5-Methyl-2-(2-nitro­phen­yloxy)-3-p-tolyl-8,9,10,11-tetra­hydro­benzo[4′,5′]thieno[3′,4′:5,6]pyrido[4,3-d]pyrimidin-4(3H)-one

Chen, H.-L.; He, H.-W.

doi:10.1107/S1600536805040870

5-Methyl-2-(2-nitrophenyloxy)-3-p-tolyl-8,9,10,11-tetrahydrobenzo[4′,5′]thieno[3′,4′:5,6]pyrido[4,3-d]pyrimidin-4(3H)-one

In the title compound, C₂₇H₂₃N₄O₄S, the three fused heterocyclic rings are essentially coplanar. The crystal stacking is mainly due to π–π interactions and intermolecular C—H

O hydrogen-bonding interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040870/sg6045sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040870/sg6045Isup2.hkl Contains datablock I

CCDC reference: 296649

checkCIF report

Key indicators

Single-crystal X-ray study
T = 292 K
Mean (C-C) = 0.004 Å
Disorder in main residue
R factor = 0.052
wR factor = 0.172
Data-to-parameter ratio = 12.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.50 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      26.00 Deg.
              C3'  -C2   -C3      1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      25.70 Deg.
              H2A  -C2   -H2C     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      25.70 Deg.
              H2B  -C2   -H2D     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      31.70 Deg.
              C4   -C5   -C4'     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      32.10 Deg.
              H5A  -C5   -H5C     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      31.90 Deg.
              H5B  -C5   -H5D     1.555   1.555   1.555

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  11 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

Comment top

Among many known heterocyclic compounds, derivatives containing pyridine groups have received much attention since they possess significant biological activity (Augusto et al., 1995). The title compound (I), belongs to this family of heterocyclic compounds and we present its crystal structure here.

In (I) (Fig. 1), the C—S bond lengths are longer than those observed in free thiophene [1.714 (3) Å; Bonham & Momany, 1963] and thieno-[2,3-c]-pyridine [1.728 (1) and 1.731 (1) Å; Nerenz et al., 1997]. Selected bond lengths and angles are listed in Table 1. The C8—S1—C1 angle in (I) is slightly less than that observed in the free thiophene [92.2 (2)°]. The C6—C7—C8—N1 and C14—C11—C12—C7 torsion angles (Tabel 1) indicate the planarity of the tricyclic system. There are some weak intermolecular C—H···O hydrogen-bonding interactions that are formed between atom O1 and the H19 atom on C19 atom (Table 2).

The short intermolecular distances between the centroids of the thiophene (Cg1) and pyrimidine (Cg3) rings [Cg1···Cg3ⁱ = 3.7496 (16) Å; symmetry code: (i) 1/2 − x, 3/2 − y, −z] indicate the existence of π–π stacking interactions (Janiak, 2000), which, together with hydrogen-bonding interactions, stabilize the crystal packing (Fig. 2)

Experimental top

2-methyl-4-amino-3-ethoxycarbonyl- 5,6,7,8-(4H)-tetrahydrobenzo[4',5'] thieno-[2,3-b]-pyridine, (II), was prepared according to the literature procedures in 90% yield (Augusto et al., 1995). Iminophosphorane of (II) was synthesized according to the literature reported in 82% yield (Wamhoff et al., 1993).

To a solution of iminophosphorane of (II) (1 mmol) in dry CH₂Cl₂ (20 ml) and catalytic amount of K₂CO₃ (0.05 mmol) are added 4-methylphenyl isocyanate (1.1 mmol) (Ding et al., 1999). After the reaction mixture was left to stand for 6 h, the solvent was removed under reduced pressure and Et₂O/petroleum ether was added to precipitate the side-product triphenylphosphine oxide which was then removed by filtration. Subsequent removal of the solvent gave the corresponding carbodiimide, which was used directly without further purification.

To the solution of carbodiimide in ethanol (15 ml) was added 2-nitrophenol (1.1 mmol) and a catalytic amount of sodium ethoxide in ethanol (Wang et al., 2004). After the mixture was stirred for 12 h at 300 K, the solution was concentrated and the residue was recrystallized from CH₃CN to give colorless prisms blocks below? of the title compound (I) in one week.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. View of (I), showing the atom-labeling scheme fot the non-H atoms and 50% probability displacement ellipsoids.
	Fig. 2. The crystal structure of (I), showing the formation of N—H···O hydrogen bonds (dashed lines).

5-Methyl-2-(2-nitrophenyloxy)-3-p-tolyl-8,9,10,11- tetrahydrobenzo[4',5']thieno[3',4':5,6]pyrido[4,3-d]pyrimidin-4(3H)-one top

Crystal data top

C₂₇H₂₂N₄O₄S	F(000) = 1040
M_r = 498.55	D_x = 1.378 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2yn	Cell parameters from 4220 reflections
a = 9.1381 (8) Å	θ = 1.8–25.0°
b = 17.0819 (14) Å	µ = 0.18 mm⁻¹
c = 16.0332 (14) Å	T = 292 K
β = 106.203 (2)°	Block, colorless
V = 2403.3 (4) Å³	0.30 × 0.20 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4220 independent reflections
Radiation source: fine-focus sealed tube	2922 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.949, T_max = 0.983	k = −20→19
12011 measured reflections	l = −19→9

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0911P)² + 0.0243P] where P = (F_o² + 2F_c²)/3
4220 reflections	(Δ/σ)_max = 0.042
340 parameters	Δρ_max = 0.28 e Å⁻³
1 restraint	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₂₇H₂₂N₄O₄S	V = 2403.3 (4) Å³
M_r = 498.55	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.1381 (8) Å	µ = 0.18 mm⁻¹
b = 17.0819 (14) Å	T = 292 K
c = 16.0332 (14) Å	0.30 × 0.20 × 0.10 mm
β = 106.203 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4220 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	2922 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.983	R_int = 0.040
12011 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	1 restraint
wR(F²) = 0.172	H-atom parameters constrained
S = 1.08	Δρ_max = 0.28 e Å⁻³
4220 reflections	Δρ_min = −0.26 e Å⁻³
340 parameters

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.

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 (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.6811 (3)	1.08955 (16)	0.00892 (19)	0.0485 (7)
C2	0.6153 (4)	1.13871 (18)	0.0669 (2)	0.0654 (9)
H2A	0.5185	1.1603	0.0336	0.078*	0.590 (9)
H2B	0.6836	1.1819	0.0898	0.078*	0.590 (9)
H2C	0.5051	1.1395	0.0448	0.078*	0.410 (9)
H2D	0.6519	1.1921	0.0673	0.078*	0.410 (9)
C3	0.5918 (9)	1.0907 (5)	0.1413 (6)	0.0579 (17)	0.590 (9)
H3A	0.5030	1.0575	0.1204	0.069*	0.590 (9)
H3B	0.5734	1.1253	0.1853	0.069*	0.590 (9)
C4	0.7306 (10)	1.0403 (5)	0.1811 (5)	0.063 (2)	0.590 (9)
H4A	0.7161	1.0128	0.2311	0.076*	0.590 (9)
H4B	0.8195	1.0737	0.2009	0.076*	0.590 (9)
C3'	0.6611 (16)	1.1074 (6)	0.1584 (10)	0.0579 (17)	0.410 (9)
H3'1	0.5986	1.1318	0.1911	0.069*	0.410 (9)
H3'2	0.7664	1.1214	0.1860	0.069*	0.410 (9)
C4'	0.6439 (15)	1.0192 (5)	0.1612 (7)	0.060 (3)	0.410 (9)
H4'1	0.5403	1.0042	0.1311	0.071*	0.410 (9)
H4'2	0.6662	1.0016	0.2210	0.071*	0.410 (9)
C5	0.7584 (4)	0.98094 (17)	0.11597 (18)	0.0537 (8)
H5A	0.8595	0.9586	0.1383	0.064*	0.590 (9)
H5B	0.6848	0.9388	0.1088	0.064*	0.590 (9)
H5C	0.8616	0.9868	0.1532	0.064*	0.410 (9)
H5D	0.7370	0.9254	0.1076	0.064*	0.410 (9)
C6	0.7450 (3)	1.01849 (15)	0.02944 (18)	0.0420 (7)
C7	0.7913 (3)	0.98478 (15)	−0.04161 (17)	0.0392 (6)
C8	0.7583 (3)	1.03251 (16)	−0.11436 (18)	0.0439 (7)
C9	0.8375 (3)	0.94591 (17)	−0.20102 (18)	0.0492 (7)
C10	0.8544 (4)	0.9291 (2)	−0.2906 (2)	0.0772 (11)
H10A	0.7804	0.8907	−0.3189	0.116*
H10B	0.9550	0.9095	−0.2854	0.116*
H10C	0.8385	0.9764	−0.3242	0.116*
C11	0.8766 (3)	0.89081 (16)	−0.13141 (17)	0.0418 (7)
C12	0.8546 (3)	0.91090 (15)	−0.05080 (17)	0.0400 (6)
C13	0.9419 (3)	0.79335 (16)	0.00820 (17)	0.0415 (7)
C14	0.9392 (3)	0.81355 (17)	−0.14083 (18)	0.0491 (7)
C15	0.9293 (3)	0.76422 (15)	0.14670 (17)	0.0419 (7)
C16	1.0389 (4)	0.7919 (2)	0.2169 (2)	0.0648 (9)
H16	1.1396	0.7951	0.2150	0.078*
C17	1.0014 (5)	0.8152 (2)	0.2903 (2)	0.0792 (11)
H17	1.0769	0.8346	0.3373	0.095*
C18	0.8568 (5)	0.81018 (19)	0.2950 (2)	0.0731 (11)
H18	0.8330	0.8269	0.3449	0.088*
C19	0.7444 (4)	0.78056 (17)	0.2267 (2)	0.0588 (9)
H19	0.6448	0.7764	0.2302	0.071*
C20	0.7814 (3)	0.75691 (15)	0.15218 (18)	0.0419 (7)
C21	1.0369 (3)	0.68896 (15)	−0.06756 (17)	0.0417 (7)
C22	1.1801 (3)	0.67276 (15)	−0.01515 (17)	0.0413 (7)
H22	1.2360	0.7112	0.0212	0.050*
C23	1.2406 (3)	0.59914 (16)	−0.01683 (19)	0.0500 (7)
H23	1.3380	0.5884	0.0184	0.060*
C24	1.1602 (4)	0.54114 (17)	−0.0695 (2)	0.0578 (8)
C25	1.0196 (4)	0.55942 (18)	−0.1235 (2)	0.0664 (9)
H25	0.9659	0.5216	−0.1617	0.080*
C26	0.9556 (4)	0.63282 (19)	−0.1226 (2)	0.0612 (9)
H26	0.8590	0.6439	−0.1587	0.073*
C27	1.2263 (5)	0.4596 (2)	−0.0695 (3)	0.0980 (14)
H27A	1.2789	0.4564	−0.1135	0.147*
H27B	1.1454	0.4218	−0.0812	0.147*
H27C	1.2964	0.4491	−0.0137	0.147*
N1	0.7821 (3)	1.01640 (14)	−0.19220 (15)	0.0500 (6)
N2	0.9710 (2)	0.76622 (13)	−0.06493 (14)	0.0418 (6)
N3	0.8878 (2)	0.86076 (13)	0.01921 (14)	0.0423 (6)
N4	0.6588 (3)	0.72550 (14)	0.0809 (2)	0.0581 (7)
O1	0.9648 (3)	0.78730 (13)	−0.20563 (13)	0.0699 (7)
O2	0.9731 (2)	0.74083 (11)	0.07406 (12)	0.0476 (5)
O3	0.6752 (3)	0.71979 (13)	0.00909 (15)	0.0685 (7)
O4	0.5418 (3)	0.7051 (2)	0.0978 (2)	0.1148 (11)
S1	0.67454 (10)	1.11959 (4)	−0.09621 (5)	0.0577 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0531 (17)	0.0441 (16)	0.0521 (18)	0.0010 (13)	0.0208 (15)	−0.0030 (14)
C2	0.082 (2)	0.0511 (18)	0.071 (2)	0.0110 (16)	0.0341 (19)	−0.0069 (17)
C3	0.062 (5)	0.052 (4)	0.070 (4)	−0.003 (4)	0.035 (5)	−0.010 (3)
C4	0.080 (5)	0.068 (5)	0.049 (4)	0.008 (4)	0.029 (4)	−0.007 (3)
C3'	0.062 (5)	0.052 (4)	0.070 (4)	−0.003 (4)	0.035 (5)	−0.010 (3)
C4'	0.073 (7)	0.061 (6)	0.052 (6)	−0.011 (5)	0.030 (6)	−0.010 (4)
C5	0.068 (2)	0.0526 (17)	0.0462 (18)	0.0092 (14)	0.0248 (15)	−0.0017 (14)
C6	0.0446 (15)	0.0417 (15)	0.0417 (16)	−0.0016 (12)	0.0152 (13)	−0.0020 (13)
C7	0.0322 (14)	0.0452 (15)	0.0411 (16)	0.0007 (11)	0.0118 (12)	0.0021 (13)
C8	0.0423 (16)	0.0463 (16)	0.0441 (17)	0.0003 (12)	0.0138 (13)	0.0034 (13)
C9	0.0528 (18)	0.0590 (18)	0.0389 (16)	0.0108 (14)	0.0180 (14)	0.0067 (14)
C10	0.104 (3)	0.094 (3)	0.0401 (19)	0.035 (2)	0.0314 (19)	0.0174 (18)
C11	0.0370 (14)	0.0572 (17)	0.0352 (15)	0.0085 (12)	0.0169 (12)	0.0038 (13)
C12	0.0380 (14)	0.0469 (15)	0.0347 (15)	0.0005 (12)	0.0096 (12)	0.0022 (12)
C13	0.0421 (16)	0.0492 (16)	0.0332 (15)	0.0082 (13)	0.0105 (13)	0.0028 (13)
C14	0.0546 (18)	0.0587 (18)	0.0371 (17)	0.0149 (14)	0.0178 (14)	0.0049 (14)
C15	0.0516 (17)	0.0455 (15)	0.0317 (15)	0.0025 (13)	0.0168 (13)	0.0050 (12)
C16	0.060 (2)	0.093 (3)	0.0442 (19)	−0.0144 (18)	0.0191 (16)	0.0055 (18)
C17	0.100 (3)	0.100 (3)	0.0382 (19)	−0.029 (2)	0.021 (2)	−0.0038 (19)
C18	0.119 (3)	0.067 (2)	0.048 (2)	−0.012 (2)	0.047 (2)	−0.0052 (17)
C19	0.074 (2)	0.0508 (17)	0.066 (2)	0.0032 (16)	0.0438 (19)	0.0107 (17)
C20	0.0501 (17)	0.0357 (14)	0.0436 (17)	−0.0007 (12)	0.0190 (14)	0.0049 (12)
C21	0.0478 (16)	0.0439 (15)	0.0359 (15)	0.0058 (12)	0.0159 (13)	0.0012 (12)
C22	0.0419 (16)	0.0458 (15)	0.0373 (15)	0.0013 (12)	0.0132 (13)	−0.0030 (12)
C23	0.0559 (18)	0.0529 (17)	0.0406 (17)	0.0144 (14)	0.0125 (14)	0.0047 (14)
C24	0.082 (2)	0.0435 (17)	0.0497 (19)	0.0104 (16)	0.0209 (18)	0.0007 (15)
C25	0.077 (2)	0.0534 (19)	0.068 (2)	−0.0090 (17)	0.0185 (19)	−0.0187 (17)
C26	0.0525 (18)	0.065 (2)	0.058 (2)	0.0021 (15)	0.0027 (16)	−0.0108 (17)
C27	0.145 (4)	0.057 (2)	0.090 (3)	0.029 (2)	0.029 (3)	−0.004 (2)
N1	0.0533 (14)	0.0562 (15)	0.0435 (15)	0.0100 (12)	0.0187 (12)	0.0092 (12)
N2	0.0452 (13)	0.0497 (13)	0.0340 (13)	0.0121 (10)	0.0170 (11)	0.0001 (10)
N3	0.0479 (13)	0.0478 (14)	0.0345 (13)	0.0098 (10)	0.0170 (11)	0.0025 (11)
N4	0.0543 (17)	0.0495 (15)	0.068 (2)	0.0007 (12)	0.0140 (15)	0.0037 (14)
O1	0.1005 (18)	0.0783 (15)	0.0439 (13)	0.0355 (13)	0.0417 (13)	0.0075 (11)
O2	0.0599 (12)	0.0514 (11)	0.0364 (11)	0.0155 (9)	0.0212 (9)	0.0084 (9)
O3	0.0752 (16)	0.0688 (15)	0.0552 (15)	−0.0030 (11)	0.0078 (13)	−0.0065 (12)
O4	0.0656 (18)	0.161 (3)	0.120 (3)	−0.0421 (19)	0.0301 (17)	−0.011 (2)
S1	0.0720 (6)	0.0453 (5)	0.0599 (6)	0.0106 (4)	0.0254 (4)	0.0080 (4)

Geometric parameters (Å, º) top

C1—C6	1.347 (4)	C11—C12	1.405 (4)
C1—C2	1.498 (4)	C11—C14	1.463 (4)
C1—S1	1.747 (3)	C12—N3	1.377 (3)
C2—C3'	1.506 (15)	C13—N3	1.285 (3)
C2—C3	1.511 (10)	C13—O2	1.354 (3)
C2—H2A	0.9700	C13—N2	1.354 (3)
C2—H2B	0.9700	C14—O1	1.213 (3)
C2—H2C	0.9700	C14—N2	1.422 (3)
C2—H2D	0.9701	C15—C16	1.366 (4)
C3—C4	1.518 (9)	C15—C20	1.384 (4)
C3—H3A	0.9700	C15—O2	1.392 (3)
C3—H3B	0.9700	C16—C17	1.371 (4)
C4—C5	1.527 (7)	C16—H16	0.9300
C4—H4A	0.9700	C17—C18	1.348 (5)
C4—H4B	0.9700	C17—H17	0.9300
C3'—C4'	1.517 (12)	C18—C19	1.373 (5)
C3'—H3'1	0.9700	C18—H18	0.9300
C3'—H3'2	0.9700	C19—C20	1.389 (4)
C4'—C5	1.572 (11)	C19—H19	0.9300
C4'—H4'1	0.9700	C20—N4	1.461 (4)
C4'—H4'2	0.9700	C21—C22	1.372 (4)
C5—C6	1.502 (4)	C21—C26	1.373 (4)
C5—H5A	0.9700	C21—N2	1.456 (3)
C5—H5B	0.9700	C22—C23	1.377 (4)
C5—H5C	0.9700	C22—H22	0.9300
C5—H5D	0.9700	C23—C24	1.374 (4)
C6—C7	1.442 (4)	C23—H23	0.9300
C7—C8	1.386 (4)	C24—C25	1.370 (5)
C7—C12	1.413 (4)	C24—C27	1.518 (4)
C8—N1	1.354 (3)	C25—C26	1.386 (4)
C8—S1	1.734 (3)	C25—H25	0.9300
C9—N1	1.329 (3)	C26—H26	0.9300
C9—C11	1.427 (4)	C27—H27A	0.9600
C9—C10	1.514 (4)	C27—H27B	0.9600
C10—H10A	0.9600	C27—H27C	0.9600
C10—H10B	0.9600	N4—O3	1.206 (3)
C10—H10C	0.9600	N4—O4	1.225 (3)

C6—C1—C2	125.1 (3)	N1—C8—S1	121.4 (2)
C6—C1—S1	113.4 (2)	C7—C8—S1	111.5 (2)
C2—C1—S1	121.5 (2)	N1—C9—C11	122.3 (3)
C1—C2—C3'	110.8 (5)	N1—C9—C10	114.6 (3)
C1—C2—C3	110.9 (4)	C11—C9—C10	123.1 (3)
C3'—C2—C3	26.0 (4)	C9—C10—H10A	109.5
C1—C2—H2A	109.5	C9—C10—H10B	109.5
C3'—C2—H2A	129.4	H10A—C10—H10B	109.5
C3—C2—H2A	109.5	C9—C10—H10C	109.5
C1—C2—H2B	109.5	H10A—C10—H10C	109.5
C3'—C2—H2B	85.9	H10B—C10—H10C	109.5
C3—C2—H2B	109.5	C12—C11—C9	119.3 (2)
H2A—C2—H2B	108.1	C12—C11—C14	118.4 (2)
C1—C2—H2C	109.6	C9—C11—C14	122.3 (2)
C3'—C2—H2C	109.9	N3—C12—C11	122.8 (2)
C3—C2—H2C	86.3	N3—C12—C7	118.3 (2)
H2A—C2—H2C	25.7	C11—C12—C7	118.8 (2)
H2B—C2—H2C	128.4	N3—C13—O2	119.5 (2)
C1—C2—H2D	109.4	N3—C13—N2	127.0 (2)
C3'—C2—H2D	109.1	O2—C13—N2	113.5 (2)
C3—C2—H2D	129.1	O1—C14—N2	118.7 (3)
H2A—C2—H2D	84.5	O1—C14—C11	126.6 (3)
H2B—C2—H2D	25.7	N2—C14—C11	114.7 (2)
H2C—C2—H2D	108.1	C16—C15—C20	118.9 (3)
C2—C3—C4	110.6 (7)	C16—C15—O2	118.2 (3)
C2—C3—H3A	109.5	C20—C15—O2	122.8 (3)
C4—C3—H3A	109.5	C15—C16—C17	120.4 (3)
C2—C3—H3B	109.5	C15—C16—H16	119.8
C4—C3—H3B	109.5	C17—C16—H16	119.8
H3A—C3—H3B	108.1	C18—C17—C16	120.9 (3)
C3—C4—C5	111.6 (7)	C18—C17—H17	119.5
C3—C4—H4A	109.3	C16—C17—H17	119.5
C5—C4—H4A	109.3	C17—C18—C19	120.3 (3)
C3—C4—H4B	109.3	C17—C18—H18	119.9
C5—C4—H4B	109.3	C19—C18—H18	119.8
H4A—C4—H4B	108.0	C18—C19—C20	119.1 (3)
C2—C3'—C4'	112.2 (10)	C18—C19—H19	120.4
C2—C3'—H3'1	109.2	C20—C19—H19	120.4
C4'—C3'—H3'1	109.2	C15—C20—C19	120.3 (3)
C2—C3'—H3'2	109.2	C15—C20—N4	122.2 (3)
C4'—C3'—H3'2	109.2	C19—C20—N4	117.5 (3)
H3'1—C3'—H3'2	107.9	C22—C21—C26	120.4 (3)
C3'—C4'—C5	108.1 (9)	C22—C21—N2	119.8 (2)
C3'—C4'—H4'1	110.1	C26—C21—N2	119.8 (2)
C5—C4'—H4'1	110.1	C21—C22—C23	119.5 (3)
C3'—C4'—H4'2	110.1	C21—C22—H22	120.3
C5—C4'—H4'2	110.1	C23—C22—H22	120.3
H4'1—C4'—H4'2	108.4	C24—C23—C22	121.4 (3)
C6—C5—C4	111.2 (3)	C24—C23—H23	119.3
C6—C5—C4'	110.8 (5)	C22—C23—H23	119.3
C4—C5—C4'	31.7 (3)	C25—C24—C23	118.1 (3)
C6—C5—H5A	109.4	C25—C24—C27	120.8 (3)
C4—C5—H5A	109.4	C23—C24—C27	121.1 (3)
C4'—C5—H5A	132.9	C24—C25—C26	121.6 (3)
C6—C5—H5B	109.4	C24—C25—H25	119.2
C4—C5—H5B	109.4	C26—C25—H25	119.2
C4'—C5—H5B	80.5	C21—C26—C25	119.0 (3)
H5A—C5—H5B	108.0	C21—C26—H26	120.5
C6—C5—H5C	109.9	C25—C26—H26	120.5
C4—C5—H5C	80.1	C24—C27—H27A	109.5
C4'—C5—H5C	109.3	C24—C27—H27B	109.5
H5A—C5—H5C	32.1	H27A—C27—H27B	109.5
H5B—C5—H5C	132.2	C24—C27—H27C	109.5
C6—C5—H5D	109.2	H27A—C27—H27C	109.5
C4—C5—H5D	132.7	H27B—C27—H27C	109.5
C4'—C5—H5D	109.6	C9—N1—C8	116.5 (2)
H5A—C5—H5D	78.6	C13—N2—C14	120.2 (2)
H5B—C5—H5D	31.9	C13—N2—C21	121.2 (2)
H5C—C5—H5D	108.1	C14—N2—C21	118.6 (2)
C1—C6—C7	111.7 (2)	C13—N3—C12	116.8 (2)
C1—C6—C5	121.9 (3)	O3—N4—O4	122.5 (3)
C7—C6—C5	126.4 (2)	O3—N4—C20	120.3 (3)
C8—C7—C12	115.9 (2)	O4—N4—C20	117.3 (3)
C8—C7—C6	112.8 (2)	C13—O2—C15	114.5 (2)
C12—C7—C6	131.2 (2)	C8—S1—C1	90.68 (13)
N1—C8—C7	127.1 (3)

C6—C1—C2—C3'	13.0 (6)	C17—C18—C19—C20	−0.9 (5)
S1—C1—C2—C3'	−169.5 (5)	C16—C15—C20—C19	2.7 (4)
C6—C1—C2—C3	−14.9 (6)	O2—C15—C20—C19	179.4 (2)
S1—C1—C2—C3	162.7 (4)	C16—C15—C20—N4	−178.1 (3)
C1—C2—C3—C4	45.2 (9)	O2—C15—C20—N4	−1.4 (4)
C3'—C2—C3—C4	−49.6 (13)	C18—C19—C20—C15	−0.9 (4)
C2—C3—C4—C5	−62.9 (11)	C18—C19—C20—N4	179.8 (3)
C1—C2—C3'—C4'	−45.2 (12)	C26—C21—C22—C23	−1.3 (4)
C3—C2—C3'—C4'	50.0 (12)	N2—C21—C22—C23	178.8 (3)
C2—C3'—C4'—C5	64.4 (14)	C21—C22—C23—C24	−0.5 (4)
C3—C4—C5—C6	45.6 (9)	C22—C23—C24—C25	2.8 (5)
C3—C4—C5—C4'	−50.0 (9)	C22—C23—C24—C27	−178.6 (3)
C3'—C4'—C5—C6	−49.3 (12)	C23—C24—C25—C26	−3.3 (5)
C3'—C4'—C5—C4	47.7 (10)	C27—C24—C25—C26	178.1 (3)
C2—C1—C6—C7	177.4 (3)	C22—C21—C26—C25	0.8 (5)
S1—C1—C6—C7	−0.3 (3)	N2—C21—C26—C25	−179.4 (3)
C2—C1—C6—C5	−0.8 (5)	C24—C25—C26—C21	1.5 (5)
S1—C1—C6—C5	−178.5 (2)	C11—C9—N1—C8	−2.7 (4)
C4—C5—C6—C1	−14.6 (5)	C10—C9—N1—C8	177.0 (3)
C4'—C5—C6—C1	19.5 (6)	C7—C8—N1—C9	2.9 (4)
C4—C5—C6—C7	167.5 (5)	S1—C8—N1—C9	−175.6 (2)
C4'—C5—C6—C7	−158.5 (5)	N3—C13—N2—C14	−1.1 (4)
C1—C6—C7—C8	−0.6 (3)	O2—C13—N2—C14	177.8 (2)
C5—C6—C7—C8	177.5 (3)	N3—C13—N2—C21	178.2 (3)
C1—C6—C7—C12	−176.2 (3)	O2—C13—N2—C21	−2.9 (4)
C5—C6—C7—C12	1.9 (5)	O1—C14—N2—C13	−179.1 (3)
C12—C7—C8—N1	−1.0 (4)	C11—C14—N2—C13	0.7 (4)
C6—C7—C8—N1	−177.3 (3)	O1—C14—N2—C21	1.6 (4)
C12—C7—C8—S1	177.61 (19)	C11—C14—N2—C21	−178.6 (2)
C6—C7—C8—S1	1.3 (3)	C22—C21—N2—C13	−63.3 (4)
N1—C9—C11—C12	0.8 (4)	C26—C21—N2—C13	116.9 (3)
C10—C9—C11—C12	−178.8 (3)	C22—C21—N2—C14	116.0 (3)
N1—C9—C11—C14	−179.3 (3)	C26—C21—N2—C14	−63.8 (4)
C10—C9—C11—C14	1.1 (5)	O2—C13—N3—C12	−178.3 (2)
C9—C11—C12—N3	179.2 (2)	N2—C13—N3—C12	0.5 (4)
C14—C11—C12—N3	−0.7 (4)	C11—C12—N3—C13	0.4 (4)
C9—C11—C12—C7	1.2 (4)	C7—C12—N3—C13	178.4 (2)
C14—C11—C12—C7	−178.7 (2)	C15—C20—N4—O3	−15.2 (4)
C8—C7—C12—N3	−179.2 (2)	C19—C20—N4—O3	164.1 (3)
C6—C7—C12—N3	−3.8 (4)	C15—C20—N4—O4	164.2 (3)
C8—C7—C12—C11	−1.1 (4)	C19—C20—N4—O4	−16.5 (4)
C6—C7—C12—C11	174.4 (3)	N3—C13—O2—C15	5.4 (4)
C12—C11—C14—O1	179.9 (3)	N2—C13—O2—C15	−173.6 (2)
C9—C11—C14—O1	0.0 (5)	C16—C15—O2—C13	−101.7 (3)
C12—C11—C14—N2	0.1 (4)	C20—C15—O2—C13	81.5 (3)
C9—C11—C14—N2	−179.8 (2)	N1—C8—S1—C1	177.5 (2)
C20—C15—C16—C17	−2.7 (5)	C7—C8—S1—C1	−1.3 (2)
O2—C15—C16—C17	−179.5 (3)	C6—C1—S1—C8	0.9 (2)
C15—C16—C17—C18	0.9 (6)	C2—C1—S1—C8	−176.9 (3)
C16—C17—C18—C19	0.9 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···O1ⁱ	0.93	2.43	3.256 (4)	148

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

Experimental details

Crystal data
Chemical formula	C₂₇H₂₂N₄O₄S
M_r	498.55
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	292
a, b, c (Å)	9.1381 (8), 17.0819 (14), 16.0332 (14)
β (°)	106.203 (2)
V (Å³)	2403.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.949, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	12011, 4220, 2922
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.172, 1.08
No. of reflections	4220
No. of parameters	340
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.26

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXL97.

Selected geometric parameters (Å, º) top

C1—S1	1.747 (3)	C8—S1	1.734 (3)

C8—S1—C1	90.68 (13)

C1—C2—C3—C4	45.2 (9)	C6—C7—C8—N1	−177.3 (3)
C1—C2—C3'—C4'	−45.2 (12)	C14—C11—C12—C7	−178.7 (2)