Buy article online - an online subscription or single-article purchase is required to access this article.
The structures of the three title isomers, namely 4-(2-methylanilino)pyridine-3-sulfonamide, (I), 4-(3-methylanilino)pyridine-3-sulfonamide, (II), and 4-(4-methylanilino)pyridine-3-sulfonamide, (III), all C
12H
13N
3O
2S, differ in their hydrogen-bonding arrangements. In all three molecules, the conformation of the 4-aminopyridine-3-sulfonamide moiety is conserved by an intramolecular N—H
O hydrogen bond and a C—H
O interaction. In the supramolecular structures of all three isomers, similar
C(6) chains are formed
via intermolecular N—H
N hydrogen bonds. N—H
O hydrogen bonds lead to
C(4) chains in (I), and to
R22(8) centrosymmetric dimers in (II) and (III). In each isomer, the overall effect of all hydrogen bonds is to form layer structures.
Supporting information
CCDC references: 290574; 290575; 290576
A mixture of 4-chloro-3-pyridinesulfonamide (36.0 g, 0.19 mol), o-, m- or p-toluidine (21.6 ml, 0.2 mol) and methanol (240 ml) was refluxed for 2 h, and then for a further 3.5 h after addition of additional o-toluidine (6.0 ml, 0.06 mol) for (I), or the mixture was stirred at 313 K for 3 h for (II) and (III), and cooled to room temperature. Water was added to the mixture and the pH was adjusted to 7 with dilute NaOH. The resulting suspension was stirred under the same conditions for an additional 1 h. Crude crystalline (I), (II) or (III) were separated by suction, washed with water and dried in a vacuum oven at 333 K and 2.7 kPa for 3 h. Yield of (I): 46.6 g (94.7%); m.p. 457–459 K. Yield of (II): 48.0 g (96.5%); m.p. 440–442 K. Yield of (III): 48.2 g (97.9%); m.p. 493–495 K. Single crystals suitable for X-ray analysis were obtained by slow evaporation from methanol solutions for (I) and (III), and from an acetone solution for (II).
The sulfonamide H and amine H atoms were located in difference Fourier maps and refined. The methyl H atoms were found in a difference Fourier map and subsequently refined as part of rigid rotating groups, with Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions and allowed to refine as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C).
For all compounds, data collection: STADI4 (Stoe & Cie, 1996); cell refinement: STADI4; data reduction: X-RED (Stoe & Cie, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: PLATON2000 (Spek, 2003) and WebLab ViewerPro (Accelrys, 2000) for (I); PLATON2000 (Spek, 2003) for (II), (III). For all compounds, software used to prepare material for publication: SHELXL97 and PARST96 (Nardelli, 1995).
(I) 4-(2-methylanilino)pyridine-3-sulfonamide
top
Crystal data top
C12H13N3O2S | F(000) = 552 |
Mr = 263.31 | Dx = 1.350 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 36 reflections |
a = 8.5118 (7) Å | θ = 8.1–14.7° |
b = 7.2369 (13) Å | µ = 0.25 mm−1 |
c = 21.181 (5) Å | T = 295 K |
β = 96.714 (15)° | Block, colourless |
V = 1295.8 (4) Å3 | 0.60 × 0.24 × 0.13 mm |
Z = 4 | |
Data collection top
Philips PW1100, updated by Stoe diffractometer | Rint = 0.001 |
Radiation source: fine-focus sealed tube | θmax = 30.0°, θmin = 3.0° |
Graphite monochromator | h = −11→11 |
ω scans | k = 0→10 |
7502 measured reflections | l = 0→29 |
3751 independent reflections | 3 standard reflections every 90 min |
2396 reflections with I > 2σ(I) | intensity decay: 4.2% |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0592P)2 + 0.4643P] where P = (Fo2 + 2Fc2)/3 |
3751 reflections | (Δ/σ)max = 0.001 |
175 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C12H13N3O2S | V = 1295.8 (4) Å3 |
Mr = 263.31 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.5118 (7) Å | µ = 0.25 mm−1 |
b = 7.2369 (13) Å | T = 295 K |
c = 21.181 (5) Å | 0.60 × 0.24 × 0.13 mm |
β = 96.714 (15)° | |
Data collection top
Philips PW1100, updated by Stoe diffractometer | Rint = 0.001 |
7502 measured reflections | 3 standard reflections every 90 min |
3751 independent reflections | intensity decay: 4.2% |
2396 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.34 e Å−3 |
3751 reflections | Δρmin = −0.20 e Å−3 |
175 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.6113 (2) | 0.4532 (3) | 0.19545 (9) | 0.0529 (5) | |
C2 | 0.7662 (2) | 0.4715 (3) | 0.21237 (9) | 0.0416 (4) | |
H2 | 0.8090 | 0.4190 | 0.2506 | 0.050* | |
C3 | 0.86740 (19) | 0.5634 (2) | 0.17668 (8) | 0.0330 (3) | |
C4 | 0.8080 (2) | 0.6439 (3) | 0.11770 (9) | 0.0353 (4) | |
C5 | 0.6437 (2) | 0.6247 (3) | 0.10094 (10) | 0.0495 (5) | |
H5 | 0.5961 | 0.6754 | 0.0631 | 0.059* | |
C6 | 0.5544 (2) | 0.5320 (3) | 0.13996 (12) | 0.0561 (6) | |
H6 | 0.4464 | 0.5225 | 0.1273 | 0.067* | |
S31 | 1.06857 (5) | 0.57920 (7) | 0.20629 (2) | 0.03636 (13) | |
O32 | 1.16523 (16) | 0.5336 (2) | 0.15706 (7) | 0.0492 (4) | |
O33 | 1.09061 (18) | 0.4710 (3) | 0.26349 (7) | 0.0602 (4) | |
N34 | 1.0888 (2) | 0.7967 (3) | 0.21814 (9) | 0.0472 (4) | |
H342 | 1.189 (3) | 0.834 (4) | 0.2218 (12) | 0.066 (8)* | |
H341 | 1.033 (3) | 0.840 (4) | 0.2481 (13) | 0.071 (8)* | |
N4 | 0.89991 (19) | 0.7320 (3) | 0.07944 (8) | 0.0429 (4) | |
H4 | 0.991 (3) | 0.738 (3) | 0.0914 (11) | 0.052 (7)* | |
C41 | 0.8353 (2) | 0.8420 (3) | 0.02616 (9) | 0.0399 (4) | |
C42 | 0.7811 (3) | 1.0192 (3) | 0.03619 (10) | 0.0481 (5) | |
C43 | 0.7196 (3) | 1.1207 (3) | −0.01762 (11) | 0.0569 (6) | |
H43 | 0.6835 | 1.2404 | −0.0124 | 0.068* | |
C44 | 0.7113 (3) | 1.0482 (4) | −0.07740 (11) | 0.0581 (6) | |
H44 | 0.6691 | 1.1179 | −0.1122 | 0.070* | |
C45 | 0.7657 (3) | 0.8718 (4) | −0.08625 (11) | 0.0619 (6) | |
H45 | 0.7598 | 0.8220 | −0.1269 | 0.074* | |
C46 | 0.8288 (3) | 0.7692 (3) | −0.03436 (10) | 0.0532 (5) | |
H46 | 0.8670 | 0.6507 | −0.0402 | 0.064* | |
C421 | 0.7854 (4) | 1.0996 (4) | 0.10168 (12) | 0.0782 (9) | |
H421 | 0.6969 | 1.0543 | 0.1214 | 0.117* | |
H422 | 0.7800 | 1.2318 | 0.0989 | 0.117* | |
H423 | 0.8820 | 1.0640 | 0.1267 | 0.117* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0391 (8) | 0.0583 (11) | 0.0632 (11) | −0.0051 (8) | 0.0140 (8) | 0.0157 (9) |
C2 | 0.0401 (9) | 0.0440 (10) | 0.0417 (10) | 0.0023 (8) | 0.0092 (8) | 0.0080 (8) |
C3 | 0.0306 (7) | 0.0350 (9) | 0.0333 (8) | 0.0026 (7) | 0.0036 (6) | 0.0015 (7) |
C4 | 0.0312 (8) | 0.0359 (9) | 0.0384 (9) | −0.0002 (7) | 0.0029 (7) | 0.0032 (7) |
C5 | 0.0334 (9) | 0.0590 (13) | 0.0541 (12) | −0.0010 (9) | −0.0033 (8) | 0.0179 (10) |
C6 | 0.0291 (8) | 0.0646 (14) | 0.0741 (15) | −0.0050 (9) | 0.0040 (9) | 0.0180 (12) |
S31 | 0.0297 (2) | 0.0449 (3) | 0.0339 (2) | 0.00596 (18) | 0.00132 (14) | −0.00222 (19) |
O32 | 0.0359 (7) | 0.0624 (9) | 0.0505 (8) | 0.0096 (6) | 0.0103 (6) | −0.0134 (7) |
O33 | 0.0496 (8) | 0.0805 (12) | 0.0478 (8) | 0.0092 (8) | −0.0054 (7) | 0.0195 (8) |
N34 | 0.0368 (8) | 0.0523 (10) | 0.0535 (10) | −0.0054 (8) | 0.0090 (7) | −0.0193 (8) |
N4 | 0.0312 (8) | 0.0557 (10) | 0.0414 (8) | −0.0016 (7) | 0.0020 (6) | 0.0138 (8) |
C41 | 0.0378 (9) | 0.0446 (10) | 0.0373 (9) | −0.0016 (8) | 0.0045 (7) | 0.0084 (8) |
C42 | 0.0523 (11) | 0.0496 (12) | 0.0420 (10) | 0.0035 (9) | 0.0044 (8) | −0.0002 (9) |
C43 | 0.0643 (14) | 0.0484 (12) | 0.0573 (13) | 0.0123 (10) | 0.0035 (11) | 0.0079 (10) |
C44 | 0.0629 (14) | 0.0646 (15) | 0.0456 (11) | 0.0068 (11) | 0.0016 (10) | 0.0155 (11) |
C45 | 0.0801 (17) | 0.0688 (15) | 0.0356 (10) | 0.0055 (13) | 0.0020 (10) | 0.0029 (10) |
C46 | 0.0667 (14) | 0.0486 (12) | 0.0447 (11) | 0.0073 (10) | 0.0077 (10) | 0.0019 (9) |
C421 | 0.114 (2) | 0.0649 (17) | 0.0538 (15) | 0.0191 (16) | 0.0020 (15) | −0.0141 (12) |
Geometric parameters (Å, º) top
N1—C2 | 1.332 (2) | N4—C41 | 1.437 (2) |
N1—C6 | 1.344 (3) | N4—H4 | 0.79 (2) |
C2—C3 | 1.381 (2) | C41—C46 | 1.381 (3) |
C2—H2 | 0.9300 | C41—C42 | 1.387 (3) |
C3—C4 | 1.417 (2) | C42—C43 | 1.405 (3) |
C3—S31 | 1.7571 (17) | C42—C421 | 1.501 (3) |
C4—N4 | 1.350 (2) | C43—C44 | 1.365 (3) |
C4—C5 | 1.409 (2) | C43—H43 | 0.9300 |
C5—C6 | 1.363 (3) | C44—C45 | 1.378 (4) |
C5—H5 | 0.9300 | C44—H44 | 0.9300 |
C6—H6 | 0.9300 | C45—C46 | 1.382 (3) |
S31—O33 | 1.4363 (16) | C45—H45 | 0.9300 |
S31—O32 | 1.4401 (14) | C46—H46 | 0.9300 |
S31—N34 | 1.5997 (19) | C421—H421 | 0.9600 |
N34—H342 | 0.89 (3) | C421—H422 | 0.9600 |
N34—H341 | 0.89 (3) | C421—H423 | 0.9600 |
| | | |
C2—N1—C6 | 115.94 (17) | C4—N4—H4 | 116.7 (17) |
N1—C2—C3 | 124.14 (18) | C41—N4—H4 | 119.6 (18) |
N1—C2—H2 | 117.9 | C46—C41—C42 | 121.12 (18) |
C3—C2—H2 | 117.9 | C46—C41—N4 | 119.19 (19) |
C2—C3—C4 | 119.97 (16) | C42—C41—N4 | 119.69 (18) |
C2—C3—S31 | 118.67 (14) | C41—C42—C43 | 117.26 (19) |
C4—C3—S31 | 121.35 (13) | C41—C42—C421 | 121.8 (2) |
N4—C4—C5 | 121.52 (17) | C43—C42—C421 | 120.9 (2) |
N4—C4—C3 | 123.45 (16) | C44—C43—C42 | 121.7 (2) |
C5—C4—C3 | 115.03 (16) | C44—C43—H43 | 119.1 |
C6—C5—C4 | 120.21 (18) | C42—C43—H43 | 119.1 |
C6—C5—H5 | 119.9 | C43—C44—C45 | 120.0 (2) |
C4—C5—H5 | 119.9 | C43—C44—H44 | 120.0 |
N1—C6—C5 | 124.69 (18) | C45—C44—H44 | 120.0 |
N1—C6—H6 | 117.7 | C44—C45—C46 | 119.7 (2) |
C5—C6—H6 | 117.7 | C44—C45—H45 | 120.2 |
O33—S31—O32 | 117.16 (10) | C46—C45—H45 | 120.2 |
O33—S31—N34 | 113.75 (11) | C41—C46—C45 | 120.2 (2) |
O32—S31—N34 | 106.21 (10) | C41—C46—H46 | 119.9 |
O33—S31—C3 | 106.94 (9) | C45—C46—H46 | 119.9 |
O32—S31—C3 | 110.00 (8) | C42—C421—H421 | 109.5 |
N34—S31—C3 | 101.68 (9) | C42—C421—H422 | 109.5 |
S31—N34—H342 | 113.4 (17) | H421—C421—H422 | 109.5 |
S31—N34—H341 | 113.6 (18) | C42—C421—H423 | 109.5 |
H342—N34—H341 | 115 (2) | H421—C421—H423 | 109.5 |
C4—N4—C41 | 122.54 (16) | H422—C421—H423 | 109.5 |
| | | |
C6—N1—C2—C3 | −0.3 (3) | C4—C3—S31—N34 | 65.22 (17) |
N1—C2—C3—C4 | −0.7 (3) | C5—C4—N4—C41 | 12.4 (3) |
N1—C2—C3—S31 | 178.81 (17) | C3—C4—N4—C41 | −168.01 (18) |
C2—C3—C4—N4 | −178.36 (19) | C4—N4—C41—C46 | −101.8 (2) |
S31—C3—C4—N4 | 2.1 (3) | C4—N4—C41—C42 | 78.3 (3) |
C2—C3—C4—C5 | 1.2 (3) | C46—C41—C42—C43 | 0.0 (3) |
S31—C3—C4—C5 | −178.26 (15) | N4—C41—C42—C43 | 179.8 (2) |
N4—C4—C5—C6 | 178.8 (2) | C46—C41—C42—C421 | 179.2 (2) |
C3—C4—C5—C6 | −0.8 (3) | N4—C41—C42—C421 | −1.0 (3) |
C2—N1—C6—C5 | 0.7 (4) | C41—C42—C43—C44 | 0.8 (4) |
C4—C5—C6—N1 | −0.1 (4) | C421—C42—C43—C44 | −178.4 (3) |
C2—C3—S31—O33 | 5.25 (18) | C42—C43—C44—C45 | −0.7 (4) |
C4—C3—S31—O33 | −175.25 (15) | C43—C44—C45—C46 | −0.2 (4) |
C2—C3—S31—O32 | 133.47 (16) | C42—C41—C46—C45 | −0.8 (3) |
C4—C3—S31—O32 | −47.03 (17) | N4—C41—C46—C45 | 179.3 (2) |
C2—C3—S31—N34 | −114.28 (16) | C44—C45—C46—C41 | 0.9 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O32 | 0.79 (3) | 2.42 (2) | 3.000 (2) | 132 (2) |
N34—H342···O33i | 0.91 (3) | 2.10 (3) | 2.990 (2) | 169 (3) |
N34—H341···N1ii | 0.86 (3) | 2.00 (3) | 2.875 (3) | 172 (3) |
C2—H2···O33 | 0.93 | 2.41 | 2.845 (2) | 109 |
C6—H6···O32iii | 0.93 | 2.55 | 3.374 (2) | 148 |
Symmetry codes: (i) −x+5/2, y+1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1, y, z. |
(II) 4-(3-methylanilino)pyridine-3-sulfonamide
top
Crystal data top
C12H13N3O2S | Z = 2 |
Mr = 263.31 | F(000) = 276 |
Triclinic, P1 | Dx = 1.399 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.7621 (9) Å | Cell parameters from 40 reflections |
b = 8.6521 (13) Å | θ = 8.2–16.4° |
c = 11.4715 (18) Å | µ = 0.26 mm−1 |
α = 98.523 (11)° | T = 295 K |
β = 102.398 (12)° | Prism, colourless |
γ = 102.991 (9)° | 0.45 × 0.30 × 0.27 mm |
V = 624.97 (16) Å3 | |
Data collection top
Philips PW1100, updated by Stoe diffractometer | Rint = 0.001 |
Radiation source: fine-focus sealed tube | θmax = 28.9°, θmin = 2.5° |
Graphite monochromator | h = −9→8 |
ω scans | k = −11→11 |
6556 measured reflections | l = 0→15 |
3278 independent reflections | 3 standard reflections every 90 min |
3014 reflections with I > 2σ(I) | intensity decay: 1.6% |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.079P)2 + 0.1589P] where P = (Fo2 + 2Fc2)/3 |
3278 reflections | (Δ/σ)max < 0.001 |
176 parameters | Δρmax = 0.48 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C12H13N3O2S | γ = 102.991 (9)° |
Mr = 263.31 | V = 624.97 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.7621 (9) Å | Mo Kα radiation |
b = 8.6521 (13) Å | µ = 0.26 mm−1 |
c = 11.4715 (18) Å | T = 295 K |
α = 98.523 (11)° | 0.45 × 0.30 × 0.27 mm |
β = 102.398 (12)° | |
Data collection top
Philips PW1100, updated by Stoe diffractometer | Rint = 0.001 |
6556 measured reflections | 3 standard reflections every 90 min |
3278 independent reflections | intensity decay: 1.6% |
3014 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.130 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.48 e Å−3 |
3278 reflections | Δρmin = −0.32 e Å−3 |
176 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.2470 (2) | 0.32954 (18) | 0.68429 (14) | 0.0437 (3) | |
C2 | 0.3465 (2) | 0.27697 (18) | 0.60477 (15) | 0.0384 (3) | |
H2 | 0.2744 | 0.1835 | 0.5461 | 0.046* | |
C3 | 0.5503 (2) | 0.35141 (17) | 0.60285 (12) | 0.0327 (3) | |
C4 | 0.6646 (2) | 0.49539 (17) | 0.68929 (13) | 0.0338 (3) | |
C5 | 0.5581 (3) | 0.5494 (2) | 0.77355 (15) | 0.0423 (3) | |
H5 | 0.6243 | 0.6424 | 0.8337 | 0.051* | |
C6 | 0.3568 (3) | 0.4651 (2) | 0.76688 (16) | 0.0454 (4) | |
H6 | 0.2916 | 0.5049 | 0.8238 | 0.055* | |
S31 | 0.66125 (5) | 0.25495 (4) | 0.49696 (3) | 0.03266 (13) | |
O32 | 0.79591 (18) | 0.37859 (13) | 0.45777 (10) | 0.0421 (3) | |
O33 | 0.49120 (18) | 0.13769 (14) | 0.40784 (10) | 0.0444 (3) | |
N34 | 0.8089 (2) | 0.15843 (17) | 0.56700 (13) | 0.0389 (3) | |
H341 | 0.925 (4) | 0.212 (3) | 0.609 (2) | 0.047 (5)* | |
H342 | 0.748 (4) | 0.085 (3) | 0.592 (2) | 0.061 (7)* | |
N4 | 0.8635 (2) | 0.57610 (17) | 0.69146 (13) | 0.0415 (3) | |
H4 | 0.900 (4) | 0.558 (3) | 0.627 (2) | 0.064 (7)* | |
C41 | 0.9877 (2) | 0.71423 (17) | 0.78238 (14) | 0.0361 (3) | |
C42 | 1.0395 (3) | 0.70311 (19) | 0.90431 (14) | 0.0411 (3) | |
H42 | 0.9891 | 0.6053 | 0.9261 | 0.049* | |
C43 | 1.1653 (3) | 0.8356 (2) | 0.99439 (15) | 0.0450 (4) | |
C44 | 1.2389 (3) | 0.9789 (2) | 0.95904 (18) | 0.0513 (4) | |
H44 | 1.3222 | 1.0691 | 1.0178 | 0.062* | |
C45 | 1.1912 (3) | 0.9906 (2) | 0.83813 (19) | 0.0535 (4) | |
H45 | 1.2442 | 1.0879 | 0.8164 | 0.064* | |
C46 | 1.0648 (3) | 0.8586 (2) | 0.74872 (16) | 0.0443 (3) | |
H46 | 1.0324 | 0.8670 | 0.6673 | 0.053* | |
C431 | 1.2201 (4) | 0.8202 (3) | 1.12567 (18) | 0.0692 (6) | |
H431 | 1.3215 | 0.7583 | 1.1373 | 0.104* | |
H432 | 1.0958 | 0.7663 | 1.1463 | 0.104* | |
H433 | 1.2781 | 0.9261 | 1.1772 | 0.104* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0324 (6) | 0.0462 (7) | 0.0540 (8) | 0.0081 (5) | 0.0158 (6) | 0.0117 (6) |
C2 | 0.0320 (7) | 0.0356 (7) | 0.0442 (8) | 0.0025 (5) | 0.0097 (6) | 0.0085 (6) |
C3 | 0.0302 (6) | 0.0323 (6) | 0.0332 (6) | 0.0039 (5) | 0.0081 (5) | 0.0064 (5) |
C4 | 0.0313 (6) | 0.0323 (6) | 0.0355 (6) | 0.0052 (5) | 0.0083 (5) | 0.0051 (5) |
C5 | 0.0382 (7) | 0.0406 (8) | 0.0452 (8) | 0.0096 (6) | 0.0124 (6) | −0.0008 (6) |
C6 | 0.0393 (8) | 0.0503 (9) | 0.0512 (9) | 0.0156 (7) | 0.0191 (7) | 0.0074 (7) |
S31 | 0.03133 (19) | 0.03083 (19) | 0.02946 (19) | −0.00222 (13) | 0.00819 (13) | 0.00224 (13) |
O32 | 0.0448 (6) | 0.0388 (6) | 0.0377 (5) | −0.0037 (4) | 0.0165 (4) | 0.0063 (4) |
O33 | 0.0405 (6) | 0.0427 (6) | 0.0352 (5) | −0.0078 (5) | 0.0051 (4) | −0.0014 (4) |
N34 | 0.0341 (6) | 0.0349 (6) | 0.0449 (7) | 0.0034 (5) | 0.0118 (5) | 0.0058 (5) |
N4 | 0.0363 (6) | 0.0398 (7) | 0.0384 (6) | −0.0038 (5) | 0.0126 (5) | −0.0056 (5) |
C41 | 0.0317 (6) | 0.0331 (7) | 0.0380 (7) | 0.0036 (5) | 0.0087 (5) | −0.0011 (5) |
C42 | 0.0430 (8) | 0.0366 (7) | 0.0412 (8) | 0.0073 (6) | 0.0112 (6) | 0.0049 (6) |
C43 | 0.0418 (8) | 0.0489 (9) | 0.0392 (7) | 0.0132 (7) | 0.0056 (6) | −0.0016 (6) |
C44 | 0.0455 (8) | 0.0395 (8) | 0.0543 (10) | 0.0032 (7) | 0.0036 (7) | −0.0091 (7) |
C45 | 0.0528 (10) | 0.0348 (8) | 0.0641 (11) | −0.0004 (7) | 0.0114 (8) | 0.0065 (7) |
C46 | 0.0456 (8) | 0.0400 (8) | 0.0430 (8) | 0.0044 (6) | 0.0102 (6) | 0.0080 (6) |
C431 | 0.0736 (14) | 0.0816 (15) | 0.0417 (10) | 0.0190 (12) | 0.0021 (9) | 0.0016 (10) |
Geometric parameters (Å, º) top
N1—C2 | 1.330 (2) | N4—C41 | 1.4229 (18) |
N1—C6 | 1.342 (2) | N4—H4 | 0.83 (3) |
C2—C3 | 1.3902 (19) | C41—C46 | 1.385 (2) |
C2—H2 | 0.9300 | C41—C42 | 1.390 (2) |
C3—C4 | 1.4157 (19) | C42—C43 | 1.392 (2) |
C3—S31 | 1.7629 (15) | C42—H42 | 0.9300 |
C4—N4 | 1.3620 (19) | C43—C44 | 1.381 (3) |
C4—C5 | 1.410 (2) | C43—C431 | 1.505 (3) |
C5—C6 | 1.372 (2) | C44—C45 | 1.379 (3) |
C5—H5 | 0.9300 | C44—H44 | 0.9300 |
C6—H6 | 0.9300 | C45—C46 | 1.387 (2) |
S31—O32 | 1.4339 (11) | C45—H45 | 0.9300 |
S31—O33 | 1.4353 (11) | C46—H46 | 0.9300 |
S31—N34 | 1.6028 (15) | C431—H431 | 0.9600 |
N34—H341 | 0.82 (2) | C431—H432 | 0.9600 |
N34—H342 | 0.80 (3) | C431—H433 | 0.9600 |
| | | |
C2—N1—C6 | 115.49 (13) | C4—N4—H4 | 116.4 (17) |
N1—C2—C3 | 124.84 (14) | C41—N4—H4 | 117.7 (17) |
N1—C2—H2 | 117.6 | C46—C41—C42 | 119.79 (14) |
C3—C2—H2 | 117.6 | C46—C41—N4 | 119.84 (14) |
C2—C3—C4 | 119.45 (13) | C42—C41—N4 | 120.32 (14) |
C2—C3—S31 | 117.97 (11) | C41—C42—C43 | 121.29 (15) |
C4—C3—S31 | 122.48 (10) | C41—C42—H42 | 119.4 |
N4—C4—C5 | 122.20 (14) | C43—C42—H42 | 119.4 |
N4—C4—C3 | 122.59 (13) | C44—C43—C42 | 117.99 (16) |
C5—C4—C3 | 115.21 (13) | C44—C43—C431 | 121.73 (17) |
C6—C5—C4 | 120.12 (15) | C42—C43—C431 | 120.27 (18) |
C6—C5—H5 | 119.9 | C45—C44—C43 | 121.21 (16) |
C4—C5—H5 | 119.9 | C45—C44—H44 | 119.4 |
N1—C6—C5 | 124.88 (15) | C43—C44—H44 | 119.4 |
N1—C6—H6 | 117.6 | C44—C45—C46 | 120.62 (17) |
C5—C6—H6 | 117.6 | C44—C45—H45 | 119.7 |
O32—S31—O33 | 119.23 (7) | C46—C45—H45 | 119.7 |
O32—S31—N34 | 106.65 (8) | C41—C46—C45 | 119.08 (16) |
O33—S31—N34 | 107.68 (8) | C41—C46—H46 | 120.5 |
O32—S31—C3 | 107.83 (7) | C45—C46—H46 | 120.5 |
O33—S31—C3 | 106.93 (7) | C43—C431—H431 | 109.5 |
N34—S31—C3 | 108.11 (7) | C43—C431—H432 | 109.5 |
S31—N34—H341 | 116.6 (15) | H431—C431—H432 | 109.5 |
S31—N34—H342 | 114.6 (18) | C43—C431—H433 | 109.5 |
H341—N34—H342 | 118 (2) | H431—C431—H433 | 109.5 |
C4—N4—C41 | 123.83 (13) | H432—C431—H433 | 109.5 |
| | | |
C6—N1—C2—C3 | 0.3 (2) | C4—C3—S31—N34 | 77.27 (13) |
N1—C2—C3—C4 | −1.0 (2) | C5—C4—N4—C41 | 4.5 (2) |
N1—C2—C3—S31 | 175.54 (12) | C3—C4—N4—C41 | −175.30 (14) |
C2—C3—C4—N4 | −178.91 (14) | C4—N4—C41—C46 | −122.31 (18) |
S31—C3—C4—N4 | 4.7 (2) | C4—N4—C41—C42 | 60.5 (2) |
C2—C3—C4—C5 | 1.3 (2) | C46—C41—C42—C43 | 1.1 (2) |
S31—C3—C4—C5 | −175.10 (11) | N4—C41—C42—C43 | 178.32 (14) |
N4—C4—C5—C6 | 179.21 (16) | C41—C42—C43—C44 | −0.4 (2) |
C3—C4—C5—C6 | −1.0 (2) | C41—C42—C43—C431 | −179.67 (17) |
C2—N1—C6—C5 | 0.1 (3) | C42—C43—C44—C45 | −0.6 (3) |
C4—C5—C6—N1 | 0.3 (3) | C431—C43—C44—C45 | 178.6 (2) |
C2—C3—S31—O32 | 145.90 (12) | C43—C44—C45—C46 | 0.9 (3) |
C4—C3—S31—O32 | −37.68 (14) | C42—C41—C46—C45 | −0.7 (2) |
C2—C3—S31—O33 | 16.55 (14) | N4—C41—C46—C45 | −177.96 (16) |
C4—C3—S31—O33 | −167.04 (12) | C44—C45—C46—C41 | −0.3 (3) |
C2—C3—S31—N34 | −99.15 (13) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O32 | 0.83 (2) | 2.17 (2) | 2.843 (2) | 138 (2) |
N4—H4···O32i | 0.83 (2) | 2.45 (3) | 3.143 (2) | 142 (2) |
N34—H341···N1ii | 0.82 (3) | 2.11 (3) | 2.917 (2) | 168 (2) |
N34—H342···O33iii | 0.80 (3) | 2.22 (3) | 2.983 (2) | 159 (3) |
C2—H2···O33 | 0.93 | 2.43 | 2.861 (2) | 108 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+1. |
(III) 4-(4-methylanilino)pyridine-3-sulfonamide
top
Crystal data top
C12H13N3O2S | F(000) = 552 |
Mr = 263.31 | Dx = 1.399 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 39 reflections |
a = 10.7730 (19) Å | θ = 8.9–16.7° |
b = 9.271 (4) Å | µ = 0.26 mm−1 |
c = 12.5769 (16) Å | T = 295 K |
β = 95.71 (2)° | Prism, colourless |
V = 1249.9 (6) Å3 | 0.53 × 0.20 × 0.15 mm |
Z = 4 | |
Data collection top
Philips PW1100, updated by Stoe diffractometer | Rint = 0.001 |
Radiation source: fine-focus sealed tube | θmax = 29.9°, θmin = 2.7° |
Graphite monochromator | h = −15→15 |
ω scans | k = 0→13 |
7224 measured reflections | l = 0→17 |
3612 independent reflections | 3 standard reflections every 90 min |
2432 reflections with I > 2σ(I) | intensity decay: 5.0% |
Refinement top
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)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.121 | w = 1/[σ2(Fo2) + (0.0611P)2 + 0.3511P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
3612 reflections | Δρmax = 0.32 e Å−3 |
176 parameters | Δρmin = −0.28 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: 0.045 (3) |
Crystal data top
C12H13N3O2S | V = 1249.9 (6) Å3 |
Mr = 263.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.7730 (19) Å | µ = 0.26 mm−1 |
b = 9.271 (4) Å | T = 295 K |
c = 12.5769 (16) Å | 0.53 × 0.20 × 0.15 mm |
β = 95.71 (2)° | |
Data collection top
Philips PW1100, updated by Stoe diffractometer | Rint = 0.001 |
7224 measured reflections | 3 standard reflections every 90 min |
3612 independent reflections | intensity decay: 5.0% |
2432 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.32 e Å−3 |
3612 reflections | Δρmin = −0.28 e Å−3 |
176 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.87305 (15) | 0.39979 (17) | 0.35781 (12) | 0.0456 (4) | |
C2 | 0.95088 (17) | 0.32681 (19) | 0.42746 (13) | 0.0392 (4) | |
H2 | 1.0246 | 0.2921 | 0.4043 | 0.047* | |
C3 | 0.92843 (15) | 0.29968 (19) | 0.53233 (12) | 0.0349 (3) | |
C4 | 0.81965 (16) | 0.3553 (2) | 0.57152 (13) | 0.0405 (4) | |
C5 | 0.73750 (18) | 0.4300 (2) | 0.49756 (15) | 0.0484 (4) | |
H5 | 0.6631 | 0.4668 | 0.5179 | 0.058* | |
C6 | 0.7677 (2) | 0.4485 (2) | 0.39468 (15) | 0.0510 (5) | |
H6 | 0.7113 | 0.4981 | 0.3472 | 0.061* | |
S31 | 1.03370 (4) | 0.18905 (5) | 0.61178 (3) | 0.03591 (13) | |
O32 | 1.07394 (12) | 0.26519 (15) | 0.70858 (9) | 0.0458 (3) | |
O33 | 1.12483 (12) | 0.14309 (16) | 0.54305 (10) | 0.0481 (3) | |
N34 | 0.96097 (17) | 0.05030 (19) | 0.64689 (14) | 0.0467 (4) | |
H341 | 0.925 (3) | 0.056 (3) | 0.698 (2) | 0.080 (9)* | |
H342 | 0.9294 (19) | −0.003 (3) | 0.5955 (18) | 0.053 (6)* | |
N4 | 0.79914 (15) | 0.3386 (2) | 0.67605 (12) | 0.0510 (4) | |
H4 | 0.858 (2) | 0.323 (3) | 0.7169 (19) | 0.061* | |
C41 | 0.68244 (16) | 0.3430 (2) | 0.71949 (13) | 0.0403 (4) | |
C42 | 0.67788 (16) | 0.4015 (2) | 0.82022 (14) | 0.0428 (4) | |
H42 | 0.7481 | 0.4453 | 0.8552 | 0.051* | |
C43 | 0.56814 (17) | 0.3945 (2) | 0.86876 (14) | 0.0476 (4) | |
H43 | 0.5666 | 0.4325 | 0.9370 | 0.057* | |
C44 | 0.46088 (17) | 0.3328 (2) | 0.81906 (15) | 0.0465 (4) | |
C45 | 0.46679 (19) | 0.2766 (3) | 0.71782 (17) | 0.0551 (5) | |
H45 | 0.3957 | 0.2355 | 0.6821 | 0.066* | |
C46 | 0.57616 (19) | 0.2802 (2) | 0.66829 (16) | 0.0539 (5) | |
H46 | 0.5781 | 0.2403 | 0.6006 | 0.065* | |
C441 | 0.3427 (2) | 0.3262 (4) | 0.8744 (2) | 0.0752 (8) | |
H441 | 0.3626 | 0.2981 | 0.9475 | 0.113* | |
H442 | 0.2866 | 0.2570 | 0.8389 | 0.113* | |
H443 | 0.3037 | 0.4195 | 0.8717 | 0.113* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0566 (9) | 0.0476 (9) | 0.0334 (7) | 0.0031 (7) | 0.0087 (6) | 0.0040 (6) |
C2 | 0.0439 (9) | 0.0428 (9) | 0.0325 (8) | 0.0010 (7) | 0.0113 (6) | −0.0001 (7) |
C3 | 0.0342 (7) | 0.0413 (9) | 0.0301 (7) | 0.0002 (7) | 0.0074 (6) | −0.0024 (6) |
C4 | 0.0390 (8) | 0.0505 (10) | 0.0331 (8) | 0.0030 (7) | 0.0092 (6) | −0.0023 (7) |
C5 | 0.0447 (9) | 0.0585 (12) | 0.0432 (9) | 0.0138 (8) | 0.0094 (7) | 0.0015 (8) |
C6 | 0.0566 (11) | 0.0551 (12) | 0.0412 (9) | 0.0113 (9) | 0.0051 (8) | 0.0088 (8) |
S31 | 0.0340 (2) | 0.0450 (2) | 0.02965 (19) | 0.00144 (17) | 0.00755 (13) | −0.00014 (16) |
O32 | 0.0450 (7) | 0.0577 (8) | 0.0342 (6) | −0.0060 (6) | 0.0005 (5) | −0.0043 (6) |
O33 | 0.0411 (7) | 0.0640 (8) | 0.0413 (7) | 0.0121 (6) | 0.0150 (5) | 0.0031 (6) |
N34 | 0.0596 (10) | 0.0475 (9) | 0.0346 (8) | −0.0084 (8) | 0.0130 (7) | −0.0019 (7) |
N4 | 0.0380 (8) | 0.0867 (13) | 0.0294 (7) | 0.0148 (8) | 0.0085 (6) | −0.0011 (8) |
C41 | 0.0379 (8) | 0.0496 (10) | 0.0346 (8) | 0.0081 (7) | 0.0102 (6) | −0.0012 (7) |
C42 | 0.0379 (8) | 0.0549 (11) | 0.0364 (8) | −0.0001 (8) | 0.0072 (6) | −0.0075 (8) |
C43 | 0.0442 (9) | 0.0626 (12) | 0.0378 (9) | 0.0044 (9) | 0.0133 (7) | −0.0071 (8) |
C44 | 0.0363 (8) | 0.0586 (12) | 0.0460 (10) | 0.0017 (8) | 0.0107 (7) | 0.0039 (8) |
C45 | 0.0434 (10) | 0.0660 (13) | 0.0555 (12) | −0.0077 (9) | 0.0025 (8) | −0.0100 (10) |
C46 | 0.0504 (11) | 0.0689 (13) | 0.0430 (10) | 0.0014 (10) | 0.0068 (8) | −0.0185 (9) |
C441 | 0.0407 (10) | 0.121 (2) | 0.0662 (14) | −0.0061 (13) | 0.0185 (10) | 0.0052 (15) |
Geometric parameters (Å, º) top
N1—C2 | 1.335 (2) | N4—C41 | 1.420 (2) |
N1—C6 | 1.346 (2) | N4—H4 | 0.79 (3) |
C2—C3 | 1.387 (2) | C41—C42 | 1.384 (2) |
C2—H2 | 0.9300 | C41—C46 | 1.385 (3) |
C3—C4 | 1.413 (2) | C42—C43 | 1.385 (2) |
C3—S31 | 1.7639 (18) | C42—H42 | 0.9300 |
C4—N4 | 1.363 (2) | C43—C44 | 1.382 (3) |
C4—C5 | 1.401 (3) | C43—H43 | 0.9300 |
C5—C6 | 1.376 (3) | C44—C45 | 1.383 (3) |
C5—H5 | 0.9300 | C44—C441 | 1.512 (3) |
C6—H6 | 0.9300 | C45—C46 | 1.387 (3) |
S31—O33 | 1.4357 (12) | C45—H45 | 0.9300 |
S31—O32 | 1.4365 (13) | C46—H46 | 0.9300 |
S31—N34 | 1.5914 (18) | C441—H441 | 0.9600 |
N34—H341 | 0.78 (3) | C441—H442 | 0.9600 |
N34—H342 | 0.86 (2) | C441—H443 | 0.9600 |
| | | |
C2—N1—C6 | 116.11 (15) | C4—N4—H4 | 116.7 (18) |
N1—C2—C3 | 123.93 (16) | C41—N4—H4 | 116.3 (18) |
N1—C2—H2 | 118.0 | C42—C41—C46 | 119.19 (16) |
C3—C2—H2 | 118.0 | C42—C41—N4 | 118.48 (16) |
C2—C3—C4 | 119.63 (16) | C46—C41—N4 | 122.12 (16) |
C2—C3—S31 | 118.74 (13) | C41—C42—C43 | 119.65 (17) |
C4—C3—S31 | 121.56 (12) | C41—C42—H42 | 120.2 |
N4—C4—C5 | 122.96 (16) | C43—C42—H42 | 120.2 |
N4—C4—C3 | 120.95 (16) | C44—C43—C42 | 122.16 (17) |
C5—C4—C3 | 116.07 (15) | C44—C43—H43 | 118.9 |
C6—C5—C4 | 119.55 (17) | C42—C43—H43 | 118.9 |
C6—C5—H5 | 120.2 | C43—C44—C45 | 117.34 (17) |
C4—C5—H5 | 120.2 | C43—C44—C441 | 120.90 (18) |
N1—C6—C5 | 124.63 (18) | C45—C44—C441 | 121.76 (19) |
N1—C6—H6 | 117.7 | C44—C45—C46 | 121.58 (18) |
C5—C6—H6 | 117.7 | C44—C45—H45 | 119.2 |
O33—S31—O32 | 119.30 (8) | C46—C45—H45 | 119.2 |
O33—S31—N34 | 108.19 (9) | C41—C46—C45 | 120.07 (17) |
O32—S31—N34 | 106.11 (9) | C41—C46—H46 | 120.0 |
O33—S31—C3 | 105.73 (8) | C45—C46—H46 | 120.0 |
O32—S31—C3 | 108.49 (8) | C44—C441—H441 | 109.5 |
N34—S31—C3 | 108.70 (9) | C44—C441—H442 | 109.5 |
S31—N34—H341 | 118 (2) | H441—C441—H442 | 109.5 |
S31—N34—H342 | 115.2 (15) | C44—C441—H443 | 109.5 |
H341—N34—H342 | 118 (2) | H441—C441—H443 | 109.5 |
C4—N4—C41 | 127.02 (16) | H442—C441—H443 | 109.5 |
| | | |
C6—N1—C2—C3 | 0.2 (3) | C4—C3—S31—N34 | 58.82 (17) |
N1—C2—C3—C4 | −2.3 (3) | C5—C4—N4—C41 | 24.2 (3) |
N1—C2—C3—S31 | 174.83 (14) | C3—C4—N4—C41 | −157.22 (19) |
C2—C3—C4—N4 | −175.64 (18) | C4—N4—C41—C42 | −145.0 (2) |
S31—C3—C4—N4 | 7.3 (3) | C4—N4—C41—C46 | 40.4 (3) |
C2—C3—C4—C5 | 3.0 (3) | C46—C41—C42—C43 | 1.0 (3) |
S31—C3—C4—C5 | −174.03 (14) | N4—C41—C42—C43 | −173.75 (18) |
N4—C4—C5—C6 | 176.8 (2) | C41—C42—C43—C44 | −1.2 (3) |
C3—C4—C5—C6 | −1.8 (3) | C42—C43—C44—C45 | 0.4 (3) |
C2—N1—C6—C5 | 1.1 (3) | C42—C43—C44—C441 | 179.7 (2) |
C4—C5—C6—N1 | −0.3 (3) | C43—C44—C45—C46 | 0.8 (3) |
C2—C3—S31—O33 | −2.31 (17) | C441—C44—C45—C46 | −178.6 (2) |
C4—C3—S31—O33 | 174.78 (15) | C42—C41—C46—C45 | 0.1 (3) |
C2—C3—S31—O32 | 126.77 (14) | N4—C41—C46—C45 | 174.6 (2) |
C4—C3—S31—O32 | −56.14 (17) | C44—C45—C46—C41 | −1.0 (3) |
C2—C3—S31—N34 | −118.27 (15) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O32 | 0.79 (2) | 2.38 (2) | 3.025 (2) | 137 (2) |
N34—H341···N1i | 0.80 (3) | 2.16 (3) | 2.940 (2) | 166 (3) |
N34—H342···O33ii | 0.87 (2) | 2.19 (2) | 3.056 (2) | 172 (2) |
C2—H2···O33 | 0.93 | 2.40 | 2.826 (3) | 108 |
C42—H42···O33iii | 0.93 | 2.56 | 3.430 (3) | 157 |
N4—H4···N1i | 0.79 (2) | 2.71 (2) | 3.222 (2) | 124 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, y+1/2, −z+3/2. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C12H13N3O2S | C12H13N3O2S | C12H13N3O2S |
Mr | 263.31 | 263.31 | 263.31 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 | Monoclinic, P21/c |
Temperature (K) | 295 | 295 | 295 |
a, b, c (Å) | 8.5118 (7), 7.2369 (13), 21.181 (5) | 6.7621 (9), 8.6521 (13), 11.4715 (18) | 10.7730 (19), 9.271 (4), 12.5769 (16) |
α, β, γ (°) | 90, 96.714 (15), 90 | 98.523 (11), 102.398 (12), 102.991 (9) | 90, 95.71 (2), 90 |
V (Å3) | 1295.8 (4) | 624.97 (16) | 1249.9 (6) |
Z | 4 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.25 | 0.26 | 0.26 |
Crystal size (mm) | 0.60 × 0.24 × 0.13 | 0.45 × 0.30 × 0.27 | 0.53 × 0.20 × 0.15 |
|
Data collection |
Diffractometer | Philips PW1100, updated by Stoe diffractometer | Philips PW1100, updated by Stoe diffractometer | Philips PW1100, updated by Stoe diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7502, 3751, 2396 | 6556, 3278, 3014 | 7224, 3612, 2432 |
Rint | 0.001 | 0.001 | 0.001 |
(sin θ/λ)max (Å−1) | 0.702 | 0.680 | 0.702 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.127, 1.02 | 0.045, 0.130, 1.11 | 0.041, 0.121, 1.02 |
No. of reflections | 3751 | 3278 | 3612 |
No. of parameters | 175 | 176 | 176 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.20 | 0.48, −0.32 | 0.32, −0.28 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O32 | 0.79 (3) | 2.42 (2) | 3.000 (2) | 132 (2) |
N34—H342···O33i | 0.91 (3) | 2.10 (3) | 2.990 (2) | 169 (3) |
N34—H341···N1ii | 0.86 (3) | 2.00 (3) | 2.875 (3) | 172 (3) |
C2—H2···O33 | 0.93 | 2.41 | 2.845 (2) | 108.5 |
C6—H6···O32iii | 0.93 | 2.55 | 3.374 (2) | 148.4 |
Symmetry codes: (i) −x+5/2, y+1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1, y, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O32 | 0.83 (2) | 2.17 (2) | 2.843 (2) | 138 (2) |
N4—H4···O32i | 0.83 (2) | 2.45 (3) | 3.143 (2) | 142 (2) |
N34—H341···N1ii | 0.82 (3) | 2.11 (3) | 2.917 (2) | 168 (2) |
N34—H342···O33iii | 0.80 (3) | 2.22 (3) | 2.983 (2) | 159 (3) |
C2—H2···O33 | 0.93 | 2.43 | 2.861 (2) | 108 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x+1, y, z; (iii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···O32 | 0.79 (2) | 2.38 (2) | 3.025 (2) | 137 (2) |
N34—H341···N1i | 0.80 (3) | 2.16 (3) | 2.940 (2) | 166 (3) |
N34—H342···O33ii | 0.87 (2) | 2.19 (2) | 3.056 (2) | 172 (2) |
C2—H2···O33 | 0.93 | 2.40 | 2.826 (3) | 108 |
C42—H42···O33iii | 0.93 | 2.56 | 3.430 (3) | 157 |
N4—H4···N1i | 0.79 (2) | 2.71 (2) | 3.222 (2) | 124 (2) |
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, y+1/2, −z+3/2. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Sulfonamides constitute an important class of drugs, with several types of pharmacological agents possessing, for example, antibacterial, anti-carbonic anhydrase, diuretic, hypoglycaemic, antithyroid and anticancer activities. From a structural point of view, sulfonamides are interesting because of their tendency to form different hydrogen-bond systems in the solid state by introducing various hydrogen-bond donors and acceptors as substituents into simple sulfonamide molecules. The most common hydrogen-bond motifs, widely observed in crystal structures of simple benzenesulfonamide, are realised via N—H···O hydrogen bonds constituting chains or rings, C(4) and R22(8) types (Etter et al., 1990; Bernstein et al., 1995). A search of the Cambridge Structural Database (CSD, Version 5.26 plus three updates; Allen, 2002) for sulfonamide structures involving R22(8) and C(4) hydrogen-bond motifs (restricting H···O contact distances from 1.0 to 2.7 Å, organic molecules only, redeterminations omitted) identified 13 structures containing R22(8) dimers and 36 structures containing C(4) chains. Only in the crystal structure of GUFQED (Tremayne et al., 1999) are both hydrogen-bond motifs present.
Here, we report the synthesis and structure of three pyridinesulfonamide isomers, (I), (II) and (III). These pyridinesulfonamides are known as intermediates and potential impurities of the drug torasemide, which is widely used as a loop diuretic (Danilovski et al., 2001).
The X-ray analyses of (I), (II) and (III) (Figs. 1–3) unambiguously confirm their ortho-, meta- and para-substitution patterns. The three isomers differ primarily in their phenyl-ring orientation with respect to the pyridine ring (Fig. 4). The dihedral angles between the best planes of the pyridyl and phenyl rings are 93.95 (7), 117.75 (5) and 122.40 (5)° in (I), (II) and (III), respectively. The conformation of the 4-aminopyridine-3-sulfonamide part of the molecule is conserved by an intramolecular N4—H4···O32 hydrogen bond and the C2—H2···O33 interaction in all three isomers. The C4—C3—S31—N34 torsion angles amount to 65.22 (17), 77.27 (13) and 58.82 (17)° in (I), (II) and (III), respectively.
Although the same intermolecular hydrogen-bonding types (sulfonamide NH2 groups as donors to sulfonamide O or pyridine N atoms) are observed in all three structures (Tables 1–3), their supramolecular structures are appreciably different.
In compound (I), two major chains, C(4) and C(6), are formed via N34—H342···O33 and N34—H341···N1 hydrogen bonds, respectively. Both chains run parallel to the b axis and combine to form a tetramolecular R44(18) motif. Additional linking across these 18-membered rings is realised by weak C6—H6···O32 interactions forming a C(7) chain parallel to the a axis. These three chains combine to form layers parallel to (001) (Fig. 5).
The observed C(4) chain motif is characteristic of simple sulfonamides. The most characteristic hydrogen-bond motif of sulfonamides, the R22(8) ring (for a discussion of both types, see Glidewell et al., 2004, and references cited therein) is, however, not observed for (I), but only for the structures of (II) and (III).
In contrast with (I), where the C(4) and C(6) chains are helical, the C(6) chains in compound (II) are formed by pure translation parallel to the a axis (Fig. 6), whereby the N34—H341···N1 hydrogen bond connects the molecules (denoted A, B, C, D, etc.). The second chain is built up from molecules (denoted A', B', C', D', etc.) related to the first chain by inversion. Centrosymmetrically related molecules B/B', etc., are connected by intermolecular N4—H4···O32 hydrogen bonds to form dimers involving R22(4) rings. By these interactions, two antiparallel C(6) chains form one ribbon through each unit cell. Two adjacent ribbons, related by translation in the b direction, are bridged by centrosymmetrically related intermolecular N34—H342···O33 hydrogen bonds, forming R22(8) rings. The net effect of these hydrogen-bonding arrangements is to form layers parallel to (001).
In compound (III) (Fig. 7), the sulfonamide group participates in the same type of centrosymmetric N—H···O hydrogen bonds as found in (II), and there are N—H···N hydrogen-bonded chains such as were observed in both (I) and (II). The overall packing of the molecule of (III) shows a network of molecules interlinked via classical and non-classical hydrogen bonds. The characteristic R22(8) hydrogen-bond motif is formed via N34—H342···O33 hydrogen bonds connecting two molecules to centrosymmetric dimers at (0, 1/2, 1/2). The dimers are further linked to each other by three additional interactions: the intermolecular N34—H341···N1 hydrogen bond forms C(6) chains parallel to the c axis, N4—H4···N1 can be considered as a weak component of a three-centre hydrogen bond, and C42—H42···O33 interactions additionally stabilize the structure. The overall effect is to form layers parallel to (100).