Diethyl trans-2,5-bis-(4-methoxy-benzyl-sulfan-yl)-1,4-dimethyl-3,6-dioxopiperazine-2,5-carboxyl-ate.

The title compound, C(28)H(34)N(2)O(8)S(2), was synthesized as part of a project to develop synthetic routes to analogues of sporidesmins, a class of secondary metabolite produced by the filamentous fungi Chaetomium and Pithomyces sp. The complete molecule is generated by crystallographic inversion symmetry: the methoxy group is essentially coplanar with the benzene ring to which it is bonded, a mean plane fitted through the non-H atoms of the aromatic ring and the meth-oxy group having an r.m.s. deviation of 0.0140 Å. Similarly, the ester group is also essentially planar (r.m.s. deviation of a plane fitted through all non-H atoms is 0.0101 Å). There is only one independent C-H⋯O inter-action, which links together adjacent mol-ecules into a two-dimensional sheet in the bc plane.

Related literature

For background information on the biological activity of sporidesmins, see: Fujimoto et al. (2004 ▶); Gardiner et al. (2005 ▶); Li et al. (2006 ▶); Saito et al. (1988 ▶); Waksman & Bugie (1944 ▶). For a discussion on the anti-cancer activity of these compounds, see: Brewer et al. (1978 ▶); Hauser et al. (1970 ▶); Kung et al. (2004 ▶); McInnes et al. (1976 ▶); Waksman & Bugie (1944 ▶). For related crystal structures, see: Isaka et al. (2005 ▶), Dubey et al. (2009 ▶); Polaske et al. (2009 ▶). For synthetic details, see: Hino & Sato (1974 ▶); Kawamura et al. (1975 ▶).

Experimental

Crystal data

C28H34N2O8S2

M = 590.69

Monoclinic,

a = 11.290 (2) Å

b = 8.2259 (16) Å

c = 16.593 (3) Å

β = 109.704 (3)°

V = 1450.9 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.24 mm−1

T = 150 K

0.32 × 0.30 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.919, T max = 0.987

11556 measured reflections

3522 independent reflections

2778 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.092

S = 1.03

3522 reflections

184 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.24 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL, publCIF (Westrip, 2009 ▶) and local programs.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022211/fj2226sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022211/fj2226Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C28H34N2O8S2	F(000) = 624
Mr = 590.69	Dx = 1.352 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5275 reflections
a = 11.290 (2) Å	θ = 2.3–28.3°
b = 8.2259 (16) Å	µ = 0.24 mm−1
c = 16.593 (3) Å	T = 150 K
β = 109.704 (3)°	Plate, colourless
V = 1450.9 (5) Å3	0.32 × 0.30 × 0.10 mm
Z = 2

Bruker SMART 1000 CCD diffractometer	3522 independent reflections
Radiation source: sealed tube	2778 reflections with I > 2σ(I)
graphite	Rint = 0.028
Thin–slice ω scans	θmax = 28.3°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
Tmin = 0.919, Tmax = 0.987	k = −10→10
11556 measured reflections	l = −21→22

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: difference Fourier map
wR(F2) = 0.092	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0397P)2 + 0.678P] where P = (Fo2 + 2Fc2)/3
3522 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
S	0.18848 (3)	0.24066 (4)	0.04288 (2)	0.02157 (10)
O1	0.59043 (11)	0.03836 (16)	−0.14348 (8)	0.0357 (3)
O2	−0.08416 (10)	0.32864 (14)	0.13178 (7)	0.0271 (3)
O3	0.07865 (11)	0.15503 (14)	0.16459 (7)	0.0301 (3)
O4	−0.16577 (11)	0.45732 (14)	−0.15608 (7)	0.0283 (3)
N	−0.05515 (11)	0.34842 (14)	−0.02822 (7)	0.0168 (2)
C1	0.32030 (15)	0.27272 (19)	−0.06556 (10)	0.0251 (3)
C2	0.44789 (16)	0.2787 (2)	−0.01800 (11)	0.0336 (4)
H2	0.4754	0.3387	0.0339	0.040*
C3	0.53537 (16)	0.1986 (2)	−0.04519 (12)	0.0363 (4)
H3	0.6222	0.2038	−0.0118	0.044*
C4	0.49678 (14)	0.1106 (2)	−0.12108 (10)	0.0247 (3)
C5	0.37024 (14)	0.1019 (2)	−0.16888 (10)	0.0256 (3)
H5	0.3426	0.0411	−0.2206	0.031*
C6	0.28382 (15)	0.1832 (2)	−0.14039 (11)	0.0283 (4)
H6	0.1970	0.1770	−0.1734	0.034*
C7	0.22463 (17)	0.3623 (2)	−0.03733 (12)	0.0313 (4)
H7A	0.1472	0.3810	−0.0870	0.038*
H7B	0.2587	0.4692	−0.0129	0.038*
C8	0.55425 (18)	−0.0657 (2)	−0.21608 (12)	0.0361 (4)
H8A	0.5000	−0.1524	−0.2077	0.054*
H8B	0.6295	−0.1137	−0.2233	0.054*
H8C	0.5084	−0.0029	−0.2673	0.054*
C9	0.05188 (13)	0.35374 (17)	0.05104 (9)	0.0167 (3)
C10	0.01900 (14)	0.26530 (18)	0.12339 (9)	0.0201 (3)
C11	−0.12546 (17)	0.2576 (2)	0.19906 (11)	0.0353 (4)
H11A	−0.0596	0.2720	0.2557	0.042*
H11B	−0.1417	0.1399	0.1887	0.042*
C12	−0.24275 (16)	0.3430 (2)	0.19672 (11)	0.0304 (4)
H12A	−0.2258	0.4595	0.2063	0.046*
H12B	−0.2721	0.2993	0.2416	0.046*
H12C	−0.3077	0.3263	0.1407	0.046*
C13	−0.10631 (15)	0.18707 (19)	−0.05932 (10)	0.0258 (3)
H13A	−0.1961	0.1967	−0.0923	0.039*
H13B	−0.0950	0.1145	−0.0104	0.039*
H13C	−0.0619	0.1424	−0.0959	0.039*
C14	−0.09368 (13)	0.47399 (17)	−0.08292 (9)	0.0178 (3)

	U11	U22	U33	U12	U13	U23
S	0.02166 (18)	0.01810 (18)	0.02652 (19)	0.00695 (14)	0.01018 (14)	0.00412 (15)
O1	0.0249 (6)	0.0441 (7)	0.0408 (7)	0.0008 (5)	0.0145 (5)	−0.0176 (6)
O2	0.0304 (6)	0.0287 (6)	0.0284 (6)	0.0097 (5)	0.0184 (5)	0.0123 (5)
O3	0.0366 (6)	0.0273 (6)	0.0291 (6)	0.0119 (5)	0.0147 (5)	0.0126 (5)
O4	0.0332 (6)	0.0242 (6)	0.0189 (5)	0.0013 (5)	−0.0027 (5)	−0.0015 (4)
N	0.0183 (6)	0.0145 (6)	0.0161 (6)	0.0000 (4)	0.0037 (5)	−0.0009 (5)
C1	0.0254 (8)	0.0225 (8)	0.0316 (8)	0.0054 (6)	0.0152 (7)	0.0069 (6)
C2	0.0301 (9)	0.0408 (10)	0.0309 (9)	0.0015 (7)	0.0117 (7)	−0.0124 (8)
C3	0.0183 (8)	0.0505 (11)	0.0367 (10)	0.0005 (7)	0.0047 (7)	−0.0152 (8)
C4	0.0211 (7)	0.0271 (8)	0.0283 (8)	0.0015 (6)	0.0116 (6)	−0.0024 (7)
C5	0.0237 (8)	0.0287 (8)	0.0237 (8)	−0.0021 (6)	0.0069 (6)	−0.0034 (6)
C6	0.0178 (7)	0.0342 (9)	0.0311 (8)	0.0026 (6)	0.0059 (6)	0.0052 (7)
C7	0.0341 (9)	0.0250 (8)	0.0439 (10)	0.0109 (7)	0.0252 (8)	0.0104 (7)
C8	0.0418 (10)	0.0350 (10)	0.0387 (10)	−0.0007 (8)	0.0228 (8)	−0.0108 (8)
C9	0.0173 (7)	0.0161 (7)	0.0158 (6)	0.0028 (5)	0.0046 (5)	0.0013 (5)
C10	0.0237 (7)	0.0191 (7)	0.0175 (7)	0.0013 (6)	0.0070 (6)	0.0006 (6)
C11	0.0384 (10)	0.0417 (10)	0.0341 (9)	0.0085 (8)	0.0233 (8)	0.0183 (8)
C12	0.0295 (8)	0.0381 (10)	0.0272 (8)	0.0022 (7)	0.0141 (7)	0.0070 (7)
C13	0.0292 (8)	0.0166 (7)	0.0273 (8)	−0.0032 (6)	0.0038 (7)	−0.0009 (6)
C14	0.0180 (7)	0.0178 (7)	0.0180 (7)	0.0024 (5)	0.0066 (6)	−0.0017 (5)

S—C7	1.8181 (17)	C5—C6	1.391 (2)
S—C9	1.8447 (14)	C6—H6	0.9500
O1—C4	1.3689 (19)	C7—H7A	0.9900
O1—C8	1.421 (2)	C7—H7B	0.9900
O2—C10	1.3255 (18)	C8—H8A	0.9800
O2—C11	1.4682 (19)	C8—H8B	0.9800
O3—C10	1.1972 (18)	C8—H8C	0.9800
O4—C14	1.2201 (17)	C9—C10	1.552 (2)
N—C9	1.4560 (17)	C9—C14i	1.531 (2)
N—C13	1.4698 (19)	C11—H11A	0.9900
N—C14	1.3469 (18)	C11—H11B	0.9900
C1—C2	1.391 (2)	C11—C12	1.488 (2)
C1—C6	1.382 (2)	C12—H12A	0.9800
C1—C7	1.507 (2)	C12—H12B	0.9800
C2—H2	0.9500	C12—H12C	0.9800
C2—C3	1.383 (2)	C13—H13A	0.9800
C3—H3	0.9500	C13—H13B	0.9800
C3—C4	1.389 (2)	C13—H13C	0.9800
C4—C5	1.382 (2)	C14—C9i	1.531 (2)
C5—H5	0.9500
C7—S—C9	100.12 (7)	H8A—C8—H8B	109.5
C4—O1—C8	117.65 (13)	H8A—C8—H8C	109.5
C10—O2—C11	116.04 (12)	H8B—C8—H8C	109.5
C9—N—C13	116.90 (11)	S—C9—N	112.23 (9)
C9—N—C14	124.53 (12)	S—C9—C10	104.14 (9)
C13—N—C14	117.16 (12)	S—C9—C14i	108.92 (9)
C2—C1—C6	117.82 (15)	N—C9—C10	110.02 (11)
C2—C1—C7	121.36 (16)	N—C9—C14i	113.91 (11)
C6—C1—C7	120.82 (15)	C10—C9—C14i	107.03 (11)
C1—C2—H2	119.5	O2—C10—O3	125.65 (14)
C1—C2—C3	121.00 (16)	O2—C10—C9	110.17 (12)
H2—C2—C3	119.5	O3—C10—C9	124.17 (13)
C2—C3—H3	119.9	O2—C11—H11A	110.2
C2—C3—C4	120.24 (15)	O2—C11—H11B	110.2
H3—C3—C4	119.9	O2—C11—C12	107.49 (13)
O1—C4—C3	115.94 (14)	H11A—C11—H11B	108.5
O1—C4—C5	124.42 (14)	H11A—C11—C12	110.2
C3—C4—C5	119.64 (15)	H11B—C11—C12	110.2
C4—C5—H5	120.4	C11—C12—H12A	109.5
C4—C5—C6	119.20 (15)	C11—C12—H12B	109.5
H5—C5—C6	120.4	C11—C12—H12C	109.5
C1—C6—C5	122.08 (14)	H12A—C12—H12B	109.5
C1—C6—H6	119.0	H12A—C12—H12C	109.5
C5—C6—H6	119.0	H12B—C12—H12C	109.5
S—C7—C1	108.65 (11)	N—C13—H13A	109.5
S—C7—H7A	110.0	N—C13—H13B	109.5
S—C7—H7B	110.0	N—C13—H13C	109.5
C1—C7—H7A	110.0	H13A—C13—H13B	109.5
C1—C7—H7B	110.0	H13A—C13—H13C	109.5
H7A—C7—H7B	108.3	H13B—C13—H13C	109.5
O1—C8—H8A	109.5	O4—C14—N	122.68 (13)
O1—C8—H8B	109.5	O4—C14—C9i	118.20 (13)
O1—C8—H8C	109.5	N—C14—C9i	119.02 (12)
C6—C1—C2—C3	0.5 (3)	C14—N—C9—C10	138.48 (13)
C7—C1—C2—C3	−178.77 (17)	C14—N—C9—C14i	18.3 (2)
C1—C2—C3—C4	0.1 (3)	C7—S—C9—N	64.78 (12)
C8—O1—C4—C3	173.97 (17)	C7—S—C9—C10	−176.24 (10)
C8—O1—C4—C5	−6.6 (2)	C7—S—C9—C14i	−62.31 (11)
C2—C3—C4—O1	178.72 (17)	C11—O2—C10—O3	1.3 (2)
C2—C3—C4—C5	−0.7 (3)	C11—O2—C10—C9	−179.23 (13)
O1—C4—C5—C6	−178.71 (16)	S—C9—C10—O2	−175.74 (10)
C3—C4—C5—C6	0.7 (3)	S—C9—C10—O3	3.69 (18)
C2—C1—C6—C5	−0.5 (2)	N—C9—C10—O2	−55.27 (15)
C7—C1—C6—C5	178.73 (15)	N—C9—C10—O3	124.16 (15)
C4—C5—C6—C1	0.0 (3)	C14i—C9—C10—O2	68.99 (14)
C2—C1—C7—S	−81.68 (18)	C14i—C9—C10—O3	−111.58 (16)
C6—C1—C7—S	99.06 (17)	C10—O2—C11—C12	−178.98 (14)
C9—S—C7—C1	−169.77 (12)	C9—N—C14—O4	164.45 (14)
C13—N—C9—S	59.98 (15)	C9—N—C14—C9i	−19.2 (2)
C13—N—C9—C10	−55.48 (16)	C13—N—C14—O4	−1.6 (2)
C13—N—C9—C14i	−175.65 (12)	C13—N—C14—C9i	174.82 (12)
C14—N—C9—S	−106.05 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O4ii	0.95	2.43	3.2647 (19)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O4i	0.95	2.43	3.2647 (19)	147

Symmetry code: (i) .