4-Phenyl­sulfon­yl-2-(p-tolyl­sulfon­yl)-1H,8H-pyrrolo­[2,3-b]indole

Badenock, J.C.; Jordan, J.A.; Pelkey, E.T.; Gribble, G.W.; Jasinski, J.P.

doi:10.1107/S1600536810039425

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 11| November 2010| Pages o2757-o2758

https://doi.org/10.1107/S1600536810039425

Open

access

4-Phenylsulfonyl-2-(p-tolylsulfonyl)-1H,8H-pyrrolo[2,3-b]indole

Jeanese C. Badenock,^a Jason A. Jordan,^a Erin T. Pelkey,^b Gordon W. Gribble ^b and Jerry P. Jasinski ^c ^*

^aDepartment of Biological and Chemical Sciences, University of the West Indies, Cave Hill, Barbados, ^bDepartment of Chemistry, Dartmouth College, Hanover, NH 03755-3564, USA, and ^cDepartment of Chemistry, Keene State College, 229 Main Street, Keene, NH 03435-2001, USA
^*Correspondence e-mail: jjasinski@keene.edu

(Received 15 September 2010; accepted 1 October 2010; online 9 October 2010)

The title compound, C₂₃H₁₈N₂O₄S₂, contains a pyrrolo group fused onto the plane of an indole ring with phenylsulfonyl and p-toluenesulfonyl groups bonded to the indole and pyrrolo rings. The angles between the mean planes of the pyrrolo-indole ring and the phenylsulfonyl and p-toluenesulfonyl rings are 73.7 (6) and 80.6 (0)°, respectively. The dihedral angle between the mean planes of the two benzene rings is 78.7 (4)°. In the crystal, both classical N—H⋯O and non-classical C—H⋯O intermolecular hydrogen-bonding interactions are observed, as well as weak π–π interactions [centroid–centroid distances = 3.6258 (8) and 3.9298 (8) Å], which contribute to the stability of the packing.

Related literature

We have been interested in the synthesis of fused indole heterocycles (Gribble et al., 2005 ) for the construction of more elaborate molecules, such as the potent antibiotics pyrroindomycins A and B (Abbanat et al., 1999 ; Ding et al., 1994 ) Both pyrrolo[2,3-b]indoles and pyrrolo[3,4-b]indoles can be synthesized in one step via the Barton–Zard pyrrole synthesis (Barton & Zard, 1985 ; Barton et al., 1990 ) from 3-nitroindoles, depending on the N-indole protecting group [Pelkey et al., 1996 ; Pelkey & Gribble, 1997 , 1999 , 2006 ). For recent examples of the Barton–Zard pyrrole synthesis, see: Bobal & Lightner (2001 ); Woydziak et al. (2005 ); Larionov & deMeijere (2005 ); Coffin et al. (2006 ); Okujima et al. (2006 ); Ono (2008 ). For related structures, see: Jackson et al. (1975 ); Moody & Ward (1984a ,b ); Yamane et al. (1986 ); Yin et al. (2010 ); Tsuji et al. (2002 ); Somei et al. (1997 ); Kawasaki et al. (2005 ); Jasinski et al. (2010 ). For MOPAC theoretical calculations, see: Schmidt & Polik (2007 ). For standard bond lengths, see: Allen et al. (1987 )

Experimental

Crystal data

C₂₃H₁₈N₂O₄S₂
M_r = 450.51
Triclinic, $[P \overline 1]$
a = 8.1547 (3) Å
b = 11.0471 (5) Å
c = 11.7185 (4) Å
α = 73.834 (4)°
β = 87.131 (3)°
γ = 79.277 (4)°
V = 996.22 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 123 K
0.41 × 0.36 × 0.29 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Ruby (Gemini) detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon,England.]$ ) T_min = 0.981, T_max = 1.000
12580 measured reflections
6592 independent reflections
5331 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.103
S = 1.09
6592 reflections
281 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯O3ⁱ	0.88	2.06	2.9244 (14)	167
C13—H13A⋯O2ⁱⁱ	0.95	2.53	3.2125 (15)	129
C22—H22A⋯O3ⁱ	0.95	2.45	3.3786 (15)	165
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y, z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon,England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon,England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810039425/fl2319sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810039425/fl2319Isup2.hkl

checkCIF report

Comment top

In view of our continued interest in the synthesis of fused indole heterocycles (Gribble et al., 2005) for the construction of more elaborate molecules, such as the potent antibiotics pyrroindomycins A and B (Abbanat et al., 1999; Ding et al., 1994), we have sought to unequivocally confirm the assigned structure of the product formed in the reaction of 3-nitro-1-(phenylsulfonyl)indole with isocyanide. Our previous studies have shown that both pyrrolo[2,3-b]indoles and pyrrolo[3,4-b]indoles can be synthesized in one step via this Barton-Zard pyrrole synthesis (Barton & Zard, 1985; Barton et al., 1990) from 3-nitroindoles depending on the N-indole protecting group (Pelkey et al., 1996; Pelkey & Gribble, 1997, 1999, 2006). Indeed, whereas our proposed fragmentation-rearrangement sequence, to afford the pyrrolo[2,3-b]indole ring system (Pelkey et al., 1996), only occurs with the phenylsulfonyl protecting group, the same reaction with N-benzyl, N-2-pyridyl, and N-ethoxycarbonyl protecting groups generates the corresponding pyrrolo[3,4-b]indole ring system. We differentiated these two isomers both by comparison of the NMR coupling constants and through the independent synthesis of the corresponding pyrrolo[2,3-b]indole. (Moody & Ward, 1984a, 1984b). To confirm this structural assignment we now report the crystal structure of the title compound, the product of the reaction of 3-nitro-1-(phenylsulfonyl)indole with tosylmethyl isocyanide, and the first crystal structure of this fused indole ring system.

The title compound contains a pyrrolo group fused onto the plane of an indole ring with phenylsulfonyl and p-toluenesulfonyl groups bonded to the indol and pyrrolo rings. The angles between the mean planes of the pyrrolo-indole ring and the phenylsulfonyl and p-toluenesulfonyl rings are 73.7 (6)° and 80.6 (0)°, respectively. The dihedral angle between the mean planes of the two benzene rings is 78.7 (4)°. The sum of the angles around the indole N atom is 345.2 (4)° indicating slightly distorted sp² hybridization. The C3═C10 indole bond length is 1.3760 (17)Å similar to that observed in 3-acetyl-2-ethyl-1-(phenylsulfonyl)indole (Jasinski et al., 2010). The remainder of the bonds are in normal ranges (Allen et al., 1987). Both classical (N—H···O) and non-classical (C—H···O) hydrogen bonding interactions are observed (Table 1, Fig. 2) as well as weak π—π interactions [Cg1···Cg3ⁱ = 3.6258 (8) Å; Cg2···Cg3ⁱ = 3.9298 (8) Å; ⁱ = -x,1 - y,1 - z; where Cg1 = N1/C9/C4/C3/C10; Cg2 = N2/C1/C2/C3/C10; Cg3 = C4—C9].

Following geometry optimization MOPAC (Schmidt & Polik, 2007) theoretical calculations at the AM1 level, the angles between the mean planes of the pyrrolo-indole ring and the phenylsulfonyl and p-toluenesulfonyl rings become 73.7 (6)° and 80.6 (0)°, respectively, and the dihedral angle between the mean planes of the two benzene rings becomes 88.6 (2)°. These observations support the influence of the hydrogen bonds and π—π interactions as contributing to the stability of crystal packing.

Related literature top

We have been interested in the synthesis of fused indole heterocycles (Gribble et al., 2005) for the construction of more elaborate molecules, such as the potent antibiotics pyrroindomycins A and B (Abbanat et al., 1999; Ding et al., 1994) Both pyrrolo[2,3-b]indoles and pyrrolo[3,4-b]indoles can be synthesized in one step via th Barton–Zard pyrrole synthesis (Barton & Zard, 1985; Barton et al., 1990) from 3-nitroindoles depending on the N-indole protecting group [Pelkey et al., 1996; Pelkey & Gribble, 1997, 1999, 2006). For recent examples of the Barton–Zard pyrrole synthesis, see: Bobal & Lightner (2001); Woydziak et al. (2005); Larionov & deMeijere (2005); Coffin et al. (2006); Okujima et al. (2006); Ono (2008). For related structures, see: Jackson et al. (1975); Moody & Ward (1984a,b); Yamane et al. (1986); Yin et al. (2010); Tsuji et al. (2002); Somei et al. (1997); Kawasaki et al. (2005); Jasinski et al. (2010). For MOPAC theoretical calculations, see: Schmidt & Polik (2007). For standard bond lengths, see: Allen et al. (1987 987)

Experimental top

This compound was prepared according to the procedure of Pelkey & Gribble (2006). To a stirred solution of 3-nitro-1-(phenylsulfonyl)indole (0.50 g, 1.67 mmol, 1 eq.) in dry THF (30 ml) was added a solution of tosylmethyl isocyanide (0.39 g, 1.99 mmol, 1.20 eq.) dissolved in dry THF (15 ml) followed by the addition of DBU (0.6 ml, 4.01 mmol, 2.4 eq.). The solution was allowed to stir for 24 h at room temperature. Removal of the solvent in vacuo gave an orange oil that was purified via flash column chromatography (3:1 hexanes–ethyl acetate) to afford the pyrroloindole (0.46 g, 62%) as a yellow solid. Crystals suitable for the X-ray study were grown from a 1:1 mixture of CH₂Cl₂ and ether [m.p. 484–487 K; literature value 509–511 K].

Structure description top

We have been interested in the synthesis of fused indole heterocycles (Gribble et al., 2005) for the construction of more elaborate molecules, such as the potent antibiotics pyrroindomycins A and B (Abbanat et al., 1999; Ding et al., 1994) Both pyrrolo[2,3-b]indoles and pyrrolo[3,4-b]indoles can be synthesized in one step via th Barton–Zard pyrrole synthesis (Barton & Zard, 1985; Barton et al., 1990) from 3-nitroindoles depending on the N-indole protecting group [Pelkey et al., 1996; Pelkey & Gribble, 1997, 1999, 2006). For recent examples of the Barton–Zard pyrrole synthesis, see: Bobal & Lightner (2001); Woydziak et al. (2005); Larionov & deMeijere (2005); Coffin et al. (2006); Okujima et al. (2006); Ono (2008). For related structures, see: Jackson et al. (1975); Moody & Ward (1984a,b); Yamane et al. (1986); Yin et al. (2010); Tsuji et al. (2002); Somei et al. (1997); Kawasaki et al. (2005); Jasinski et al. (2010). For MOPAC theoretical calculations, see: Schmidt & Polik (2007). For standard bond lengths, see: Allen et al. (1987 987)

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2007); cell refinement: CrysAlis PRO (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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

	Fig. 1. Molecular structure of the title compound showing the atom labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the title compound viewed down the a axis. Dashed lines indicate classical N—H···O and non-classical C—H···O hydrogen bonds with a bifurcated O3 acceptor atom.

4-Phenylsulfonyl-2-(p-tolylsulfonyl)-1H,8H- pyrrolo[2,3-b]indole top

Crystal data top

C₂₃H₁₈N₂O₄S₂	Z = 2
M_r = 450.51	F(000) = 468
Triclinic, P1	D_x = 1.502 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1547 (3) Å	Cell parameters from 7126 reflections
b = 11.0471 (5) Å	θ = 5.0–32.7°
c = 11.7185 (4) Å	µ = 0.30 mm⁻¹
α = 73.834 (4)°	T = 123 K
β = 87.131 (3)°	Prism, colorless
γ = 79.277 (4)°	0.41 × 0.36 × 0.29 mm
V = 996.22 (7) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer with Ruby (Gemini) detector	6592 independent reflections
Radiation source: Enhance (Cu) X-ray Source	5331 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
Detector resolution: 10.5081 pixels mm^-1	θ_max = 32.8°, θ_min = 5.1°
ω scans	h = −11→11
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −16→16
T_min = 0.981, T_max = 1.000	l = −17→13
12580 measured reflections

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0572P)² + 0.0394P] where P = (F_o² + 2F_c²)/3
6592 reflections	(Δ/σ)_max < 0.001
281 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₂₃H₁₈N₂O₄S₂	γ = 79.277 (4)°
M_r = 450.51	V = 996.22 (7) Å³
Triclinic, P1	Z = 2
a = 8.1547 (3) Å	Mo Kα radiation
b = 11.0471 (5) Å	µ = 0.30 mm⁻¹
c = 11.7185 (4) Å	T = 123 K
α = 73.834 (4)°	0.41 × 0.36 × 0.29 mm
β = 87.131 (3)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with Ruby (Gemini) detector	6592 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	5331 reflections with I > 2σ(I)
T_min = 0.981, T_max = 1.000	R_int = 0.020
12580 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.09	Δρ_max = 0.52 e Å⁻³
6592 reflections	Δρ_min = −0.33 e Å⁻³
281 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
S1	0.24124 (3)	0.40940 (3)	0.21069 (3)	0.01455 (7)
S2	0.53714 (4)	0.07067 (3)	0.67939 (3)	0.01540 (7)
O1	0.28990 (11)	0.27445 (8)	0.22946 (8)	0.01961 (18)
O2	0.10331 (10)	0.48046 (9)	0.13513 (8)	0.01992 (19)
O3	0.61740 (11)	−0.00088 (8)	0.59944 (8)	0.02005 (19)
O4	0.63277 (11)	0.09255 (9)	0.76857 (8)	0.02102 (19)
N1	0.19171 (12)	0.42667 (9)	0.34605 (9)	0.01529 (19)
N2	0.36818 (12)	0.22963 (9)	0.48254 (9)	0.01541 (19)
H2B	0.3722	0.1694	0.4462	0.018*
C1	0.43829 (15)	0.21752 (11)	0.59259 (10)	0.0155 (2)
C2	0.40399 (15)	0.33305 (11)	0.62081 (11)	0.0169 (2)
H2A	0.4367	0.3501	0.6906	0.020*
C3	0.30982 (15)	0.42085 (11)	0.52414 (11)	0.0160 (2)
C4	0.21746 (15)	0.55003 (11)	0.47483 (11)	0.0161 (2)
C5	0.18616 (17)	0.66151 (12)	0.51200 (12)	0.0218 (3)
H5A	0.2306	0.6628	0.5850	0.026*
C6	0.08910 (17)	0.77060 (12)	0.44084 (12)	0.0242 (3)
H6A	0.0680	0.8471	0.4653	0.029*
C7	0.02218 (16)	0.76964 (12)	0.33428 (12)	0.0232 (3)
H7A	−0.0436	0.8457	0.2871	0.028*
C8	0.04966 (15)	0.65990 (12)	0.29554 (12)	0.0200 (2)
H8A	0.0027	0.6588	0.2233	0.024*
C9	0.14851 (14)	0.55177 (11)	0.36653 (11)	0.0159 (2)
C10	0.29295 (14)	0.35350 (11)	0.44405 (10)	0.0146 (2)
C11	0.41636 (14)	0.48258 (11)	0.16669 (10)	0.0142 (2)
C12	0.57366 (15)	0.40983 (12)	0.20143 (11)	0.0186 (2)
H12A	0.5850	0.3233	0.2480	0.022*
C13	0.71326 (15)	0.46588 (13)	0.16684 (12)	0.0214 (3)
H13A	0.8213	0.4177	0.1901	0.026*
C14	0.69552 (16)	0.59186 (13)	0.09850 (11)	0.0210 (3)
H14A	0.7918	0.6295	0.0746	0.025*
C15	0.53830 (17)	0.66374 (13)	0.06448 (12)	0.0214 (3)
H15A	0.5276	0.7502	0.0176	0.026*
C16	0.39661 (15)	0.60964 (12)	0.09882 (11)	0.0184 (2)
H16A	0.2886	0.6584	0.0764	0.022*
C17	0.37346 (15)	−0.00606 (11)	0.75228 (10)	0.0155 (2)
C18	0.34028 (16)	−0.00884 (12)	0.87037 (11)	0.0188 (2)
H18A	0.4056	0.0289	0.9110	0.023*
C19	0.21030 (16)	−0.06741 (12)	0.92891 (11)	0.0197 (2)
H19A	0.1885	−0.0706	1.0100	0.024*
C20	0.11216 (15)	−0.12121 (11)	0.86952 (11)	0.0175 (2)
C21	0.14575 (16)	−0.11501 (12)	0.74970 (11)	0.0188 (2)
H21A	0.0777	−0.1496	0.7080	0.023*
C22	0.27672 (15)	−0.05922 (11)	0.69078 (11)	0.0178 (2)
H22A	0.3001	−0.0573	0.6101	0.021*
C23	−0.02767 (17)	−0.18520 (13)	0.93246 (13)	0.0244 (3)
H23A	−0.0415	−0.1727	1.0122	0.037*
H23B	−0.0010	−0.2771	0.9388	0.037*
H23C	−0.1315	−0.1475	0.8873	0.037*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01309 (13)	0.01663 (14)	0.01399 (14)	−0.00350 (10)	−0.00090 (10)	−0.00358 (10)
S2	0.01639 (14)	0.01312 (13)	0.01499 (14)	−0.00131 (10)	0.00004 (10)	−0.00193 (10)
O1	0.0238 (4)	0.0173 (4)	0.0193 (4)	−0.0061 (3)	−0.0006 (3)	−0.0059 (3)
O2	0.0137 (4)	0.0273 (5)	0.0173 (4)	−0.0036 (3)	−0.0034 (3)	−0.0031 (4)
O3	0.0205 (4)	0.0163 (4)	0.0219 (5)	−0.0005 (3)	0.0043 (3)	−0.0056 (3)
O4	0.0204 (4)	0.0218 (4)	0.0201 (5)	−0.0053 (4)	−0.0037 (3)	−0.0028 (4)
N1	0.0165 (5)	0.0145 (4)	0.0133 (5)	−0.0013 (4)	0.0001 (4)	−0.0022 (4)
N2	0.0189 (5)	0.0120 (4)	0.0147 (5)	−0.0012 (4)	−0.0003 (4)	−0.0036 (4)
C1	0.0183 (5)	0.0139 (5)	0.0127 (5)	−0.0018 (4)	0.0003 (4)	−0.0017 (4)
C2	0.0211 (6)	0.0146 (5)	0.0143 (5)	−0.0028 (4)	0.0004 (4)	−0.0030 (4)
C3	0.0187 (5)	0.0139 (5)	0.0145 (5)	−0.0024 (4)	0.0018 (4)	−0.0033 (4)
C4	0.0167 (5)	0.0141 (5)	0.0156 (5)	−0.0025 (4)	0.0029 (4)	−0.0018 (4)
C5	0.0275 (7)	0.0167 (5)	0.0203 (6)	−0.0016 (5)	0.0019 (5)	−0.0054 (5)
C6	0.0270 (7)	0.0148 (6)	0.0287 (7)	0.0000 (5)	0.0040 (5)	−0.0059 (5)
C7	0.0203 (6)	0.0169 (6)	0.0271 (7)	0.0024 (5)	0.0020 (5)	−0.0014 (5)
C8	0.0175 (6)	0.0186 (6)	0.0201 (6)	0.0007 (5)	−0.0008 (4)	−0.0014 (5)
C9	0.0149 (5)	0.0143 (5)	0.0173 (6)	−0.0019 (4)	0.0040 (4)	−0.0033 (4)
C10	0.0153 (5)	0.0134 (5)	0.0139 (5)	−0.0024 (4)	0.0013 (4)	−0.0020 (4)
C11	0.0120 (5)	0.0178 (5)	0.0134 (5)	−0.0037 (4)	0.0006 (4)	−0.0046 (4)
C12	0.0160 (5)	0.0184 (5)	0.0191 (6)	−0.0007 (4)	−0.0011 (4)	−0.0029 (5)
C13	0.0129 (5)	0.0288 (7)	0.0222 (6)	−0.0022 (5)	−0.0004 (4)	−0.0073 (5)
C14	0.0178 (6)	0.0301 (7)	0.0187 (6)	−0.0112 (5)	0.0043 (4)	−0.0085 (5)
C15	0.0253 (6)	0.0202 (6)	0.0177 (6)	−0.0073 (5)	0.0011 (5)	−0.0019 (5)
C16	0.0177 (5)	0.0188 (5)	0.0165 (6)	−0.0016 (4)	−0.0013 (4)	−0.0019 (4)
C17	0.0171 (5)	0.0114 (5)	0.0153 (5)	−0.0007 (4)	0.0000 (4)	−0.0006 (4)
C18	0.0227 (6)	0.0174 (5)	0.0153 (6)	−0.0035 (5)	−0.0030 (4)	−0.0024 (4)
C19	0.0235 (6)	0.0200 (6)	0.0141 (6)	−0.0035 (5)	0.0010 (4)	−0.0026 (4)
C20	0.0190 (6)	0.0128 (5)	0.0184 (6)	−0.0013 (4)	0.0013 (4)	−0.0018 (4)
C21	0.0226 (6)	0.0151 (5)	0.0197 (6)	−0.0041 (4)	−0.0003 (5)	−0.0057 (4)
C22	0.0224 (6)	0.0148 (5)	0.0153 (6)	−0.0012 (4)	0.0018 (4)	−0.0044 (4)
C23	0.0258 (7)	0.0244 (6)	0.0241 (7)	−0.0098 (5)	0.0058 (5)	−0.0062 (5)

Geometric parameters (Å, º) top

S1—O1	1.4263 (9)	C8—H8A	0.9500
S1—O2	1.4316 (9)	C11—C16	1.3914 (16)
S1—N1	1.6707 (10)	C11—C12	1.3941 (16)
S1—C11	1.7557 (12)	C12—C13	1.3856 (18)
S2—O4	1.4322 (9)	C12—H12A	0.9500
S2—O3	1.4455 (9)	C13—C14	1.3839 (19)
S2—C1	1.7300 (12)	C13—H13A	0.9500
S2—C17	1.7701 (12)	C14—C15	1.3889 (18)
N1—C10	1.4084 (15)	C14—H14A	0.9500
N1—C9	1.4446 (15)	C15—C16	1.3895 (18)
N2—C10	1.3506 (14)	C15—H15A	0.9500
N2—C1	1.3990 (15)	C16—H16A	0.9500
N2—H2B	0.8800	C17—C18	1.3896 (17)
C1—C2	1.3818 (17)	C17—C22	1.3970 (17)
C2—C3	1.4184 (17)	C18—C19	1.3958 (17)
C2—H2A	0.9500	C18—H18A	0.9500
C3—C10	1.3760 (17)	C19—C20	1.3932 (18)
C3—C4	1.4567 (16)	C19—H19A	0.9500
C4—C5	1.3937 (18)	C20—C21	1.4022 (17)
C4—C9	1.4075 (17)	C20—C23	1.5065 (17)
C5—C6	1.3877 (18)	C21—C22	1.3897 (17)
C5—H5A	0.9500	C21—H21A	0.9500
C6—C7	1.391 (2)	C22—H22A	0.9500
C6—H6A	0.9500	C23—H23A	0.9800
C7—C8	1.3861 (19)	C23—H23B	0.9800
C7—H7A	0.9500	C23—H23C	0.9800
C8—C9	1.3871 (16)

O1—S1—O2	121.13 (6)	N2—C10—C3	111.89 (11)
O1—S1—N1	104.32 (5)	N2—C10—N1	134.91 (11)
O2—S1—N1	106.30 (5)	C3—C10—N1	112.99 (10)
O1—S1—C11	109.10 (5)	C16—C11—C12	121.61 (11)
O2—S1—C11	109.09 (5)	C16—C11—S1	120.24 (9)
N1—S1—C11	105.77 (5)	C12—C11—S1	118.15 (9)
O4—S2—O3	120.17 (6)	C13—C12—C11	118.89 (11)
O4—S2—C1	108.32 (6)	C13—C12—H12A	120.6
O3—S2—C1	107.11 (6)	C11—C12—H12A	120.6
O4—S2—C17	107.49 (6)	C14—C13—C12	120.11 (12)
O3—S2—C17	107.91 (6)	C14—C13—H13A	119.9
C1—S2—C17	104.84 (6)	C12—C13—H13A	119.9
C10—N1—C9	103.92 (10)	C13—C14—C15	120.63 (12)
C10—N1—S1	119.83 (8)	C13—C14—H14A	119.7
C9—N1—S1	121.49 (8)	C15—C14—H14A	119.7
C10—N2—C1	105.31 (10)	C14—C15—C16	120.20 (12)
C10—N2—H2B	127.3	C14—C15—H15A	119.9
C1—N2—H2B	127.3	C16—C15—H15A	119.9
C2—C1—N2	110.47 (10)	C15—C16—C11	118.56 (11)
C2—C1—S2	128.02 (10)	C15—C16—H16A	120.7
N2—C1—S2	121.31 (9)	C11—C16—H16A	120.7
C1—C2—C3	105.85 (11)	C18—C17—C22	120.89 (11)
C1—C2—H2A	127.1	C18—C17—S2	118.71 (10)
C3—C2—H2A	127.1	C22—C17—S2	120.37 (9)
C10—C3—C2	106.48 (10)	C17—C18—C19	119.56 (12)
C10—C3—C4	106.28 (10)	C17—C18—H18A	120.2
C2—C3—C4	147.16 (12)	C19—C18—H18A	120.2
C5—C4—C9	118.78 (11)	C20—C19—C18	120.61 (12)
C5—C4—C3	134.52 (12)	C20—C19—H19A	119.7
C9—C4—C3	106.70 (10)	C18—C19—H19A	119.7
C6—C5—C4	119.01 (13)	C19—C20—C21	118.85 (11)
C6—C5—H5A	120.5	C19—C20—C23	120.83 (11)
C4—C5—H5A	120.5	C21—C20—C23	120.31 (12)
C5—C6—C7	121.04 (12)	C22—C21—C20	121.23 (12)
C5—C6—H6A	119.5	C22—C21—H21A	119.4
C7—C6—H6A	119.5	C20—C21—H21A	119.4
C8—C7—C6	121.29 (12)	C21—C22—C17	118.83 (11)
C8—C7—H7A	119.4	C21—C22—H22A	120.6
C6—C7—H7A	119.4	C17—C22—H22A	120.6
C7—C8—C9	117.26 (12)	C20—C23—H23A	109.5
C7—C8—H8A	121.4	C20—C23—H23B	109.5
C9—C8—H8A	121.4	H23A—C23—H23B	109.5
C8—C9—C4	122.62 (11)	C20—C23—H23C	109.5
C8—C9—N1	127.30 (11)	H23A—C23—H23C	109.5
C4—C9—N1	110.05 (10)	H23B—C23—H23C	109.5

O1—S1—N1—C10	42.28 (10)	C2—C3—C10—N2	0.36 (14)
O2—S1—N1—C10	171.37 (9)	C4—C3—C10—N2	−177.43 (10)
C11—S1—N1—C10	−72.74 (10)	C2—C3—C10—N1	175.95 (10)
O1—S1—N1—C9	174.84 (9)	C4—C3—C10—N1	−1.84 (13)
O2—S1—N1—C9	−56.07 (10)	C9—N1—C10—N2	176.61 (13)
C11—S1—N1—C9	59.82 (10)	S1—N1—C10—N2	−43.72 (18)
C10—N2—C1—C2	0.64 (13)	C9—N1—C10—C3	2.39 (13)
C10—N2—C1—S2	175.91 (9)	S1—N1—C10—C3	142.06 (9)
O4—S2—C1—C2	−20.80 (13)	O1—S1—C11—C16	154.12 (10)
O3—S2—C1—C2	−151.78 (11)	O2—S1—C11—C16	19.79 (12)
C17—S2—C1—C2	93.73 (12)	N1—S1—C11—C16	−94.18 (11)
O4—S2—C1—N2	164.83 (9)	O1—S1—C11—C12	−25.73 (11)
O3—S2—C1—N2	33.85 (11)	O2—S1—C11—C12	−160.07 (10)
C17—S2—C1—N2	−80.63 (10)	N1—S1—C11—C12	85.96 (11)
N2—C1—C2—C3	−0.43 (14)	C16—C11—C12—C13	−0.25 (19)
S2—C1—C2—C3	−175.30 (9)	S1—C11—C12—C13	179.61 (10)
C1—C2—C3—C10	0.05 (13)	C11—C12—C13—C14	−0.3 (2)
C1—C2—C3—C4	176.14 (18)	C12—C13—C14—C15	0.4 (2)
C10—C3—C4—C5	179.76 (14)	C13—C14—C15—C16	0.0 (2)
C2—C3—C4—C5	3.7 (3)	C14—C15—C16—C11	−0.49 (19)
C10—C3—C4—C9	0.47 (13)	C12—C11—C16—C15	0.64 (19)
C2—C3—C4—C9	−175.62 (18)	S1—C11—C16—C15	−179.22 (10)
C9—C4—C5—C6	−0.39 (18)	O4—S2—C17—C18	12.96 (11)
C3—C4—C5—C6	−179.62 (13)	O3—S2—C17—C18	143.93 (9)
C4—C5—C6—C7	0.5 (2)	C1—S2—C17—C18	−102.15 (10)
C5—C6—C7—C8	0.1 (2)	O4—S2—C17—C22	−168.94 (9)
C6—C7—C8—C9	−0.90 (19)	O3—S2—C17—C22	−37.97 (11)
C7—C8—C9—C4	1.05 (18)	C1—S2—C17—C22	75.95 (11)
C7—C8—C9—N1	178.71 (12)	C22—C17—C18—C19	1.07 (17)
C5—C4—C9—C8	−0.41 (18)	S2—C17—C18—C19	179.16 (9)
C3—C4—C9—C8	179.01 (11)	C17—C18—C19—C20	−1.00 (18)
C5—C4—C9—N1	−178.44 (11)	C18—C19—C20—C21	−0.28 (18)
C3—C4—C9—N1	0.99 (13)	C18—C19—C20—C23	179.65 (11)
C10—N1—C9—C8	−179.91 (11)	C19—C20—C21—C22	1.53 (18)
S1—N1—C9—C8	41.26 (16)	C23—C20—C21—C22	−178.40 (11)
C10—N1—C9—C4	−2.01 (12)	C20—C21—C22—C17	−1.47 (18)
S1—N1—C9—C4	−140.84 (9)	C18—C17—C22—C21	0.15 (17)
C1—N2—C10—C3	−0.61 (13)	S2—C17—C22—C21	−177.91 (9)
C1—N2—C10—N1	−174.88 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3ⁱ	0.88	2.06	2.9244 (14)	167
C13—H13A···O2ⁱⁱ	0.95	2.53	3.2125 (15)	129
C22—H22A···O3ⁱ	0.95	2.45	3.3786 (15)	165

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

Experimental details

Crystal data
Chemical formula	C₂₃H₁₈N₂O₄S₂
M_r	450.51
Crystal system, space group	Triclinic, P1
Temperature (K)	123
a, b, c (Å)	8.1547 (3), 11.0471 (5), 11.7185 (4)
α, β, γ (°)	73.834 (4), 87.131 (3), 79.277 (4)
V (Å³)	996.22 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.41 × 0.36 × 0.29

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with Ruby (Gemini) detector
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.981, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	12580, 6592, 5331
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.762

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.103, 1.09
No. of reflections	6592
No. of parameters	281
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.33

Computer programs: CrysAlis PRO (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3ⁱ	0.88	2.06	2.9244 (14)	166.7
C13—H13A···O2ⁱⁱ	0.95	2.53	3.2125 (15)	129.3
C22—H22A···O3ⁱ	0.95	2.45	3.3786 (15)	165.0

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

Acknowledgements

JCB wishes to thank the UWI and the Government of Barbados for funding this research. JPJ thanks Dr Ray Butcher and Howard University for assistance with the data collection and acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase the X-ray diffractometer.

References

Abbanat, D., Maiese, W. & Greenstein, M. (1999). J. Antibiot. 52, 117–126. Web of Science CrossRef PubMed CAS Google Scholar
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CSD CrossRef Web of Science Google Scholar
Barton, D. H. R., Kervagoret, J. & Zard, S. Z. (1990). Tetrahedron, 46, 7587–7598. CAS Google Scholar
Barton, D. H. R. & Zard, S. Z. (1985). J. Chem. Soc. Chem. Commun. pp. 1098–1100. CrossRef Web of Science Google Scholar
Bobal, P. & Lightner, D. A. (2001). J. Heterocycl. Chem. 38, 527–530. CrossRef CAS Google Scholar
Coffin, A. R., Roussell, M. A., Tserlin, E. & Pelkey, E. T. (2006). J. Org. Chem. 71, 6678–6681. Web of Science CrossRef PubMed CAS Google Scholar
Ding, W., Williams, D. R., Northcote, P., Siegel, M. M., Tsao, R., Ashcroft, J., Morton, G. O., Alluri, M. & Abranat, D. (1994). J. Antibiot. 47, 1250–1257. CrossRef CAS PubMed Web of Science Google Scholar
Gribble, G. W., Saulnier, M. G., Pelkey, E. T., Kishbaugh, T. L. S., Liu, Y. B., Jiang, J., Trujillo, H. A., Keavy, D. J., Davis, D. A., Conway, S. C., Switzer, F. L., Roy, S., Silva, R. A., Obaza-Nutaitis, J. A., Sibi, M. P., Moskalev, N. V., Barden, T. C., Chang, L., Habeski, W. M., Pelcman, B., Sponholtz, W. R., Chau, R. W., Allison, B. D., Garaas, S. D., Sinha, M. S., McGowan, M. A., Reese, M. R. & Harpp, K. S. (2005). Curr. Org. Chem. 9, 1493–1519. Web of Science CrossRef CAS Google Scholar
Jackson, A. H., Johnston, D. N. & Shannon, P. V. R. (1975). J. Chem. Soc. Chem. Commun. pp. 911–912. CrossRef CAS Web of Science Google Scholar
Jasinski, J. P., Rinderspacher, A. & Gribble, G. W. (2010). J. Chem. Crystallogr. 40, 40–47. Web of Science CSD CrossRef CAS Google Scholar
Kawasaki, T., Ogawa, A., Terashima, R., Saheki, T., Ban, N., Sekiguchi, H., Sakaguchi, K. & Sakamoto, M. (2005). J. Org. Chem. 70, 2957–2966. Web of Science CrossRef PubMed CAS Google Scholar
Larionov, O. V. & deMeijere, A. (2005). Angew. Chem. Int. Ed. 44, 5664–5667. Web of Science CrossRef CAS Google Scholar
Moody, C. J. & Ward, J. G. (1984a). J. Chem. Soc, Perkin Trans. 1, pp. 2903–2909. Google Scholar
Moody, C. J. & Ward, J. G. (1984b). J. Chem. Soc. Chem. Commun. pp. 646–647. CrossRef Web of Science Google Scholar
Okujima, T., Jin, G., Hashimoto, Y., Yamada, H., Uno, H. & Ono, N. (2006). Heterocycles, 70, 619–626. CAS Google Scholar
Ono, N. (2008). Heterocycles, 75, 243–284. CrossRef CAS Google Scholar
Oxford Diffraction (2007). CrysAlis PRO and CrysAlis RED. Oxford Diffraction Ltd, Abingdon,England. Google Scholar
Pelkey, E. T., Chang, L. & Gribble, G. W. (1996). Chem. Commun. pp. 1909–1910. CrossRef Web of Science Google Scholar
Pelkey, E. T. & Gribble, G. W. (1997). Chem. Commun. pp. 1873–1874. CrossRef Google Scholar
Pelkey, E. T. & Gribble, G. W. (1999). Synthesis, pp.1117–1122. Google Scholar
Pelkey, E. T. & Gribble, G. W. (2006). Can. J. Chem. 84, 1338–1342. Web of Science CrossRef CAS Google Scholar
Schmidt, J. R. & Polik, W. F. (2007). WebMO Pro. WebMO, LLC, Holland, MI, USA, available from http://www.webmo.net. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Somei, M., Yamada, F., Izumi, T. & Nakajou, M. (1997). Heterocycles, 45, 2327–2330. CrossRef CAS Google Scholar
Tsuji, R., Nakagawa, M. & Nishida, A. (2002). Heterocycles, 58, 587–593. CAS Google Scholar
Woydziak, Z. R., Boiadjiev, S. E., Norona, W. S., McDonagh, A. F. & Lightner, D. A. (2005). J. Org. Chem. 70, 8417–8423. Web of Science CrossRef PubMed CAS Google Scholar
Yamane, K., Yamamoto, H., Satoh, A., Tamura, Y. & Nozoe, T. (1986). Bull. Chem. Soc. Jpn, 59, 3326–3328. CrossRef CAS Web of Science Google Scholar
Yin, W.-B., Yu, X., Xie, X.-L. & Li, S.-M. (2010). Org. Biomol. Chem. 8, 2430–2438. Web of Science CrossRef CAS PubMed Google Scholar