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Acta Cryst. (2012). E68, o2647-o2648    [ doi:10.1107/S1600536812034149 ]

5a-Butyl-1,3,8,10-tetrachloro-7,13-bis(4-nitrobenzoyl)-5a,6a,12a,12b-tetrahydro-7H,13H-thieno[2,3-b:4,5-b']bis(1,4-benzoxazine)

K. Tang and M. E. Kastner

Abstract top

The title compound, C34H24Cl4N4O8S, is a linear pentacyclic system formed of two substituted benzoxazinyl groups fused to 2-n-butyltetrahydrothiophene. The oxazine ring, which is fused to the n-butyl-substituted side of the thiophene ring, is in a boat conformation. The other fused oxazine ring and the tetrahydrothiene ring are each in an envelope conformation. The bridgehead C atom [alpha] to both the S and N atoms forms the flap of each envelope. This results in a twist of the pentacyclic system such that the dihedral angle between the terminal dichlorobenzene rings is 82.92 (8)°. In the crystal, inversion-related molecules form a weakly hydrogen-bonded dimer, with two C-H...O interactions between an H atom on the oxazine ring and an amide O atom. Additionally, C-H...O interactions occur between an H atom on a screw-related nitrobenzene ring and an O atom on the nitrobenzene ring of one molecule. One of the Cl atoms and the butyl group are disordered over two sets of sites with occupancy ratios of 0.94 (2):0.06 (2) and 0.624 (4):0.376 (4), respectively.

Comment top

The title compound was synthesized as part of a study of inverse electron-demand Diels-Alder reactions (Heine et al., 1993).

The title molecule (Fig. 1), it is a linear pentacyclic system formed of two substituted benzoxazinyl groups fused to 2-n-butyltetrahydrothiophene. The oxazine ring (N1/O1/C1–C4) is in a boat conformation with O1 and N1 displaced by 0.536 (3) and 0.478 (3) Å, respectively, from the plane of C1–C4 atoms (r.m.s.d = 0.019 Å). In the dichlorobenzoxazinyl ring (O1/N2/Cl1–C8/Cl1/Cl2), the atoms O1/N1/C3–C8 lie in aplane (rmsd 0.0278 Å) while the atoms C1, C2, Cl1 and Cl2 lie 1.035 (3), 0.960 (3), 0.269 (2) and 0.014 (2) Å, respectively, out of this plane. In the other dichlorobenzoxazinyl ring (O5/N3/C16–C23/Cl3/Cl4), the atoms N3, O5, C16 and C18–C23, are coplanar (r.m.s.d = 0.0289 Å) while the atoms C17, Cl3, Cl4A and Cl4B are displaced from this plane by 0.553 (3), 0.170 (2), 0.52 (7) and 0.003 (8) Å, respectively. The dihedral angle between the terminal dichlorobenzene rings is 82.92 (8)o. The tetrahydrothiophene ring (S1/C1/C2/C16/C17) is in a C17- envelope conformation with C17 displaced by 0.630 (3)Å from the plane of the remaining ring atoms (r.m.s.d = 0.042 Å). The oxazine ring (N3/O5/C16–C19) is also in a C17-envelope conformation with C17 displaced by 0.572 (3) Å from the plane the other five atoms in the ring (r.m.s.d = 0.035 Å). The dihedral angles between the nitro groups and their associated benzene rings are: 5.9 (5)° for N/O3/O4 and 14.1 (3)° for N4/O7/O8.

In the crystal two inversion-related molecules form a weakly hydrogen-bonded dimer with C2—H2 ···O2 interactions (Table 1 and Fig. 2) Additionally, C14—H14···O3 hydrogen bonding interactions form between an oxygen on the nitrobenzene ring of one molecule and a hydrogen on a screw related nitrobenzene ring.

Related literature top

For the synthesis of the title compound, see: Heine et al. (1993). For the crystal structure of a related compound, see: Garbauskas et al. (1985).

Experimental top

The title compound was synthesized by following a reported procedure (Heine et al., (1993). The crystals suitable for X-ray crystallographic analysis were grown from a solution of acetonitrile by slow evaporation at room temperature.

Refinement top

The H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93, 0.96, 0.97 and 0.98 Å, for aryl, methyl, methylene and methyne H-atoms, respectively. The Uiso(H) were allowed at 1.5Ueq(C methyl) or 1.2Ueq(C non-methyl).

The n-butyl group was disordered [ratio: 0.624 (4):0.376 (4)] and the bond distances were constrained to chemically acceptable values. A chlorine atom, Cl4, was also disordered with a population ratio of 0.94 (2):0.06 (2).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms. Cl4 and the n-butyl group are disordered and only one position is shown.
[Figure 2] Fig. 2. A view of the C—-H···O hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen- bonding were omitted for clarity.
[Figure 3] Fig. 3. The molecular structure of the title compound with labels for the disordered atoms and 30% probability displacement ellipsoids for non-H atoms.
[Figure 4] Fig. 4. An enhanced figure of the molecule.
[Figure 5] Fig. 5. An enhanced figure of the unit cell.
5a-Butyl-1,3,8,10-tetrachloro-7,13-bis(4-nitrobenzoyl)-5a,6a,12a,12b- tetrahydro-7H,13H-thieno[2,3-b:4,5- b']bis(1,4-benzoxazine) top
Crystal data top
C34H24Cl4N4O8SF(000) = 1616
Mr = 790.44Dx = 1.470 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 20 reflections
a = 12.855 (3) Åθ = 10–12.5°
b = 10.139 (1) ŵ = 0.45 mm−1
c = 27.845 (5) ÅT = 293 K
β = 100.23 (2)°Needle, colorless
V = 3571.5 (11) Å30.5 × 0.2 × 0.1 mm
Z = 4
Data collection top
Siemens R3m/V
diffractometer		Rint = 0.032
Radiation source: fine-focus sealed tubeθmax = 27.6°, θmin = 1.6°
Graphite monochromatorh = 0→16
θ 2 θ scansk = 0→13
8579 measured reflectionsl = −36→35
8215 independent reflections3 standard reflections every 97 reflections
5039 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0624P)2]
where P = (Fo2 + 2Fc2)/3
8215 reflections(Δ/σ)max = 0.017
476 parametersΔρmax = 0.34 e Å−3
6 restraintsΔρmin = −0.32 e Å−3
Crystal data top
C34H24Cl4N4O8SV = 3571.5 (11) Å3
Mr = 790.44Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.855 (3) ŵ = 0.45 mm−1
b = 10.139 (1) ÅT = 293 K
c = 27.845 (5) Å0.5 × 0.2 × 0.1 mm
β = 100.23 (2)°
Data collection top
Siemens R3m/V
diffractometer		Rint = 0.032
8579 measured reflectionsθmax = 27.6°
8215 independent reflections3 standard reflections every 97 reflections
5039 reflections with I > 2σ(I) intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.123Δρmax = 0.34 e Å−3
S = 1.01Δρmin = −0.32 e Å−3
8215 reflectionsAbsolute structure: ?
476 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
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
xyzUiso*/UeqOcc. (<1)
Cl10.86026 (6)0.33223 (7)0.62869 (3)0.05638 (19)
Cl20.95304 (6)0.70359 (9)0.76649 (3)0.0707 (2)
Cl31.04827 (5)0.89267 (7)0.45592 (2)0.05211 (18)
Cl4A0.704 (3)0.903 (6)0.3231 (17)0.1013 (10)0.06 (2)
Cl4B0.7177 (2)0.8654 (5)0.31026 (17)0.1013 (10)0.94 (2)
S0.76688 (6)0.84957 (6)0.55950 (2)0.04857 (18)
O10.64969 (13)0.75499 (16)0.62293 (5)0.0394 (4)
O20.57552 (17)0.37288 (18)0.53786 (6)0.0611 (5)
O30.5516 (3)−0.0704 (3)0.71927 (11)0.1308 (13)
O40.5328 (3)0.0893 (3)0.76668 (10)0.1139 (11)
O50.70106 (13)0.65736 (18)0.47193 (5)0.0461 (4)
O61.06030 (14)0.62308 (17)0.49661 (6)0.0481 (4)
O71.2038 (3)0.5453 (3)0.74913 (9)0.1113 (10)
O81.2033 (2)0.7573 (3)0.75138 (8)0.0896 (8)
N10.67147 (14)0.51822 (18)0.58817 (6)0.0334 (4)
N20.5500 (2)0.0458 (3)0.72858 (11)0.0791 (8)
N30.91180 (15)0.72470 (19)0.51363 (6)0.0373 (4)
N41.1870 (2)0.6530 (3)0.72987 (10)0.0715 (7)
C10.65006 (19)0.7586 (2)0.57105 (8)0.0369 (5)
C20.65631 (18)0.6171 (2)0.54903 (7)0.0325 (5)
H20.58940.59860.52710.039*
C30.72924 (18)0.6790 (2)0.64898 (8)0.0357 (5)
C40.74216 (17)0.5532 (2)0.63131 (8)0.0335 (5)
C50.82759 (19)0.4781 (2)0.65429 (8)0.0392 (5)
C60.8903 (2)0.5241 (3)0.69675 (9)0.0460 (6)
H60.94520.47260.71320.055*
C70.8704 (2)0.6469 (3)0.71427 (8)0.0471 (6)
C80.7918 (2)0.7280 (3)0.69062 (8)0.0441 (6)
H80.78130.81210.70220.053*
C90.6174 (2)0.4013 (2)0.57913 (8)0.0394 (5)
C100.6058 (2)0.3136 (2)0.62103 (9)0.0403 (6)
C110.6156 (2)0.1783 (2)0.61429 (10)0.0538 (7)
H110.63430.14710.58560.065*
C120.5980 (2)0.0908 (3)0.64951 (11)0.0592 (8)
H120.60590.00050.64550.071*
C130.5685 (2)0.1405 (3)0.69056 (10)0.0509 (7)
C140.5575 (2)0.2728 (3)0.69851 (10)0.0533 (7)
H140.53750.30300.72710.064*
C150.5767 (2)0.3602 (2)0.66308 (9)0.0453 (6)
H150.56990.45050.66760.054*
C160.74536 (17)0.6109 (2)0.51966 (7)0.0335 (5)
H160.77110.52020.51820.040*
C170.83346 (18)0.7009 (2)0.54434 (8)0.0351 (5)
H170.86840.65910.57470.042*
C180.76444 (19)0.7222 (2)0.44547 (8)0.0403 (6)
C190.86932 (19)0.7570 (2)0.46436 (8)0.0368 (5)
C200.92359 (19)0.8300 (2)0.43419 (9)0.0410 (6)
C210.8790 (2)0.8600 (3)0.38661 (9)0.0516 (7)
H210.91780.90440.36650.062*
C220.7756 (2)0.8230 (3)0.36943 (9)0.0587 (8)
C230.7176 (2)0.7562 (3)0.39837 (9)0.0538 (7)
H230.64760.73400.38650.065*
C241.01125 (19)0.6649 (2)0.52636 (9)0.0392 (5)
C251.05379 (19)0.6615 (2)0.58040 (9)0.0422 (6)
C261.0972 (2)0.5471 (3)0.60153 (10)0.0582 (8)
H261.09700.47150.58260.070*
C271.1411 (2)0.5429 (3)0.65061 (11)0.0658 (8)
H271.16950.46510.66500.079*
C281.1417 (2)0.6559 (3)0.67727 (9)0.0535 (7)
C291.0998 (2)0.7720 (3)0.65746 (10)0.0618 (8)
H291.10240.84790.67640.074*
C301.0537 (2)0.7742 (3)0.60879 (10)0.0584 (8)
H301.02250.85120.59500.070*
C31A0.5497 (2)0.8317 (3)0.54905 (9)0.0552 (7)
H31A0.56150.92520.55490.066*0.624 (4)
H31B0.53740.81830.51400.066*0.624 (4)
C32A0.4516 (5)0.7932 (9)0.5675 (4)0.074 (2)0.624 (4)
H32A0.46210.80110.60280.089*0.624 (4)
H32B0.43200.70300.55850.089*0.624 (4)
C33A0.3653 (4)0.8902 (6)0.5431 (2)0.0687 (13)0.624 (4)
H33A0.38610.98040.55150.082*0.624 (4)
H33B0.35440.88100.50790.082*0.624 (4)
C34A0.2662 (4)0.8563 (8)0.5617 (3)0.104 (2)0.624 (4)
H34A0.23990.77280.54850.156*0.624 (4)
H34B0.21390.92320.55180.156*0.624 (4)
H34C0.28110.85110.59660.156*0.624 (4)
H31C0.54510.83780.51400.066*0.376 (4)
H31D0.55220.92050.56210.066*0.376 (4)
C32B0.4516 (7)0.7606 (17)0.5604 (7)0.074 (2)0.376 (4)
H32C0.46130.75520.59570.089*0.376 (4)
H32D0.45610.67090.54890.089*0.376 (4)
C33B0.3355 (7)0.8037 (9)0.5432 (4)0.0687 (13)0.376 (4)
H33C0.32090.80990.50790.082*0.376 (4)
H33D0.28850.73810.55300.082*0.376 (4)
C34B0.3156 (9)0.9355 (11)0.5651 (5)0.104 (2)0.376 (4)
H34D0.33100.92950.60000.156*0.376 (4)
H34E0.24290.95980.55480.156*0.376 (4)
H34F0.36031.00100.55430.156*0.376 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0574 (4)0.0453 (4)0.0640 (4)0.0154 (3)0.0044 (3)−0.0023 (3)
Cl20.0673 (5)0.0899 (6)0.0467 (4)−0.0176 (4)−0.0120 (3)−0.0106 (4)
Cl30.0555 (4)0.0480 (4)0.0555 (4)−0.0114 (3)0.0173 (3)0.0002 (3)
Cl4A0.0683 (7)0.195 (2)0.0404 (11)0.0100 (9)0.0105 (7)0.0446 (13)
Cl4B0.0683 (7)0.195 (2)0.0404 (11)0.0100 (9)0.0105 (7)0.0446 (13)
S0.0659 (5)0.0321 (3)0.0518 (4)−0.0050 (3)0.0216 (3)−0.0053 (3)
O10.0462 (9)0.0421 (9)0.0305 (8)0.0102 (8)0.0081 (7)−0.0036 (7)
O20.0892 (15)0.0464 (11)0.0408 (10)−0.0161 (10)−0.0071 (10)−0.0045 (8)
O30.229 (4)0.0590 (17)0.125 (2)−0.021 (2)0.085 (3)0.0261 (16)
O40.194 (3)0.092 (2)0.0727 (16)0.003 (2)0.0686 (19)0.0203 (15)
O50.0429 (10)0.0654 (12)0.0296 (8)−0.0093 (9)0.0054 (7)0.0029 (8)
O60.0498 (11)0.0483 (10)0.0480 (10)0.0046 (9)0.0132 (8)−0.0026 (8)
O70.147 (3)0.102 (2)0.0679 (16)0.0114 (19)−0.0277 (16)0.0222 (15)
O80.0913 (18)0.106 (2)0.0600 (14)0.0006 (15)−0.0163 (12)−0.0223 (14)
N10.0385 (11)0.0317 (10)0.0291 (9)−0.0023 (8)0.0038 (8)−0.0002 (8)
N20.102 (2)0.069 (2)0.0735 (19)−0.0069 (17)0.0343 (17)0.0208 (16)
N30.0373 (11)0.0438 (11)0.0303 (10)−0.0007 (9)0.0047 (8)0.0020 (8)
N40.0691 (18)0.087 (2)0.0508 (15)0.0045 (16)−0.0092 (13)0.0002 (15)
C10.0467 (14)0.0328 (12)0.0320 (11)0.0063 (11)0.0094 (10)−0.0013 (9)
C20.0356 (12)0.0309 (11)0.0302 (11)0.0005 (10)0.0041 (9)−0.0007 (9)
C30.0401 (13)0.0385 (13)0.0291 (11)−0.0004 (10)0.0082 (9)−0.0006 (9)
C40.0379 (13)0.0339 (12)0.0288 (11)−0.0028 (10)0.0059 (9)0.0007 (9)
C50.0409 (14)0.0358 (13)0.0403 (13)0.0009 (11)0.0061 (10)0.0049 (10)
C60.0436 (15)0.0502 (15)0.0410 (14)−0.0003 (12)−0.0018 (11)0.0096 (12)
C70.0487 (15)0.0562 (16)0.0334 (12)−0.0095 (13)−0.0006 (11)−0.0007 (11)
C80.0529 (15)0.0437 (14)0.0354 (13)−0.0046 (12)0.0068 (11)−0.0051 (11)
C90.0471 (14)0.0333 (12)0.0376 (13)−0.0004 (11)0.0067 (11)−0.0038 (10)
C100.0456 (14)0.0353 (13)0.0399 (13)−0.0074 (11)0.0078 (11)−0.0019 (10)
C110.083 (2)0.0342 (14)0.0486 (15)−0.0082 (13)0.0236 (14)−0.0053 (11)
C120.085 (2)0.0327 (14)0.0626 (18)−0.0065 (14)0.0212 (16)0.0009 (13)
C130.0582 (17)0.0443 (15)0.0527 (16)−0.0083 (13)0.0166 (13)0.0093 (12)
C140.0617 (18)0.0567 (17)0.0469 (15)−0.0014 (14)0.0245 (13)−0.0017 (13)
C150.0530 (16)0.0354 (13)0.0503 (15)−0.0003 (12)0.0166 (12)−0.0025 (11)
C160.0405 (13)0.0317 (11)0.0294 (11)0.0003 (10)0.0090 (9)−0.0007 (9)
C170.0409 (13)0.0343 (12)0.0305 (11)−0.0021 (10)0.0072 (10)0.0004 (9)
C180.0436 (14)0.0474 (14)0.0318 (12)0.0003 (11)0.0120 (10)−0.0017 (10)
C190.0425 (13)0.0384 (13)0.0302 (11)0.0037 (11)0.0084 (10)−0.0001 (10)
C200.0459 (14)0.0395 (13)0.0409 (13)0.0047 (11)0.0168 (11)0.0014 (11)
C210.0589 (18)0.0593 (17)0.0406 (14)0.0050 (14)0.0196 (12)0.0096 (12)
C220.0577 (18)0.087 (2)0.0319 (13)0.0132 (16)0.0105 (12)0.0116 (14)
C230.0450 (15)0.081 (2)0.0350 (13)0.0040 (14)0.0062 (11)0.0062 (13)
C240.0400 (13)0.0312 (12)0.0454 (13)−0.0050 (11)0.0042 (11)0.0010 (10)
C250.0373 (13)0.0427 (14)0.0447 (13)−0.0008 (11)0.0022 (11)0.0000 (11)
C260.0675 (19)0.0477 (16)0.0551 (17)0.0168 (14)−0.0011 (14)−0.0082 (13)
C270.073 (2)0.0572 (18)0.0605 (18)0.0225 (16)−0.0067 (16)0.0054 (15)
C280.0487 (16)0.0618 (18)0.0453 (15)0.0036 (14)−0.0040 (12)0.0029 (13)
C290.077 (2)0.0492 (17)0.0542 (17)−0.0015 (15)−0.0024 (15)−0.0121 (14)
C300.074 (2)0.0413 (15)0.0522 (16)0.0025 (14)−0.0095 (14)−0.0007 (13)
C31A0.0674 (19)0.0580 (17)0.0371 (13)0.0326 (15)0.0008 (12)−0.0029 (12)
C32A0.0482 (18)0.132 (6)0.044 (4)0.040 (2)0.0079 (16)−0.020 (4)
C33A0.051 (3)0.076 (4)0.081 (3)0.016 (3)0.016 (2)0.003 (3)
C34A0.047 (4)0.133 (7)0.134 (5)0.019 (3)0.023 (4)−0.014 (5)
C32B0.0482 (18)0.132 (6)0.044 (4)0.040 (2)0.0079 (16)−0.020 (4)
C33B0.051 (3)0.076 (4)0.081 (3)0.016 (3)0.016 (2)0.003 (3)
C34B0.047 (4)0.133 (7)0.134 (5)0.019 (3)0.023 (4)−0.014 (5)
Geometric parameters (Å, º) top
Cl1—C51.726 (2)C14—H140.9300
Cl2—C71.739 (2)C15—H150.9300
Cl3—C201.730 (3)C16—C171.520 (3)
Cl4A—C221.66 (3)C16—H160.9800
Cl4B—C221.737 (4)C17—H170.9800
S—C171.820 (2)C18—C231.386 (3)
S—C11.839 (3)C18—C191.402 (3)
O1—C31.379 (3)C19—C201.396 (3)
O1—C11.446 (3)C20—C211.381 (3)
O2—C91.214 (3)C21—C221.383 (4)
O3—N21.207 (4)C21—H210.9300
O4—N21.205 (3)C22—C231.370 (4)
O5—C181.361 (3)C23—H230.9300
O5—C161.430 (3)C24—C251.507 (3)
O6—C241.204 (3)C25—C261.373 (3)
O7—N41.219 (4)C25—C301.389 (3)
O8—N41.214 (3)C26—C271.384 (4)
N1—C91.375 (3)C26—H260.9300
N1—C41.417 (3)C27—C281.365 (4)
N1—C21.468 (3)C27—H270.9300
N2—C131.479 (3)C28—C291.369 (4)
N3—C241.402 (3)C29—C301.379 (4)
N3—C191.422 (3)C29—H290.9300
N3—C171.452 (3)C30—H300.9300
N4—C281.477 (4)C31A—C32A1.495 (7)
C1—C31A1.519 (3)C31A—H31A0.9700
C1—C21.568 (3)C31A—H31B0.9700
C2—C161.522 (3)C32A—C33A1.546 (7)
C2—H20.9800C32A—H32A0.9700
C3—C81.381 (3)C32A—H32B0.9700
C3—C41.387 (3)C33A—C34A1.498 (7)
C4—C51.395 (3)C33A—H33A0.9700
C5—C61.388 (3)C33A—H33B0.9700
C6—C71.378 (4)C34A—H34A0.9600
C6—H60.9300C34A—H34B0.9600
C7—C81.376 (4)C34A—H34C0.9600
C8—H80.9300C32B—C33B1.547 (9)
C9—C101.495 (3)C32B—H32C0.9700
C10—C151.375 (3)C32B—H32D0.9700
C10—C111.393 (3)C33B—C34B1.508 (9)
C11—C121.371 (4)C33B—H33C0.9700
C11—H110.9300C33B—H33D0.9700
C12—C131.363 (4)C34B—H34D0.9600
C12—H120.9300C34B—H34E0.9600
C13—C141.371 (4)C34B—H34F0.9600
C14—C151.381 (3)
C17—S—C193.28 (10)C16—C17—H17108.7
C3—O1—C1113.94 (16)S—C17—H17108.7
C18—O5—C16118.98 (17)O5—C18—C23115.5 (2)
C9—N1—C4126.79 (18)O5—C18—C19123.1 (2)
C9—N1—C2117.17 (18)C23—C18—C19121.3 (2)
C4—N1—C2116.04 (17)C20—C19—C18117.2 (2)
O4—N2—O3124.0 (3)C20—C19—N3123.7 (2)
O4—N2—C13118.1 (3)C18—C19—N3118.9 (2)
O3—N2—C13118.0 (3)C21—C20—C19121.8 (2)
C24—N3—C19121.34 (19)C21—C20—Cl3117.11 (19)
C24—N3—C17118.40 (19)C19—C20—Cl3121.00 (18)
C19—N3—C17114.75 (18)C20—C21—C22118.8 (2)
O8—N4—O7124.1 (3)C20—C21—H21120.6
O8—N4—C28118.3 (3)C22—C21—H21120.6
O7—N4—C28117.5 (3)C23—C22—C21121.4 (2)
O1—C1—C31A105.18 (18)C23—C22—Cl4A114.3 (13)
O1—C1—C2112.17 (17)C21—C22—Cl4A120.4 (11)
C31A—C1—C2112.8 (2)C23—C22—Cl4B119.6 (2)
O1—C1—S109.56 (15)C21—C22—Cl4B119.0 (2)
C31A—C1—S110.25 (18)C22—C23—C18119.3 (3)
C2—C1—S106.90 (15)C22—C23—H23120.4
N1—C2—C16110.95 (18)C18—C23—H23120.4
N1—C2—C1110.10 (16)O6—C24—N3122.9 (2)
C16—C2—C1110.10 (18)O6—C24—C25122.5 (2)
N1—C2—H2108.5N3—C24—C25114.5 (2)
C16—C2—H2108.5C26—C25—C30119.5 (2)
C1—C2—H2108.5C26—C25—C24119.6 (2)
O1—C3—C8120.5 (2)C30—C25—C24120.9 (2)
O1—C3—C4116.83 (19)C25—C26—C27120.9 (3)
C8—C3—C4122.7 (2)C25—C26—H26119.6
C3—C4—C5118.2 (2)C27—C26—H26119.6
C3—C4—N1115.59 (19)C28—C27—C26118.2 (3)
C5—C4—N1125.9 (2)C28—C27—H27120.9
C6—C5—C4119.9 (2)C26—C27—H27120.9
C6—C5—Cl1119.49 (19)C27—C28—C29122.6 (3)
C4—C5—Cl1120.52 (18)C27—C28—N4119.0 (3)
C7—C6—C5119.2 (2)C29—C28—N4118.3 (3)
C7—C6—H6120.4C28—C29—C30118.6 (3)
C5—C6—H6120.4C28—C29—H29120.7
C8—C7—C6122.5 (2)C30—C29—H29120.7
C8—C7—Cl2119.4 (2)C29—C30—C25120.2 (3)
C6—C7—Cl2118.1 (2)C29—C30—H30119.9
C7—C8—C3117.1 (2)C25—C30—H30119.9
C7—C8—H8121.4C32A—C31A—C1116.2 (4)
C3—C8—H8121.4C32A—C31A—H31A108.2
O2—C9—N1120.2 (2)C1—C31A—H31A108.2
O2—C9—C10120.6 (2)C32A—C31A—H31B108.2
N1—C9—C10119.1 (2)C1—C31A—H31B108.2
C15—C10—C11119.9 (2)H31A—C31A—H31B107.4
C15—C10—C9122.7 (2)C31A—C32A—C33A105.4 (5)
C11—C10—C9117.2 (2)C31A—C32A—H32A110.7
C12—C11—C10120.7 (2)C33A—C32A—H32A110.7
C12—C11—H11119.6C31A—C32A—H32B110.7
C10—C11—H11119.6C33A—C32A—H32B110.7
C13—C12—C11117.8 (3)H32A—C32A—H32B108.8
C13—C12—H12121.1C34A—C33A—C32A106.9 (5)
C11—C12—H12121.1C34A—C33A—H33A110.3
C12—C13—C14123.3 (2)C32A—C33A—H33A110.4
C12—C13—N2117.7 (3)C34A—C33A—H33B110.4
C14—C13—N2119.0 (3)C32A—C33A—H33B110.4
C13—C14—C15118.4 (2)H33A—C33A—H33B108.6
C13—C14—H14120.8C33B—C32B—H32C105.8
C15—C14—H14120.8C33B—C32B—H32D105.8
C10—C15—C14119.8 (2)H32C—C32B—H32D106.2
C10—C15—H15120.1C34B—C33B—C32B110.4 (11)
C14—C15—H15120.1C34B—C33B—H33C109.6
O5—C16—C17111.36 (18)C32B—C33B—H33C109.6
O5—C16—C2105.82 (17)C34B—C33B—H33D109.6
C17—C16—C2107.66 (17)C32B—C33B—H33D109.6
O5—C16—H16110.6H33C—C33B—H33D108.1
C17—C16—H16110.6C33B—C34B—H34D109.5
C2—C16—H16110.6C33B—C34B—H34E109.5
N3—C17—C16111.85 (17)H34D—C34B—H34E109.5
N3—C17—S113.76 (16)C33B—C34B—H34F109.5
C16—C17—S105.00 (15)H34D—C34B—H34F109.5
N3—C17—H17108.7H34E—C34B—H34F109.5
C3—O1—C1—C31A173.0 (2)N1—C2—C16—C17−88.4 (2)
C3—O1—C1—C250.0 (2)C1—C2—C16—C1733.7 (2)
C3—O1—C1—S−68.5 (2)C24—N3—C17—C16−107.8 (2)
C17—S—C1—O1107.13 (15)C19—N3—C17—C1646.4 (3)
C17—S—C1—C31A−137.58 (17)C24—N3—C17—S133.40 (18)
C17—S—C1—C2−14.64 (15)C19—N3—C17—S−72.4 (2)
C9—N1—C2—C16−97.4 (2)O5—C16—C17—N3−51.8 (2)
C4—N1—C2—C1681.7 (2)C2—C16—C17—N3−167.39 (18)
C9—N1—C2—C1140.5 (2)O5—C16—C17—S72.02 (19)
C4—N1—C2—C1−40.5 (2)C2—C16—C17—S−43.55 (19)
O1—C1—C2—N1−6.0 (3)C1—S—C17—N3156.25 (16)
C31A—C1—C2—N1−124.5 (2)C1—S—C17—C1633.63 (15)
S—C1—C2—N1114.15 (17)C16—O5—C18—C23175.8 (2)
O1—C1—C2—C16−128.59 (19)C16—O5—C18—C19−6.2 (3)
C31A—C1—C2—C16112.9 (2)O5—C18—C19—C20−176.4 (2)
S—C1—C2—C16−8.5 (2)C23—C18—C19—C201.6 (4)
C1—O1—C3—C8131.2 (2)O5—C18—C19—N3−0.7 (4)
C1—O1—C3—C4−48.9 (3)C23—C18—C19—N3177.2 (2)
O1—C3—C4—C5174.5 (2)C24—N3—C19—C20−51.9 (3)
C8—C3—C4—C5−5.6 (3)C17—N3—C19—C20154.7 (2)
O1—C3—C4—N10.1 (3)C24—N3—C19—C18132.7 (2)
C8—C3—C4—N1−180.0 (2)C17—N3—C19—C18−20.7 (3)
C9—N1—C4—C3−134.9 (2)C18—C19—C20—C21−4.1 (4)
C2—N1—C4—C346.1 (3)N3—C19—C20—C21−179.5 (2)
C9—N1—C4—C551.2 (3)C18—C19—C20—Cl3173.25 (18)
C2—N1—C4—C5−127.8 (2)N3—C19—C20—Cl3−2.2 (3)
C3—C4—C5—C66.7 (3)C19—C20—C21—C223.8 (4)
N1—C4—C5—C6−179.6 (2)Cl3—C20—C21—C22−173.7 (2)
C3—C4—C5—Cl1−169.92 (17)C20—C21—C22—C23−0.8 (4)
N1—C4—C5—Cl13.8 (3)C20—C21—C22—Cl4A156 (3)
C4—C5—C6—C7−3.3 (4)C20—C21—C22—Cl4B177.8 (3)
Cl1—C5—C6—C7173.38 (19)C21—C22—C23—C18−1.6 (5)
C5—C6—C7—C8−1.6 (4)Cl4A—C22—C23—C18−160 (3)
C5—C6—C7—Cl2−178.06 (19)Cl4B—C22—C23—C18179.7 (3)
C6—C7—C8—C32.8 (4)O5—C18—C23—C22179.3 (3)
Cl2—C7—C8—C3179.19 (18)C19—C18—C23—C221.2 (4)
O1—C3—C8—C7−179.2 (2)C19—N3—C24—O6−9.3 (3)
C4—C3—C8—C70.9 (4)C17—N3—C24—O6143.2 (2)
C4—N1—C9—O2−165.7 (2)C19—N3—C24—C25168.6 (2)
C2—N1—C9—O213.3 (3)C17—N3—C24—C25−39.0 (3)
C4—N1—C9—C1017.7 (3)O6—C24—C25—C26−48.0 (4)
C2—N1—C9—C10−163.4 (2)N3—C24—C25—C26134.1 (3)
O2—C9—C10—C15−130.6 (3)O6—C24—C25—C30129.3 (3)
N1—C9—C10—C1546.1 (4)N3—C24—C25—C30−48.5 (3)
O2—C9—C10—C1143.3 (4)C30—C25—C26—C27−0.3 (4)
N1—C9—C10—C11−140.1 (3)C24—C25—C26—C27177.1 (3)
C15—C10—C11—C12−0.9 (4)C25—C26—C27—C28−1.0 (5)
C9—C10—C11—C12−175.0 (3)C26—C27—C28—C290.6 (5)
C10—C11—C12—C131.4 (5)C26—C27—C28—N4179.2 (3)
C11—C12—C13—C14−1.1 (5)O8—N4—C28—C27167.9 (3)
C11—C12—C13—N2−179.8 (3)O7—N4—C28—C27−13.4 (5)
O4—N2—C13—C12173.8 (3)O8—N4—C28—C29−13.5 (4)
O3—N2—C13—C12−7.3 (5)O7—N4—C28—C29165.2 (3)
O4—N2—C13—C14−4.9 (5)C27—C28—C29—C301.1 (5)
O3—N2—C13—C14174.0 (3)N4—C28—C29—C30−177.5 (3)
C12—C13—C14—C150.3 (5)C28—C29—C30—C25−2.4 (5)
N2—C13—C14—C15179.0 (3)C26—C25—C30—C292.0 (4)
C11—C10—C15—C140.1 (4)C24—C25—C30—C29−175.3 (3)
C9—C10—C15—C14173.8 (2)O1—C1—C31A—C32A−44.4 (6)
C13—C14—C15—C100.2 (4)C2—C1—C31A—C32A78.1 (6)
C18—O5—C16—C1731.9 (3)S—C1—C31A—C32A−162.5 (5)
C18—O5—C16—C2148.64 (19)C1—C31A—C32A—C33A174.9 (4)
N1—C2—C16—O5152.39 (17)C31A—C32A—C33A—C34A−178.8 (7)
C1—C2—C16—O5−85.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.982.553.491 (3)162
C14—H14···O3ii0.932.413.298 (4)160
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···O2i0.982.553.491 (3)161.5
C14—H14···O3ii0.932.413.298 (4)160.0
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y+1/2, −z+3/2.
Acknowledgements top

The authors thank the National Science Foundation for grant # ILI8951058 for financial assistance.

references
References top

Garbauskas, M. F., Williams, E. A. & Heine, H. W. (1985). Acta Cryst. C41, 1217–1222.

Heine, H. W., Williams, D. K., Rutherford, J. L., Ramphal, J. & Williams, E. A. (1993). Heterocycles, 35, 1125–1140.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.