N-[2-(Amino­sulfon­yl)-5,6-dihydro-6-methyl-7,7-dioxo-4H-thieno[2,3-b]thio­pyran-4-yl]acetamide

The title compound, C₁₀H₁₄N₂O₅S₃, has been synthesized as a key inter­mediate in the synthesis of topically active carbonic anhydrase inhibitor MK-0507. N—H...O hydrogen bonds are responsible for the formation of centrosymmetric dimers and zigzag mol­ecular chains. The inter­molecular non-bonded S...O separation in the crystal structure is 3.415 (2) Å, indicating a strong inter­molecular inter­action between the amino­sulfonyl and S-dioxide groups.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.039
• wR factor = 0.113
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT322_ALERT_2_C Check Hybridisation of  S3     in Main Residue .          ?
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety         C1
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4A    ..  O2      ..       2.66 Ang.

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

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

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

N-[2-(Aminosulfonyl)-5,6-dihydro-6-methyl-7,7-dioxo-4H-thieno[2,3-b]thiopyran- 4-yl]acetamide

Crystal data

C10H14N2O5S3	Dx = 1.537 Mg m^−3
Mr = 338.41	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 1543 reflections
a = 9.842 (3) Å	θ = 2.7–21.2°
b = 15.290 (5) Å	µ = 0.53 mm^−1
c = 19.434 (6) Å	T = 273 K
V = 2924.5 (15) Å^3	Prism, yellow
Z = 8	0.20 × 0.10 × 0.10 mm
F(000) = 1408

Data collection

Bruker SMART CCD area-detector diffractometer	2865 independent reflections
Radiation source: fine-focus sealed tube	1657 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.902, Tmax = 0.949	k = −18→18
13578 measured reflections	l = −21→23

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.114	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0614P)^2] where P = (Fo^2 + 2Fc^2)/3
2865 reflections	(Δ/σ)max < 0.001
189 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.69903 (7)	1.15481 (6)	0.44816 (4)	0.0557 (3)
S2	0.79478 (7)	0.85375 (5)	0.62454 (4)	0.0505 (2)
S3	0.80151 (7)	0.98826 (6)	0.51162 (4)	0.0592 (3)
O1	0.38603 (18)	1.05191 (13)	0.77603 (10)	0.0547 (6)
O2	0.94068 (19)	0.85823 (15)	0.62653 (11)	0.0696 (7)
O3	0.7354 (2)	0.78026 (14)	0.58968 (11)	0.0726 (7)
O4	0.7151 (2)	1.10588 (18)	0.38596 (10)	0.0780 (8)
O5	0.5834 (2)	1.20888 (17)	0.45935 (12)	0.0835 (8)
N1	0.5962 (2)	1.04367 (14)	0.73323 (10)	0.0379 (6)
H1D	0.6771	1.0648	0.7342	0.046*
N2	0.8316 (3)	1.2135 (2)	0.45555 (16)	0.0568 (8)
C1	0.5621 (3)	1.1138 (2)	0.84373 (14)	0.0577 (8)
H1A	0.4893	1.1272	0.8749	0.087*
H1B	0.6057	1.1670	0.8295	0.087*
H1C	0.6271	1.0768	0.8664	0.087*
C2	0.5067 (3)	1.06762 (17)	0.78214 (12)	0.0371 (6)
C3	0.5591 (2)	0.98322 (18)	0.67911 (12)	0.0370 (7)
H3A	0.4623	0.9916	0.6694	0.044*
C4	0.5782 (3)	0.88916 (19)	0.70225 (14)	0.0450 (7)
H4A	0.5349	0.8818	0.7467	0.054*
H4B	0.5321	0.8510	0.6699	0.054*
C5	0.7253 (3)	0.86017 (18)	0.70804 (13)	0.0431 (7)
H5A	0.7758	0.9040	0.7345	0.052*
C6	0.7424 (3)	0.77119 (19)	0.74257 (19)	0.0631 (9)
H6A	0.7057	0.7735	0.7883	0.095*
H6B	0.8371	0.7566	0.7447	0.095*
H6C	0.6950	0.7275	0.7164	0.095*
C7	0.7348 (3)	0.95092 (19)	0.58759 (13)	0.0428 (7)
C8	0.6361 (2)	1.00300 (18)	0.61395 (13)	0.0378 (7)
C9	0.6145 (2)	1.07701 (19)	0.57109 (13)	0.0429 (7)
H9A	0.5515	1.1207	0.5807	0.051*
C10	0.6953 (2)	1.0770 (2)	0.51497 (13)	0.0462 (7)
H2A	0.902 (3)	1.187 (2)	0.4409 (15)	0.062 (11)*
H2B	0.835 (3)	1.245 (2)	0.4893 (18)	0.072 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0437 (4)	0.0873 (7)	0.0360 (4)	−0.0057 (4)	−0.0037 (3)	0.0124 (4)
S2	0.0503 (4)	0.0584 (6)	0.0427 (5)	0.0166 (4)	−0.0052 (3)	−0.0120 (4)
S3	0.0535 (5)	0.0876 (7)	0.0365 (4)	0.0149 (4)	0.0103 (3)	−0.0014 (4)
O1	0.0321 (11)	0.0668 (14)	0.0654 (14)	−0.0013 (10)	0.0123 (9)	−0.0105 (11)
O2	0.0452 (12)	0.0978 (19)	0.0658 (15)	0.0286 (12)	0.0005 (10)	−0.0062 (13)
O3	0.1000 (17)	0.0563 (16)	0.0615 (15)	0.0161 (13)	−0.0225 (12)	−0.0267 (12)
O4	0.0881 (17)	0.116 (2)	0.0298 (12)	−0.0377 (15)	−0.0074 (10)	−0.0014 (12)
O5	0.0476 (13)	0.122 (2)	0.0806 (17)	0.0217 (13)	0.0058 (11)	0.0463 (16)
N1	0.0270 (11)	0.0477 (14)	0.0390 (13)	−0.0061 (10)	0.0028 (9)	−0.0055 (11)
N2	0.0501 (18)	0.073 (2)	0.0471 (17)	−0.0069 (15)	0.0096 (14)	−0.0081 (16)
C1	0.069 (2)	0.062 (2)	0.0423 (18)	−0.0053 (16)	0.0021 (15)	−0.0044 (16)
C2	0.0381 (15)	0.0359 (17)	0.0372 (15)	0.0015 (12)	0.0048 (13)	0.0049 (13)
C3	0.0289 (13)	0.0472 (19)	0.0350 (15)	−0.0018 (12)	0.0000 (11)	−0.0063 (13)
C4	0.0445 (16)	0.0455 (19)	0.0450 (18)	−0.0066 (14)	−0.0018 (12)	−0.0039 (14)
C5	0.0481 (17)	0.0428 (18)	0.0382 (16)	−0.0032 (13)	−0.0075 (12)	−0.0051 (13)
C6	0.079 (2)	0.046 (2)	0.064 (2)	0.0017 (17)	−0.0144 (17)	−0.0004 (17)
C7	0.0379 (15)	0.057 (2)	0.0337 (16)	0.0081 (13)	−0.0004 (12)	−0.0063 (14)
C8	0.0325 (14)	0.0475 (18)	0.0334 (15)	0.0008 (13)	−0.0017 (11)	−0.0050 (13)
C9	0.0380 (15)	0.0526 (19)	0.0381 (16)	0.0025 (13)	0.0004 (12)	0.0028 (14)
C10	0.0379 (14)	0.069 (2)	0.0316 (15)	0.0012 (14)	−0.0035 (12)	−0.0001 (15)

Geometric parameters (Å, º)

S1—O5	1.423 (2)	C1—H1B	0.9600
S1—O4	1.430 (2)	C1—H1C	0.9600
S1—N2	1.590 (3)	C3—C8	1.507 (3)
S1—C10	1.761 (3)	C3—C4	1.519 (4)
S2—O3	1.436 (2)	C3—H3A	0.9800
S2—O2	1.438 (2)	C4—C5	1.518 (4)
S2—C7	1.753 (3)	C4—H4A	0.9700
S2—C5	1.764 (3)	C4—H4B	0.9700
S3—C7	1.714 (3)	C5—C6	1.526 (4)
S3—C10	1.714 (3)	C5—H5A	0.9800
O1—C2	1.218 (3)	C6—H6A	0.9600
N1—C2	1.346 (3)	C6—H6B	0.9600
N1—C3	1.447 (3)	C6—H6C	0.9600
N1—H1D	0.8600	C7—C8	1.357 (4)
N2—H2A	0.85 (3)	C8—C9	1.421 (4)
N2—H2B	0.81 (4)	C9—C10	1.350 (3)
C1—C2	1.493 (4)	C9—H9A	0.9300
C1—H1A	0.9600
O5—S1—O4	121.41 (14)	C8—C3—H3A	107.5
O5—S1—N2	108.30 (18)	C4—C3—H3A	107.5
O4—S1—N2	106.35 (16)	C5—C4—C3	114.6 (2)
O5—S1—C10	105.24 (13)	C5—C4—H4A	108.6
O4—S1—C10	105.80 (15)	C3—C4—H4A	108.6
N2—S1—C10	109.37 (14)	C5—C4—H4B	108.6
O3—S2—O2	117.13 (13)	C3—C4—H4B	108.6
O3—S2—C7	109.46 (13)	H4A—C4—H4B	107.6
O2—S2—C7	107.87 (14)	C4—C5—C6	113.4 (2)
O3—S2—C5	108.66 (15)	C4—C5—S2	108.53 (19)
O2—S2—C5	111.08 (13)	C6—C5—S2	108.2 (2)
C7—S2—C5	101.49 (13)	C4—C5—H5A	108.9
C7—S3—C10	89.86 (13)	C6—C5—H5A	108.9
C2—N1—C3	121.5 (2)	S2—C5—H5A	108.9
C2—N1—H1D	119.3	C5—C6—H6A	109.5
C3—N1—H1D	119.3	C5—C6—H6B	109.5
S1—N2—H2A	112 (2)	H6A—C6—H6B	109.5
S1—N2—H2B	116 (2)	C5—C6—H6C	109.5
H2A—N2—H2B	121 (3)	H6A—C6—H6C	109.5
C2—C1—H1A	109.5	H6B—C6—H6C	109.5
C2—C1—H1B	109.5	C8—C7—S3	113.8 (2)
H1A—C1—H1B	109.5	C8—C7—S2	125.7 (2)
C2—C1—H1C	109.5	S3—C7—S2	120.43 (15)
H1A—C1—H1C	109.5	C7—C8—C9	110.7 (2)
H1B—C1—H1C	109.5	C7—C8—C3	124.0 (3)
O1—C2—N1	121.0 (2)	C9—C8—C3	125.3 (2)
O1—C2—C1	121.9 (2)	C10—C9—C8	112.7 (3)
N1—C2—C1	117.1 (2)	C10—C9—H9A	123.7
N1—C3—C8	110.8 (2)	C8—C9—H9A	123.7
N1—C3—C4	111.0 (2)	C9—C10—S3	112.9 (2)
C8—C3—C4	112.1 (2)	C9—C10—S1	127.5 (2)
N1—C3—H3A	107.5	S3—C10—S1	119.60 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···O3^i	0.81 (4)	2.14 (4)	2.876 (4)	150 (3)
N2—H2A···O2^ii	0.85 (3)	2.14 (3)	2.962 (4)	161 (3)
N1—H1D···O1^iii	0.86	2.07	2.861 (3)	152
C5—H5A···O1^iii	0.98	2.52	3.346 (3)	142
C4—H4A···O2^iv	0.97	2.66	3.623 (4)	174
C3—H3A···O4^v	0.98	2.53	3.276 (3)	132

Symmetry codes: (i) −x+3/2, y+1/2, z; (ii) −x+2, −y+2, −z+1; (iii) x+1/2, y, −z+3/2; (iv) x−1/2, y, −z+3/2; (v) −x+1, −y+2, −z+1.