The X-ray crystal structures of solvates of sulfapyridine have been determined to be conformational polymorphs. 4-Amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide (polymorph III), C11H11N3O2S, (1), 4-amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide 1,3-dioxane monosolvate, C11H11N3O2S·C4H8O2, (2), and 4-amino-N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide tetrahydrofuran monosolvate, C11H11N3O2S·C4H8O, (3), crystallized as the imide form, while piperidin-1-ium 4-amino-N-(pyridin-2-yl)benzenesulfonamidate, C5H12N+·C11H10N3O2S-, (4), crystallized as the piperidinium salt. The tetrahydrofuran and dioxane solvent molecules in their respective structures were disordered and were refined using a disorder model. Three-dimensional hydrogen-bonding networks exist in all structures between at least one sulfone O atom and the aniline N atom.
Supporting information
CCDC references: 862231; 862232; 862233; 862234
All the sulfapyridine crystals were prepared by slow evaporation from a
saturated solution of sulfapyridine and solvent [ethanol for (I), dioxane for
(II), tetrahydrofuran for (III), and piperidine for (IV)]. Mixtures were
allowed to stand at room temperature for a few days after mixing. Single
crystals were collected from the evaporation mixtures and allowed to air dry.
H atoms were located in difference maps except in the disordered dioxane and
tetrahydrofuran solvent molecules where they were calculated. The dioxane and
the tetrahydrofuran solvent molecules were refined with a disorder model. In
this model, the disordered pair in each structure was divided into parts 1 and
2 with constraints applied such that the sum of the occupancies was 1.0 and
bond lengths of similar bond types were equal and within a defined tolerance,
i.e. Csp3—Csp3 bonds were constrained to be equal
within a tolerance of 0.002 Å and Csp3—Osp3 bonds were
constrained to be equal within a tolerance of 0.002 Å. H atoms bonded to N
atoms likely to be involved in hydrogen-bonding interactions were allowed to
refine independently assuming they converged to chemically reasonable values.
In sulfapyridine, H atoms bonded to N1 and N3 were allowed to refine
independently. In the dioxane solvent molecule, only the H atom on N2 was
allowed to refine independently (H3A and H3B bonded to N3 did
not converge during refinement to chemically reasonable values). In the
piperidinium cation, the H atoms on N3 were allowed to refine independently.
In the tetrahydrofuran solvent molecule, all atoms were allowed to refine
independently, except those bonded to the tetrahydrofuran ring. All other H
atoms were treated as riding, with C—H distances of 0.95 Å and N—H
distances of 0.88 Å. The Uiso(H) values of the riding atoms were
set at 1.2 times the Ueq values of the parent atom. The resolution of
the data collected for the piperidine solvate is of lower resolution than the
data collected for the other crystals in this series. This is due to the weak
scattering at high theta angle. The Bruker SMART X2S software does not
allow the user to modify the scan rate. However, even with the data collected
at the faster scan rate, the quality of the final refined structure is
comparable in quality to the other sulfapyridine structures in this series.
For all compounds, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
(1) 4-amino-
N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide
top
Crystal data top
C11H11N3O2S | F(000) = 1040 |
Mr = 249.29 | Dx = 1.453 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 3053 reflections |
a = 12.7350 (16) Å | θ = 2.7–25.0° |
b = 11.6945 (15) Å | µ = 0.28 mm−1 |
c = 15.3357 (18) Å | T = 173 K |
β = 93.546 (3)° | Block, yellow |
V = 2279.6 (5) Å3 | 0.75 × 0.70 × 0.35 mm |
Z = 8 | |
Data collection top
Bruker SMART X2S diffractometer | 1987 independent reflections |
Radiation source: microfocus sealed tube | 1743 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.043 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | h = −15→14 |
Tmin = 0.819, Tmax = 0.909 | k = −13→13 |
6574 measured reflections | l = −15→17 |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0447P)2 + 2.3901P] where P = (Fo2 + 2Fc2)/3 |
1987 reflections | (Δ/σ)max = 0.001 |
166 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
C11H11N3O2S | V = 2279.6 (5) Å3 |
Mr = 249.29 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 12.7350 (16) Å | µ = 0.28 mm−1 |
b = 11.6945 (15) Å | T = 173 K |
c = 15.3357 (18) Å | 0.75 × 0.70 × 0.35 mm |
β = 93.546 (3)° | |
Data collection top
Bruker SMART X2S diffractometer | 1987 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | 1743 reflections with I > 2σ(I) |
Tmin = 0.819, Tmax = 0.909 | Rint = 0.043 |
6574 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.096 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.31 e Å−3 |
1987 reflections | Δρmin = −0.40 e Å−3 |
166 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 | |
S1 | 0.20295 (3) | 0.04278 (3) | 0.56159 (3) | 0.01977 (17) | |
O1 | 0.13357 (11) | −0.05260 (10) | 0.54268 (9) | 0.0276 (3) | |
O2 | 0.20233 (10) | 0.13306 (10) | 0.49613 (8) | 0.0244 (3) | |
N1 | 0.31848 (12) | −0.01057 (12) | 0.58007 (11) | 0.0235 (4) | |
N2 | 0.40667 (13) | 0.17069 (13) | 0.57700 (11) | 0.0228 (4) | |
N3 | 0.12411 (15) | 0.23650 (15) | 0.90740 (12) | 0.0313 (4) | |
C1 | 0.16910 (13) | 0.10389 (15) | 0.66023 (12) | 0.0200 (4) | |
C2 | 0.14436 (14) | 0.03156 (15) | 0.72860 (13) | 0.0227 (4) | |
H2 | 0.1390 | −0.0485 | 0.7188 | 0.027* | |
C3 | 0.12780 (14) | 0.07514 (15) | 0.80965 (12) | 0.0232 (4) | |
H3 | 0.1101 | 0.0251 | 0.8553 | 0.028* | |
C4 | 0.13683 (14) | 0.19362 (15) | 0.82585 (12) | 0.0220 (4) | |
C5 | 0.15854 (15) | 0.26569 (15) | 0.75575 (13) | 0.0245 (4) | |
H5 | 0.1618 | 0.3460 | 0.7647 | 0.029* | |
C6 | 0.17511 (14) | 0.22172 (15) | 0.67432 (12) | 0.0225 (4) | |
H6 | 0.1906 | 0.2715 | 0.6279 | 0.027* | |
C7 | 0.40435 (15) | 0.05569 (15) | 0.59211 (12) | 0.0219 (4) | |
C8 | 0.50124 (15) | 0.00607 (18) | 0.62270 (14) | 0.0327 (5) | |
H8 | 0.5050 | −0.0740 | 0.6331 | 0.039* | |
C9 | 0.58889 (17) | 0.07112 (19) | 0.63746 (16) | 0.0402 (6) | |
H9 | 0.6530 | 0.0361 | 0.6581 | 0.048* | |
C10 | 0.58575 (16) | 0.19013 (18) | 0.62248 (15) | 0.0372 (5) | |
H10 | 0.6467 | 0.2360 | 0.6337 | 0.045* | |
C11 | 0.49401 (15) | 0.23712 (17) | 0.59179 (13) | 0.0297 (5) | |
H11 | 0.4902 | 0.3169 | 0.5804 | 0.036* | |
H1 | 0.352 (2) | 0.203 (2) | 0.5520 (15) | 0.038 (6)* | |
H3A | 0.1224 (19) | 0.186 (2) | 0.9494 (16) | 0.044 (7)* | |
H3B | 0.1467 (19) | 0.303 (2) | 0.9171 (16) | 0.044 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0240 (3) | 0.0146 (2) | 0.0205 (3) | −0.00291 (16) | 0.00035 (19) | −0.00017 (16) |
O1 | 0.0330 (8) | 0.0220 (7) | 0.0278 (8) | −0.0090 (5) | 0.0013 (6) | −0.0043 (5) |
O2 | 0.0301 (7) | 0.0193 (6) | 0.0236 (7) | −0.0013 (5) | −0.0012 (5) | 0.0037 (5) |
N1 | 0.0271 (9) | 0.0157 (7) | 0.0278 (9) | 0.0004 (6) | 0.0032 (7) | 0.0023 (6) |
N2 | 0.0228 (8) | 0.0195 (8) | 0.0258 (9) | −0.0010 (6) | −0.0006 (7) | 0.0033 (6) |
N3 | 0.0527 (12) | 0.0199 (9) | 0.0218 (10) | −0.0033 (8) | 0.0048 (8) | −0.0007 (8) |
C1 | 0.0198 (9) | 0.0181 (9) | 0.0218 (10) | −0.0005 (7) | −0.0006 (7) | −0.0012 (7) |
C2 | 0.0240 (9) | 0.0170 (9) | 0.0268 (11) | −0.0023 (7) | −0.0001 (8) | 0.0001 (7) |
C3 | 0.0268 (10) | 0.0201 (9) | 0.0227 (11) | −0.0032 (7) | 0.0014 (8) | 0.0044 (8) |
C4 | 0.0227 (9) | 0.0207 (9) | 0.0223 (10) | 0.0014 (7) | −0.0010 (7) | −0.0008 (8) |
C5 | 0.0314 (10) | 0.0144 (9) | 0.0278 (11) | 0.0009 (7) | 0.0019 (8) | −0.0005 (8) |
C6 | 0.0257 (10) | 0.0182 (9) | 0.0235 (11) | −0.0007 (7) | 0.0012 (8) | 0.0039 (7) |
C7 | 0.0266 (10) | 0.0206 (9) | 0.0190 (10) | 0.0012 (7) | 0.0044 (8) | 0.0024 (7) |
C8 | 0.0304 (11) | 0.0258 (10) | 0.0421 (13) | 0.0036 (8) | 0.0042 (9) | 0.0111 (9) |
C9 | 0.0261 (11) | 0.0424 (12) | 0.0514 (15) | 0.0037 (9) | −0.0029 (10) | 0.0159 (11) |
C10 | 0.0266 (11) | 0.0389 (12) | 0.0451 (14) | −0.0097 (9) | −0.0048 (9) | 0.0087 (10) |
C11 | 0.0302 (11) | 0.0246 (10) | 0.0341 (12) | −0.0073 (8) | 0.0019 (9) | 0.0046 (8) |
Geometric parameters (Å, º) top
S1—O1 | 1.4413 (13) | C3—C4 | 1.411 (2) |
S1—O2 | 1.4566 (13) | C3—H3 | 0.9500 |
S1—N1 | 1.6070 (15) | C4—C5 | 1.407 (3) |
S1—C1 | 1.7509 (18) | C5—C6 | 1.379 (3) |
N1—C7 | 1.344 (2) | C5—H5 | 0.9500 |
N2—C11 | 1.364 (2) | C6—H6 | 0.9500 |
N2—C7 | 1.365 (2) | C7—C8 | 1.417 (3) |
N2—H1 | 0.86 (3) | C8—C9 | 1.358 (3) |
N3—C4 | 1.366 (3) | C8—H8 | 0.9500 |
N3—H3A | 0.87 (3) | C9—C10 | 1.411 (3) |
N3—H3B | 0.84 (3) | C9—H9 | 0.9500 |
C1—C6 | 1.396 (2) | C10—C11 | 1.349 (3) |
C1—C2 | 1.398 (3) | C10—H10 | 0.9500 |
C2—C3 | 1.372 (3) | C11—H11 | 0.9500 |
C2—H2 | 0.9500 | | |
| | | |
O1—S1—O2 | 116.43 (8) | N3—C4—C3 | 120.57 (17) |
O1—S1—N1 | 106.15 (8) | C5—C4—C3 | 118.13 (17) |
O2—S1—N1 | 111.65 (8) | C6—C5—C4 | 121.13 (16) |
O1—S1—C1 | 108.00 (8) | C6—C5—H5 | 119.4 |
O2—S1—C1 | 107.97 (8) | C4—C5—H5 | 119.4 |
N1—S1—C1 | 106.12 (8) | C5—C6—C1 | 119.88 (17) |
C7—N1—S1 | 121.92 (13) | C5—C6—H6 | 120.1 |
C11—N2—C7 | 123.97 (17) | C1—C6—H6 | 120.1 |
C11—N2—H1 | 117.3 (15) | N1—C7—N2 | 124.80 (17) |
C7—N2—H1 | 118.5 (15) | N1—C7—C8 | 119.60 (17) |
C4—N3—H3A | 116.1 (16) | N2—C7—C8 | 115.60 (17) |
C4—N3—H3B | 116.3 (17) | C9—C8—C7 | 121.04 (19) |
H3A—N3—H3B | 121 (2) | C9—C8—H8 | 119.5 |
C6—C1—C2 | 119.59 (17) | C7—C8—H8 | 119.5 |
C6—C1—S1 | 121.49 (14) | C8—C9—C10 | 120.70 (19) |
C2—C1—S1 | 118.68 (13) | C8—C9—H9 | 119.6 |
C3—C2—C1 | 120.61 (16) | C10—C9—H9 | 119.6 |
C3—C2—H2 | 119.7 | C11—C10—C9 | 118.29 (19) |
C1—C2—H2 | 119.7 | C11—C10—H10 | 120.9 |
C2—C3—C4 | 120.59 (17) | C9—C10—H10 | 120.9 |
C2—C3—H3 | 119.7 | C10—C11—N2 | 120.37 (18) |
C4—C3—H3 | 119.7 | C10—C11—H11 | 119.8 |
N3—C4—C5 | 121.30 (17) | | |
| | | |
O1—S1—N1—C7 | 173.78 (14) | C3—C4—C5—C6 | −2.8 (3) |
O2—S1—N1—C7 | 45.93 (17) | C4—C5—C6—C1 | 0.8 (3) |
C1—S1—N1—C7 | −71.48 (16) | C2—C1—C6—C5 | 1.2 (3) |
O1—S1—C1—C6 | −144.54 (15) | S1—C1—C6—C5 | −173.21 (14) |
O2—S1—C1—C6 | −17.86 (17) | S1—N1—C7—N2 | −10.6 (3) |
N1—S1—C1—C6 | 101.98 (16) | S1—N1—C7—C8 | 169.32 (15) |
O1—S1—C1—C2 | 41.03 (16) | C11—N2—C7—N1 | 178.21 (18) |
O2—S1—C1—C2 | 167.72 (13) | C11—N2—C7—C8 | −1.8 (3) |
N1—S1—C1—C2 | −72.44 (15) | N1—C7—C8—C9 | −178.5 (2) |
C6—C1—C2—C3 | −1.1 (3) | N2—C7—C8—C9 | 1.5 (3) |
S1—C1—C2—C3 | 173.39 (14) | C7—C8—C9—C10 | −0.1 (4) |
C1—C2—C3—C4 | −0.9 (3) | C8—C9—C10—C11 | −1.1 (4) |
C2—C3—C4—N3 | −177.60 (18) | C9—C10—C11—N2 | 0.9 (3) |
C2—C3—C4—C5 | 2.8 (3) | C7—N2—C11—C10 | 0.6 (3) |
N3—C4—C5—C6 | 177.62 (18) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···O2i | 0.86 (3) | 2.15 (2) | 2.874 (2) | 140 (2) |
N2—H1···O2 | 0.86 (3) | 2.19 (2) | 2.847 (2) | 132 (2) |
N3—H1A···O1ii | 0.87 (3) | 2.12 (3) | 2.985 (2) | 172 (2) |
N3—H1B···N1iii | 0.84 (3) | 2.23 (3) | 3.050 (2) | 168 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y, z+1/2; (iii) −x+1/2, y+1/2, −z+3/2. |
(2) 4-amino-
N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide 1,3-dioxane
monosolvate
top
Crystal data top
C11H11N3O2S·C4H8O2 | F(000) = 712 |
Mr = 337.39 | Dx = 1.415 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 6136 reflections |
a = 9.0258 (10) Å | θ = 2.3–25.0° |
b = 9.9264 (12) Å | µ = 0.23 mm−1 |
c = 17.988 (2) Å | T = 173 K |
β = 100.720 (3)° | Block, colourless |
V = 1583.5 (3) Å3 | 0.75 × 0.63 × 0.38 mm |
Z = 4 | |
Data collection top
Bruker SMART X2S diffractometer | 2778 independent reflections |
Radiation source: microfocus sealed tube | 2488 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.028 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | h = −10→10 |
Tmin = 0.847, Tmax = 0.918 | k = −11→11 |
13599 measured reflections | l = −21→21 |
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)] = 0.050 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.157 | w = 1/[σ2(Fo2) + (0.0882P)2 + 1.9762P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2778 reflections | Δρmax = 0.59 e Å−3 |
268 parameters | Δρmin = −0.56 e Å−3 |
377 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0026 (14) |
Crystal data top
C11H11N3O2S·C4H8O2 | V = 1583.5 (3) Å3 |
Mr = 337.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.0258 (10) Å | µ = 0.23 mm−1 |
b = 9.9264 (12) Å | T = 173 K |
c = 17.988 (2) Å | 0.75 × 0.63 × 0.38 mm |
β = 100.720 (3)° | |
Data collection top
Bruker SMART X2S diffractometer | 2778 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | 2488 reflections with I > 2σ(I) |
Tmin = 0.847, Tmax = 0.918 | Rint = 0.028 |
13599 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 377 restraints |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.59 e Å−3 |
2778 reflections | Δρmin = −0.56 e Å−3 |
268 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 | Occ. (<1) |
S1 | 0.20843 (7) | 0.30900 (6) | 0.94602 (3) | 0.0218 (2) | |
O1 | 0.1117 (2) | 0.42247 (19) | 0.95387 (10) | 0.0280 (4) | |
O2 | 0.1851 (2) | 0.19084 (18) | 0.98994 (10) | 0.0289 (5) | |
O3A | 0.5235 (4) | 0.2848 (3) | 0.64699 (19) | 0.0261 (9) | 0.490 (4) |
O3B | 0.6401 (7) | 0.1660 (6) | 0.6473 (3) | 0.0763 (16) | 0.510 (4) |
O4A | 0.5713 (7) | 0.2699 (6) | 0.7843 (3) | 0.0660 (15) | 0.490 (4) |
O4B | 0.6867 (3) | 0.1352 (3) | 0.76941 (17) | 0.0192 (8) | 0.510 (4) |
N1 | 0.3760 (2) | 0.3681 (2) | 0.96608 (11) | 0.0234 (5) | |
N2 | 0.6313 (2) | 0.3557 (2) | 0.97731 (12) | 0.0243 (5) | |
N3 | 0.0756 (3) | 0.1605 (3) | 0.62164 (14) | 0.0444 (7) | |
H3B | 0.0355 | 0.0817 | 0.6074 | 0.053* | |
H3A | 0.0950 | 0.2182 | 0.5876 | 0.053* | |
C1 | 0.1744 (3) | 0.2605 (3) | 0.85035 (13) | 0.0221 (5) | |
C2 | 0.1112 (3) | 0.1360 (3) | 0.82776 (15) | 0.0270 (6) | |
H2 | 0.0908 | 0.0735 | 0.8646 | 0.032* | |
C3 | 0.0781 (3) | 0.1030 (3) | 0.75183 (15) | 0.0307 (6) | |
H3 | 0.0344 | 0.0179 | 0.7368 | 0.037* | |
C4 | 0.1080 (3) | 0.1933 (3) | 0.69691 (15) | 0.0285 (6) | |
C5 | 0.1734 (3) | 0.3184 (3) | 0.72014 (15) | 0.0282 (6) | |
H5 | 0.1960 | 0.3803 | 0.6835 | 0.034* | |
C6 | 0.2050 (3) | 0.3518 (3) | 0.79595 (14) | 0.0256 (6) | |
H6 | 0.2477 | 0.4372 | 0.8112 | 0.031* | |
C7 | 0.4972 (3) | 0.2893 (3) | 0.96250 (13) | 0.0228 (5) | |
C8 | 0.5032 (3) | 0.1508 (3) | 0.94450 (14) | 0.0267 (6) | |
H8 | 0.4128 | 0.0996 | 0.9337 | 0.032* | |
C9 | 0.6384 (3) | 0.0904 (3) | 0.94255 (15) | 0.0319 (6) | |
H9 | 0.6409 | −0.0026 | 0.9305 | 0.038* | |
C10 | 0.7732 (3) | 0.1635 (3) | 0.95802 (16) | 0.0325 (6) | |
H10 | 0.8671 | 0.1211 | 0.9568 | 0.039* | |
C11 | 0.7665 (3) | 0.2969 (3) | 0.97483 (15) | 0.0295 (6) | |
H11 | 0.8563 | 0.3490 | 0.9848 | 0.035* | |
C12A | 0.6796 (10) | 0.3127 (14) | 0.6765 (11) | 0.050 (2) | 0.490 (4) |
H12A | 0.7023 | 0.4077 | 0.6660 | 0.060* | 0.490 (4) |
H12B | 0.7441 | 0.2541 | 0.6514 | 0.060* | 0.490 (4) |
C12B | 0.6926 (13) | 0.2960 (12) | 0.6759 (10) | 0.053 (2) | 0.510 (4) |
H12C | 0.6148 | 0.3661 | 0.6607 | 0.064* | 0.510 (4) |
H12D | 0.7859 | 0.3221 | 0.6581 | 0.064* | 0.510 (4) |
C13A | 0.7134 (15) | 0.2880 (13) | 0.7605 (11) | 0.050 (2) | 0.490 (4) |
H13A | 0.7767 | 0.2065 | 0.7721 | 0.060* | 0.490 (4) |
H13B | 0.7682 | 0.3657 | 0.7871 | 0.060* | 0.490 (4) |
C13B | 0.7220 (16) | 0.2745 (8) | 0.7599 (11) | 0.042 (2) | 0.510 (4) |
H13C | 0.8288 | 0.2934 | 0.7821 | 0.050* | 0.510 (4) |
H13D | 0.6568 | 0.3337 | 0.7844 | 0.050* | 0.510 (4) |
C14A | 0.5181 (11) | 0.1433 (9) | 0.7508 (7) | 0.045 (2) | 0.490 (4) |
H14A | 0.4212 | 0.1203 | 0.7660 | 0.054* | 0.490 (4) |
H14B | 0.5917 | 0.0718 | 0.7702 | 0.054* | 0.490 (4) |
C14B | 0.5309 (7) | 0.1053 (9) | 0.7405 (6) | 0.0352 (18) | 0.510 (4) |
H14C | 0.4667 | 0.1546 | 0.7704 | 0.042* | 0.510 (4) |
H14D | 0.5130 | 0.0077 | 0.7457 | 0.042* | 0.510 (4) |
C15A | 0.4957 (11) | 0.1471 (8) | 0.6650 (7) | 0.036 (2) | 0.490 (4) |
H15A | 0.5675 | 0.0859 | 0.6465 | 0.043* | 0.490 (4) |
H15B | 0.3916 | 0.1202 | 0.6420 | 0.043* | 0.490 (4) |
C15B | 0.4881 (11) | 0.1454 (12) | 0.6582 (7) | 0.050 (2) | 0.510 (4) |
H15C | 0.4362 | 0.0722 | 0.6261 | 0.059* | 0.510 (4) |
H15D | 0.4269 | 0.2288 | 0.6508 | 0.059* | 0.510 (4) |
H2A | 0.630 (3) | 0.446 (3) | 0.9945 (17) | 0.033 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0213 (4) | 0.0236 (4) | 0.0209 (4) | 0.0015 (2) | 0.0046 (2) | −0.0012 (2) |
O1 | 0.0250 (9) | 0.0308 (10) | 0.0285 (9) | 0.0053 (8) | 0.0058 (7) | −0.0036 (8) |
O2 | 0.0318 (10) | 0.0300 (10) | 0.0266 (10) | −0.0008 (8) | 0.0093 (8) | 0.0033 (7) |
O3A | 0.0283 (19) | 0.0238 (18) | 0.0237 (18) | 0.0063 (14) | −0.0017 (14) | 0.0089 (14) |
O3B | 0.086 (3) | 0.078 (3) | 0.068 (3) | 0.002 (3) | 0.022 (3) | −0.004 (3) |
O4A | 0.066 (3) | 0.064 (3) | 0.068 (3) | −0.005 (3) | 0.015 (3) | −0.007 (3) |
O4B | 0.0220 (16) | 0.0152 (16) | 0.0179 (16) | 0.0043 (12) | −0.0025 (12) | −0.0003 (12) |
N1 | 0.0224 (11) | 0.0238 (11) | 0.0227 (10) | 0.0021 (9) | 0.0012 (8) | −0.0030 (8) |
N2 | 0.0223 (11) | 0.0260 (12) | 0.0240 (11) | 0.0020 (9) | 0.0026 (8) | −0.0028 (9) |
N3 | 0.0505 (16) | 0.0559 (17) | 0.0260 (13) | −0.0166 (13) | 0.0048 (11) | −0.0109 (11) |
C1 | 0.0188 (12) | 0.0244 (12) | 0.0228 (12) | 0.0018 (10) | 0.0035 (9) | −0.0021 (10) |
C2 | 0.0263 (13) | 0.0262 (13) | 0.0292 (13) | −0.0033 (11) | 0.0064 (10) | −0.0007 (10) |
C3 | 0.0291 (14) | 0.0285 (14) | 0.0337 (14) | −0.0075 (11) | 0.0042 (11) | −0.0078 (11) |
C4 | 0.0229 (13) | 0.0367 (15) | 0.0251 (13) | −0.0009 (11) | 0.0022 (10) | −0.0073 (10) |
C5 | 0.0294 (14) | 0.0311 (14) | 0.0247 (13) | −0.0014 (11) | 0.0061 (11) | 0.0022 (10) |
C6 | 0.0250 (13) | 0.0245 (13) | 0.0272 (13) | −0.0024 (10) | 0.0046 (10) | −0.0016 (10) |
C7 | 0.0235 (13) | 0.0268 (13) | 0.0177 (11) | 0.0025 (10) | 0.0032 (10) | 0.0006 (9) |
C8 | 0.0274 (13) | 0.0254 (13) | 0.0273 (13) | 0.0018 (10) | 0.0052 (10) | −0.0010 (10) |
C9 | 0.0364 (15) | 0.0273 (14) | 0.0322 (14) | 0.0062 (11) | 0.0071 (12) | −0.0031 (11) |
C10 | 0.0255 (14) | 0.0376 (15) | 0.0341 (15) | 0.0105 (12) | 0.0052 (11) | −0.0026 (12) |
C11 | 0.0217 (13) | 0.0384 (15) | 0.0275 (13) | 0.0025 (11) | 0.0026 (10) | −0.0034 (11) |
C12A | 0.048 (4) | 0.046 (4) | 0.054 (4) | −0.010 (4) | 0.007 (4) | −0.001 (4) |
C12B | 0.058 (4) | 0.047 (4) | 0.056 (4) | −0.007 (4) | 0.015 (4) | 0.015 (4) |
C13A | 0.041 (4) | 0.054 (5) | 0.051 (4) | −0.006 (4) | −0.005 (4) | −0.001 (5) |
C13B | 0.041 (4) | 0.030 (3) | 0.052 (4) | 0.002 (3) | 0.006 (4) | −0.001 (3) |
C14A | 0.047 (4) | 0.041 (5) | 0.044 (4) | −0.008 (3) | 0.001 (3) | 0.008 (4) |
C14B | 0.033 (3) | 0.032 (4) | 0.039 (4) | −0.002 (3) | 0.006 (3) | −0.005 (3) |
C15A | 0.027 (3) | 0.041 (4) | 0.043 (4) | 0.001 (3) | 0.015 (3) | −0.004 (4) |
C15B | 0.049 (4) | 0.057 (5) | 0.037 (4) | −0.001 (4) | −0.008 (4) | −0.007 (4) |
Geometric parameters (Å, º) top
S1—O1 | 1.4478 (19) | C7—C8 | 1.416 (4) |
S1—O2 | 1.4512 (19) | C8—C9 | 1.365 (4) |
S1—N1 | 1.600 (2) | C8—H8 | 0.9500 |
S1—C1 | 1.758 (2) | C9—C10 | 1.399 (4) |
O3A—C12A | 1.437 (5) | C9—H9 | 0.9500 |
O3A—C15A | 1.437 (5) | C10—C11 | 1.363 (4) |
O3B—C15B | 1.437 (5) | C10—H10 | 0.9500 |
O3B—C12B | 1.437 (5) | C11—H11 | 0.9500 |
O4A—C13A | 1.437 (5) | C12A—C13A | 1.505 (7) |
O4A—C14A | 1.438 (5) | C12A—H12A | 0.9900 |
O4B—C13B | 1.437 (5) | C12A—H12B | 0.9900 |
O4B—C14B | 1.437 (5) | C12B—C13B | 1.500 (7) |
N1—C7 | 1.356 (3) | C12B—H12C | 0.9900 |
N2—C7 | 1.360 (3) | C12B—H12D | 0.9900 |
N2—C11 | 1.360 (3) | C13A—H13A | 0.9900 |
N2—H2A | 0.95 (3) | C13A—H13B | 0.9900 |
N3—C4 | 1.370 (4) | C13B—H13C | 0.9900 |
N3—H3B | 0.8800 | C13B—H13D | 0.9900 |
N3—H3A | 0.8800 | C14A—C15A | 1.520 (7) |
C1—C2 | 1.389 (4) | C14A—H14A | 0.9900 |
C1—C6 | 1.399 (4) | C14A—H14B | 0.9900 |
C2—C3 | 1.382 (4) | C14B—C15B | 1.512 (7) |
C2—H2 | 0.9500 | C14B—H14C | 0.9900 |
C3—C4 | 1.397 (4) | C14B—H14D | 0.9900 |
C3—H3 | 0.9500 | C15A—H15A | 0.9900 |
C4—C5 | 1.404 (4) | C15A—H15B | 0.9900 |
C5—C6 | 1.381 (4) | C15B—H15C | 0.9900 |
C5—H5 | 0.9500 | C15B—H15D | 0.9900 |
C6—H6 | 0.9500 | | |
| | | |
O1—S1—O2 | 115.12 (11) | C10—C11—H11 | 120.0 |
O1—S1—N1 | 104.73 (11) | O3A—C12A—C13A | 110.0 (14) |
O2—S1—N1 | 113.62 (11) | O3A—C12A—H12A | 109.7 |
O1—S1—C1 | 108.05 (11) | C13A—C12A—H12A | 109.7 |
O2—S1—C1 | 107.15 (12) | O3A—C12A—H12B | 109.7 |
N1—S1—C1 | 107.87 (11) | C13A—C12A—H12B | 109.7 |
C12A—O3A—C15A | 107.5 (8) | H12A—C12A—H12B | 108.2 |
C15B—O3B—C12B | 109.8 (9) | O3B—C12B—C13B | 102.6 (11) |
C13A—O4A—C14A | 103.4 (8) | O3B—C12B—H12C | 111.2 |
C13B—O4B—C14B | 112.3 (8) | C13B—C12B—H12C | 111.2 |
C7—N1—S1 | 120.97 (18) | O3B—C12B—H12D | 111.2 |
C7—N2—C11 | 123.8 (2) | C13B—C12B—H12D | 111.2 |
C7—N2—H2A | 117.0 (18) | H12C—C12B—H12D | 109.2 |
C11—N2—H2A | 118.9 (19) | O4A—C13A—C12A | 107.1 (14) |
C4—N3—H3B | 120.0 | O4A—C13A—H13A | 110.3 |
C4—N3—H3A | 120.0 | C12A—C13A—H13A | 110.3 |
H3B—N3—H3A | 120.0 | O4A—C13A—H13B | 110.3 |
C2—C1—C6 | 119.7 (2) | C12A—C13A—H13B | 110.3 |
C2—C1—S1 | 121.15 (19) | H13A—C13A—H13B | 108.5 |
C6—C1—S1 | 119.08 (19) | O4B—C13B—C12B | 104.8 (11) |
C3—C2—C1 | 120.1 (2) | O4B—C13B—H13C | 110.8 |
C3—C2—H2 | 120.0 | C12B—C13B—H13C | 110.8 |
C1—C2—H2 | 120.0 | O4B—C13B—H13D | 110.8 |
C2—C3—C4 | 120.8 (2) | C12B—C13B—H13D | 110.8 |
C2—C3—H3 | 119.6 | H13C—C13B—H13D | 108.9 |
C4—C3—H3 | 119.6 | O4A—C14A—C15A | 112.0 (9) |
N3—C4—C3 | 120.8 (3) | O4A—C14A—H14A | 109.2 |
N3—C4—C5 | 120.3 (3) | C15A—C14A—H14A | 109.2 |
C3—C4—C5 | 118.9 (2) | O4A—C14A—H14B | 109.2 |
C6—C5—C4 | 120.3 (2) | C15A—C14A—H14B | 109.2 |
C6—C5—H5 | 119.9 | H14A—C14A—H14B | 107.9 |
C4—C5—H5 | 119.9 | O4B—C14B—C15B | 110.8 (8) |
C5—C6—C1 | 120.2 (2) | O4B—C14B—H14C | 109.5 |
C5—C6—H6 | 119.9 | C15B—C14B—H14C | 109.5 |
C1—C6—H6 | 119.9 | O4B—C14B—H14D | 109.5 |
N1—C7—N2 | 114.0 (2) | C15B—C14B—H14D | 109.5 |
N1—C7—C8 | 129.5 (2) | H14C—C14B—H14D | 108.1 |
N2—C7—C8 | 116.4 (2) | O3A—C15A—C14A | 104.9 (8) |
C9—C8—C7 | 120.3 (3) | O3A—C15A—H15A | 110.8 |
C9—C8—H8 | 119.9 | C14A—C15A—H15A | 110.8 |
C7—C8—H8 | 119.9 | O3A—C15A—H15B | 110.8 |
C8—C9—C10 | 121.1 (3) | C14A—C15A—H15B | 110.8 |
C8—C9—H9 | 119.5 | H15A—C15A—H15B | 108.8 |
C10—C9—H9 | 119.5 | O3B—C15B—C14B | 95.4 (8) |
C11—C10—C9 | 118.4 (3) | O3B—C15B—H15C | 112.7 |
C11—C10—H10 | 120.8 | C14B—C15B—H15C | 112.7 |
C9—C10—H10 | 120.8 | O3B—C15B—H15D | 112.7 |
N2—C11—C10 | 120.1 (3) | C14B—C15B—H15D | 112.7 |
N2—C11—H11 | 120.0 | H15C—C15B—H15D | 110.1 |
| | | |
O1—S1—N1—C7 | −178.20 (18) | C11—N2—C7—N1 | −178.2 (2) |
O2—S1—N1—C7 | 55.4 (2) | C11—N2—C7—C8 | 0.7 (4) |
C1—S1—N1—C7 | −63.3 (2) | N1—C7—C8—C9 | 178.6 (2) |
O1—S1—C1—C2 | −114.5 (2) | N2—C7—C8—C9 | −0.1 (4) |
O2—S1—C1—C2 | 10.1 (2) | C7—C8—C9—C10 | −0.1 (4) |
N1—S1—C1—C2 | 132.7 (2) | C8—C9—C10—C11 | −0.3 (4) |
O1—S1—C1—C6 | 62.3 (2) | C7—N2—C11—C10 | −1.2 (4) |
O2—S1—C1—C6 | −173.06 (19) | C9—C10—C11—N2 | 0.9 (4) |
N1—S1—C1—C6 | −50.4 (2) | C15A—O3A—C12A—C13A | −58.2 (10) |
C6—C1—C2—C3 | −0.3 (4) | C15B—O3B—C12B—C13B | 75.0 (10) |
S1—C1—C2—C3 | 176.5 (2) | C14A—O4A—C13A—C12A | 68.9 (10) |
C1—C2—C3—C4 | 0.3 (4) | O3A—C12A—C13A—O4A | −10.9 (11) |
C2—C3—C4—N3 | 179.8 (3) | C14B—O4B—C13B—C12B | −62.8 (9) |
C2—C3—C4—C5 | 0.4 (4) | O3B—C12B—C13B—O4B | 1.3 (10) |
N3—C4—C5—C6 | 179.5 (3) | C13A—O4A—C14A—C15A | −61.2 (12) |
C3—C4—C5—C6 | −1.1 (4) | C13B—O4B—C14B—C15B | 56.2 (10) |
C4—C5—C6—C1 | 1.1 (4) | C12A—O3A—C15A—C14A | 65.4 (10) |
C2—C1—C6—C5 | −0.4 (4) | O4A—C14A—C15A—O3A | −5.3 (9) |
S1—C1—C6—C5 | −177.3 (2) | C12B—O3B—C15B—C14B | −80.5 (12) |
S1—N1—C7—N2 | 176.74 (17) | O4B—C14B—C15B—O3B | 12.4 (9) |
S1—N1—C7—C8 | −2.0 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.95 (3) | 1.98 (3) | 2.930 (3) | 178 (3) |
N3—H3A···O2ii | 0.88 | 2.26 | 3.104 (3) | 162 |
N3—H3B···O1iii | 0.88 | 2.22 | 3.071 (3) | 162 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+1/2, z−1/2; (iii) −x, y−1/2, −z+3/2. |
(3) 4-amino-
N-(1,2-dihydropyridin-2-ylidene)benzenesulfonamide
tetrahydrofuran monosolvate
top
Crystal data top
C11H11N3O2S·C4H8O | F(000) = 680 |
Mr = 321.39 | Dx = 1.336 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3068 reflections |
a = 11.212 (2) Å | θ = 2.4–25.4° |
b = 12.449 (2) Å | µ = 0.22 mm−1 |
c = 11.6209 (19) Å | T = 173 K |
β = 99.888 (5)° | Block, colourless |
V = 1597.8 (5) Å3 | 1.00 × 0.65 × 0.50 mm |
Z = 4 | |
Data collection top
Bruker SMART X2S diffractometer | 2809 independent reflections |
Radiation source: microfocus sealed tube | 2232 reflections with I > 2σ(I) |
Doubly curved silicon crytsal monochromator | Rint = 0.046 |
ϕ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | h = −9→13 |
Tmin = 0.811, Tmax = 0.899 | k = −14→14 |
7648 measured reflections | l = −13→13 |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.102P)2 + 0.2263P] where P = (Fo2 + 2Fc2)/3 |
2809 reflections | (Δ/σ)max = 0.009 |
271 parameters | Δρmax = 0.48 e Å−3 |
273 restraints | Δρmin = −0.39 e Å−3 |
Crystal data top
C11H11N3O2S·C4H8O | V = 1597.8 (5) Å3 |
Mr = 321.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.212 (2) Å | µ = 0.22 mm−1 |
b = 12.449 (2) Å | T = 173 K |
c = 11.6209 (19) Å | 1.00 × 0.65 × 0.50 mm |
β = 99.888 (5)° | |
Data collection top
Bruker SMART X2S diffractometer | 2809 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | 2232 reflections with I > 2σ(I) |
Tmin = 0.811, Tmax = 0.899 | Rint = 0.046 |
7648 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 273 restraints |
wR(F2) = 0.163 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.48 e Å−3 |
2809 reflections | Δρmin = −0.39 e Å−3 |
271 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 | Occ. (<1) |
S1 | 0.72186 (5) | 0.32545 (5) | 0.06833 (5) | 0.0472 (3) | |
O1 | 0.74470 (19) | 0.33014 (15) | −0.04977 (16) | 0.0626 (5) | |
O2 | 0.70244 (17) | 0.22051 (13) | 0.11454 (17) | 0.0585 (5) | |
O3A | 0.7328 (6) | 0.6274 (4) | 0.4348 (4) | 0.1471 (19) | 0.822 (9) |
O3B | 0.660 (2) | 0.679 (2) | 0.386 (2) | 0.147 (4) | 0.178 (9) |
N1 | 0.60726 (18) | 0.40371 (17) | 0.06921 (17) | 0.0505 (5) | |
N2 | 0.46902 (19) | 0.49345 (17) | 0.1544 (2) | 0.0515 (5) | |
N3 | 1.1285 (3) | 0.5312 (3) | 0.3839 (4) | 0.0868 (10) | |
C1 | 0.8458 (2) | 0.38275 (18) | 0.1603 (2) | 0.0455 (6) | |
C2 | 0.8842 (2) | 0.3445 (2) | 0.2728 (2) | 0.0516 (6) | |
C3 | 0.9773 (2) | 0.3938 (2) | 0.3456 (3) | 0.0595 (7) | |
C4 | 1.0371 (2) | 0.4827 (2) | 0.3090 (3) | 0.0591 (7) | |
C5 | 0.9995 (3) | 0.5191 (2) | 0.1950 (3) | 0.0632 (7) | |
C6 | 0.9052 (3) | 0.4705 (2) | 0.1223 (3) | 0.0564 (7) | |
C7 | 0.5560 (2) | 0.41654 (19) | 0.1654 (2) | 0.0458 (6) | |
C8 | 0.5805 (3) | 0.3625 (2) | 0.2731 (2) | 0.0579 (7) | |
C9 | 0.5197 (3) | 0.3896 (3) | 0.3609 (3) | 0.0750 (9) | |
C10 | 0.4335 (3) | 0.4694 (3) | 0.3462 (3) | 0.0839 (11) | |
C11 | 0.4082 (3) | 0.5201 (3) | 0.2412 (3) | 0.0673 (8) | |
C12A | 0.7370 (8) | 0.6469 (6) | 0.3152 (6) | 0.140 (2) | 0.822 (9) |
H12A | 0.7696 | 0.5841 | 0.2785 | 0.169* | 0.822 (9) |
H12B | 0.6559 | 0.6648 | 0.2711 | 0.169* | 0.822 (9) |
C12B | 0.763 (3) | 0.6373 (11) | 0.346 (3) | 0.144 (4) | 0.178 (9) |
H12C | 0.8159 | 0.5960 | 0.4076 | 0.173* | 0.178 (9) |
H12D | 0.7411 | 0.5922 | 0.2754 | 0.173* | 0.178 (9) |
C13 | 0.8166 (7) | 0.7360 (6) | 0.3213 (6) | 0.165 (2) | |
H13A | 0.9009 | 0.7108 | 0.3241 | 0.198* | |
H13B | 0.7943 | 0.7819 | 0.2514 | 0.198* | |
C14 | 0.8078 (7) | 0.7936 (5) | 0.4207 (7) | 0.166 (2) | |
H14A | 0.7731 | 0.8656 | 0.4002 | 0.200* | |
H14B | 0.8885 | 0.8024 | 0.4699 | 0.200* | |
C15A | 0.7305 (10) | 0.7329 (6) | 0.4803 (8) | 0.157 (3) | 0.822 (9) |
H15A | 0.6472 | 0.7623 | 0.4652 | 0.188* | 0.822 (9) |
H15B | 0.7605 | 0.7334 | 0.5655 | 0.188* | 0.822 (9) |
C15B | 0.712 (4) | 0.753 (4) | 0.473 (4) | 0.159 (4) | 0.178 (9) |
H15C | 0.6544 | 0.8099 | 0.4864 | 0.191* | 0.178 (9) |
H15D | 0.7427 | 0.7161 | 0.5482 | 0.191* | 0.178 (9) |
H2 | 0.846 (3) | 0.288 (2) | 0.297 (2) | 0.059 (8)* | |
H2A | 0.449 (2) | 0.526 (2) | 0.077 (3) | 0.062 (8)* | |
H3 | 1.007 (3) | 0.376 (3) | 0.426 (3) | 0.087 (10)* | |
H3A | 1.137 (4) | 0.503 (4) | 0.448 (4) | 0.115 (18)* | |
H3B | 1.154 (4) | 0.579 (3) | 0.355 (3) | 0.087 (13)* | |
H5 | 1.040 (3) | 0.582 (3) | 0.177 (3) | 0.094 (11)* | |
H6 | 0.880 (3) | 0.494 (3) | 0.049 (3) | 0.069 (9)* | |
H8 | 0.632 (3) | 0.313 (2) | 0.288 (2) | 0.048 (7)* | |
H9 | 0.535 (3) | 0.346 (3) | 0.432 (3) | 0.091 (11)* | |
H10 | 0.396 (4) | 0.481 (3) | 0.399 (3) | 0.102 (13)* | |
H11 | 0.346 (3) | 0.573 (3) | 0.216 (3) | 0.078 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0533 (4) | 0.0396 (4) | 0.0485 (4) | 0.0077 (3) | 0.0081 (3) | −0.0027 (2) |
O1 | 0.0738 (12) | 0.0663 (13) | 0.0486 (11) | 0.0175 (9) | 0.0135 (9) | −0.0078 (8) |
O2 | 0.0647 (11) | 0.0374 (10) | 0.0714 (12) | 0.0016 (8) | 0.0062 (9) | −0.0026 (8) |
O3A | 0.189 (5) | 0.106 (3) | 0.158 (4) | 0.007 (3) | 0.063 (3) | 0.040 (3) |
O3B | 0.167 (7) | 0.132 (7) | 0.154 (7) | −0.013 (6) | 0.061 (6) | −0.002 (6) |
N1 | 0.0531 (11) | 0.0511 (12) | 0.0477 (12) | 0.0120 (9) | 0.0101 (9) | 0.0041 (9) |
N2 | 0.0535 (11) | 0.0535 (12) | 0.0471 (13) | 0.0153 (10) | 0.0074 (9) | 0.0043 (10) |
N3 | 0.0760 (19) | 0.083 (2) | 0.098 (3) | −0.0259 (17) | 0.0048 (17) | −0.003 (2) |
C1 | 0.0477 (12) | 0.0393 (12) | 0.0518 (14) | 0.0070 (10) | 0.0148 (10) | 0.0018 (10) |
C2 | 0.0502 (13) | 0.0461 (14) | 0.0586 (15) | −0.0020 (11) | 0.0096 (11) | 0.0095 (12) |
C3 | 0.0556 (14) | 0.0641 (17) | 0.0567 (16) | −0.0012 (12) | 0.0042 (12) | 0.0066 (13) |
C4 | 0.0501 (13) | 0.0583 (16) | 0.0703 (17) | −0.0046 (12) | 0.0145 (12) | −0.0084 (13) |
C5 | 0.0701 (17) | 0.0479 (16) | 0.0762 (19) | −0.0083 (13) | 0.0252 (14) | 0.0044 (13) |
C6 | 0.0696 (16) | 0.0480 (15) | 0.0546 (16) | −0.0007 (12) | 0.0197 (13) | 0.0069 (12) |
C7 | 0.0458 (12) | 0.0429 (13) | 0.0482 (13) | 0.0032 (10) | 0.0064 (10) | 0.0004 (10) |
C8 | 0.0555 (14) | 0.0609 (16) | 0.0583 (16) | 0.0185 (14) | 0.0124 (12) | 0.0133 (13) |
C9 | 0.0780 (19) | 0.095 (2) | 0.0548 (17) | 0.0274 (17) | 0.0187 (14) | 0.0238 (16) |
C10 | 0.083 (2) | 0.117 (3) | 0.0563 (18) | 0.041 (2) | 0.0247 (16) | 0.0137 (18) |
C11 | 0.0680 (17) | 0.080 (2) | 0.0555 (17) | 0.0287 (16) | 0.0153 (13) | 0.0053 (14) |
C12A | 0.168 (5) | 0.128 (4) | 0.133 (4) | −0.027 (4) | 0.051 (4) | −0.050 (4) |
C12B | 0.186 (8) | 0.113 (6) | 0.150 (8) | −0.016 (7) | 0.075 (7) | −0.014 (7) |
C13 | 0.198 (5) | 0.150 (5) | 0.164 (5) | −0.045 (4) | 0.083 (4) | −0.001 (4) |
C14 | 0.192 (5) | 0.109 (4) | 0.197 (6) | −0.023 (4) | 0.029 (4) | −0.036 (4) |
C15A | 0.193 (6) | 0.170 (6) | 0.119 (4) | 0.041 (5) | 0.056 (4) | −0.018 (4) |
C15B | 0.192 (8) | 0.142 (8) | 0.151 (7) | 0.026 (7) | 0.050 (6) | −0.015 (7) |
Geometric parameters (Å, º) top
S1—O1 | 1.440 (2) | C7—C8 | 1.406 (4) |
S1—O2 | 1.4431 (18) | C8—C9 | 1.363 (4) |
S1—N1 | 1.614 (2) | C8—H8 | 0.84 (3) |
S1—C1 | 1.753 (3) | C9—C10 | 1.376 (5) |
O3A—C15A | 1.418 (6) | C9—H9 | 0.98 (4) |
O3A—C12A | 1.419 (6) | C10—C11 | 1.360 (5) |
O3B—C15B | 1.419 (6) | C10—H10 | 0.81 (4) |
O3B—C12B | 1.419 (6) | C11—H11 | 0.97 (3) |
N1—C7 | 1.352 (3) | C12A—C13 | 1.418 (6) |
N2—C11 | 1.351 (4) | C12A—H12A | 0.9900 |
N2—C7 | 1.357 (3) | C12A—H12B | 0.9900 |
N2—H2A | 0.97 (3) | C12B—C13 | 1.417 (7) |
N3—C4 | 1.366 (4) | C12B—H12C | 0.9900 |
N3—H3A | 0.82 (5) | C12B—H12D | 0.9900 |
N3—H3B | 0.77 (4) | C13—C14 | 1.378 (9) |
C1—C2 | 1.388 (4) | C13—H13A | 0.9900 |
C1—C6 | 1.391 (4) | C13—H13B | 0.9900 |
C2—C3 | 1.371 (4) | C14—C15A | 1.417 (6) |
C2—H2 | 0.89 (3) | C14—C15B | 1.417 (7) |
C3—C4 | 1.398 (4) | C14—H14A | 0.9900 |
C3—H3 | 0.96 (4) | C14—H14B | 0.9900 |
C4—C5 | 1.395 (4) | C15A—H15A | 0.9900 |
C5—C6 | 1.375 (4) | C15A—H15B | 0.9900 |
C5—H5 | 0.94 (4) | C15B—H15C | 0.9900 |
C6—H6 | 0.90 (3) | C15B—H15D | 0.9900 |
| | | |
O1—S1—O2 | 117.02 (11) | N2—C11—H11 | 111.8 (18) |
O1—S1—N1 | 104.69 (11) | C10—C11—H11 | 128.0 (18) |
O2—S1—N1 | 111.89 (11) | C13—C12A—O3A | 102.2 (5) |
O1—S1—C1 | 108.22 (12) | C13—C12A—H12A | 111.3 |
O2—S1—C1 | 107.21 (11) | O3A—C12A—H12A | 111.3 |
N1—S1—C1 | 107.41 (11) | C13—C12A—H12B | 111.3 |
C15A—O3A—C12A | 102.3 (6) | O3A—C12A—H12B | 111.3 |
C15B—O3B—C12B | 102.3 (7) | H12A—C12A—H12B | 109.2 |
C7—N1—S1 | 121.91 (17) | C13—C12B—O3B | 98.2 (14) |
C11—N2—C7 | 123.3 (2) | C13—C12B—H12C | 112.1 |
C11—N2—H2A | 121.3 (17) | O3B—C12B—H12C | 112.1 |
C7—N2—H2A | 115.3 (17) | C13—C12B—H12D | 112.2 |
C4—N3—H3A | 110 (3) | O3B—C12B—H12D | 112.2 |
C4—N3—H3B | 111 (3) | H12C—C12B—H12D | 109.8 |
H3A—N3—H3B | 139 (4) | C14—C13—C12B | 100.8 (13) |
C2—C1—C6 | 118.8 (2) | C14—C13—C12A | 108.3 (5) |
C2—C1—S1 | 121.30 (19) | C12B—C13—C12A | 17.9 (19) |
C6—C1—S1 | 119.9 (2) | C14—C13—H13A | 110.0 |
C3—C2—C1 | 120.5 (3) | C12B—C13—H13A | 98.7 |
C3—C2—H2 | 121.2 (18) | C12A—C13—H13A | 110.0 |
C1—C2—H2 | 118.3 (18) | C14—C13—H13B | 110.0 |
C2—C3—C4 | 121.4 (3) | C12B—C13—H13B | 127.7 |
C2—C3—H3 | 127 (2) | C12A—C13—H13B | 110.0 |
C4—C3—H3 | 112 (2) | H13A—C13—H13B | 108.4 |
N3—C4—C5 | 122.3 (3) | C13—C14—C15A | 105.7 (5) |
N3—C4—C3 | 120.1 (3) | C13—C14—C15B | 110.2 (10) |
C5—C4—C3 | 117.6 (3) | C15A—C14—C15B | 13 (3) |
C6—C5—C4 | 121.1 (3) | C13—C14—H14A | 110.6 |
C6—C5—H5 | 125 (2) | C15A—C14—H14A | 110.6 |
C4—C5—H5 | 114 (2) | C15B—C14—H14A | 97.6 |
C5—C6—C1 | 120.6 (3) | C13—C14—H14B | 110.6 |
C5—C6—H6 | 122 (2) | C15A—C14—H14B | 110.6 |
C1—C6—H6 | 118 (2) | C15B—C14—H14B | 118.3 |
N1—C7—N2 | 114.0 (2) | H14A—C14—H14B | 108.7 |
N1—C7—C8 | 129.4 (2) | C14—C15A—O3A | 105.0 (5) |
N2—C7—C8 | 116.7 (2) | C14—C15A—H15A | 110.7 |
C9—C8—C7 | 120.1 (3) | O3A—C15A—H15A | 110.7 |
C9—C8—H8 | 116.2 (18) | C14—C15A—H15B | 110.7 |
C7—C8—H8 | 123.7 (18) | O3A—C15A—H15B | 110.7 |
C8—C9—C10 | 121.1 (3) | H15A—C15A—H15B | 108.8 |
C8—C9—H9 | 117 (2) | C14—C15B—O3B | 99.7 (14) |
C10—C9—H9 | 121 (2) | C14—C15B—H15C | 111.8 |
C11—C10—C9 | 118.7 (3) | O3B—C15B—H15C | 111.8 |
C11—C10—H10 | 122 (3) | C14—C15B—H15D | 111.8 |
C9—C10—H10 | 119 (3) | O3B—C15B—H15D | 111.9 |
N2—C11—C10 | 120.1 (3) | H15C—C15B—H15D | 109.6 |
| | | |
O1—S1—N1—C7 | 177.3 (2) | N1—C7—C8—C9 | 178.5 (3) |
O2—S1—N1—C7 | 49.6 (2) | N2—C7—C8—C9 | −1.2 (4) |
C1—S1—N1—C7 | −67.8 (2) | C7—C8—C9—C10 | 0.3 (5) |
O1—S1—C1—C2 | −145.9 (2) | C8—C9—C10—C11 | 1.0 (6) |
O2—S1—C1—C2 | −18.8 (2) | C7—N2—C11—C10 | 0.4 (5) |
N1—S1—C1—C2 | 101.6 (2) | C9—C10—C11—N2 | −1.4 (6) |
O1—S1—C1—C6 | 36.2 (2) | C15A—O3A—C12A—C13 | 39.6 (10) |
O2—S1—C1—C6 | 163.29 (19) | C15B—O3B—C12B—C13 | −53 (3) |
N1—S1—C1—C6 | −76.3 (2) | O3B—C12B—C13—C14 | 46 (2) |
C6—C1—C2—C3 | 1.3 (4) | O3B—C12B—C13—C12A | −70 (4) |
S1—C1—C2—C3 | −176.6 (2) | O3A—C12A—C13—C14 | −28.3 (10) |
C1—C2—C3—C4 | −0.7 (4) | O3A—C12A—C13—C12B | 39 (3) |
C2—C3—C4—N3 | 179.1 (3) | C12B—C13—C14—C15A | −11.5 (19) |
C2—C3—C4—C5 | −0.7 (4) | C12A—C13—C14—C15A | 5.3 (10) |
N3—C4—C5—C6 | −178.4 (3) | C12B—C13—C14—C15B | −24 (4) |
C3—C4—C5—C6 | 1.3 (4) | C12A—C13—C14—C15B | −8 (3) |
C4—C5—C6—C1 | −0.7 (4) | C13—C14—C15A—O3A | 20.0 (11) |
C2—C1—C6—C5 | −0.6 (4) | C15B—C14—C15A—O3A | 132 (7) |
S1—C1—C6—C5 | 177.3 (2) | C12A—O3A—C15A—C14 | −37.3 (11) |
S1—N1—C7—N2 | 173.50 (18) | C13—C14—C15B—O3B | −8 (4) |
S1—N1—C7—C8 | −6.2 (4) | C15A—C14—C15B—O3B | −80 (4) |
C11—N2—C7—N1 | −178.8 (3) | C12B—O3B—C15B—C14 | 37 (4) |
C11—N2—C7—C8 | 0.9 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.97 (3) | 1.92 (3) | 2.892 (3) | 173 (2) |
N3—H3A···O3Aii | 0.82 (5) | 2.43 (5) | 3.103 (7) | 140 (4) |
N3—H3B···O2iii | 0.77 (4) | 2.37 (4) | 3.023 (4) | 143 (4) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) −x+2, y+1/2, −z+1/2. |
(4) piperidin-1-ium 4-amino-
N-(pyridin-2-yl)benzenesulfonamidate
top
Crystal data top
C5H12N+·C11H10N3O2S− | F(000) = 712 |
Mr = 334.44 | Dx = 1.335 Mg m−3 Dm = 0 Mg m−3 Dm measured by not measured |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 1508 reflections |
a = 8.6639 (16) Å | θ = 2.4–21.4° |
b = 12.586 (2) Å | µ = 0.21 mm−1 |
c = 15.833 (3) Å | T = 173 K |
β = 105.447 (6)° | Block, colourless |
V = 1664.1 (5) Å3 | 0.27 × 0.25 × 0.14 mm |
Z = 4 | |
Data collection top
Bruker SMART X2S diffractometer | 1922 independent reflections |
Radiation source: microfocus sealed tube | 1482 reflections with I > 2σ(I) |
Doubly curved silicon crystal monochromator | Rint = 0.068 |
ϕ and ω scans | θmax = 21.6°, θmin = 2.1° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | h = −8→7 |
Tmin = 0.946, Tmax = 0.971 | k = −12→12 |
7118 measured reflections | l = −15→16 |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0394P)2 + 0.2051P] where P = (Fo2 + 2Fc2)/3 |
1922 reflections | (Δ/σ)max = 0.001 |
216 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
C5H12N+·C11H10N3O2S− | V = 1664.1 (5) Å3 |
Mr = 334.44 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.6639 (16) Å | µ = 0.21 mm−1 |
b = 12.586 (2) Å | T = 173 K |
c = 15.833 (3) Å | 0.27 × 0.25 × 0.14 mm |
β = 105.447 (6)° | |
Data collection top
Bruker SMART X2S diffractometer | 1922 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | 1482 reflections with I > 2σ(I) |
Tmin = 0.946, Tmax = 0.971 | Rint = 0.068 |
7118 measured reflections | θmax = 21.6° |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.090 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.20 e Å−3 |
1922 reflections | Δρmin = −0.31 e Å−3 |
216 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 | |
S1 | 0.41673 (8) | 0.79423 (5) | 0.54918 (5) | 0.0204 (2) | |
O1 | 0.5272 (2) | 0.86371 (15) | 0.52049 (12) | 0.0262 (5) | |
O2 | 0.4671 (2) | 0.68354 (14) | 0.56238 (12) | 0.0259 (5) | |
N1 | 0.2509 (3) | 0.81171 (17) | 0.48073 (14) | 0.0221 (6) | |
N2 | −0.0219 (3) | 0.80428 (18) | 0.43191 (16) | 0.0290 (6) | |
N3 | 0.3801 (3) | 0.9632 (3) | 0.8937 (2) | 0.0314 (7) | |
H3A | 0.397 (3) | 0.920 (2) | 0.9345 (18) | 0.011 (9)* | |
H3B | 0.389 (3) | 1.025 (2) | 0.9013 (19) | 0.021 (10)* | |
N4 | 0.7822 (3) | 1.00336 (18) | 0.61447 (15) | 0.0244 (6) | |
H4A | 0.7701 | 1.0594 | 0.5760 | 0.029* | |
H4B | 0.6973 | 0.9578 | 0.5941 | 0.029* | |
C1 | 0.4042 (3) | 0.8423 (2) | 0.65175 (18) | 0.0179 (7) | |
C2 | 0.4191 (3) | 0.7752 (2) | 0.72328 (19) | 0.0208 (7) | |
H2 | 0.4352 | 0.7013 | 0.7170 | 0.025* | |
C3 | 0.4109 (3) | 0.8147 (2) | 0.80329 (19) | 0.0227 (7) | |
H3 | 0.4206 | 0.7676 | 0.8513 | 0.027* | |
C4 | 0.3884 (3) | 0.9230 (2) | 0.81448 (18) | 0.0199 (7) | |
C5 | 0.3703 (3) | 0.9901 (2) | 0.74187 (19) | 0.0218 (7) | |
H5 | 0.3524 | 1.0638 | 0.7477 | 0.026* | |
C6 | 0.3782 (3) | 0.9501 (2) | 0.66184 (18) | 0.0216 (7) | |
H6 | 0.3657 | 0.9966 | 0.6133 | 0.026* | |
C7 | 0.1102 (3) | 0.7587 (2) | 0.48441 (18) | 0.0212 (7) | |
C8 | 0.0997 (3) | 0.6696 (2) | 0.53403 (19) | 0.0305 (8) | |
H8 | 0.1940 | 0.6376 | 0.5697 | 0.037* | |
C9 | −0.0479 (4) | 0.6279 (3) | 0.5313 (2) | 0.0376 (9) | |
H9 | −0.0562 | 0.5674 | 0.5656 | 0.045* | |
C10 | −0.1840 (3) | 0.6741 (3) | 0.4786 (2) | 0.0373 (9) | |
H10 | −0.2876 | 0.6471 | 0.4760 | 0.045* | |
C11 | −0.1635 (3) | 0.7607 (3) | 0.4302 (2) | 0.0353 (9) | |
H11 | −0.2566 | 0.7920 | 0.3927 | 0.042* | |
C12 | 0.9636 (4) | 0.8581 (2) | 0.6827 (2) | 0.0388 (9) | |
H12A | 1.0682 | 0.8246 | 0.6855 | 0.047* | |
H12B | 0.8794 | 0.8033 | 0.6644 | 0.047* | |
C13 | 0.9639 (4) | 0.8995 (3) | 0.7722 (2) | 0.0439 (10) | |
H13A | 1.0545 | 0.9493 | 0.7930 | 0.053* | |
H13B | 0.9785 | 0.8396 | 0.8141 | 0.053* | |
C14 | 0.8082 (3) | 0.9561 (3) | 0.76901 (19) | 0.0330 (8) | |
H14A | 0.7186 | 0.9046 | 0.7542 | 0.040* | |
H14B | 0.8131 | 0.9866 | 0.8273 | 0.040* | |
C15 | 0.7783 (3) | 1.0437 (2) | 0.70140 (19) | 0.0300 (8) | |
H15A | 0.6726 | 1.0763 | 0.6972 | 0.036* | |
H15B | 0.8609 | 1.0995 | 0.7202 | 0.036* | |
C16 | 0.9334 (3) | 0.9468 (2) | 0.61644 (19) | 0.0300 (8) | |
H16A | 1.0238 | 0.9976 | 0.6313 | 0.036* | |
H16B | 0.9270 | 0.9172 | 0.5577 | 0.036* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0170 (4) | 0.0250 (5) | 0.0177 (5) | −0.0003 (3) | 0.0017 (3) | 0.0006 (3) |
O1 | 0.0208 (10) | 0.0358 (12) | 0.0225 (12) | −0.0060 (9) | 0.0065 (9) | 0.0015 (9) |
O2 | 0.0259 (11) | 0.0254 (12) | 0.0243 (12) | 0.0061 (8) | 0.0032 (9) | −0.0010 (9) |
N1 | 0.0166 (13) | 0.0302 (15) | 0.0171 (15) | −0.0032 (10) | 0.0003 (10) | 0.0014 (11) |
N2 | 0.0218 (15) | 0.0343 (16) | 0.0276 (16) | 0.0001 (12) | 0.0006 (12) | −0.0048 (12) |
N3 | 0.0438 (18) | 0.027 (2) | 0.023 (2) | −0.0049 (15) | 0.0079 (14) | −0.0040 (18) |
N4 | 0.0205 (13) | 0.0290 (15) | 0.0198 (15) | −0.0014 (10) | −0.0017 (11) | 0.0025 (12) |
C1 | 0.0137 (15) | 0.0211 (18) | 0.0164 (18) | −0.0003 (12) | −0.0001 (12) | 0.0000 (14) |
C2 | 0.0163 (15) | 0.0198 (17) | 0.024 (2) | 0.0007 (12) | 0.0012 (13) | −0.0011 (15) |
C3 | 0.0206 (16) | 0.0285 (19) | 0.0170 (19) | −0.0042 (13) | 0.0016 (13) | 0.0025 (15) |
C4 | 0.0125 (15) | 0.0274 (19) | 0.0190 (19) | −0.0056 (12) | 0.0026 (12) | −0.0057 (16) |
C5 | 0.0184 (16) | 0.0205 (17) | 0.025 (2) | −0.0015 (12) | 0.0024 (13) | −0.0028 (16) |
C6 | 0.0170 (15) | 0.0253 (19) | 0.021 (2) | −0.0024 (12) | 0.0020 (13) | 0.0035 (15) |
C7 | 0.0206 (18) | 0.0274 (18) | 0.0142 (18) | 0.0009 (13) | 0.0025 (13) | −0.0064 (14) |
C8 | 0.0247 (18) | 0.039 (2) | 0.025 (2) | −0.0049 (14) | 0.0022 (14) | 0.0061 (16) |
C9 | 0.033 (2) | 0.043 (2) | 0.038 (2) | −0.0109 (16) | 0.0108 (16) | 0.0036 (16) |
C10 | 0.0184 (18) | 0.051 (2) | 0.042 (2) | −0.0094 (15) | 0.0064 (16) | −0.0096 (19) |
C11 | 0.0181 (19) | 0.042 (2) | 0.041 (2) | −0.0004 (15) | −0.0008 (15) | −0.0078 (18) |
C12 | 0.0286 (18) | 0.038 (2) | 0.049 (3) | 0.0108 (15) | 0.0087 (16) | 0.0057 (18) |
C13 | 0.0274 (19) | 0.069 (3) | 0.031 (2) | 0.0042 (16) | −0.0005 (15) | 0.0249 (19) |
C14 | 0.0245 (18) | 0.053 (2) | 0.0214 (19) | −0.0045 (15) | 0.0053 (14) | 0.0006 (16) |
C15 | 0.0297 (18) | 0.0330 (19) | 0.030 (2) | −0.0015 (14) | 0.0117 (15) | −0.0072 (16) |
C16 | 0.0283 (18) | 0.036 (2) | 0.027 (2) | 0.0073 (14) | 0.0097 (14) | −0.0033 (15) |
Geometric parameters (Å, º) top
S1—O1 | 1.4554 (19) | C6—H6 | 0.9500 |
S1—O2 | 1.4583 (19) | C7—C8 | 1.386 (4) |
S1—N1 | 1.568 (2) | C8—C9 | 1.372 (4) |
S1—C1 | 1.763 (3) | C8—H8 | 0.9500 |
N1—C7 | 1.404 (4) | C9—C10 | 1.379 (4) |
N2—C11 | 1.338 (4) | C9—H9 | 0.9500 |
N2—C7 | 1.350 (3) | C10—C11 | 1.371 (4) |
N3—C4 | 1.372 (4) | C10—H10 | 0.9500 |
N3—H3A | 0.83 (3) | C11—H11 | 0.9500 |
N3—H3B | 0.79 (3) | C12—C16 | 1.506 (4) |
N4—C15 | 1.476 (3) | C12—C13 | 1.508 (4) |
N4—C16 | 1.484 (3) | C12—H12A | 0.9900 |
N4—H4A | 0.9200 | C12—H12B | 0.9900 |
N4—H4B | 0.9200 | C13—C14 | 1.515 (4) |
C1—C2 | 1.391 (4) | C13—H13A | 0.9900 |
C1—C6 | 1.392 (4) | C13—H13B | 0.9900 |
C2—C3 | 1.380 (4) | C14—C15 | 1.510 (4) |
C2—H2 | 0.9500 | C14—H14A | 0.9900 |
C3—C4 | 1.394 (4) | C14—H14B | 0.9900 |
C3—H3 | 0.9500 | C15—H15A | 0.9900 |
C4—C5 | 1.401 (4) | C15—H15B | 0.9900 |
C5—C6 | 1.382 (4) | C16—H16A | 0.9900 |
C5—H5 | 0.9500 | C16—H16B | 0.9900 |
| | | |
O1—S1—O2 | 114.96 (11) | C7—C8—H8 | 120.2 |
O1—S1—N1 | 104.93 (12) | C8—C9—C10 | 119.9 (3) |
O2—S1—N1 | 114.67 (11) | C8—C9—H9 | 120.1 |
O1—S1—C1 | 106.75 (12) | C10—C9—H9 | 120.1 |
O2—S1—C1 | 106.58 (12) | C11—C10—C9 | 117.1 (3) |
N1—S1—C1 | 108.59 (12) | C11—C10—H10 | 121.4 |
C7—N1—S1 | 123.39 (19) | C9—C10—H10 | 121.4 |
C11—N2—C7 | 117.4 (3) | N2—C11—C10 | 124.7 (3) |
C4—N3—H3A | 115.4 (19) | N2—C11—H11 | 117.7 |
C4—N3—H3B | 118 (2) | C10—C11—H11 | 117.7 |
H3A—N3—H3B | 123 (3) | C16—C12—C13 | 110.8 (3) |
C15—N4—C16 | 112.6 (2) | C16—C12—H12A | 109.5 |
C15—N4—H4A | 109.1 | C13—C12—H12A | 109.5 |
C16—N4—H4A | 109.1 | C16—C12—H12B | 109.5 |
C15—N4—H4B | 109.1 | C13—C12—H12B | 109.5 |
C16—N4—H4B | 109.1 | H12A—C12—H12B | 108.1 |
H4A—N4—H4B | 107.8 | C12—C13—C14 | 110.7 (2) |
C2—C1—C6 | 118.8 (3) | C12—C13—H13A | 109.5 |
C2—C1—S1 | 121.8 (2) | C14—C13—H13A | 109.5 |
C6—C1—S1 | 119.5 (2) | C12—C13—H13B | 109.5 |
C3—C2—C1 | 120.8 (3) | C14—C13—H13B | 109.5 |
C3—C2—H2 | 119.6 | H13A—C13—H13B | 108.1 |
C1—C2—H2 | 119.6 | C15—C14—C13 | 110.5 (3) |
C2—C3—C4 | 120.8 (3) | C15—C14—H14A | 109.6 |
C2—C3—H3 | 119.6 | C13—C14—H14A | 109.6 |
C4—C3—H3 | 119.6 | C15—C14—H14B | 109.6 |
N3—C4—C3 | 121.3 (3) | C13—C14—H14B | 109.6 |
N3—C4—C5 | 120.4 (3) | H14A—C14—H14B | 108.1 |
C3—C4—C5 | 118.3 (3) | N4—C15—C14 | 111.6 (2) |
C6—C5—C4 | 120.7 (3) | N4—C15—H15A | 109.3 |
C6—C5—H5 | 119.6 | C14—C15—H15A | 109.3 |
C4—C5—H5 | 119.6 | N4—C15—H15B | 109.3 |
C5—C6—C1 | 120.6 (3) | C14—C15—H15B | 109.3 |
C5—C6—H6 | 119.7 | H15A—C15—H15B | 108.0 |
C1—C6—H6 | 119.7 | N4—C16—C12 | 111.0 (2) |
N2—C7—C8 | 121.3 (2) | N4—C16—H16A | 109.4 |
N2—C7—N1 | 112.0 (2) | C12—C16—H16A | 109.4 |
C8—C7—N1 | 126.6 (2) | N4—C16—H16B | 109.4 |
C9—C8—C7 | 119.5 (3) | C12—C16—H16B | 109.4 |
C9—C8—H8 | 120.2 | H16A—C16—H16B | 108.0 |
| | | |
C7—N1—S1—O1 | 179.8 (2) | S1—C1—C6—C5 | −179.0 (2) |
C7—N1—S1—O2 | 52.7 (3) | C11—N2—C7—C8 | 0.5 (4) |
C7—N1—S1—C1 | −66.4 (2) | C11—N2—C7—N1 | −179.8 (2) |
O1—S1—C1—C2 | −131.7 (2) | S1—N1—C7—N2 | 165.5 (2) |
O2—S1—C1—C2 | −8.3 (2) | S1—N1—C7—C8 | −14.9 (4) |
N1—S1—C1—C2 | 115.7 (2) | N2—C7—C8—C9 | −1.3 (4) |
O1—S1—C1—C6 | 48.6 (2) | N1—C7—C8—C9 | 179.1 (3) |
O2—S1—C1—C6 | 171.92 (19) | C7—C8—C9—C10 | 0.7 (5) |
N1—S1—C1—C6 | −64.1 (2) | C8—C9—C10—C11 | 0.6 (5) |
C6—C1—C2—C3 | −1.0 (4) | C7—N2—C11—C10 | 0.9 (5) |
S1—C1—C2—C3 | 179.22 (19) | C9—C10—C11—N2 | −1.4 (5) |
C1—C2—C3—C4 | −0.4 (4) | C16—C12—C13—C14 | 56.4 (3) |
C2—C3—C4—N3 | −180.0 (2) | C12—C13—C14—C15 | −55.7 (4) |
C2—C3—C4—C5 | 1.6 (4) | C16—N4—C15—C14 | −55.2 (3) |
N3—C4—C5—C6 | −179.9 (2) | C13—C14—C15—N4 | 54.9 (3) |
C3—C4—C5—C6 | −1.5 (4) | C15—N4—C16—C12 | 55.3 (3) |
C4—C5—C6—C1 | 0.0 (4) | C13—C12—C16—N4 | −55.6 (3) |
C2—C1—C6—C5 | 1.2 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O2i | 0.83 (3) | 2.35 (3) | 3.169 (4) | 172 (2) |
N3—H3B···O2ii | 0.79 (3) | 2.34 (3) | 3.071 (4) | 155 (3) |
N4—H4A···N1iii | 0.92 | 1.84 | 2.746 (3) | 168 |
N4—H4B···O1iv | 0.92 | 2.01 | 2.904 (3) | 165 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x, −y+2, −z+1; (iv) x−1, y, z. |
Experimental details
| (1) | (2) | (3) | (4) |
Crystal data |
Chemical formula | C11H11N3O2S | C11H11N3O2S·C4H8O2 | C11H11N3O2S·C4H8O | C5H12N+·C11H10N3O2S− |
Mr | 249.29 | 337.39 | 321.39 | 334.44 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, P21/c | Monoclinic, P21/c | Monoclinic, P21/c |
Temperature (K) | 173 | 173 | 173 | 173 |
a, b, c (Å) | 12.7350 (16), 11.6945 (15), 15.3357 (18) | 9.0258 (10), 9.9264 (12), 17.988 (2) | 11.212 (2), 12.449 (2), 11.6209 (19) | 8.6639 (16), 12.586 (2), 15.833 (3) |
β (°) | 93.546 (3) | 100.720 (3) | 99.888 (5) | 105.447 (6) |
V (Å3) | 2279.6 (5) | 1583.5 (3) | 1597.8 (5) | 1664.1 (5) |
Z | 8 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.28 | 0.23 | 0.22 | 0.21 |
Crystal size (mm) | 0.75 × 0.70 × 0.35 | 0.75 × 0.63 × 0.38 | 1.00 × 0.65 × 0.50 | 0.27 × 0.25 × 0.14 |
|
Data collection |
Diffractometer | Bruker SMART X2S diffractometer | Bruker SMART X2S diffractometer | Bruker SMART X2S diffractometer | Bruker SMART X2S diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | Empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | Empirical (using intensity measurements) (SADABS; Sheldrick, 2004) | Empirical (using intensity measurements) (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.819, 0.909 | 0.847, 0.918 | 0.811, 0.899 | 0.946, 0.971 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6574, 1987, 1743 | 13599, 2778, 2488 | 7648, 2809, 2232 | 7118, 1922, 1482 |
Rint | 0.043 | 0.028 | 0.046 | 0.068 |
θmax (°) | 25.0 | 25.0 | 25.0 | 21.6 |
(sin θ/λ)max (Å−1) | 0.595 | 0.594 | 0.594 | 0.517 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.096, 1.05 | 0.050, 0.157, 1.08 | 0.053, 0.163, 1.08 | 0.037, 0.090, 1.02 |
No. of reflections | 1987 | 2778 | 2809 | 1922 |
No. of parameters | 166 | 268 | 271 | 216 |
No. of restraints | 0 | 377 | 273 | 0 |
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 | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.40 | 0.59, −0.56 | 0.48, −0.39 | 0.20, −0.31 |
Hydrogen-bond geometry (Å, º) for (1) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H1···O2i | 0.86 (3) | 2.15 (2) | 2.874 (2) | 140 (2) |
N2—H1···O2 | 0.86 (3) | 2.19 (2) | 2.847 (2) | 132 (2) |
N3—H1A···O1ii | 0.87 (3) | 2.12 (3) | 2.985 (2) | 172 (2) |
N3—H1B···N1iii | 0.84 (3) | 2.23 (3) | 3.050 (2) | 168 (2) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) x, −y, z+1/2; (iii) −x+1/2, y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (2) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.95 (3) | 1.98 (3) | 2.930 (3) | 178 (3) |
N3—H3A···O2ii | 0.88 | 2.26 | 3.104 (3) | 161.7 |
N3—H3B···O1iii | 0.88 | 2.22 | 3.071 (3) | 162.4 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, −y+1/2, z−1/2; (iii) −x, y−1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (3) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.97 (3) | 1.92 (3) | 2.892 (3) | 173 (2) |
N3—H3A···O3Aii | 0.82 (5) | 2.43 (5) | 3.103 (7) | 140 (4) |
N3—H3B···O2iii | 0.77 (4) | 2.37 (4) | 3.023 (4) | 143 (4) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+2, −y+1, −z+1; (iii) −x+2, y+1/2, −z+1/2. |
Hydrogen-bond geometry (Å, º) for (4) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O2i | 0.83 (3) | 2.35 (3) | 3.169 (4) | 172 (2) |
N3—H3B···O2ii | 0.79 (3) | 2.34 (3) | 3.071 (4) | 155 (3) |
N4—H4A···N1iii | 0.92 | 1.84 | 2.746 (3) | 168.2 |
N4—H4B···O1iv | 0.92 | 2.01 | 2.904 (3) | 165.2 |
Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x, −y+2, −z+1; (iv) x−1, y, z. |
Table 2. Dihedral angles (°) topPlanes | (1) | (2) | (3) | (4) |
Phenyl and pyridine | 86.37 (9) | 85.35 (13) | 87.13 (19) | 89.01 (9) |
Phenyl and C1/S1/N1 | 75.14 (7) | 48.76 (12) | 76.67 (18) | 64.24 (12) |
Pyridine and C1/S1/N1 | 76.25 (7) | 63.88 (12) | 70.37 (11) | 74.45 (10) |
Table 3. Torsion angles (°) top | (1) | (2) | (3) | (4) |
N2—C7—N1—S1 | -10.6 (3) | 176.74 (17) | 173.50 (18) | 165.5 (2) |
C8—C7—N1—S1 | 169.32 (15) | -2.0 (4) | -6.2 (4) | -14.9 (4) |
C6—C1—S1—N1 | 101.98 (16) | -50.4 (2) | -76.3 (2) | -64.1 (2) |
C2—C1—S1—N1 | -72.44 (15) | 132.7 (2) | 101.6 (2) | 115.7 (2) |
O1—S1—N1—C7 | 173.78 (14) | -178.20 (18) | 177.3 (2) | 179.8 (2) |
C1—S1—N1—C7 | -71.48 (16) | -63.3 (2) | -67.8 (2) | -66.4 (2) |
O2—S1—N1—C7 | 45.93 (17) | 55.4 (2) | 49.6 (2) | 52.7 (2) |
Table 4. Hydrogen-bond geometry (Å, °) topSymmetry codes: (i) -x+1/2, -y+1/2, -z+1;
(ii) x, -y, z+1/2;
(iii) -x+1/2, y+1/2, -z+3/2;
(iv) -x+1, -y+1, -z+2;
(v) x, -y+1/2, z-1/2;
(vi) -x, y-1/2, -z+3/2;
(vii) -x+1, -y+1, -z;
(viii) -x+2, y+1, -z+1;
(ix) -x+2, y+1/2, -z+1/2;
(x) x, -y+3/2, z+1/2;
(xi) -x+1, y+1/2, -z+3/2;
(xii) -x, -y+2, -z+1;
(xiii) x-1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
(I) | | | | |
N2—H1···O2 | 0.86 (2) | 2.19 (2) | 2.847 (2) | 132 (2) |
N2—H1···O2i | 0.86 (2) | 2.15 (2) | 2.874 (2) | 140 (2) |
N3—H1A···O1ii | 0.87 (2) | 2.12 (2) | 2.985 (2) | 172 (2) |
N3—H1B···N1iii | 0.84 (2) | 2.23 (2) | 3.050 (2) | 168 (2) |
(II) | | | | |
N2—H2A···N1iv | 0.95 (3) | 1.98 (3) | 2.930 (3) | 178 (3) |
N3—H3A···O2v | 0.88 | 2.26 | 3.104 (3) | 162 |
N3—H3B···O1vi | 0.88 | 2.22 | 3.071 (3) | 162 |
(III) | | | | |
N2—H2A···N1vii | 0.97 (3) | 1.92 (3) | 2.892 (3) | 173 (2) |
N3—H3A···O3Aviii | 0.82 (5) | 2.43 (5) | 3.103 (7) | 140 (4) |
N3—H3B···O2ix | 0.77 (4) | 2.37 (4) | 3.023 (4) | 143 (4) |
(IV) | | | | |
N3—H3A···O2x | 0.83 (3) | 2.35 (3) | 3.169 (4) | 172 (2) |
N3—H3B···O2xi | 0.79 (3) | 2.34 (3) | 3.071 (4) | 155 (3) |
N4—H4A···N1xii | 0.92 | 1.84 | 2.746 (3) | 168 |
N4—H4B···O1xiii | 0.92 | 2.00 | 2.904 (3) | 165 |
Sulfapyridine is a member of the sulfonamide class of pharmaceuticals known for its antibacterial, antithyroid and antidiabetic properties. It was the first synthetic antibacterial agent effective against pneumonia.
Our initial interest in sulfapyridine was prompted by its ability to form conformational polymorphs, molecules that adopt different molecular conformations in different crystalline forms. The X-ray crystal structures of five polymorphs of sulfapyridine [numbered as (II)–(VI) according to a comprehensive study of polymorphism in sulfonamides by Yang & Guillory (1972)] have been reported (Bar & Bernstein, 1985; Bernstein, 1988; Gelbrich et al., 2007; Basak et al., 1984) in the Cambridge Structural Database (CSD; Version 5.32; Allen, 2002). The pharmaceutical industry is particularly interested in polymorphism because it can result in seemingly identical compounds with different pharmacological activity and/or bioavailability due to varying levels of thermodynamic stability, equilibrium solubilities and rates of dissolution.
In an effort to crystallize sulfapyridine, (I), in its different polymorphic forms, we have prepared three new crystalline sulfapyridine solvates: sulfapyridine dioxane solvate, (II), sulfapyridine tetrahydrofuran solvate, (III), and sulfapyridine piperidine solvate, (IV). We report here the crystal structures at 173 K along with the crystal structure of sulfapyridine (polymorph III) redetermined at 173 K. The crystal structure of a sulfapyridine tetrahydrofuran solvate with different unit cell dimensions than (2) was determined previously at 150 K (Meyer et al., 2000). The conformations of the sulfapyridine molecules in these solvate structures provide additional examples of conformational polymorphism.
Sulfapyridine, (I) (polymorph III; Fig. 1), and the sulfapyridine molecules in sulfapyridine dioxane solvate, (II) (Fig. 2), and the sulfapyridine tetrahydrofuran solvate, (III) (Fig. 3), crystallized in the imide tautomeric form with the H atoms bonded to N2, the pyridine N atom. This seems to be the preference for sulfapyridine structures (Bar & Bernstein, 1985). Conversely, the sulfapyridine piperidine solvate, (IV) (Fig. 4), crystallized in the amide tautomeric form as the piperidinium salt with the H atom located on the piperidine N atom. The conformation of the sulfapyridine molecules can be best described in terms of the angles between the three planar groups (i.e. the C1/S1/N1 plane, the benzene ring plane and the pyridine ring plane) and rotation around the C1—S1, S1—N1 and N1—C7 bonds. The angles between the planes are given in Table 2 and the torsion angles describing these rotations are given in Table 3. The solvated structures are generally similar to each other, although there is some rotational flexibility in the torsion angles resulting in a range of approximately 30° in the orientation of the benzene rings (described by the torsion angle C2—C1—S1—N1) ranging from 101.6 (2)° in the THF solvate, (III), to 132.7 (2)° in the dioxane solvate, (II). The orientation of the pyridine rings (described by the torsion angle N2—C7—N1—S1) showed a range of approximately 12° from 165.45 (19)° in the piperidinium salt, (IV), to 176.73 (17)° in the dioxane solvate, (II). This torsion angle in (I) [10.7 (3)°] suggests that the pyridine ring plane is flipped over relative to the pyridine rings in the solvated structures. In all imide tautomers, the orientation of the pyridine ring is stabilized by hydrogen bonding involving the pyridine N2 atom. The dihedral angles between the benzene ring plane and the pyridine ring plane are consistently near perpendicular in all four structures, ranging from 85.35 (13)° in the dioxane solvate, (II), to 89.03 (14)° in the piperidine salt, (IV). The solvent in each of the solvated structures is located in this area with the center of mass of the solvate approximately bisecting this dihedral angle, resulting in an approximately equal distance between the center of mass of the solvate and the centers of mass of the pyridine and benzene ring planes. The variations in the molecular structures of the sulfapyridine molecules suggest that these molecules are conformational polymorphs.
Each of the sulfapyridine solvate structures reported here crystallized with one solvent molecule per asymmetric unit. While the piperidinium cation in (IV) was crystallographically well behaved, the dioxane solvent molecule in (II) and the tetrahydrofuran solvent molecule in (III) were found to be disordered and were refined with a disorder model. In both disordered models, the solvent O atoms were partially occupied above and below the best C atom plane of the solvent molecules. In the disordered dioxane molecule, the occupancies of the two conformations refined to 0.510 (4) and 0.490 (4), and in the tetrahydrofuran molecule the occupancies refined to 0.822 (9) and 0.178 (9). The displacement parameters in the tetrahydrofuran solvent molecule were unusually large, implying that the channel where it was located was sufficiently large to allow it significant translational flexibility. There were no hydrogen-bonding interactions involving the dioxane solvent molecule. However, there appeared to be a very weak hydrogen-bond interaction between one of the partially occupied tetrahydrofuran O atoms (O3) and the sulfapyridine molecule through the aniline N3 atom [N3···O3 = 3.102 (7) Å, H3A···O3 = 2.42 (5) Å and N3—H3A···O3 = 142 (4)°]. In the piperidinium cation, atom N4 forms a hydrogen bond to the sulfapyridine anion through the amide N1 atom [N4···N1 = 2.746 (3) Å, H4A···N1 = 1.84 Å and N4—H4A···N1 168°].
The packing of (I) (Fig. 5) was described previously as an interleaved herringbone motif (Bar & Bernstein, 1985). The packing in the dioxane solvate, (II) (Fig. 6), and the tetrahydrofuran solvate, (III) (Fig. 7), are similar to the packing in (I) in that the benzene and pyridine ring planes form parallel sheets. In both solvate structures, channels of solvent molecules separate the sheets. In the piperidinium salt, (IV) (Fig. 8), the benzene rings in the sulfapyridine anions stack in pairs along the a axis, leaving solvent pockets between pairs of planes. In all three solvate structures and (I), hydrogen bonds exist between at least one sulfone O atom and the aniline N3 atom. In addition, the dioxane and tetrahydrofuran structures show a hydrogen bond between the pyridine atom N2 and the amide atom N1 in an adjacent molecule. Hydrogen-bonding interactions are listed in Table 4.