Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101018595/sk1503sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101018595/sk1503Isup2.hkl |
CCDC reference: 182026
Slow evaporation of a solution of (I) in methanol gave colourless crystals suitable for X-ray analysis.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: HELENA (Spek, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1990); software used to prepare material for publication: SHELXL97.
C12H12N2O3S | F(000) = 1104 |
Mr = 264.30 | Dx = 1.453 Mg m−3 |
Orthorhombic, Pbca | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 25 reflections |
a = 8.059 (1) Å | θ = 30–40° |
b = 12.116 (1) Å | µ = 2.42 mm−1 |
c = 24.744 (2) Å | T = 293 K |
V = 2416.1 (4) Å3 | Needle, colourless |
Z = 8 | 0.64 × 0.31 × 0.19 mm |
Enraf-Nonius CAD-4 diffractometer | 2257 reflections with I > 2σ(I) |
Radiation source: long fine-focus sealed tube | Rint = 0.011 |
Graphite monochromator | θmax = 71.9°, θmin = 3.6° |
θ/2θ scans | h = −9→9 |
Absorption correction: analytical (North et al., 1968) | k = 0→14 |
Tmin = 0.306, Tmax = 0.656 | l = 0→30 |
4729 measured reflections | 3 standard reflections every 200 reflections |
2366 independent reflections | intensity decay: 3% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.032 | All H-atom parameters refined |
wR(F2) = 0.096 | w = 1/[σ2(Fo2) + (0.0635P)2 + 0.4886P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
2366 reflections | Δρmax = 0.24 e Å−3 |
212 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (2) |
C12H12N2O3S | V = 2416.1 (4) Å3 |
Mr = 264.30 | Z = 8 |
Orthorhombic, Pbca | Cu Kα radiation |
a = 8.059 (1) Å | µ = 2.42 mm−1 |
b = 12.116 (1) Å | T = 293 K |
c = 24.744 (2) Å | 0.64 × 0.31 × 0.19 mm |
Enraf-Nonius CAD-4 diffractometer | 2257 reflections with I > 2σ(I) |
Absorption correction: analytical (North et al., 1968) | Rint = 0.011 |
Tmin = 0.306, Tmax = 0.656 | 3 standard reflections every 200 reflections |
4729 measured reflections | intensity decay: 3% |
2366 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.096 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.24 e Å−3 |
2366 reflections | Δρmin = −0.31 e Å−3 |
212 parameters |
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 | ||
C1 | 0.6341 (3) | 0.22801 (16) | −0.02154 (9) | 0.0642 (5) | |
C2 | 0.7231 (3) | 0.15945 (16) | −0.05550 (8) | 0.0601 (5) | |
C3 | 0.7953 (2) | 0.06568 (16) | −0.03440 (7) | 0.0565 (4) | |
C4 | 0.7806 (2) | 0.04045 (13) | 0.01998 (6) | 0.0475 (4) | |
C5 | 0.69306 (17) | 0.11064 (11) | 0.05346 (6) | 0.0374 (3) | |
C6 | 0.6196 (2) | 0.20474 (14) | 0.03275 (8) | 0.0536 (4) | |
O7 | 0.67108 (13) | 0.09362 (8) | 0.10838 (4) | 0.0404 (3) | |
C8 | 0.74286 (17) | 0.00172 (10) | 0.13191 (5) | 0.0330 (3) | |
C9 | 0.65682 (19) | −0.09512 (12) | 0.13105 (7) | 0.0429 (3) | |
N10 | 0.71742 (18) | −0.18453 (9) | 0.15635 (5) | 0.0461 (3) | |
C11 | 0.8617 (2) | −0.17949 (12) | 0.18302 (6) | 0.0465 (4) | |
C12 | 0.9512 (2) | −0.08399 (11) | 0.18597 (6) | 0.0407 (3) | |
C13 | 0.89577 (16) | 0.01331 (10) | 0.15974 (5) | 0.0301 (3) | |
N14 | 0.97024 (14) | 0.11339 (8) | 0.15794 (4) | 0.0324 (3) | |
S15 | 1.13367 (4) | 0.13824 (3) | 0.193283 (12) | 0.03378 (15) | |
O16 | 1.12025 (13) | 0.09799 (9) | 0.24791 (4) | 0.0439 (3) | |
O17 | 1.16398 (16) | 0.25480 (9) | 0.18717 (4) | 0.0504 (3) | |
C18 | 1.3016 (2) | 0.06796 (18) | 0.16336 (8) | 0.0565 (4) | |
H9 | 0.555 (3) | −0.1052 (16) | 0.1134 (7) | 0.051 (5)* | |
H12 | 1.044 (2) | −0.0837 (15) | 0.2055 (7) | 0.046 (4)* | |
H6 | 0.559 (3) | 0.2483 (18) | 0.0572 (8) | 0.068 (6)* | |
H3 | 0.862 (3) | 0.0198 (19) | −0.0583 (9) | 0.068 (6)* | |
H4 | 0.830 (3) | −0.0222 (18) | 0.0340 (8) | 0.060 (5)* | |
H1 | 0.584 (4) | 0.295 (2) | −0.0362 (11) | 0.091 (8)* | |
H2 | 0.729 (3) | 0.1757 (19) | −0.0926 (9) | 0.071 (6)* | |
H18A | 1.399 (3) | 0.082 (2) | 0.1859 (9) | 0.080 (7)* | |
H18B | 1.317 (3) | 0.095 (2) | 0.1277 (10) | 0.074 (7)* | |
H11 | 0.899 (2) | −0.2409 (18) | 0.1997 (7) | 0.052 (5)* | |
H18C | 1.269 (4) | −0.014 (2) | 0.1650 (9) | 0.086 (7)* | |
H10 | 0.651 (3) | −0.247 (2) | 0.1541 (9) | 0.071 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0764 (13) | 0.0436 (9) | 0.0727 (12) | 0.0033 (8) | −0.0258 (9) | 0.0143 (8) |
C2 | 0.0692 (12) | 0.0586 (10) | 0.0523 (9) | −0.0138 (9) | −0.0179 (8) | 0.0100 (8) |
C3 | 0.0609 (10) | 0.0587 (10) | 0.0500 (9) | 0.0022 (8) | −0.0063 (7) | −0.0035 (8) |
C4 | 0.0534 (9) | 0.0394 (7) | 0.0498 (8) | 0.0096 (6) | −0.0075 (7) | −0.0012 (6) |
C5 | 0.0342 (6) | 0.0296 (6) | 0.0485 (7) | −0.0003 (5) | −0.0111 (6) | −0.0003 (5) |
C6 | 0.0588 (10) | 0.0356 (8) | 0.0664 (11) | 0.0109 (7) | −0.0153 (8) | 0.0002 (7) |
O7 | 0.0426 (5) | 0.0286 (5) | 0.0501 (6) | 0.0107 (4) | −0.0051 (4) | −0.0029 (4) |
C8 | 0.0368 (6) | 0.0216 (6) | 0.0405 (6) | 0.0024 (5) | 0.0020 (5) | −0.0014 (5) |
C9 | 0.0397 (7) | 0.0312 (7) | 0.0577 (9) | −0.0052 (5) | 0.0041 (6) | −0.0087 (6) |
N10 | 0.0581 (8) | 0.0220 (5) | 0.0581 (7) | −0.0103 (5) | 0.0114 (6) | −0.0033 (5) |
C11 | 0.0758 (11) | 0.0205 (6) | 0.0432 (7) | −0.0001 (6) | 0.0033 (7) | 0.0054 (5) |
C12 | 0.0559 (9) | 0.0232 (6) | 0.0428 (7) | 0.0021 (6) | −0.0087 (6) | 0.0041 (5) |
C13 | 0.0374 (6) | 0.0197 (6) | 0.0332 (6) | 0.0009 (5) | 0.0037 (5) | 0.0000 (4) |
N14 | 0.0361 (6) | 0.0196 (5) | 0.0415 (6) | −0.0004 (4) | −0.0013 (4) | 0.0021 (4) |
S15 | 0.0371 (2) | 0.0272 (2) | 0.0370 (2) | −0.00319 (11) | 0.00110 (11) | −0.00497 (11) |
O16 | 0.0584 (7) | 0.0361 (5) | 0.0372 (5) | −0.0017 (4) | −0.0028 (4) | −0.0033 (4) |
O17 | 0.0632 (7) | 0.0316 (6) | 0.0564 (6) | −0.0170 (5) | −0.0009 (5) | −0.0021 (4) |
C18 | 0.0377 (8) | 0.0718 (12) | 0.0600 (10) | 0.0033 (8) | 0.0017 (7) | −0.0227 (9) |
C1—C6 | 1.377 (3) | C9—H9 | 0.94 (2) |
C1—C2 | 1.382 (3) | N10—C11 | 1.338 (2) |
C1—H1 | 0.97 (3) | N10—H10 | 0.92 (2) |
C2—C3 | 1.379 (3) | C11—C12 | 1.366 (2) |
C2—H2 | 0.94 (2) | C11—H11 | 0.90 (2) |
C3—C4 | 1.385 (2) | C12—C13 | 1.418 (2) |
C3—H3 | 0.97 (2) | C12—H12 | 0.893 (19) |
C4—C5 | 1.381 (2) | C13—N14 | 1.354 (2) |
C4—H4 | 0.92 (2) | N14—S15 | 1.6094 (11) |
C5—C6 | 1.383 (2) | S15—O16 | 1.4411 (10) |
C5—O7 | 1.3859 (17) | S15—O17 | 1.4412 (11) |
C6—H6 | 0.94 (2) | S15—C18 | 1.7623 (17) |
O7—C8 | 1.3833 (15) | C18—H18A | 0.98 (3) |
C8—C9 | 1.363 (2) | C18—H18B | 0.95 (2) |
C8—C13 | 1.418 (2) | C18—H18C | 1.03 (3) |
C9—N10 | 1.343 (2) | ||
C6—C1—C2 | 120.93 (16) | C11—N10—C9 | 120.6 (1) |
C6—C1—H1 | 119.8 (16) | C11—N10—H10 | 124.5 (14) |
C2—C1—H1 | 119.2 (16) | C9—N10—H10 | 114.9 (14) |
C3—C2—C1 | 118.94 (17) | N10—C11—C12 | 121.61 (14) |
C3—C2—H2 | 121.4 (15) | N10—C11—H11 | 118.6 (13) |
C1—C2—H2 | 119.6 (14) | C12—C11—H11 | 119.8 (13) |
C2—C3—C4 | 120.88 (17) | C11—C12—C13 | 120.89 (14) |
C2—C3—H3 | 118.3 (13) | C11—C12—H12 | 118.4 (12) |
C4—C3—H3 | 120.8 (13) | C13—C12—H12 | 120.7 (12) |
C5—C4—C3 | 119.40 (15) | N14—C13—C12 | 128.31 (12) |
C5—C4—H4 | 119.9 (13) | N14—C13—C8 | 117.26 (11) |
C3—C4—H4 | 120.7 (13) | C12—C13—C8 | 114.43 (12) |
C4—C5—C6 | 120.26 (15) | C13—N14—S15 | 120.84 (9) |
C4—C5—O7 | 124.19 (12) | O16—S15—O17 | 116.28 (6) |
C6—C5—O7 | 115.55 (14) | O16—S15—N14 | 112.64 (6) |
C1—C6—C5 | 119.58 (17) | O17—S15—N14 | 105.37 (6) |
C1—C6—H6 | 123.9 (13) | O16—S15—C18 | 106.76 (9) |
C5—C6—H6 | 116.5 (13) | O17—S15—C18 | 107.41 (9) |
C8—O7—C5 | 118.63 (10) | N14—S15—C18 | 108.05 (7) |
C9—C8—O7 | 118.27 (13) | S15—C18—H18A | 107.2 (15) |
C9—C8—C13 | 122.33 (12) | S15—C18—H18B | 108.9 (15) |
O7—C8—C13 | 119.20 (11) | H18A—C18—H18B | 111 (2) |
N10—C9—C8 | 120.14 (14) | S15—C18—H18C | 104.7 (16) |
N10—C9—H9 | 115.5 (12) | H18A—C18—H18C | 110 (2) |
C8—C9—H9 | 124.4 (12) | H18B—C18—H18C | 113.7 (19) |
C6—C1—C2—C3 | 1.1 (3) | C8—C9—N10—C11 | 0.6 (2) |
C1—C2—C3—C4 | −0.5 (3) | C9—N10—C11—C12 | 0.6 (2) |
C2—C3—C4—C5 | −0.4 (3) | N10—C11—C12—C13 | −1.3 (2) |
C3—C4—C5—C6 | 0.6 (2) | C11—C12—C13—N14 | −178.87 (14) |
C3—C4—C5—O7 | −179.77 (14) | C11—C12—C13—C8 | 0.8 (2) |
C2—C1—C6—C5 | −0.9 (3) | C9—C8—C13—N14 | −179.88 (12) |
C4—C5—C6—C1 | 0.0 (2) | O7—C8—C13—N14 | −5.20 (17) |
O7—C5—C6—C1 | −179.63 (15) | C9—C8—C13—C12 | 0.44 (19) |
C4—C5—O7—C8 | 1.08 (19) | O7—C8—C13—C12 | 175.13 (11) |
C6—C5—O7—C8 | −179.28 (13) | C12—C13—N14—S15 | −6.85 (19) |
C5—O7—C8—C9 | −86.36 (15) | C8—C13—N14—S15 | 173.52 (9) |
C5—O7—C8—C13 | 98.74 (14) | C13—N14—S15—O16 | −44.58 (12) |
O7—C8—C9—N10 | −175.86 (12) | C13—N14—S15—O17 | −172.32 (10) |
C13—C8—C9—N10 | −1.1 (2) | C13—N14—S15—C18 | 73.10 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···N14i | 0.93 (2) | 1.96 (2) | 2.878 (2) | 172 (2) |
C2—H2···O17ii | 0.94 (2) | 2.54 (2) | 3.453 (2) | 163 (2) |
C11—H11···O16iii | 0.90 (2) | 2.35 (2) | 3.195 (2) | 156 (1) |
C12—H12···O16 | 0.89 (2) | 2.51 (2) | 3.011 (2) | 116 (1) |
C18—H18A···O16iv | 0.98 (2) | 2.43 (2) | 3.398 (2) | 171 (2) |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x−1/2, −y+1/2, −z; (iii) −x+2, y−1/2, −z+1/2; (iv) x+1/2, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H12N2O3S |
Mr | 264.30 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 8.059 (1), 12.116 (1), 24.744 (2) |
V (Å3) | 2416.1 (4) |
Z | 8 |
Radiation type | Cu Kα |
µ (mm−1) | 2.42 |
Crystal size (mm) | 0.64 × 0.31 × 0.19 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Analytical (North et al., 1968) |
Tmin, Tmax | 0.306, 0.656 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4729, 2366, 2257 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.096, 1.07 |
No. of reflections | 2366 |
No. of parameters | 212 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.24, −0.31 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, HELENA (Spek, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1990), SHELXL97.
C8—C9 | 1.363 (2) | C11—C12 | 1.366 (2) |
C8—C13 | 1.418 (2) | C12—C13 | 1.418 (2) |
C9—N10 | 1.343 (2) | C13—N14 | 1.354 (2) |
N10—C11 | 1.338 (2) | ||
C11—N10—C9 | 120.6 (1) |
D—H···A | D—H | H···A | D···A | D—H···A |
N10—H10···N14i | 0.93 (2) | 1.96 (2) | 2.878 (2) | 172 (2) |
C2—H2···O17ii | 0.94 (2) | 2.54 (2) | 3.453 (2) | 163 (2) |
C11—H11···O16iii | 0.90 (2) | 2.35 (2) | 3.195 (2) | 156 (1) |
C12—H12···O16 | 0.89 (2) | 2.51 (2) | 3.011 (2) | 116 (1) |
C18—H18A···O16iv | 0.98 (2) | 2.43 (2) | 3.398 (2) | 171 (2) |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x−1/2, −y+1/2, −z; (iii) −x+2, y−1/2, −z+1/2; (iv) x+1/2, y, −z+1/2. |
C-N-C (°) | C-N (Å) | |
(a) | 120.54 | 1.313 |
(b) | 116.96 | 1.401 |
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N-(3-Phenoxy-4-pyridyl)methanesulfonamide, also known as FJ1, (I), a strict pyridine analogue of nimesulide, has been structurally studied to compare it with nimesulide, (II), a selective inhibitor of cyclooxygenase-2 (COX-2) (Dupont, Pirotte et al., 1995), and to try to understand its unexpected inactivity towards the cyclooxygenases (Julémont, 2001). \sch
The molecular structure of (I) is shown in Fig. 1. The pyridine group appears as a pyridinium nucleus and the sulfonamide group is deprotonated. Bond lengths and angles (Table 1), in particular C11—N10—C9 [120.59 (12)°, greater than in the pyridine ring, between 116 and 118°] and C13—N14 [1.354 (2) Å], agree with a zwitterionic structure where N14 is deprotonated and N10 protonated. Such a structure was also observed in a pyridylsulfonylcyanoguanidine compound, where the main bond lengths and angles are comparable (Dupont, Masereel et al., 1995).
A geometry optimization by an ab initio 6–31g* method at the B3LYP level using GAUSSIAN98 (Frisch et al., 1998) was performed on the zwitterionic form of (I), (a), and the neutral form, (b). The results are as follows: form (a) C—N—C 120.54° and C—N 1.313 Å; form (b) C—N—C 116.96° and C—N 1.401 Å. After optimization, the bond lengths and angles of (a) are the closest to those in the crystal structure. In nimesulide, where the sulfonamide group is not deprotonated, the C13—N14 bond length is longer [1.409 (4) Å] than that in (I) [1.354 (2) Å] because of the weaker delocalization.
Unlike nimesulide, (I) does not show any strong intramolecular hydrogen bonds. The crystal cohesion comes principally from van der Waals interactions and an intermolecular charge-assisted (Giacovazzo et al., 1992) and strongly directional N10—H10···N14 hydrogen bond (Table 2).
In the Cambridge Structural Database (CSD; Version 5.21; Allen & Kennard, 1993), 31 structures possess a pyridinium group and intermolecular hydrogen bonds are observed. Strongly directional hydrogen bonds are found in only nine structures; the others have weaker hydrogen bonds and less directionality. The acceptor changes from structure to structure and is either neutral or charged: –COO-, –CO-, –OH, –PO3H-, –N- or –N (pyridine group).
The crystal packing of (I) also involves four C—H···O interactions (Fig. 2) that may be classified as weak donor-strong acceptor hydrogen bonds (Desiraju & Steiner, 1999). Indeed, H···A lengths are between 2 and 3 Å, D···A lengths between 3 and 4 Å and X—H···A angles between 90 and 180° (Table 2). The two rings and the sulfone of (I) are involved in these. One of these is an intramolecular hydrogen bond (C12—H12···O16) that should partly contribute to the molecular conformation of the sulfonamide group of (I).
In conclusion, (I) appears structurally different from nimesulide in its zwitterionic form and its interactions within the crystal packing. Consequently,binding of (I) onto the COX-2 enzyme will be also different. The positive charge on the pyridine group would lead to unfavourable interaction. The loss of the intramolecular hydrogen bond in (I) induces a different position of the phenoxy group with regard to nimesulide.