(4S,5S)-2-(2-Thien-yl)-1,3-dioxolane-4,5-dicarboxamide.

In the title compound, C(9)H(10)N(2)O(4)S, which is an important inter-mediate for the preparation of anti-tumor platinum drugs, the dioxolane ring adopts an envelope conformation with the C atom bonded to the thienyl ring at the flap position. Intra-molecular N-H⋯O and C-H⋯O hydrogen bonds result in the formation of two five-membered rings having envelope conformations. In the crystal structure, inter-molecular N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

Related literature

For general background, see: Kim et al. (1994 ▶); Pandey et al. (1997 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C9H10N2O4S

M = 242.25

Monoclinic,

a = 8.9250 (18) Å

b = 4.796 (1) Å

c = 12.109 (2) Å

β = 90.60 (3)°

V = 518.29 (18) Å3

Z = 2

Mo Kα radiation

μ = 0.31 mm−1

T = 294 K

0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.912, T max = 0.969

2135 measured reflections

2007 independent reflections

1820 reflections with I > 2σ(I)

R int = 0.015

3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.124

S = 1.01

2007 reflections

146 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.34 e Å−3

Absolute structure: Flack (1983 ▶), 876 Friedel pairs

Flack parameter: 0.04 (12)

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008368/hk2628sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008368/hk2628Isup2.hkl

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

C9H10N2O4S	F(000) = 252
Mr = 242.25	Dx = 1.552 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 8.9250 (18) Å	θ = 9–13°
b = 4.796 (1) Å	µ = 0.31 mm−1
c = 12.109 (2) Å	T = 294 K
β = 90.60 (3)°	Block, colorless
V = 518.29 (18) Å3	0.30 × 0.20 × 0.10 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	1820 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.015
graphite	θmax = 26.0°, θmin = 1.7°
ω/2θ scans	h = 0→10
Absorption correction: ψ scan (North et al., 1968)	k = −5→5
Tmin = 0.912, Tmax = 0.969	l = −14→14
2135 measured reflections	3 standard reflections every 120 min
2007 independent reflections	intensity decay: 1%

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.09P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.124	(Δ/σ)max < 0.001
S = 1.01	Δρmax = 0.25 e Å−3
2007 reflections	Δρmin = −0.34 e Å−3
146 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.134 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 876 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.04 (12)

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	0.14355 (10)	0.3977 (2)	0.03359 (7)	0.0579 (3)
O1	0.1962 (2)	0.0273 (4)	0.23675 (15)	0.0388 (5)
O2	0.4057 (2)	0.2850 (4)	0.21945 (16)	0.0409 (5)
O3	0.1404 (2)	0.2632 (5)	0.51056 (16)	0.0475 (6)
O4	0.5298 (2)	−0.1909 (4)	0.3765 (2)	0.0496 (6)
N1	0.0403 (3)	0.4070 (7)	0.3492 (2)	0.0504 (6)
H1A	−0.0214	0.5180	0.3811	0.060*
H1B	0.0405	0.3944	0.2784	0.060*
N2	0.6553 (2)	0.2124 (5)	0.39050 (18)	0.0383 (5)
H2A	0.7383	0.1315	0.4079	0.046*
H2B	0.6516	0.3912	0.3856	0.046*
C1	0.1625 (4)	0.3760 (10)	−0.1056 (3)	0.0639 (10)
H1C	0.1063	0.4803	−0.1558	0.077*
C2	0.2684 (4)	0.1899 (10)	−0.1349 (3)	0.0622 (10)
H2C	0.2952	0.1552	−0.2076	0.075*
C3	0.3340 (4)	0.0537 (9)	−0.0427 (2)	0.0548 (8)
H3A	0.4071	−0.0837	−0.0480	0.066*
C4	0.2777 (3)	0.1472 (6)	0.0543 (2)	0.0397 (7)
C5	0.3239 (3)	0.0656 (6)	0.1672 (2)	0.0381 (6)
H5A	0.3843	−0.1049	0.1653	0.046*
C6	0.3965 (3)	0.2327 (6)	0.3351 (2)	0.0323 (6)
H6A	0.3940	0.4094	0.3757	0.039*
C7	0.2451 (3)	0.0773 (6)	0.3475 (2)	0.0329 (6)
H7A	0.2605	−0.0999	0.3863	0.039*
C8	0.1346 (3)	0.2558 (6)	0.4091 (2)	0.0347 (6)
C9	0.5335 (3)	0.0618 (6)	0.3713 (2)	0.0319 (6)

	U11	U22	U33	U12	U13	U23
S	0.0688 (6)	0.0563 (5)	0.0484 (4)	0.0176 (4)	0.0005 (4)	0.0024 (4)
O1	0.0370 (10)	0.0429 (11)	0.0365 (10)	−0.0130 (8)	0.0048 (8)	−0.0072 (8)
O2	0.0340 (9)	0.0457 (11)	0.0428 (10)	−0.0131 (8)	−0.0024 (7)	0.0140 (9)
O3	0.0439 (11)	0.0656 (15)	0.0331 (10)	−0.0154 (10)	0.0051 (8)	−0.0026 (10)
O4	0.0446 (11)	0.0252 (11)	0.0788 (16)	−0.0001 (8)	−0.0073 (10)	0.0023 (9)
N1	0.0458 (13)	0.0636 (17)	0.0418 (12)	0.0139 (14)	0.0058 (10)	−0.0047 (15)
N2	0.0315 (11)	0.0310 (12)	0.0523 (14)	−0.0012 (9)	−0.0047 (9)	0.0023 (10)
C1	0.082 (2)	0.066 (2)	0.0434 (17)	−0.002 (2)	−0.0114 (16)	0.0095 (18)
C2	0.065 (2)	0.083 (3)	0.0388 (17)	−0.011 (2)	0.0067 (14)	−0.0020 (17)
C3	0.0546 (18)	0.068 (2)	0.0412 (16)	0.0068 (17)	0.0039 (13)	−0.0059 (16)
C4	0.0343 (13)	0.0417 (16)	0.0432 (15)	−0.0043 (11)	0.0030 (11)	0.0010 (13)
C5	0.0369 (13)	0.0371 (15)	0.0405 (14)	−0.0013 (12)	0.0075 (11)	−0.0011 (12)
C6	0.0313 (12)	0.0255 (12)	0.0402 (14)	−0.0037 (10)	0.0006 (10)	0.0013 (10)
C7	0.0343 (13)	0.0280 (13)	0.0364 (13)	−0.0069 (11)	0.0005 (10)	0.0015 (11)
C8	0.0271 (12)	0.0412 (16)	0.0360 (14)	−0.0115 (11)	0.0017 (10)	−0.0035 (11)
C9	0.0314 (12)	0.0339 (15)	0.0304 (12)	0.0005 (10)	0.0005 (10)	−0.0003 (10)

S—C1	1.698 (3)	C1—C2	1.350 (6)
S—C4	1.713 (3)	C1—H1C	0.9300
O1—C5	1.436 (3)	C2—C3	1.415 (5)
O1—C7	1.426 (3)	C2—H2C	0.9300
O2—C5	1.425 (3)	C3—C4	1.359 (4)
O2—C6	1.426 (3)	C3—H3A	0.9300
O3—C8	1.230 (3)	C4—C5	1.477 (4)
O4—C9	1.214 (4)	C5—H5A	0.9800
N1—C8	1.322 (4)	C6—C7	1.552 (3)
N1—H1A	0.8600	C6—C9	1.532 (4)
N1—H1B	0.8600	C6—H6A	0.9800
N2—C9	1.324 (3)	C7—C8	1.509 (4)
N2—H2A	0.8600	C7—H7A	0.9800
N2—H2B	0.8600
C1—S—C4	91.47 (18)	O2—C5—O1	103.9 (2)
C7—O1—C5	107.04 (19)	O2—C5—C4	110.6 (2)
C5—O2—C6	105.76 (18)	O2—C5—H5A	110.3
C8—N1—H1A	120.0	C4—C5—H5A	110.3
C8—N1—H1B	120.0	O2—C6—C7	103.76 (19)
H1A—N1—H1B	120.0	O2—C6—C9	108.7 (2)
C9—N2—H2A	120.0	O2—C6—H6A	110.0
C9—N2—H2B	120.0	C7—C6—H6A	110.0
H2A—N2—H2B	120.0	C9—C6—C7	114.1 (2)
S—C1—H1C	123.9	C9—C6—H6A	110.0
C2—C1—S	112.3 (3)	O1—C7—C6	104.4 (2)
C2—C1—H1C	123.9	O1—C7—C8	111.4 (2)
C1—C2—C3	112.5 (3)	O1—C7—H7A	110.2
C1—C2—H2C	123.7	C6—C7—H7A	110.2
C3—C2—H2C	123.7	C8—C7—C6	110.5 (2)
C2—C3—H3A	124.0	C8—C7—H7A	110.2
C4—C3—C2	112.1 (3)	O3—C8—N1	123.5 (3)
C4—C3—H3A	124.0	O3—C8—C7	119.3 (2)
C3—C4—S	111.7 (2)	N1—C8—C7	117.1 (2)
C3—C4—C5	127.7 (3)	O4—C9—N2	123.9 (3)
C5—C4—S	120.6 (2)	O4—C9—C6	121.8 (2)
O1—C5—C4	111.2 (2)	N2—C9—C6	114.2 (2)
O1—C5—H5A	110.3
C4—S—C1—C2	−1.2 (3)	S—C4—C5—O2	−69.8 (3)
C1—S—C4—C3	0.2 (3)	C3—C4—C5—O1	−137.8 (3)
C1—S—C4—C5	177.7 (2)	C3—C4—C5—O2	107.3 (4)
C7—O1—C5—O2	−34.8 (2)	O2—C6—C7—O1	7.5 (3)
C7—O1—C5—C4	−153.8 (2)	O2—C6—C7—C8	−112.4 (2)
C5—O1—C7—C8	135.7 (2)	C9—C6—C7—O1	−110.7 (2)
C5—O1—C7—C6	16.5 (3)	C9—C6—C7—C8	129.4 (2)
C6—O2—C5—O1	39.8 (2)	O1—C7—C8—O3	162.6 (2)
C6—O2—C5—C4	159.2 (2)	O1—C7—C8—N1	−20.4 (3)
C5—O2—C6—C7	−28.8 (3)	C6—C7—C8—O3	−81.8 (3)
C5—O2—C6—C9	93.0 (2)	C6—C7—C8—N1	95.1 (3)
S—C1—C2—C3	1.7 (5)	O2—C6—C9—O4	−94.2 (3)
C1—C2—C3—C4	−1.6 (5)	O2—C6—C9—N2	82.7 (3)
C2—C3—C4—S	0.7 (4)	C7—C6—C9—O4	21.0 (4)
C2—C3—C4—C5	−176.6 (3)	C7—C6—C9—N2	−162.1 (2)
S—C4—C5—O1	45.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3i	0.86	2.06	2.909 (4)	167
N1—H1B···O1	0.86	2.30	2.673 (4)	106
N2—H2A···O3ii	0.86	2.29	3.059 (3)	149
N2—H2B···O4iii	0.86	2.28	3.077 (3)	154
C6—H6A···O4iii	0.98	2.27	3.049 (3)	136
C7—H7A···O4	0.98	2.45	2.866 (3)	105

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3i	0.86	2.06	2.909 (4)	167
N1—H1B⋯O1	0.86	2.30	2.673 (4)	106
N2—H2A⋯O3ii	0.86	2.29	3.059 (3)	149
N2—H2B⋯O4iii	0.86	2.28	3.077 (3)	154
C6—H6A⋯O4iii	0.98	2.27	3.049 (3)	136
C7—H7A⋯O4	0.98	2.45	2.866 (3)	105

Symmetry codes: (i) ; (ii) ; (iii) .