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The conformations of the two approximately isomorphous structures 4′-{[benzoyl(4-chlorophenylhydrazono)methyl]sulfonyl}acetanilide, C22H18ClN3O4S, and 4′-{[benzoyl(4-methoxyphenylhydrazono)methyl]sulfonyl}acetanilide, C23H21N3O5S, are stabilized by resonance-assisted intramolecular hydrogen bonds linking the hydrazone moieties and sulfonyl groups. The stronger bond is observed in the former compound. The difference in electronic properties between the Cl atom and the methoxy group is too small to significantly alter the non-bonding interactions of the sulfonyl and β-carbonyl groups.
Supporting information
CCDC references: 173390; 173391
Compounds (I) and (II) were synthesized by the reaction of p-acetanilide
benzoylmethyl sulfone with p-chlorophenyldiazonium chloride and
p-methoxyphenyldiazonium chloride, respectively. The reactions were
carried out in alkaline ethyl alcohol solutions (Zakrzewski, 1996). The
crystals used for data collection were obtained by vapour diffusion: samples
were dissolved in a 2:1 mixture of chloroform and isopropyl alcohol, and
equilibrated at room temperature against pure isopropyl alcohol for 6 and 14 d, respectively.
All H atoms were located in a difference Fourier map calculated after three
cycles of anisotropic refinement. Positional and isotropic displacement
parameters of H2 and H3 in (I) and (II) were allowed to refine freely.
Positional parameters of all remaining H atoms were constrained using AFIX 44
and AFIX 134 in SHELXL97 (Sheldrick, 1997) for the phenyl and methyl
groups, respectively. Common displacement parameters were applied to H atoms
of the individual phenyl and methyl groups [C—H = 0.83 (4)–1.04 and
0.86 (3)–0.99 Å for (I) and (II), respectively].
Data collection: KM-4 Software (Kuma Diffraction, 1991) for (I); P3 (Siemens, 1989) for (II). Cell refinement: KM-4 Software for (I); P3 for (II). Data reduction: DATAPROC (Gałdecki et al., 1995) for (I); XDISK (Siemens, 1991) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: InsightII (Molecular Simulations, 1997) and XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.
(I) 4'-{[benzoyl(4-chlorophenylhydrazono)methyl]sulfonyl}acetanilide
top
Crystal data top
C22H18ClN3O4S | F(000) = 944 |
Mr = 455.90 | Dx = 1.434 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.603 (4) Å | Cell parameters from 60 reflections |
b = 7.596 (1) Å | θ = 5–15° |
c = 24.110 (4) Å | µ = 0.32 mm−1 |
β = 96.44 (2)° | T = 293 K |
V = 2111.6 (9) Å3 | Prism, yellow |
Z = 4 | 0.50 × 0.45 × 0.30 mm |
Data collection top
Kuma KM-4 diffractometer | Rint = 0.036 |
Radiation source: fine-focus sealed tube | θmax = 25°, θmin = 1.7° |
Graphite monochromator | h = −13→13 |
ω/2θ scans | k = −1→9 |
4434 measured reflections | l = 0→28 |
3719 independent reflections | 3 standard reflections every 100 reflections |
2531 reflections with I > 2σ(I) | intensity decay: 10% |
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)] = 0.050 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0292P)2 + 3.1336P] where P = (Fo2 + 2Fc2)/3 |
3719 reflections | (Δ/σ)max = 0.002 |
306 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
C22H18ClN3O4S | V = 2111.6 (9) Å3 |
Mr = 455.90 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.603 (4) Å | µ = 0.32 mm−1 |
b = 7.596 (1) Å | T = 293 K |
c = 24.110 (4) Å | 0.50 × 0.45 × 0.30 mm |
β = 96.44 (2)° | |
Data collection top
Kuma KM-4 diffractometer | Rint = 0.036 |
4434 measured reflections | 3 standard reflections every 100 reflections |
3719 independent reflections | intensity decay: 10% |
2531 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.135 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.22 e Å−3 |
3719 reflections | Δρmin = −0.30 e Å−3 |
306 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 | |
S | 0.61868 (9) | 0.60363 (15) | 0.18650 (4) | 0.0585 (3) | |
Cl | 0.47058 (12) | 0.2171 (2) | 0.52316 (4) | 0.0921 (4) | |
O1 | 0.6105 (3) | 0.7858 (4) | 0.17140 (11) | 0.0743 (9) | |
O2 | 0.7079 (2) | 0.5511 (5) | 0.23044 (10) | 0.0755 (9) | |
O3 | 0.3862 (2) | 0.5934 (4) | 0.12263 (10) | 0.0666 (8) | |
O4 | 0.6324 (3) | −0.0928 (4) | 0.00754 (13) | 0.0799 (9) | |
N1 | 0.4748 (2) | 0.4714 (4) | 0.26002 (11) | 0.0463 (7) | |
N2 | 0.5589 (3) | 0.4417 (5) | 0.29851 (12) | 0.0518 (8) | |
H2 | 0.628 (4) | 0.459 (6) | 0.2941 (18) | 0.088 (16)* | |
N3 | 0.6403 (3) | 0.1915 (5) | −0.01967 (14) | 0.0569 (9) | |
H3 | 0.633 (4) | 0.256 (6) | −0.0490 (17) | 0.074 (14)* | |
C1 | 0.4851 (3) | 0.5346 (5) | 0.21046 (14) | 0.0484 (9) | |
C2 | 0.3792 (3) | 0.5511 (5) | 0.17141 (13) | 0.0479 (9) | |
C3 | 0.2618 (3) | 0.5137 (5) | 0.18941 (13) | 0.0454 (8) | |
C4 | 0.2289 (3) | 0.5739 (5) | 0.23997 (14) | 0.0515 (9) | |
H4 | 0.283 (2) | 0.635 (3) | 0.2659 (11) | 0.072 (6)* | |
C5 | 0.1172 (3) | 0.5443 (6) | 0.25196 (16) | 0.0611 (11) | |
H5 | 0.0922 (10) | 0.5897 (18) | 0.2893 (14) | 0.072 (6)* | |
C6 | 0.0395 (4) | 0.4571 (6) | 0.21595 (17) | 0.0690 (13) | |
H6 | −0.033 (3) | 0.4396 (10) | 0.2246 (4) | 0.072 (6)* | |
C7 | 0.0708 (4) | 0.3951 (6) | 0.16619 (17) | 0.0689 (12) | |
H7 | 0.020 (2) | 0.335 (3) | 0.1427 (11) | 0.072 (6)* | |
C8 | 0.1817 (3) | 0.4263 (5) | 0.15270 (15) | 0.0560 (10) | |
H8 | 0.2039 (9) | 0.3855 (17) | 0.1164 (14) | 0.072 (6)* | |
C9 | 0.6342 (3) | 0.4788 (5) | 0.12698 (14) | 0.0497 (9) | |
C10 | 0.6524 (4) | 0.2996 (6) | 0.13097 (17) | 0.0669 (12) | |
H10 | 0.6628 (6) | 0.244 (2) | 0.1664 (14) | 0.059 (6)* | |
C11 | 0.6554 (4) | 0.2008 (6) | 0.08308 (16) | 0.0698 (13) | |
H11 | 0.6641 (6) | 0.094 (5) | 0.08530 (19) | 0.059 (6)* | |
C12 | 0.6436 (3) | 0.2822 (5) | 0.03106 (14) | 0.0496 (9) | |
C13 | 0.6327 (3) | 0.4635 (5) | 0.02829 (15) | 0.0484 (9) | |
H13 | 0.6302 (3) | 0.521 (2) | −0.0066 (14) | 0.059 (6)* | |
C14 | 0.6256 (3) | 0.5606 (5) | 0.07553 (14) | 0.0496 (9) | |
H14 | 0.6156 (5) | 0.676 (5) | 0.07315 (17) | 0.059 (6)* | |
C15 | 0.6326 (3) | 0.0163 (6) | −0.02914 (18) | 0.0608 (11) | |
C16 | 0.6238 (4) | −0.0357 (6) | −0.08984 (19) | 0.0840 (16) | |
H161 | 0.5635 (18) | 0.0218 (18) | −0.1090 (6) | 0.138 (13)* | |
H162 | 0.6122 (6) | −0.154 (4) | −0.0930 (2) | 0.138 (13)* | |
H163 | 0.691 (2) | −0.0068 (11) | −0.1040 (5) | 0.138 (13)* | |
C17 | 0.5355 (3) | 0.3827 (5) | 0.35146 (13) | 0.0443 (8) | |
C18 | 0.4232 (3) | 0.3653 (6) | 0.36444 (15) | 0.0595 (11) | |
H18 | 0.361 (3) | 0.3889 (11) | 0.3381 (11) | 0.067 (6)* | |
C19 | 0.4057 (3) | 0.3120 (6) | 0.41750 (15) | 0.0638 (12) | |
H19 | 0.335 (3) | 0.3000 (8) | 0.4263 (4) | 0.067 (6)* | |
C20 | 0.4973 (3) | 0.2780 (5) | 0.45611 (14) | 0.0539 (10) | |
C21 | 0.6070 (4) | 0.2875 (6) | 0.44284 (16) | 0.0685 (12) | |
H21 | 0.672 (3) | 0.2565 (14) | 0.4703 (11) | 0.067 (6)* | |
C22 | 0.6264 (3) | 0.3413 (6) | 0.39015 (15) | 0.0623 (11) | |
H22 | 0.701 (3) | 0.3494 (7) | 0.3810 (4) | 0.067 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0580 (6) | 0.0750 (7) | 0.0460 (5) | −0.0130 (5) | 0.0214 (4) | 0.0020 (5) |
Cl | 0.1214 (10) | 0.1121 (11) | 0.0470 (6) | 0.0171 (9) | 0.0280 (6) | 0.0208 (6) |
O1 | 0.099 (2) | 0.0637 (19) | 0.0662 (18) | −0.0203 (17) | 0.0381 (16) | −0.0003 (15) |
O2 | 0.0473 (15) | 0.130 (3) | 0.0505 (16) | −0.0166 (17) | 0.0100 (12) | 0.0048 (17) |
O3 | 0.0652 (17) | 0.095 (2) | 0.0413 (14) | 0.0081 (16) | 0.0158 (12) | 0.0225 (14) |
O4 | 0.094 (2) | 0.0602 (19) | 0.088 (2) | 0.0048 (17) | 0.0228 (18) | 0.0212 (17) |
N1 | 0.0482 (16) | 0.0527 (18) | 0.0394 (16) | 0.0006 (15) | 0.0108 (13) | 0.0030 (14) |
N2 | 0.0422 (17) | 0.072 (2) | 0.0424 (17) | −0.0043 (17) | 0.0110 (14) | 0.0050 (15) |
N3 | 0.069 (2) | 0.057 (2) | 0.0483 (19) | 0.0063 (17) | 0.0254 (16) | 0.0091 (17) |
C1 | 0.052 (2) | 0.054 (2) | 0.0415 (19) | −0.0046 (18) | 0.0157 (16) | 0.0024 (17) |
C2 | 0.056 (2) | 0.052 (2) | 0.0373 (19) | 0.0049 (18) | 0.0141 (15) | 0.0048 (16) |
C3 | 0.050 (2) | 0.051 (2) | 0.0359 (17) | 0.0050 (17) | 0.0076 (15) | 0.0090 (16) |
C4 | 0.058 (2) | 0.059 (2) | 0.039 (2) | 0.0051 (19) | 0.0111 (16) | −0.0004 (17) |
C5 | 0.061 (2) | 0.079 (3) | 0.046 (2) | 0.011 (2) | 0.0208 (19) | 0.009 (2) |
C6 | 0.050 (2) | 0.094 (3) | 0.065 (3) | 0.000 (2) | 0.014 (2) | 0.020 (3) |
C7 | 0.064 (3) | 0.085 (3) | 0.056 (2) | −0.018 (2) | 0.002 (2) | 0.006 (2) |
C8 | 0.064 (2) | 0.066 (3) | 0.0388 (19) | 0.002 (2) | 0.0080 (17) | 0.0020 (18) |
C9 | 0.047 (2) | 0.061 (3) | 0.0436 (19) | 0.0008 (19) | 0.0175 (15) | 0.0081 (18) |
C10 | 0.085 (3) | 0.072 (3) | 0.046 (2) | 0.016 (2) | 0.022 (2) | 0.022 (2) |
C11 | 0.102 (3) | 0.054 (3) | 0.059 (3) | 0.024 (2) | 0.031 (2) | 0.021 (2) |
C12 | 0.049 (2) | 0.056 (2) | 0.048 (2) | 0.0067 (18) | 0.0206 (16) | 0.0066 (18) |
C13 | 0.049 (2) | 0.057 (2) | 0.0420 (19) | −0.0015 (18) | 0.0175 (15) | 0.0138 (18) |
C14 | 0.053 (2) | 0.052 (2) | 0.046 (2) | −0.0017 (18) | 0.0161 (16) | 0.0061 (17) |
C15 | 0.061 (2) | 0.054 (3) | 0.071 (3) | 0.005 (2) | 0.026 (2) | 0.006 (2) |
C16 | 0.104 (4) | 0.074 (3) | 0.079 (3) | −0.012 (3) | 0.032 (3) | −0.016 (3) |
C17 | 0.0429 (18) | 0.054 (2) | 0.0370 (17) | −0.0006 (17) | 0.0091 (14) | 0.0028 (16) |
C18 | 0.0435 (19) | 0.090 (3) | 0.046 (2) | 0.001 (2) | 0.0071 (16) | 0.018 (2) |
C19 | 0.051 (2) | 0.088 (3) | 0.056 (2) | 0.001 (2) | 0.0212 (19) | 0.014 (2) |
C20 | 0.067 (2) | 0.055 (2) | 0.042 (2) | 0.007 (2) | 0.0146 (18) | 0.0033 (17) |
C21 | 0.058 (2) | 0.097 (3) | 0.049 (2) | 0.011 (2) | −0.0004 (19) | 0.015 (2) |
C22 | 0.043 (2) | 0.092 (3) | 0.053 (2) | 0.003 (2) | 0.0094 (17) | 0.007 (2) |
Geometric parameters (Å, º) top
S—O1 | 1.431 (3) | C20—C21 | 1.349 (5) |
S—O2 | 1.451 (3) | C21—C22 | 1.377 (5) |
S—C1 | 1.792 (3) | N3—C12 | 1.400 (5) |
S—C9 | 1.746 (4) | N3—C15 | 1.352 (5) |
O3—C2 | 1.231 (4) | O4—C15 | 1.212 (5) |
N1—N2 | 1.289 (4) | C15—C16 | 1.508 (6) |
N1—C1 | 1.306 (4) | Cl—C20 | 1.742 (3) |
N2—C17 | 1.408 (4) | N2—H2 | 0.83 (4) |
C1—C2 | 1.467 (5) | N3—H3 | 0.86 (4) |
C2—C3 | 1.502 (5) | C4—H4 | 0.95 |
C3—C8 | 1.380 (5) | C5—H5 | 1.04 |
C3—C4 | 1.395 (5) | C6—H6 | 0.90 |
C4—C5 | 1.378 (5) | C7—H7 | 0.90 |
C5—C6 | 1.352 (6) | C8—H8 | 0.99 |
C6—C7 | 1.375 (6) | C10—H10 | 0.95 |
C7—C8 | 1.383 (5) | C11—H11 | 0.82 |
C9—C10 | 1.379 (6) | C13—H13 | 0.94 |
C9—C14 | 1.381 (5) | C14—H14 | 0.88 |
C10—C11 | 1.381 (6) | C16—H161 | 0.91 |
C11—C12 | 1.391 (5) | C16—H162 | 0.91 |
C12—C13 | 1.384 (5) | C16—H163 | 0.91 |
C13—C14 | 1.367 (5) | C18—H18 | 0.92 |
C17—C22 | 1.364 (5) | C19—H19 | 0.87 |
C17—C18 | 1.380 (5) | C21—H21 | 0.98 |
C18—C19 | 1.379 (5) | C22—H22 | 0.92 |
C19—C20 | 1.357 (5) | | |
| | | |
S···O3 | 2.954 (3) | O1···N2 | 4.122 (4) |
S···N2 | 3.115 (3) | O2···N2 | 2.647 (4) |
O1···C2 | 3.222 (5) | N2···C2 | 3.605 (5) |
O2···C2 | 3.918 (5) | | |
| | | |
O1—S—O2 | 118.2 (2) | C21—C20—C19 | 121.0 (3) |
O1—S—C1 | 109.28 (18) | C21—C20—Cl | 120.3 (3) |
O1—S—C9 | 109.02 (17) | C19—C20—Cl | 118.7 (3) |
O2—S—C1 | 104.82 (16) | C20—C21—C22 | 119.4 (4) |
O2—S—C9 | 108.63 (18) | C17—C22—C21 | 120.4 (4) |
C1—S—C9 | 106.19 (17) | N1—N2—H2 | 123 (3) |
N2—N1—C1 | 125.7 (3) | C17—N2—H2 | 117 (3) |
N1—N2—C17 | 120.1 (3) | C15—N3—H3 | 115 (3) |
N1—C1—C2 | 117.6 (3) | C12—N3—H3 | 115 (3) |
S—C1—N1 | 125.0 (3) | C5—C4—H4 | 120.5 |
S—C1—C2 | 117.4 (2) | C3—C4—H4 | 120.5 |
O3—C2—C1 | 119.7 (3) | C6—C5—H5 | 119.3 |
O3—C2—C3 | 119.0 (3) | C4—C5—H5 | 119.3 |
C1—C2—C3 | 121.3 (3) | C5—C6—H6 | 119.8 |
C15—N3—C12 | 128.8 (3) | C7—C6—H6 | 119.8 |
C8—C3—C4 | 119.2 (3) | C6—C7—H7 | 120.3 |
C8—C3—C2 | 118.2 (3) | C8—C7—H7 | 120.3 |
C4—C3—C2 | 122.4 (3) | C3—C8—H8 | 119.7 |
C5—C4—C3 | 119.1 (4) | C7—C8—H8 | 119.7 |
C6—C5—C4 | 121.3 (4) | C9—C10—H10 | 120.1 |
C5—C6—C7 | 120.4 (4) | C11—C10—H10 | 120.1 |
C6—C7—C8 | 119.4 (4) | C10—C11—H11 | 119.9 |
C3—C8—C7 | 120.6 (4) | C12—C11—H11 | 119.9 |
C10—C9—C14 | 120.1 (4) | C14—C13—H13 | 119.6 |
C10—C9—S | 120.5 (3) | C12—C13—H13 | 119.6 |
C14—C9—S | 119.3 (3) | C13—C14—H14 | 120.0 |
C9—C10—C11 | 119.7 (4) | C9—C14—H14 | 120.0 |
C10—C11—C12 | 120.2 (4) | C15—C16—H161 | 109.5 |
C13—C12—C11 | 119.0 (4) | C15—C16—H162 | 109.5 |
C13—C12—N3 | 117.0 (3) | H161—C16—H162 | 109.5 |
C11—C12—N3 | 124.0 (4) | C15—C16—H163 | 109.5 |
C14—C13—C12 | 120.7 (3) | H161—C16—H163 | 109.5 |
C13—C14—C9 | 120.0 (4) | H162—C16—H163 | 109.5 |
O4—C15—N3 | 123.7 (4) | C19—C18—H18 | 120.6 |
O4—C15—C16 | 121.6 (4) | C17—C18—H18 | 120.6 |
N3—C15—C16 | 114.7 (4) | C20—C19—H19 | 119.8 |
C22—C17—C18 | 120.0 (3) | C18—C19—H19 | 119.8 |
C22—C17—N2 | 118.7 (3) | C20—C21—H21 | 120.3 |
C18—C17—N2 | 121.3 (3) | C22—C21—H21 | 120.3 |
C19—C18—C17 | 118.7 (3) | C17—C22—H22 | 119.8 |
C20—C19—C18 | 120.4 (4) | C21—C22—H22 | 119.8 |
| | | |
S—C1—C2—O3 | 7.4 (5) | N1—C1—C2—C3 | 5.9 (5) |
S—C1—N1—N2 | −3.1 (6) | N2—N1—C1—C2 | 177.1 (3) |
O1—S—C1—C2 | 59.5 (3) | C1—N1—N2—C17 | 176.3 (4) |
O1—S—C1—N1 | −120.2 (3) | C9—S—C1—N1 | 122.4 (3) |
O2—S—C1—C2 | −172.8 (3) | C9—S—C1—C2 | −57.9 (3) |
O2—S—C1—N1 | 7.5 (4) | C12—N3—C15—O4 | −3.4 (7) |
S—C1—C2—C3 | −173.9 (3) | C12—N3—C15—C16 | 176.5 (4) |
N1—C1—C2—O3 | −172.8 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.83 (4) | 2.01 (4) | 2.647 (4) | 132 (3) |
N3—H3···O3i | 0.86 (4) | 2.10 (4) | 2.959 (4) | 178 (4) |
C11—H11···O4 | 0.82 | 2.35 | 2.873 (6) | 123 |
C21—H21···O4ii | 0.98 | 2.54 | 3.254 (5) | 130 |
C14—H14···O4iii | 0.88 | 2.39 | 3.107 (5) | 139 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y+1, z. |
(II) 4'-{[benzoyl(4-methoxyphenylhydrazono)methyl]sulfonyl}acetanilide
top
Crystal data top
C23H21N3O5S | F(000) = 944 |
Mr = 451.49 | Dx = 1.380 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.4897 (12) Å | Cell parameters from 48 reflections |
b = 7.4158 (9) Å | θ = 4.5–10.2° |
c = 25.507 (3) Å | µ = 0.19 mm−1 |
β = 91.53 (3)° | T = 293 K |
V = 2172.5 (4) Å3 | Plate, yellow |
Z = 4 | 0.55 × 0.35 × 0.15 mm |
Data collection top
Siemens P3 diffractometer | Rint = 0.052 |
Radiation source: fine-focus sealed tube | θmax = 25°, θmin = 1.9° |
Graphite monochromator | h = −1→13 |
ω/2θ scans | k = −1→8 |
5473 measured reflections | l = −30→30 |
3823 independent reflections | 3 standard reflections every 97 reflections |
2647 reflections with I > 2σ(I) | intensity decay: 18% |
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)] = 0.042 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0674P)2 + 0.2858P] where P = (Fo2 + 2Fc2)/3 |
3823 reflections | (Δ/σ)max = 0.002 |
317 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
C23H21N3O5S | V = 2172.5 (4) Å3 |
Mr = 451.49 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.4897 (12) Å | µ = 0.19 mm−1 |
b = 7.4158 (9) Å | T = 293 K |
c = 25.507 (3) Å | 0.55 × 0.35 × 0.15 mm |
β = 91.53 (3)° | |
Data collection top
Siemens P3 diffractometer | Rint = 0.052 |
5473 measured reflections | 3 standard reflections every 97 reflections |
3823 independent reflections | intensity decay: 18% |
2647 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.22 e Å−3 |
3823 reflections | Δρmin = −0.34 e Å−3 |
317 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 | |
S | 0.61621 (5) | 0.59505 (10) | 0.17476 (2) | 0.0521 (2) | |
O1 | 0.60399 (17) | 0.7844 (3) | 0.16310 (7) | 0.0666 (6) | |
O2 | 0.70669 (15) | 0.5408 (3) | 0.21149 (7) | 0.0706 (6) | |
O3 | 0.38431 (15) | 0.5667 (3) | 0.12279 (6) | 0.0559 (5) | |
O4 | 0.6503 (2) | −0.0913 (3) | −0.00458 (8) | 0.0757 (6) | |
O5 | 0.46487 (18) | 0.2345 (3) | 0.48744 (7) | 0.0756 (6) | |
N1 | 0.47501 (15) | 0.4549 (3) | 0.25010 (7) | 0.0398 (5) | |
N2 | 0.55876 (17) | 0.4410 (3) | 0.28465 (7) | 0.0453 (5) | |
H2 | 0.630 (3) | 0.465 (4) | 0.2764 (11) | 0.070 (9)* | |
N3 | 0.63852 (18) | 0.2040 (3) | −0.02660 (8) | 0.0483 (5) | |
H3 | 0.628 (2) | 0.276 (4) | −0.0542 (11) | 0.053 (7)* | |
C1 | 0.48435 (19) | 0.5148 (3) | 0.20211 (9) | 0.0429 (6) | |
C2 | 0.37866 (19) | 0.5247 (3) | 0.16923 (8) | 0.0411 (5) | |
C3 | 0.26206 (19) | 0.4801 (3) | 0.19102 (8) | 0.0392 (5) | |
C4 | 0.2266 (2) | 0.5384 (3) | 0.23990 (9) | 0.0440 (6) | |
H4 | 0.2798 (15) | 0.5993 (18) | 0.2628 (7) | 0.057 (3)* | |
C5 | 0.1139 (2) | 0.5073 (4) | 0.25510 (10) | 0.0524 (7) | |
H5 | 0.0898 (7) | 0.5480 (13) | 0.2885 (10) | 0.057 (3)* | |
C6 | 0.0364 (2) | 0.4183 (4) | 0.22238 (11) | 0.0578 (7) | |
H6 | −0.040 (2) | 0.3982 (7) | 0.2329 (3) | 0.057 (3)* | |
C7 | 0.0705 (2) | 0.3588 (4) | 0.17432 (11) | 0.0555 (7) | |
H7 | 0.0185 (15) | 0.2965 (19) | 0.1526 (6) | 0.057 (3)* | |
C8 | 0.1824 (2) | 0.3916 (3) | 0.15829 (9) | 0.0473 (6) | |
H8 | 0.2044 (7) | 0.3543 (12) | 0.1255 (10) | 0.057 (3)* | |
C9 | 0.6335 (2) | 0.4780 (4) | 0.11585 (9) | 0.0472 (6) | |
C10 | 0.6465 (2) | 0.2921 (4) | 0.11625 (11) | 0.0591 (7) | |
H10 | 0.6528 (3) | 0.229 (2) | 0.1488 (10) | 0.063 (4)* | |
C11 | 0.6503 (2) | 0.1982 (4) | 0.06995 (10) | 0.0584 (7) | |
H11 | 0.6575 (3) | 0.079 (4) | 0.07039 (10) | 0.063 (4)* | |
C12 | 0.64300 (19) | 0.2895 (3) | 0.02237 (9) | 0.0441 (6) | |
C13 | 0.6359 (2) | 0.4766 (3) | 0.02270 (10) | 0.0468 (6) | |
H13 | 0.6355 (2) | 0.538 (2) | −0.0084 (10) | 0.063 (4)* | |
C14 | 0.6293 (2) | 0.5702 (4) | 0.06881 (10) | 0.0493 (6) | |
H14 | 0.6218 (3) | 0.698 (4) | 0.06842 (10) | 0.063 (4)* | |
C15 | 0.6394 (2) | 0.0249 (4) | −0.03769 (11) | 0.0525 (6) | |
C16 | 0.6277 (3) | −0.0188 (4) | −0.09492 (11) | 0.0659 (8) | |
H161 | 0.5726 (11) | 0.0659 (16) | −0.1120 (4) | 0.119 (8)* | |
H162 | 0.5986 (6) | −0.143 (2) | −0.09927 (15) | 0.119 (8)* | |
H163 | 0.7044 (15) | −0.0080 (5) | −0.1111 (3) | 0.119 (8)* | |
C17 | 0.53525 (18) | 0.3858 (3) | 0.33639 (8) | 0.0391 (5) | |
C18 | 0.4251 (2) | 0.3332 (3) | 0.35020 (9) | 0.0458 (6) | |
H18 | 0.3646 (17) | 0.3325 (4) | 0.3256 (7) | 0.057 (4)* | |
C19 | 0.4068 (2) | 0.2820 (4) | 0.40092 (9) | 0.0487 (6) | |
H19 | 0.334 (2) | 0.2445 (11) | 0.4101 (3) | 0.057 (4)* | |
C20 | 0.4951 (2) | 0.2857 (4) | 0.43840 (9) | 0.0499 (6) | |
C21 | 0.6048 (2) | 0.3385 (4) | 0.42436 (10) | 0.0608 (7) | |
H21 | 0.6663 (17) | 0.3415 (4) | 0.4496 (7) | 0.057 (4)* | |
C22 | 0.6241 (2) | 0.3872 (4) | 0.37291 (10) | 0.0545 (7) | |
H22 | 0.697 (2) | 0.4206 (11) | 0.3634 (3) | 0.057 (4)* | |
C23 | 0.5531 (3) | 0.2246 (6) | 0.52671 (12) | 0.0906 (12) | |
H231 | 0.6058 (12) | 0.126 (2) | 0.5189 (2) | 0.118 (8)* | |
H232 | 0.5183 (7) | 0.2033 (7) | 0.5605 (7) | 0.118 (8)* | |
H233 | 0.5962 (10) | 0.337 (2) | 0.52788 (12) | 0.118 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S | 0.0471 (3) | 0.0709 (5) | 0.0389 (3) | −0.0078 (3) | 0.0141 (2) | −0.0010 (3) |
O1 | 0.0778 (13) | 0.0587 (12) | 0.0647 (13) | −0.0157 (10) | 0.0300 (10) | −0.0059 (10) |
O2 | 0.0440 (9) | 0.1245 (18) | 0.0437 (10) | −0.0098 (11) | 0.0093 (8) | 0.0027 (11) |
O3 | 0.0560 (10) | 0.0772 (13) | 0.0349 (9) | 0.0039 (9) | 0.0088 (7) | 0.0157 (9) |
O4 | 0.1111 (17) | 0.0494 (12) | 0.0662 (14) | 0.0074 (11) | −0.0021 (12) | 0.0135 (10) |
O5 | 0.0836 (13) | 0.1034 (17) | 0.0399 (11) | −0.0027 (12) | 0.0059 (9) | 0.0156 (11) |
N1 | 0.0426 (10) | 0.0446 (11) | 0.0324 (10) | 0.0025 (9) | 0.0058 (8) | −0.0005 (8) |
N2 | 0.0359 (10) | 0.0646 (14) | 0.0356 (11) | −0.0010 (10) | 0.0056 (8) | 0.0014 (10) |
N3 | 0.0604 (13) | 0.0472 (13) | 0.0380 (12) | 0.0092 (10) | 0.0134 (9) | 0.0086 (10) |
C1 | 0.0424 (12) | 0.0493 (14) | 0.0377 (13) | −0.0014 (11) | 0.0098 (9) | 0.0022 (11) |
C2 | 0.0468 (13) | 0.0447 (13) | 0.0322 (13) | 0.0059 (11) | 0.0091 (9) | 0.0035 (10) |
C3 | 0.0431 (12) | 0.0424 (13) | 0.0324 (11) | 0.0041 (10) | 0.0035 (9) | 0.0067 (10) |
C4 | 0.0477 (13) | 0.0496 (14) | 0.0349 (13) | 0.0037 (11) | 0.0052 (10) | 0.0010 (11) |
C5 | 0.0552 (15) | 0.0646 (17) | 0.0380 (13) | 0.0071 (13) | 0.0139 (11) | 0.0041 (12) |
C6 | 0.0460 (13) | 0.0717 (19) | 0.0562 (16) | −0.0042 (13) | 0.0101 (12) | 0.0156 (14) |
C7 | 0.0536 (14) | 0.0634 (18) | 0.0494 (15) | −0.0138 (13) | −0.0032 (12) | 0.0047 (13) |
C8 | 0.0545 (14) | 0.0529 (15) | 0.0345 (12) | 0.0012 (12) | −0.0009 (10) | 0.0016 (11) |
C9 | 0.0439 (13) | 0.0628 (17) | 0.0353 (13) | 0.0029 (12) | 0.0112 (10) | 0.0051 (12) |
C10 | 0.0743 (18) | 0.0642 (19) | 0.0392 (15) | 0.0167 (15) | 0.0115 (12) | 0.0152 (13) |
C11 | 0.0817 (19) | 0.0529 (16) | 0.0414 (15) | 0.0229 (14) | 0.0138 (12) | 0.0103 (12) |
C12 | 0.0414 (12) | 0.0525 (15) | 0.0390 (13) | 0.0089 (11) | 0.0125 (9) | 0.0086 (11) |
C13 | 0.0532 (14) | 0.0519 (15) | 0.0358 (13) | 0.0028 (12) | 0.0136 (10) | 0.0132 (11) |
C14 | 0.0542 (14) | 0.0511 (15) | 0.0433 (14) | 0.0021 (12) | 0.0140 (11) | 0.0082 (12) |
C15 | 0.0511 (14) | 0.0547 (17) | 0.0521 (16) | 0.0044 (12) | 0.0092 (11) | 0.0066 (13) |
C16 | 0.0777 (19) | 0.0611 (18) | 0.0594 (18) | −0.0011 (15) | 0.0101 (14) | −0.0057 (14) |
C17 | 0.0394 (11) | 0.0439 (13) | 0.0342 (11) | 0.0024 (10) | 0.0032 (9) | −0.0018 (10) |
C18 | 0.0420 (12) | 0.0596 (16) | 0.0357 (12) | −0.0046 (11) | 0.0005 (10) | −0.0009 (11) |
C19 | 0.0449 (13) | 0.0588 (16) | 0.0429 (14) | −0.0067 (12) | 0.0079 (10) | 0.0019 (12) |
C20 | 0.0592 (14) | 0.0567 (16) | 0.0340 (12) | 0.0042 (13) | 0.0038 (10) | 0.0049 (12) |
C21 | 0.0508 (14) | 0.087 (2) | 0.0437 (15) | 0.0048 (14) | −0.0103 (11) | 0.0039 (15) |
C22 | 0.0357 (12) | 0.082 (2) | 0.0463 (14) | 0.0014 (13) | 0.0021 (10) | 0.0043 (14) |
C23 | 0.114 (3) | 0.116 (3) | 0.0415 (16) | 0.003 (2) | −0.0097 (17) | 0.0160 (18) |
Geometric parameters (Å, º) top
S—O1 | 1.441 (2) | N3—C12 | 1.401 (3) |
S—O2 | 1.438 (2) | N3—C15 | 1.358 (3) |
S—C1 | 1.787 (2) | O4—C15 | 1.211 (3) |
S—C9 | 1.751 (3) | C15—C16 | 1.498 (4) |
O3—C2 | 1.228 (3) | O5—C20 | 1.361 (3) |
N1—N2 | 1.291 (3) | O5—C23 | 1.408 (4) |
N1—C1 | 1.309 (3) | N2—H2 | 0.86 (3) |
N2—C17 | 1.415 (3) | N3—H3 | 0.89 (3) |
C1—C2 | 1.459 (3) | C4—H4 | 0.95 |
C2—C3 | 1.501 (3) | C5—H5 | 0.95 |
C3—C8 | 1.387 (3) | C6—H6 | 0.94 |
C3—C4 | 1.391 (3) | C7—H7 | 0.93 |
C4—C5 | 1.381 (3) | C8—H8 | 0.92 |
C5—C6 | 1.373 (4) | C10—H10 | 0.95 |
C6—C7 | 1.370 (4) | C11—H11 | 0.89 |
C7—C8 | 1.382 (4) | C13—H13 | 0.92 |
C9—C10 | 1.386 (4) | C14—H14 | 0.95 |
C9—C14 | 1.381 (3) | C16—H161 | 0.99 |
C10—C11 | 1.373 (4) | C16—H162 | 0.99 |
C11—C12 | 1.390 (3) | C16—H163 | 0.99 |
C12—C13 | 1.390 (3) | C18—H18 | 0.92 |
C13—C14 | 1.370 (3) | C19—H19 | 0.92 |
C17—C22 | 1.363 (3) | C21—H21 | 0.94 |
C17—C18 | 1.378 (3) | C22—H22 | 0.91 |
C18—C19 | 1.370 (3) | C23—H231 | 0.97 |
C19—C20 | 1.376 (3) | C23—H232 | 0.97 |
C20—C21 | 1.376 (4) | C23—H233 | 0.97 |
C21—C22 | 1.385 (4) | | |
| | | |
S···O3 | 2.952 (2) | O1···N2 | 4.056 (3) |
S···N2 | 3.114 (2) | O2···N2 | 2.663 (3) |
O1···C2 | 3.234 (3) | N2···C2 | 3.607 (3) |
O2···C2 | 3.894 (3) | | |
| | | |
O1—S—O2 | 118.15 (13) | C20—C21—C22 | 119.5 (2) |
O1—S—C1 | 109.04 (11) | C17—C22—C21 | 120.7 (2) |
O1—S—C9 | 108.56 (12) | N1—N2—H2 | 120.4 (19) |
O2—S—C1 | 104.97 (11) | C17—N2—H2 | 119.5 (19) |
O2—S—C9 | 108.87 (12) | C15—N3—H3 | 115.3 (17) |
C1—S—C9 | 106.67 (12) | C12—N3—H3 | 115.6 (17) |
N2—N1—C1 | 125.93 (19) | C5—C4—H4 | 120.0 |
N1—N2—C17 | 120.15 (18) | C3—C4—H4 | 120.0 |
N1—C1—C2 | 117.82 (19) | C6—C5—H5 | 119.8 |
S—C1—N1 | 124.71 (17) | C4—C5—H5 | 119.8 |
S—C1—C2 | 117.40 (16) | C7—C6—H6 | 119.9 |
O3—C2—C1 | 120.2 (2) | C5—C6—H6 | 119.9 |
O3—C2—C3 | 118.9 (2) | C6—C7—H7 | 120.0 |
C1—C2—C3 | 120.89 (19) | C8—C7—H7 | 120.0 |
C15—N3—C12 | 128.9 (2) | C7—C8—H8 | 119.7 |
C20—O5—C23 | 118.1 (2) | C3—C8—H8 | 119.7 |
C8—C3—C4 | 118.9 (2) | C11—C10—H10 | 119.9 |
C8—C3—C2 | 117.5 (2) | C9—C10—H10 | 119.9 |
C4—C3—C2 | 123.3 (2) | C10—C11—H11 | 120.0 |
C5—C4—C3 | 119.9 (2) | C12—C11—H11 | 120.0 |
C6—C5—C4 | 120.5 (2) | C14—C13—H13 | 119.5 |
C7—C6—C5 | 120.2 (2) | C12—C13—H13 | 119.5 |
C7—C8—C3 | 120.6 (2) | C13—C14—H14 | 120.2 |
C6—C7—C8 | 119.9 (3) | C9—C14—H14 | 120.2 |
C14—C9—C10 | 120.0 (3) | C15—C16—H161 | 109.5 |
C14—C9—S | 119.9 (2) | C15—C16—H162 | 109.5 |
C10—C9—S | 120.1 (2) | H161—C16—H162 | 109.5 |
C11—C10—C9 | 120.3 (3) | C15—C16—H163 | 109.5 |
C10—C11—C12 | 120.1 (3) | H161—C16—H163 | 109.5 |
C13—C12—C11 | 118.9 (2) | H162—C16—H163 | 109.5 |
C13—C12—N3 | 117.2 (2) | C19—C18—H18 | 120.5 |
C11—C12—N3 | 123.9 (2) | C17—C18—H18 | 120.5 |
C14—C13—C12 | 121.1 (2) | C18—C19—H19 | 119.3 |
C13—C14—C9 | 119.6 (2) | C20—C19—H19 | 119.3 |
O4—C15—N3 | 123.5 (3) | C20—C21—H21 | 120.3 |
O4—C15—C16 | 122.0 (3) | C22—C21—H21 | 120.3 |
N3—C15—C16 | 114.5 (2) | C17—C22—H22 | 119.7 |
C22—C17—C18 | 120.2 (2) | C21—C22—H22 | 119.7 |
C22—C17—N2 | 118.5 (2) | O5—C23—H231 | 109.5 |
C18—C17—N2 | 121.3 (2) | O5—C23—H232 | 109.5 |
C19—C18—C17 | 119.0 (2) | H231—C23—H232 | 109.5 |
C18—C19—C20 | 121.4 (2) | O5—C23—H233 | 109.5 |
O5—C20—C19 | 115.5 (2) | H231—C23—H233 | 109.5 |
O5—C20—C21 | 125.2 (2) | H232—C23—H233 | 109.5 |
C19—C20—C21 | 119.2 (2) | | |
| | | |
S—C1—C2—O3 | 8.4 (3) | N2—N1—C1—C2 | −178.4 (2) |
S—C1—N1—N2 | −1.4 (4) | C1—N1—N2—C17 | 175.6 (2) |
O1—S—C1—C2 | 62.1 (2) | C9—S—C1—N1 | 128.0 (2) |
O1—S—C1—N1 | −114.9 (2) | C9—S—C1—C2 | −55.0 (2) |
O2—S—C1—C2 | −170.4 (2) | C12—N3—C15—O4 | −3.9 (4) |
O2—S—C1—N1 | 12.6 (3) | C12—N3—C15—C16 | 177.2 (2) |
S—C1—C2—C3 | −173.0 (2) | C23—O5—C20—C21 | −3.7 (4) |
N1—C1—C2—O3 | −174.4 (2) | C23—O5—C20—C19 | 176.1 (3) |
N1—C1—C2—C3 | 4.2 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 (3) | 1.98 (3) | 2.663 (3) | 135 (2) |
N3—H3···O3i | 0.89 (3) | 2.10 (3) | 2.991 (3) | 174 (2) |
C11—H11···O4 | 0.89 | 2.29 | 2.867 (4) | 122 |
C21—H21···O4ii | 0.94 | 2.55 | 3.474 (4) | 167 |
C14—H14···O4iii | 0.95 | 2.46 | 3.144 (3) | 129 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y+1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C22H18ClN3O4S | C23H21N3O5S |
Mr | 455.90 | 451.49 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 11.603 (4), 7.596 (1), 24.110 (4) | 11.4897 (12), 7.4158 (9), 25.507 (3) |
β (°) | 96.44 (2) | 91.53 (3) |
V (Å3) | 2111.6 (9) | 2172.5 (4) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.32 | 0.19 |
Crystal size (mm) | 0.50 × 0.45 × 0.30 | 0.55 × 0.35 × 0.15 |
|
Data collection |
Diffractometer | Kuma KM-4 diffractometer | Siemens P3 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4434, 3719, 2531 | 5473, 3823, 2647 |
Rint | 0.036 | 0.052 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.135, 1.06 | 0.042, 0.127, 1.03 |
No. of reflections | 3719 | 3823 |
No. of parameters | 306 | 317 |
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 |
Δρmax, Δρmin (e Å−3) | 0.22, −0.30 | 0.22, −0.34 |
Selected geometric parameters (Å, º) for (I) topS—O1 | 1.431 (3) | N2—C17 | 1.408 (4) |
S—O2 | 1.451 (3) | C1—C2 | 1.467 (5) |
S—C1 | 1.792 (3) | C2—C3 | 1.502 (5) |
S—C9 | 1.746 (4) | N3—C12 | 1.400 (5) |
O3—C2 | 1.231 (4) | N3—C15 | 1.352 (5) |
N1—N2 | 1.289 (4) | O4—C15 | 1.212 (5) |
N1—C1 | 1.306 (4) | Cl—C20 | 1.742 (3) |
| | | |
S···O3 | 2.954 (3) | O1···C2 | 3.222 (5) |
S···N2 | 3.115 (3) | O2···C2 | 3.918 (5) |
| | | |
O1—S—O2 | 118.2 (2) | N1—C1—C2 | 117.6 (3) |
O1—S—C1 | 109.28 (18) | S—C1—N1 | 125.0 (3) |
O1—S—C9 | 109.02 (17) | S—C1—C2 | 117.4 (2) |
O2—S—C1 | 104.82 (16) | O3—C2—C1 | 119.7 (3) |
O2—S—C9 | 108.63 (18) | O3—C2—C3 | 119.0 (3) |
C1—S—C9 | 106.19 (17) | C1—C2—C3 | 121.3 (3) |
N2—N1—C1 | 125.7 (3) | C15—N3—C12 | 128.8 (3) |
N1—N2—C17 | 120.1 (3) | | |
| | | |
S—C1—C2—O3 | 7.4 (5) | O1—S—C1—N1 | −120.2 (3) |
S—C1—N1—N2 | −3.1 (6) | O2—S—C1—C2 | −172.8 (3) |
O1—S—C1—C2 | 59.5 (3) | O2—S—C1—N1 | 7.5 (4) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.83 (4) | 2.01 (4) | 2.647 (4) | 132 (3) |
N3—H3···O3i | 0.86 (4) | 2.10 (4) | 2.959 (4) | 178 (4) |
C11—H11···O4 | 0.82 | 2.35 | 2.873 (6) | 123 |
C21—H21···O4ii | 0.98 | 2.54 | 3.254 (5) | 130 |
C14—H14···O4iii | 0.88 | 2.39 | 3.107 (5) | 139 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y+1, z. |
Selected geometric parameters (Å, º) for (II) topS—O1 | 1.441 (2) | C1—C2 | 1.459 (3) |
S—O2 | 1.438 (2) | C2—C3 | 1.501 (3) |
S—C1 | 1.787 (2) | N3—C12 | 1.401 (3) |
S—C9 | 1.751 (3) | N3—C15 | 1.358 (3) |
O3—C2 | 1.228 (3) | O4—C15 | 1.211 (3) |
N1—N2 | 1.291 (3) | O5—C20 | 1.361 (3) |
N1—C1 | 1.309 (3) | O5—C23 | 1.408 (4) |
N2—C17 | 1.415 (3) | | |
| | | |
S···O3 | 2.952 (2) | O1···C2 | 3.234 (3) |
S···N2 | 3.114 (2) | O2···C2 | 3.894 (3) |
| | | |
O1—S—O2 | 118.15 (13) | N1—C1—C2 | 117.82 (19) |
O1—S—C1 | 109.04 (11) | S—C1—N1 | 124.71 (17) |
O1—S—C9 | 108.56 (12) | S—C1—C2 | 117.40 (16) |
O2—S—C1 | 104.97 (11) | O3—C2—C1 | 120.2 (2) |
O2—S—C9 | 108.87 (12) | O3—C2—C3 | 118.9 (2) |
C1—S—C9 | 106.67 (12) | C1—C2—C3 | 120.89 (19) |
N2—N1—C1 | 125.93 (19) | C15—N3—C12 | 128.9 (2) |
N1—N2—C17 | 120.15 (18) | C20—O5—C23 | 118.1 (2) |
| | | |
S—C1—C2—O3 | 8.4 (3) | O1—S—C1—N1 | −114.9 (2) |
S—C1—N1—N2 | −1.4 (4) | O2—S—C1—C2 | −170.4 (2) |
O1—S—C1—C2 | 62.1 (2) | O2—S—C1—N1 | 12.6 (3) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O2 | 0.86 (3) | 1.98 (3) | 2.663 (3) | 135 (2) |
N3—H3···O3i | 0.89 (3) | 2.10 (3) | 2.991 (3) | 174 (2) |
C11—H11···O4 | 0.89 | 2.29 | 2.867 (4) | 122 |
C21—H21···O4ii | 0.94 | 2.55 | 3.474 (4) | 167 |
C14—H14···O4iii | 0.95 | 2.46 | 3.144 (3) | 129 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, y+1, z. |
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X-ray and ab initio molecular orbital investigations of phenyl benzoyl(phenylhydrazono)methyl sulfones have shown that strongly electron-withdrawing substituents bonded to the phenylhydrazone moiety increase the strength of the intramolecular resonance-assisted N—H···O═S hydrogen bonds (Jeffrey, 1997) and prompt simultaneous contraction of the intramolecular contacts between the oppositely charged atoms of the sulfonyl and β-carbonyl groups (Wolf, 2001a, and references therein). The latter effect promotes electron density back-donation towards the S atoms and therefore reduces the strongly electron-withdrawing character of the sulfonyl groups. In this paper, the essentially isomorphous crystal structures of 4'-{[benzoyl(4-chlorophenylhydrazono)methyl]sulfonyl}acetanilide, (I), and 4'-{[benzoyl(4-methoxyphenylhydrazono)methyl]sulfonyl}acetanilide, (II), are reported. Their terminal substituents attached to the α-phenylhydrazone group have opposite electronic properties. The para-Cl atom in (I) shows electron-withdrawing ability, whereas the p-methoxy group in (II) has electron-donating character. The Hammett σp constants are 0.23 and -0.27, respectively (Hansch et al., 1995). An interesting feature of (I) and (II) is their antimycotic activity, which increases after exposing fungi colonies with added fungicide to radiation characteristic of daylight (Wolf, 1999; 2000; Zakrzewski & Kacała, 1998; Zakrzewski, 1999). \sch
The molecular structures of (I) and (II) are shown in Figs. 1 and 2. The superposition of both structures (Fig. 3) clearly shows the similarity of their conformations. The root mean square deviation calculated from the least-squares fit of all relevant non-H atoms is 0.87 Å.
In (I) and (II), the S═O2 sulfonyl double bonds, carbonyl groups and phenylhydrazone moieties are approximately coplanar. Their configuration can be defined as EZE. This three-letter symbol was initially used to describe the conformation of 2,2-diacylethenamines (Gómez-Sánchez et al., 1987) and applied further to β-diketoarylhydrazones (Bertolasi, Gilli et al., 1994; Bertolasi, Nanni et al., 1994). In the compounds investigated, the above three letters indicate, relative to the C1═N1 bond, the positions of the carbonyl C2═O3, the sulfonyl S═O2 and the N2—C17 bond bearing the phenyl ring.
The central fragments of both molecules are constrained by strong intramolecular hydrogen bonds assisted by resonance (resonance-assisted hydrogen bonds, RAHB). These bonds connect the hydrazone and sulfonyl groups. The six-membered RAHB rings in (I) and (II) are practically planar (r.m.s. deviations from the O2/S/C1/N1/N2/H2 planes are 0.03 and 0.07 Å, respectively). The N2···O2 distance in (I) [2.647 (4) Å] is shorter than that in (II) [2.663 (3) Å]. On the other hand, the S═O2 bond in (I) is longer [1.451 (3) Å] than that in (II) [1.438 (2) Å]. This characteristic variation of bond lengths and D···A distances indicates that a stronger RAHB exists in (I) (Gilli et al., 1994).
Atomic charges derived from electrostatic potentials were calculated using GAUSSIAN98 (Frisch et al., 1998), at the RHF/6–311+G(d,p) level for the X-ray determined coordinates. Grid points were selected according to the Merz-Singh-Kollman procedure (Bessler et al., 1990; Singh & Kollman, 1984). Large positive atomic charges are located on atoms S and C2 [1.25 and 0.52, and 1.26 and 0.47 e for (I) and (II), respectively]. All O atoms are negatively charged. Atomic charges on O1, O2 and O3 are within the range -0.52 to -0.68 e. Electrostatic attraction of the oppositely charged atoms generates intramolecular contacts between the atom pairs S···O3 and O1···C2; details are summarized in Tables 2 and 5.
A similar situation was observed in all three α-hydrazono-β-ketosulfones reported in the Cambridge Structural Database (Allen & Kennard, 1993), 4'-{[benzoyl(4-tolylhydrazono)methyl]sulfonyl}acetanilide, (III) (Wolf, 1999), phenyl benzoyl(phenylhydrazono)methyl sulfone, (IV), and phenyl benzoyl(4-nitrophenylhydrazono)methyl sulfone, (V) (Wolf, 2001a). In (V), the strongly electron-withdrawing p-nitro group attached to the phenylhydrazone moiety hinders electron density redistribution from the hydrazone fragment towards the electron-deficient S and β-carbonyl C, and thus helps to conserve large positive charges on those atoms. This effect strengthens intramolecular hydrogen bonding and, in addition, favours electrostatic attraction of the oppositely charged atoms of the sulfonyl and carbonyl dipoles. Finally, it results in a significant shortening of the intramolecular S···O3 contact in (V) [(2.818 (3) Å] when compared with (IV) [(2.976 (1) Å]. In the title compounds, (I) and (II), the S···O3 distances are significantly contracted below the van der Waals limit (3.32 Å; Bondi, 1964). Nevertheless, both contacts are practically equal [2.954 (3) and 2.952 (2) Å]. This observation indicates that the divergence of the electronic properties of the Cl atom and methoxy group was too small to alter the non-bonding interactions of the sulfonyl and β-carbonyl group significantly.
Bond lengths in (I) and (II) are close to those observed in related compounds (Wolf, 1999, 2001a). In particular, the S—C1 bonds are longer [1.792 (3) and 1.787 (2) Å, respectively] than the conventional S-Csp3 single bond (1.779 Å; Allen et al., 1992). Similar bond elongation in (III), (IV) and (V) [1.795 (3), 1.798 (2) and 1.784 (1) Å, respectively] was attributed to hyperconjugative (Juaristi & Cuevas, 1995; Graczyk & Mikołajczyk, 1994; Cramer, 1996) interactions involving σ(S—C1) - π*(C═O3) bonding and non-bonding atomic orbitals. The resulting transfer of electron density from S towards O3 increases charge separation between the sulfonyl and carbonyl groups and, finally, intensifies the electrostatic attraction of the oppositely charged atoms S and O3. A similar pattern of intramolecular interactions was observed in α-unsubstituted β-ketosulfones and β-ketosulfoxides (Distefano et al., 1991, 1996; Dal Colle et al., 1995; Olivato et al., 1998, 2000; Wolf, 2001b).
In the crystal lattice, molecules of (I) and (II) form centrosymmetric dimers, which are connected by intermolecular hydrogen bonds involving the β-carbonyl O3 atoms and the N3—H2 bonds of the terminal acetamide moieties. According to Etter's graph-set terminology (Etter, 1990; Bernstein et al., 1995), these bond systems can be described as R22(20). Additionally, the O4 atoms of the acetamide groups are involved in three close contacts with the surrounding H atoms of the phenyl rings. According to the liberal definition of Desiraju & Steiner (1999), these contacts could be classified as C—H···O hydrogen bonds. Details are summarized in Tables 3 and 6.