0390 (18)	0.067 (2)	0.0087 (15)	−0.0048 (16)	−0.0080 (15)
C11	0.157 (7)	0.091 (5)	0.086 (5)	0.063 (5)	0.027 (4)	0.017 (4)

Geometric parameters (Å, º) top

S1—C9	1.736 (4)	C17—H17B	0.9902
S1—C2	1.757 (4)	C17—H17C	0.9902
S2—C15	1.692 (4)	C12—C5	1.525 (5)
S2—C12	1.714 (4)	C7—C1	1.502 (6)
N1—C9	1.363 (5)	C5—H5	1.0000
N1—C3	1.375 (5)	C10—C11	1.433 (7)
N1—C5	1.471 (5)	C10—O3	1.467 (5)
C6—C7	1.355 (6)	C10—H10A	0.9900
C6—C16	1.468 (6)	C10—H10B	0.9900
C6—C5	1.508 (6)	C14—C15	1.328 (6)
O1—C4	1.221 (5)	C14—H14	0.9500
C9—N2	1.296 (5)	C4—C8	1.506 (6)
N2—C7	1.385 (5)	C1—H1A	0.9828
C3—C2	1.348 (5)	C1—H1B	0.9828
C3—C17	1.505 (6)	C1—H1C	0.9828
C13—C12	1.410 (5)	C8—H8A	0.9913
C13—C14	1.442 (6)	C8—H8B	0.9913
C13—H13	0.9500	C8—H8C	0.9913
O2—C16	1.207 (5)	C15—H15	0.9500
C2—C4	1.472 (6)	C11—H11A	0.9800
C16—O3	1.335 (5)	C11—H11B	0.9800
C17—H17A	0.9902	C11—H11C	0.9800

C9—S1—C2	91.04 (19)	C6—C5—C12	113.0 (3)
C15—S2—C12	91.6 (2)	N1—C5—H5	109.1
C9—N1—C3	116.3 (3)	C6—C5—H5	109.1
C9—N1—C5	116.9 (3)	C12—C5—H5	109.1
C3—N1—C5	124.2 (3)	C11—C10—O3	110.9 (4)
C7—C6—C16	123.5 (4)	C11—C10—H10A	109.5
C7—C6—C5	119.8 (4)	O3—C10—H10A	109.5
C16—C6—C5	116.7 (4)	C11—C10—H10B	109.4
N2—C9—N1	127.2 (4)	O3—C10—H10B	109.5
N2—C9—S1	123.7 (3)	H10A—C10—H10B	108.0
N1—C9—S1	109.1 (3)	C15—C14—C13	114.8 (4)
C9—N2—C7	116.2 (4)	C15—C14—H14	122.6
C2—C3—N1	112.4 (3)	C13—C14—H14	122.6
C2—C3—C17	128.6 (4)	O1—C4—C2	120.4 (4)
N1—C3—C17	119.0 (3)	O1—C4—C8	121.0 (4)
C12—C13—C14	108.1 (4)	C2—C4—C8	118.6 (4)
C12—C13—H13	126.0	C7—C1—H1A	109.8
C14—C13—H13	125.9	C7—C1—H1B	109.7
C3—C2—C4	128.2 (4)	H1A—C1—H1B	109.2
C3—C2—S1	111.2 (3)	C7—C1—H1C	109.8
C4—C2—S1	120.5 (3)	H1A—C1—H1C	109.2
O2—C16—O3	121.8 (4)	H1B—C1—H1C	109.2
O2—C16—C6	126.6 (5)	C4—C8—H8A	110.6
O3—C16—C6	111.5 (4)	C4—C8—H8B	110.6
C3—C17—H17A	110.5	H8A—C8—H8B	108.3
C3—C17—H17B	110.5	C4—C8—H8C	110.6
H17A—C17—H17B	108.4	H8A—C8—H8C	108.3
C3—C17—H17C	110.5	H8B—C8—H8C	108.3
H17A—C17—H17C	108.4	C14—C15—S2	112.9 (3)
H17B—C17—H17C	108.4	C14—C15—H15	123.5
C13—C12—C5	125.8 (3)	S2—C15—H15	123.5
C13—C12—S2	112.6 (3)	C16—O3—C10	118.1 (4)
C5—C12—S2	121.6 (3)	C10—C11—H11A	109.5
C6—C7—N2	121.9 (4)	C10—C11—H11B	109.5
C6—C7—C1	125.3 (4)	H11A—C11—H11B	109.5
N2—C7—C1	112.8 (4)	C10—C11—H11C	109.5
N1—C5—C6	108.3 (3)	H11A—C11—H11C	109.5
N1—C5—C12	108.2 (3)	H11B—C11—H11C	109.5

C3—N1—C9—N2	−179.9 (4)	C5—C6—C7—N2	11.1 (6)
C5—N1—C9—N2	−17.4 (6)	C16—C6—C7—C1	8.2 (6)
C3—N1—C9—S1	−0.2 (4)	C5—C6—C7—C1	−169.4 (4)
C5—N1—C9—S1	162.2 (2)	C9—N2—C7—C6	9.1 (6)
C2—S1—C9—N2	179.7 (4)	C9—N2—C7—C1	−170.4 (4)
C2—S1—C9—N1	0.0 (3)	C9—N1—C5—C6	33.4 (4)
N1—C9—N2—C7	−6.0 (6)	C3—N1—C5—C6	−165.7 (3)
S1—C9—N2—C7	174.4 (3)	C9—N1—C5—C12	−89.4 (4)
C9—N1—C3—C2	0.4 (5)	C3—N1—C5—C12	71.5 (4)
C5—N1—C3—C2	−160.6 (3)	C7—C6—C5—N1	−31.2 (5)
C9—N1—C3—C17	−179.8 (3)	C16—C6—C5—N1	151.0 (3)
C5—N1—C3—C17	19.2 (5)	C7—C6—C5—C12	88.6 (4)
N1—C3—C2—C4	175.6 (4)	C16—C6—C5—C12	−89.2 (4)
C17—C3—C2—C4	−4.2 (7)	C13—C12—C5—N1	20.6 (5)
N1—C3—C2—S1	−0.4 (4)	S2—C12—C5—N1	−162.0 (3)
C17—C3—C2—S1	179.8 (3)	C13—C12—C5—C6	−99.3 (4)
C9—S1—C2—C3	0.2 (3)	S2—C12—C5—C6	78.1 (4)
C9—S1—C2—C4	−176.1 (3)	C12—C13—C14—C15	−1.3 (5)
C7—C6—C16—O2	2.5 (7)	C3—C2—C4—O1	16.3 (7)
C5—C6—C16—O2	−179.8 (4)	S1—C2—C4—O1	−168.1 (3)
C7—C6—C16—O3	179.4 (4)	C3—C2—C4—C8	−162.5 (4)
C5—C6—C16—O3	−2.8 (5)	S1—C2—C4—C8	13.1 (5)
C14—C13—C12—C5	178.8 (4)	C13—C14—C15—S2	0.7 (5)
C14—C13—C12—S2	1.3 (4)	C12—S2—C15—C14	0.1 (4)
C15—S2—C12—C13	−0.8 (3)	O2—C16—O3—C10	−0.2 (6)
C15—S2—C12—C5	−178.5 (3)	C6—C16—O3—C10	−177.3 (3)
C16—C6—C7—N2	−171.2 (4)	C11—C10—O3—C16	−87.9 (6)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the S2/C12–C15 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···O1ⁱ	0.98	2.64	3.598 (6)	166
C13—H13···O2ⁱⁱ	0.95	2.63	3.269 (8)	125
C11—H11A···Cg1ⁱⁱⁱ	0.98	2.89	3.693 (2)	139

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