N-Cinnamo­ylsaccharin

The title compound [systematic name: 2-cinnamoyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide], C₁₆H₁₁NO₄S, contains both saccharin and cinnamo­yl groups. The mol­ecule is approximately planar in the solid state, and adjacent mol­ecules are connected by C-H...O and C-H...[pi](phen­yl) inter­actions. In the C-H...[pi] inter­action, the C...CgA distance is 3.916 (4) Å (CgA is the non-fused benzene ring centroid) and the C-H...[pi] angle is 156 (2)°. A feature of the mol­ecular geometry is the narrow C-S-N angle of 92.51 (9)° in the five-membered ring. This angle relieves strain from the ring and makes it possible for the whole saccharin group to become quite planar.

S1. Comment

Derivatives of saccharin are known for their biological activity (Strupczewski et al., 1995). The saccharyl system has also been used as a cheap and effective leaving group in important chemical transformations, such as the derivatization of phenols prior to their conversion into arenes by transfer hydrogenolysis (Brigas & Johnstone, 1990). Cinnamic acid derivatives show antibacterial, antifungal (Takeichi, 1962) and antioxidant activities (Natella et al., 1999). Cinnamic acids with substitutions on the phenyl ring showing antibacterial and antimicrobial activities have also been reported (Ramanan & Rao, 1987). Taking into account these important features of the saccharin and cinnamoyl groups, we have undertaken the X-ray diffraction study of the title compound, (I), in order to understand the molecular features which stabilize its observed conformation.

A view of (I) with the atom-labelling scheme is shown in Fig. 1. The saccharin group (C10/C11–C16/N1/S1/O4) is planar to within 0.0526 (2) Å, and the two sulfone O atoms (O2 and O3) lie approximately 1.23 Å above and below this plane. The crystal structure of (I) can be described as being built from essentially planar fragments, viz. a three-atom bridge (C7/C8/C9) linking the aromatic ring (C1–C6) with the saccharin group. The dihedral angle between the saccharin group and the aromatic ring (C1–C6) is 13.3 (2)°. Two intramolecular C—H···O hydrogen-bond-like contacts (Fig. 1 and Table 2) may contribute to the stability of this conformation. The small C12—S1—N1 angle of 92.51 (9)° in the five-membered ring, similar to the value of 92.7 (1)° found in saccharin itself (Bart, 1968), results from a compromise with ring strain, and makes it possible for the whole saccharin group to become quite planar.

There are two intermolecular C—H···O contacts in the structure of (I) (Table 2). The supramolecular aggregation is determined by two almost equal C—H···O hydrogen bonds. In these two interactions, aromatic atom C16 in the molecule at (x, y, z) acts as a hydrogen-bond donor to carbonyl atom O1 in the molecule at (x + 1/2, y − 1/2, z) and aromatic atom C15 in the molecule at (x, y, z) acts as a hydrogen-bond donor to sulfoxide atom O2 in the molecule at (x + 1/2, y − 1/2, z). Because of these interactions, molecules of (I) are arranged so that C—H···O hydrogen bonds form an S(5)S(6)[R₂²(9)]S(5)S(6) motif (Bernstein et al., 1995) (Fig 2).

In the extended structure of (I), there is a weak C—H···π intermolecular interaction involving C14—H14 with the centroid [CgA] of ring A (C1–C6) of the molecule at (x,-y,1/2 + z); see Table 2 for details. This varied set of hydrogen-bonding and π···ring interactions contributes to the stabilization of the crystal structure (Fig. 3).

S2. Experimental

A mixture of sodium saccharine (0.1 mol) and cinnamoyl chloride (0.1 mol) in tetrahydrofuran (100 ml) was stirred under reflux for 5 h. The precipitate of NaCl was filtered off. After filtration and evaporation of the solvent, the residual solid was recrystallized from tetrahydrofuran as colourless crystals of (I) (m.p. 497–501 K, 65% yield).

S3. Refinement

All H atoms were located in a difference Fourier map and their positional and isotropic displacement parameters were refined. The C—H bond lengths are in the range 0.91 (3)–1.00 (3) Å and the U_iso(H) values lie in the range 0.049 (6)–0.085 (9) Ų.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1994); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme and with displacement ellipsoids at the 50% probability level.
	Fig. 2. A view of the centrosymmetric dimer of (I).
	Fig. 3. A stereoview of part of the crystal structure of (I).

2-cinnamoyl-1,2-benzisothiazol-3(2H)-one 1,1-dioxide

Crystal data

C16H11NO4S	F(000) = 1296
Mr = 313.32	Dx = 1.425 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2yc	Cell parameters from 3237 reflections
a = 13.714 (3) Å	θ = 2.5–30.0°
b = 10.456 (4) Å	µ = 0.24 mm^−1
c = 20.781 (3) Å	T = 293 K
β = 101.365 (5)°	Prism, colourless
V = 2921.4 (14) Å^3	0.75 × 0.65 × 0.50 mm
Z = 8

Data collection

Rigaku AFC-7S diffractometer	2325 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
ω/2θ scans	h = −19→19
Absorption correction: for a sphere (Dwiggins, 1975)	k = −14→14
Tmin = 0.818, Tmax = 0.866	l = −29→29
3054 measured reflections	3 standard reflections every 150 reflections
2939 independent reflections	intensity decay: −0.2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	All H-atom parameters refined
wR(F^2) = 0.138	w = 1/[σ^2(Fo^2) + (0.088P)^2 + 1.695P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2939 reflections	Δρmax = 0.42 e Å^−3
244 parameters	Δρmin = −0.41 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0034 (7)

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
C1	0.26617 (19)	0.3923 (2)	0.30413 (12)	0.0546 (6)
C2	0.2226 (2)	0.4370 (3)	0.24296 (13)	0.0658 (7)
C3	0.2689 (2)	0.5320 (3)	0.21345 (13)	0.0682 (7)
C4	0.3572 (2)	0.5819 (3)	0.24543 (14)	0.0693 (7)
C5	0.4015 (2)	0.5378 (3)	0.30733 (13)	0.0603 (6)
C6	0.35743 (16)	0.4406 (2)	0.33671 (10)	0.0466 (5)
C7	0.40657 (17)	0.3943 (2)	0.40144 (11)	0.0507 (5)
C8	0.38053 (17)	0.2928 (2)	0.43204 (11)	0.0484 (5)
C9	0.43674 (15)	0.2573 (2)	0.49674 (10)	0.0475 (5)
C10	0.31568 (14)	0.0741 (2)	0.50998 (10)	0.0431 (5)
C11	0.32167 (14)	−0.0350 (2)	0.55608 (10)	0.0445 (5)
C12	0.40780 (15)	−0.0377 (2)	0.60323 (10)	0.0449 (5)
C13	0.4284 (2)	−0.1325 (3)	0.65031 (13)	0.0609 (6)
C14	0.3570 (3)	−0.2261 (3)	0.64872 (16)	0.0751 (8)
C15	0.2690 (2)	−0.2235 (3)	0.60270 (16)	0.0721 (8)
C16	0.25029 (19)	−0.1287 (3)	0.55589 (13)	0.0577 (6)
N1	0.40356 (12)	0.14856 (17)	0.52802 (8)	0.0431 (4)
O1	0.51134 (13)	0.30976 (18)	0.52541 (9)	0.0681 (5)
O2	0.57451 (11)	0.05719 (17)	0.58034 (8)	0.0556 (4)
O3	0.48326 (13)	0.17949 (16)	0.65004 (7)	0.0591 (4)
O4	0.24855 (11)	0.09728 (17)	0.46506 (8)	0.0560 (4)
S1	0.48233 (3)	0.09468 (5)	0.59656 (2)	0.0420 (2)
H1	0.2345 (18)	0.328 (3)	0.3242 (12)	0.056 (7)*
H2	0.161 (2)	0.402 (3)	0.2207 (14)	0.079 (9)*
H3	0.231 (2)	0.561 (3)	0.1697 (16)	0.082 (9)*
H4	0.391 (2)	0.643 (3)	0.2260 (15)	0.085 (9)*
H5	0.464 (2)	0.578 (3)	0.3293 (13)	0.065 (8)*
H7	0.466 (2)	0.436 (3)	0.4227 (13)	0.065 (7)*
H8	0.324 (2)	0.249 (3)	0.4144 (13)	0.070 (8)*
H13	0.491 (2)	−0.135 (3)	0.6826 (14)	0.072 (8)*
H14	0.368 (2)	−0.292 (3)	0.6779 (14)	0.080 (9)*
H15	0.223 (2)	−0.289 (3)	0.6015 (13)	0.073 (8)*
H16	0.1909 (19)	−0.123 (2)	0.5242 (12)	0.049 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0600 (13)	0.0547 (13)	0.0469 (13)	−0.0076 (11)	0.0049 (10)	0.0005 (11)
C2	0.0740 (17)	0.0631 (16)	0.0536 (15)	0.0006 (13)	−0.0038 (13)	−0.0013 (12)
C3	0.0870 (19)	0.0669 (16)	0.0496 (14)	0.0176 (15)	0.0103 (13)	0.0097 (12)
C4	0.0805 (19)	0.0644 (16)	0.0679 (17)	0.0078 (14)	0.0266 (15)	0.0212 (14)
C5	0.0589 (14)	0.0587 (15)	0.0642 (15)	−0.0034 (11)	0.0143 (11)	0.0101 (12)
C6	0.0515 (11)	0.0457 (11)	0.0435 (11)	0.0003 (9)	0.0113 (9)	−0.0013 (9)
C7	0.0481 (11)	0.0551 (13)	0.0471 (12)	−0.0072 (10)	0.0053 (9)	−0.0017 (10)
C8	0.0483 (11)	0.0541 (13)	0.0411 (11)	−0.0070 (10)	0.0045 (9)	−0.0029 (9)
C9	0.0436 (10)	0.0521 (12)	0.0456 (12)	−0.0066 (9)	0.0064 (9)	0.0014 (10)
C10	0.0341 (9)	0.0535 (12)	0.0429 (11)	−0.0055 (8)	0.0102 (8)	−0.0094 (9)
C11	0.0395 (9)	0.0515 (12)	0.0454 (11)	−0.0074 (9)	0.0155 (8)	−0.0094 (9)
C12	0.0438 (10)	0.0503 (12)	0.0429 (11)	−0.0079 (9)	0.0142 (8)	−0.0046 (9)
C13	0.0635 (15)	0.0624 (15)	0.0568 (15)	−0.0069 (11)	0.0116 (12)	0.0089 (12)
C14	0.087 (2)	0.0637 (17)	0.079 (2)	−0.0139 (14)	0.0254 (16)	0.0179 (15)
C15	0.0765 (18)	0.0637 (17)	0.0817 (19)	−0.0268 (14)	0.0290 (15)	−0.0020 (14)
C16	0.0480 (12)	0.0640 (15)	0.0638 (15)	−0.0176 (10)	0.0173 (11)	−0.0128 (12)
N1	0.0369 (8)	0.0496 (10)	0.0406 (9)	−0.0075 (7)	0.0025 (6)	−0.0012 (7)
O1	0.0573 (10)	0.0748 (12)	0.0632 (10)	−0.0269 (9)	−0.0097 (8)	0.0155 (9)
O2	0.0372 (7)	0.0701 (10)	0.0593 (9)	−0.0014 (7)	0.0092 (6)	0.0043 (8)
O3	0.0679 (10)	0.0627 (10)	0.0446 (9)	−0.0119 (8)	0.0056 (7)	−0.0133 (7)
O4	0.0361 (7)	0.0768 (11)	0.0512 (9)	−0.0074 (7)	−0.0006 (6)	−0.0020 (8)
S1	0.0370 (3)	0.0496 (3)	0.0380 (3)	−0.00695 (19)	0.00377 (19)	−0.0023 (2)

Geometric parameters (Å, º)

C1—C2	1.376 (4)	C10—O4	1.200 (2)
C1—C6	1.395 (3)	C10—N1	1.422 (2)
C1—H1	0.94 (3)	C10—C11	1.482 (3)
C2—C3	1.385 (4)	C11—C12	1.378 (3)
C2—H2	0.95 (3)	C11—C16	1.384 (3)
C3—C4	1.366 (4)	C12—C13	1.383 (3)
C3—H3	1.00 (3)	C12—S1	1.742 (2)
C4—C5	1.388 (4)	C13—C14	1.381 (4)
C4—H4	0.92 (3)	C13—H13	0.98 (3)
C5—C6	1.384 (3)	C14—C15	1.385 (5)
C5—H5	0.98 (3)	C14—H14	0.91 (3)
C6—C7	1.463 (3)	C15—C16	1.377 (4)
C7—C8	1.322 (3)	C15—H15	0.92 (3)
C7—H7	0.95 (3)	C16—H16	0.94 (2)
C8—C9	1.460 (3)	N1—S1	1.705 (2)
C8—H8	0.91 (3)	O2—S1	1.426 (2)
C9—O1	1.209 (3)	O3—S1	1.420 (2)
C9—N1	1.428 (3)
C2—C1—C6	120.6 (2)	N1—C10—C11	108.4 (2)
C2—C1—H1	119.9 (15)	C12—C11—C16	119.6 (2)
C6—C1—H1	119.5 (15)	C12—C11—C10	113.93 (17)
C1—C2—C3	120.0 (3)	C16—C11—C10	126.4 (2)
C1—C2—H2	120.1 (18)	C11—C12—C13	123.0 (2)
C3—C2—H2	119.9 (18)	C11—C12—S1	111.2 (2)
C4—C3—C2	119.9 (3)	C13—C12—S1	125.8 (2)
C4—C3—H3	125.3 (19)	C14—C13—C12	116.5 (3)
C2—C3—H3	114.8 (19)	C14—C13—H13	121.4 (18)
C3—C4—C5	120.5 (3)	C12—C13—H13	122.1 (18)
C3—C4—H4	121 (2)	C13—C14—C15	121.4 (3)
C5—C4—H4	118 (2)	C13—C14—H14	120 (2)
C6—C5—C4	120.2 (3)	C15—C14—H14	119 (2)
C6—C5—H5	121.6 (16)	C16—C15—C14	121.2 (3)
C4—C5—H5	118.2 (16)	C16—C15—H15	118.7 (18)
C5—C6—C1	118.7 (2)	C14—C15—H15	120.0 (18)
C5—C6—C7	119.1 (2)	C15—C16—C11	118.3 (2)
C1—C6—C7	122.2 (2)	C15—C16—H16	123.4 (15)
C8—C7—C6	126.1 (2)	C11—C16—H16	118.3 (15)
C8—C7—H7	115.8 (16)	C10—N1—C9	130.2 (2)
C6—C7—H7	117.9 (16)	C10—N1—S1	113.8 (1)
C7—C8—C9	120.2 (2)	C9—N1—S1	115.9 (1)
C7—C8—H8	120.0 (18)	O3—S1—O2	119.0 (1)
C9—C8—H8	119.5 (18)	O3—S1—N1	110.7 (1)
O1—C9—N1	116.8 (2)	O2—S1—N1	109.79 (9)
O1—C9—C8	125.5 (2)	O3—S1—C12	110.4 (1)
N1—C9—C8	117.6 (2)	O2—S1—C12	111.2 (1)
O4—C10—N1	125.1 (2)	N1—S1—C12	92.51 (9)
O4—C10—C11	126.5 (2)
C6—C1—C2—C3	−0.7 (4)	C13—C14—C15—C16	1.3 (5)
C1—C2—C3—C4	−0.6 (4)	C14—C15—C16—C11	−0.4 (4)
C2—C3—C4—C5	0.2 (4)	C12—C11—C16—C15	−1.1 (4)
C3—C4—C5—C6	1.4 (4)	C10—C11—C16—C15	179.8 (2)
C4—C5—C6—C1	−2.7 (4)	O4—C10—N1—C9	−5.2 (4)
C4—C5—C6—C7	178.8 (2)	C11—C10—N1—C9	175.1 (2)
C2—C1—C6—C5	2.3 (4)	O4—C10—N1—S1	177.03 (17)
C2—C1—C6—C7	−179.2 (2)	C11—C10—N1—S1	−2.7 (2)
C5—C6—C7—C8	−171.2 (2)	O1—C9—N1—C10	174.1 (2)
C1—C6—C7—C8	10.4 (4)	C8—C9—N1—C10	−8.3 (3)
C6—C7—C8—C9	179.9 (2)	O1—C9—N1—S1	−8.2 (3)
C7—C8—C9—O1	−4.1 (4)	C8—C9—N1—S1	169.44 (16)
C7—C8—C9—N1	178.5 (2)	C10—N1—S1—O3	−109.24 (16)
O4—C10—C11—C12	−179.9 (2)	C9—N1—S1—O3	72.67 (18)
N1—C10—C11—C12	−0.2 (2)	C10—N1—S1—O2	117.33 (15)
O4—C10—C11—C16	−0.8 (4)	C9—N1—S1—O2	−60.75 (18)
N1—C10—C11—C16	178.9 (2)	C10—N1—S1—C12	3.72 (16)
C16—C11—C12—C13	1.7 (3)	C9—N1—S1—C12	−174.37 (16)
C10—C11—C12—C13	−179.1 (2)	C11—C12—S1—O3	109.52 (16)
C16—C11—C12—S1	−176.33 (17)	C13—C12—S1—O3	−68.5 (2)
C10—C11—C12—S1	2.8 (2)	C11—C12—S1—O2	−116.08 (16)
C11—C12—C13—C14	−0.8 (4)	C13—C12—S1—O2	65.9 (2)
S1—C12—C13—C14	177.0 (2)	C11—C12—S1—N1	−3.72 (16)
C12—C13—C14—C15	−0.8 (4)	C13—C12—S1—N1	178.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1	0.95 (3)	2.49 (3)	2.832 (3)	101.4 (18)
C8—H8···O4	0.91 (3)	2.26 (3)	2.901 (3)	127 (2)
C15—H15···O2^i	0.92 (3)	2.57 (3)	3.478 (3)	169 (2)
C16—H16···O1^i	0.94 (2)	2.56 (3)	3.277 (3)	132.6 (18)
C14—H14···CgA^ii	0.91 (3)	3.07 (3)	3.916 (4)	156 (2)

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