Saccharin, redetermined at 120 K: a three-dimensional hydrogen-bonded framework

Wardell, J.L.; Low, J.N.; Glidewell, C.

doi:10.1107/S1600536805016600

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 6| June 2005| Pages o1944-o1946

https://doi.org/10.1107/S1600536805016600

Saccharin, redetermined at 120 K: a three-dimensional hydrogen-bonded framework

James L. Wardell,^a John N. Low ^b and Christopher Glidewell ^c ^*

^aInstituto de Química, Departamento de Química Inorgânica, Universidade Federal do Rio de Janeiro, 21945-970 Rio de Janeiro, RJ, Brazil, ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and ^cSchool of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland
^*Correspondence e-mail: cg@st-andrews.ac.uk

(Received 20 May 2005; accepted 24 May 2005; online 31 May 2005)

Molecules of the title compound, C₇H₅NO₃S, are linked by paired N—H⋯O=C hydrogen bonds into R₂²(8) dimers and these dimers are linked into a three-dimensional framework structure by a combination of three independent C—H⋯O hydrogen bonds.

Comment

The structure of saccharin, (I), was determined some years ago (Bart, 1968 ; Okaya, 1969 ) using diffraction data collected at ambient temperature, and accordingly the precision of some of the interatomic distances is fairly modest. While in one report (Bart, 1968) the precision on the bond angles is satisfactory, in the other (Okaya, 1969) no s.u. values were quoted for the interbond angles. The molecules were reported to form centrosymmetric dimers constructed from paired N—H⋯O=C hydrogen bonds.

We have now taken the opportunity to redetermine this structure using diffraction data collected at 120 (2) K; this has permitted refinement to a rather lower R factor and has provided interatomic distances of significantly higher precision (Fig. 1 and Table 1). The cell dimensions and space group indicate that the same phase is present at 120 K as at ambient temperature.

The molecules are linked by a combination of N—H⋯O and C—H⋯O hydrogen bonds in which all three O atoms act as acceptors (Table 2). The N—H⋯O hydrogen bond, which utilizes a carbonyl O atom as acceptor, generates a centrosymmetric R₂²(8) dimer (Fig. 2), exactly as reported previously; for the sake of convenience, the reference molecule has been selected so that this dimer lies across ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ). These dimers are linked into a single three-dimensional framework by three independent C—H⋯O hydrogen bonds, each utilizing a different O atom as acceptor (Table 2). The hydrogen bond involving C2 as donor links the R₂²(8) dimer centred at ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ) to those centred at (− $[{1\over 2}]$ , 0, 0), (− $[{1\over 2}]$ , 1, 0), ( $[{3\over 2}]$ , 0, 1) and ( $[{3\over 2}]$ , 1, 1), thereby generating a (−102) sheet. The hydrogen bond involving C4 as the donor links the ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ) dimer to those centred at ( $[{1\over 2}]$ , −1, 0), ( $[{1\over 2}]$ , −1, 1), ( $[{1\over 2}]$ , 2, 0) and ( $[{1\over 2}]$ , 2, 1), so forming a (100) sheet. This sheet is reinforced by the third, rather weak, C—H⋯O hydrogen bond where C5 is the donor; this interaction links the ( $[{1\over 2}]$ , $[{1\over 2}]$ , $[{1\over 2}]$ ) dimer to those centred at ( $[{1\over 2}]$ , 0, 0), ( $[{1\over 2}]$ , 1, 0), ( $[{1\over 2}]$ , 0, 1) and ( $[{1\over 2}]$ , 1, 1), so that the (100) sheet is of considerable complexity. The combination of the (100) and ( $[\overline 1]$ 02) sheets suffices to link all of the molecules into a single framework.

The original reports on the structure of (I) (Bart, 1968; Okaya, 1969) made no mention of the C—H⋯O hydrogen bonds; at the time of those reports, the notion that such interactions could be of structural significance was not widely recognized and certainly not widely accepted.

Figure 1
The molecule of (I)

, showing the atom-labelling scheme. Displacement ellipsoid are drawn at the 30% probability level.

Figure 2
Part of the crystal structure of (I)

, showing the formation of an R₂²(8) dimer. For clarity, H atoms bonded to C atoms have been omitted. Hydrogen bonds are indicated by dashed lines. Atoms marked with an asterisk (*) are at the symmetry position (1 − x, 1 − y, 1 − z).

Experimental

Crystals of compound (I) suitable for single-crystal X-ray diffraction were grown from an ethanol solution.

Crystal data

C₇H₅NO₃S
M_r = 183.18
Monoclinic, P 2₁ /c
a = 9.4722 (4) Å
b = 6.9227 (2) Å
c = 11.7322 (3) Å
β = 103.203 (3)°
V = 748.98 (4) Å³
Z = 4
D_x = 1.624 Mg m⁻³
Mo Kα radiation
Cell parameters from 1706 reflections
θ = 3.6–27.5°
μ = 0.39 mm⁻¹
T = 120 (2) K
Lath, colourless
0.44 × 0.16 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan(SADABS; Sheldrick, 2003 )T_min = 0.847, T_max = 0.958
12303 measured reflections
1706 independent reflections
1490 reflections with I > 2σ(I)
R_int = 0.052
θ_max = 27.5°
h = −11 → 12
k = −8 → 9
l = −14 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.092
S = 1.11
1706 reflections
109 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0203P)² + 0.8656P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

S1—O1	1.4291 (15)
S1—O2	1.4323 (15)
S1—N1	1.6643 (16)
S1—C1	1.7560 (19)
N1—C7	1.374 (2)
C7—O3	1.223 (2)
C7—C6	1.481 (3)
C1—C2	1.387 (3)
C2—C3	1.393 (3)
C3—C4	1.390 (3)
C4—C5	1.392 (3)
C5—C6	1.382 (3)
C6—C1	1.391 (3)

O1—S1—O2	117.37 (9)
O1—S1—N1	110.37 (9)
O2—S1—N1	109.48 (9)
O1—S1—C1	111.71 (9)
O2—S1—C1	112.68 (9)
N1—S1—C1	92.41 (8)
S1—N1—C7	115.65 (13)
O3—C7—N1	124.53 (17)
O3—C7—C6	126.12 (17)
N1—C7—C6	109.34 (16)
S1—C1—C6	110.01 (14)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.95	1.86	2.786 (2)	167
C2—H2⋯O2ⁱⁱ	0.95	2.46	3.377 (3)	161
C4—H4⋯O1ⁱⁱⁱ	0.95	2.55	3.375 (2)	145
C5—H5⋯O3^iv	0.95	2.50	3.169 (2)	128
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y-{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

All H atoms were located in difference maps and then treated as riding atoms with C—H = 0.95 Å and N—H = 0.95 Å, and with U_iso(H) = 1.2 U_eq(C,N).

Data collection: COLLECT (Hooft, 1999 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: WinGX (Farrugia, 1999 ) and SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: OSCAIL (McArdle, 2003 ) and SHELXL97 (Sheldrick, 1997 ); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805016600/lh6438sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805016600/lh6438Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: WinGX (Farrugia, 1999) and SIR92 (Altomare et al., 1993); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Saccharin top

Crystal data top

C₇H₅NO₃S	F(000) = 376
M_r = 183.18	D_x = 1.624 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1706 reflections
a = 9.4722 (4) Å	θ = 3.6–27.5°
b = 6.9227 (2) Å	µ = 0.39 mm⁻¹
c = 11.7322 (3) Å	T = 120 K
β = 103.203 (3)°	Lath, colourless
V = 748.98 (4) Å³	0.44 × 0.16 × 0.11 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1706 independent reflections
Radiation source: Bruker–Nonius FR91 rotating anode	1490 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.6°
φ and ω scans	h = −11→12
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −8→9
T_min = 0.847, T_max = 0.958	l = −14→15
12303 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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0203P)² + 0.8656P] where P = (F_o² + 2F_c²)/3
1706 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.21067 (5)	0.22909 (7)	0.34594 (4)	0.01955 (15)
O1	0.24538 (17)	0.1705 (2)	0.23876 (12)	0.0271 (3)
O2	0.08217 (15)	0.3423 (2)	0.33788 (13)	0.0287 (4)
O3	0.52054 (15)	0.3079 (2)	0.60463 (11)	0.0216 (3)
N1	0.35108 (18)	0.3420 (2)	0.43105 (14)	0.0207 (4)
C1	0.2223 (2)	0.0356 (3)	0.44441 (16)	0.0184 (4)
C2	0.1361 (2)	−0.1284 (3)	0.43285 (18)	0.0256 (4)
C3	0.1685 (2)	−0.2627 (3)	0.52349 (19)	0.0271 (5)
C4	0.2818 (2)	−0.2340 (3)	0.62062 (18)	0.0256 (4)
C5	0.3685 (2)	−0.0699 (3)	0.62963 (17)	0.0218 (4)
C6	0.3373 (2)	0.0646 (3)	0.54037 (15)	0.0170 (4)
C7	0.4147 (2)	0.2483 (3)	0.53308 (16)	0.0177 (4)
H1	0.3838	0.4622	0.4087	0.025*
H2	0.0588	−0.1481	0.3664	0.031*
H3	0.1117	−0.3767	0.5188	0.033*
H4	0.3004	−0.3275	0.6815	0.031*
H5	0.4470	−0.0508	0.6953	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0205 (3)	0.0188 (3)	0.0173 (2)	−0.00189 (18)	0.00002 (17)	−0.00062 (17)
O1	0.0372 (9)	0.0252 (8)	0.0189 (7)	−0.0036 (6)	0.0067 (6)	−0.0018 (6)
O2	0.0221 (8)	0.0307 (8)	0.0303 (8)	0.0049 (6)	−0.0002 (6)	0.0014 (6)
O3	0.0239 (7)	0.0222 (7)	0.0169 (6)	−0.0054 (6)	0.0008 (5)	−0.0016 (5)
N1	0.0235 (9)	0.0165 (8)	0.0195 (8)	−0.0048 (6)	−0.0003 (6)	0.0015 (6)
C1	0.0204 (9)	0.0176 (9)	0.0176 (9)	−0.0012 (7)	0.0053 (7)	−0.0021 (7)
C2	0.0225 (10)	0.0275 (11)	0.0264 (10)	−0.0062 (9)	0.0048 (8)	−0.0070 (9)
C3	0.0307 (11)	0.0191 (10)	0.0349 (11)	−0.0085 (8)	0.0146 (9)	−0.0033 (8)
C4	0.0344 (12)	0.0202 (10)	0.0253 (10)	−0.0029 (8)	0.0130 (9)	0.0015 (8)
C5	0.0279 (10)	0.0196 (9)	0.0186 (9)	−0.0012 (8)	0.0067 (8)	0.0001 (7)
C6	0.0197 (9)	0.0161 (9)	0.0159 (8)	−0.0010 (7)	0.0056 (7)	−0.0034 (7)
C7	0.0197 (9)	0.0168 (9)	0.0174 (9)	−0.0017 (7)	0.0057 (7)	−0.0027 (7)

Geometric parameters (Å, º) top

S1—O1	1.4291 (15)	C2—C3	1.393 (3)
S1—O2	1.4323 (15)	C2—H2	0.95
S1—N1	1.6643 (16)	C3—C4	1.390 (3)
S1—C1	1.7560 (19)	C3—H3	0.95
N1—C7	1.374 (2)	C4—C5	1.392 (3)
N1—H1	0.9462	C4—H4	0.95
C7—O3	1.223 (2)	C5—C6	1.382 (3)
C7—C6	1.481 (3)	C5—H5	0.95
C1—C2	1.387 (3)	C6—C1	1.391 (3)

O1—S1—O2	117.37 (9)	C1—C2—C3	116.72 (18)
O1—S1—N1	110.37 (9)	C1—C2—H2	121.6
O2—S1—N1	109.48 (9)	C3—C2—H2	121.6
O1—S1—C1	111.71 (9)	C4—C3—C2	121.65 (19)
O2—S1—C1	112.68 (9)	C4—C3—H3	119.2
N1—S1—C1	92.41 (8)	C2—C3—H3	119.2
S1—N1—C7	115.65 (13)	C3—C4—C5	120.71 (19)
C7—N1—H1	123.4	C3—C4—H4	119.6
S1—N1—H1	120.9	C5—C4—H4	119.6
O3—C7—N1	124.53 (17)	C6—C5—C4	118.18 (18)
O3—C7—C6	126.12 (17)	C6—C5—H5	120.9
N1—C7—C6	109.34 (16)	C4—C5—H5	120.9
C2—C1—C6	122.17 (18)	C5—C6—C1	120.57 (18)
C2—C1—S1	127.80 (15)	C5—C6—C7	126.84 (17)
S1—C1—C6	110.01 (14)	C1—C6—C7	112.59 (16)

O1—S1—N1—C7	−113.64 (15)	C1—C2—C3—C4	−0.1 (3)
O2—S1—N1—C7	115.70 (15)	C2—C3—C4—C5	−0.9 (3)
C1—S1—N1—C7	0.60 (16)	C3—C4—C5—C6	1.0 (3)
S1—N1—C7—O3	178.42 (15)	C4—C5—C6—C1	−0.1 (3)
S1—N1—C7—C6	−0.3 (2)	C4—C5—C6—C7	179.60 (18)
O1—S1—C1—C2	−66.2 (2)	C2—C1—C6—C5	−1.0 (3)
O2—S1—C1—C2	68.4 (2)	S1—C1—C6—C5	−179.60 (15)
N1—S1—C1—C2	−179.26 (19)	C2—C1—C6—C7	179.32 (18)
O1—S1—C1—C6	112.34 (14)	S1—C1—C6—C7	0.7 (2)
O2—S1—C1—C6	−113.01 (14)	O3—C7—C6—C5	1.3 (3)
N1—S1—C1—C6	−0.72 (15)	N1—C7—C6—C5	−179.96 (18)
C6—C1—C2—C3	1.1 (3)	O3—C7—C6—C1	−178.97 (19)
S1—C1—C2—C3	179.43 (16)	N1—C7—C6—C1	−0.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.95	1.86	2.786 (2)	167
C2—H2···O2ⁱⁱ	0.95	2.46	3.377 (3)	161
C4—H4···O1ⁱⁱⁱ	0.95	2.55	3.375 (2)	145
C5—H5···O3^iv	0.95	2.50	3.169 (2)	128

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

Acknowledgements

X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bart, J. C. J. (1968). J. Chem. Soc. B, pp. 376–382. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Ferguson, G. (1999). PRPKAPPA. University of Guelph, Canada. Google Scholar
Hooft, R. W. W. (1999). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
McArdle, P. (2003). OSCAIL for Windows. Version 10. Crystallography Centre, Chemistry Department, NUI Galway, Ireland. Google Scholar
Okaya, Y. (1969). Acta Cryst. B25, 2257–2263. CSD CrossRef IUCr Journals Web of Science Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (1997). SHELXL97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2003). SADABS. Version 2.10. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.