X-ray investigations of sulfur-containing fungicides. II. Intramolecular forces governing the ­conformation of four novel α-phenylazo- and α-­phenylhydrazono-β-ketosulfones

The crystal and molecular structures of four novel β-ketosulfones, phenyl benzoyl(phenylhydrazono)methyl sulfone (I), phenyl benzoyl(4-nitrophenylhydrazono)methyl sulfone (II), (benzoyl)(phenyl)(phenylazo)methyl phenyl sulfone (III) and (benzoyl)(phenyl)(3-chlorophenylazo)methyl 4-tolyl sulfone (IV), have been investigated using X-ray analysis and density functional theory supplemented by ab initio Hartree–Fock calculations. The conformations of (I) and (II) are stabilized by strong intramolecular resonance-assisted hydrogen bonds formed between the sulfonyl and the α-hydrazono moieties. The following increase of a positive charge on the S atoms is compensated via π-conjugation and stereoelectronic back-donation from the nearby β-carbonyl group. Compounds (III) and (IV) adopt a strongly distorted propeller shape with pivotal tetrahedral C1 atoms. Distortion mostly follows from the approximate coplanarity of the α-azophenyl and α-phenyl moieties opposite each other. The main stereoelectronic interactions involve the donation of electron density from the α-azo N2 towards the sulfonyl S and the β-carbonyl C2 atoms.

Computing details

Data collection: P3 (Siemens, 1989) for (I), (III), (IV); KM-4 (Kuma Diffraction, 1991) for (II). Cell refinement: P3 (Siemens, 1989) for (I), (III), (IV); KM-4 (Kuma Diffraction, 1991) for (II). Data reduction: XDISK (Siemens, 1991) for (I), (III), (IV); DATAPROC 9.0 (Kuma Diffraction, 1995) for (II). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (I), (IV); SHELXS97 (Sheldrick, 1990) for (II), (III). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: InsightII (MSI, 1997), XP (Siemens, 1990); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1.

(I) benzoylphenylhydrazonophenylsulfonylmethane

Crystal data

C20H16N2O3S	Z = 2
Mr = 364.43	F(000) = 380
Triclinic, P1	Dx = 1.397 Mg m^−3
a = 5.6784 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.3204 (15) Å	Cell parameters from 48 reflections
c = 14.1087 (19) Å	θ = 4.7–17.3°
α = 102.441 (11)°	µ = 0.21 mm^−1
β = 97.544 (10)°	T = 290 K
γ = 97.447 (11)°	Approximately sphere shaped, pale yellow
V = 866.1 (2) Å^3	0.25 × 0.23 × 0.21 mm

Data collection

Siemens P3 diffractometer	Rint = 0.057
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 1.9°
Graphite monochromator	h = −2→7
ω–2θ scans	k = −14→14
5669 measured reflections	l = −18→18
4010 independent reflections	3 standard reflections every 97 reflections
3221 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	All H-atom parameters refined
wR(F^2) = 0.097	w = 1/[σ^2(Fo^2) + (0.0457P)^2 + 0.2341P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.003
4010 reflections	Δρmax = 0.39 e Å^−3
300 parameters	Δρmin = −0.37 e Å^−3
0 restraints	Extinction correction: SHELXL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.020 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S	0.15888 (7)	0.75202 (3)	0.39492 (3)	0.03474 (12)
O1	0.4135 (2)	0.77732 (11)	0.42784 (9)	0.0469 (3)
O2	0.0102 (2)	0.81742 (11)	0.45619 (8)	0.0479 (3)
O3	0.3813 (2)	0.67186 (12)	0.21719 (9)	0.0514 (3)
N1	−0.0757 (2)	0.84472 (11)	0.25045 (9)	0.0332 (3)
N2	−0.1909 (2)	0.90846 (12)	0.31177 (10)	0.0379 (3)
H2	−0.179 (3)	0.9008 (18)	0.3701 (15)	0.050 (5)*
C1	0.0793 (3)	0.77679 (13)	0.27497 (10)	0.0323 (3)
C2	0.1981 (3)	0.71295 (13)	0.19662 (11)	0.0344 (3)
C3	0.0872 (3)	0.69559 (13)	0.09174 (10)	0.0343 (3)
C4	0.2336 (3)	0.71915 (18)	0.02450 (13)	0.0486 (4)
H4	0.394 (4)	0.758 (2)	0.0491 (16)	0.065 (6)*
C5	0.1411 (4)	0.6914 (2)	−0.07471 (14)	0.0584 (5)
H5	0.253 (4)	0.707 (2)	−0.1203 (18)	0.081 (7)*
C6	−0.0938 (4)	0.63613 (18)	−0.10762 (13)	0.0531 (4)
H6	−0.153 (4)	0.613 (2)	−0.1768 (17)	0.071 (6)*
C7	−0.2398 (3)	0.61208 (19)	−0.04140 (14)	0.0544 (5)
H7	−0.402 (4)	0.572 (2)	−0.0662 (17)	0.070 (6)*
C8	−0.1513 (3)	0.64416 (17)	0.05869 (13)	0.0459 (4)
H8	−0.256 (4)	0.6298 (19)	0.1051 (16)	0.060 (6)*
C9	0.0583 (3)	0.59328 (13)	0.37649 (10)	0.0325 (3)
C10	−0.1783 (3)	0.54531 (16)	0.33365 (12)	0.0411 (3)
H10	−0.283 (3)	0.5970 (18)	0.3150 (14)	0.050 (5)*
C11	−0.2554 (3)	0.42169 (17)	0.32251 (13)	0.0469 (4)
H11	−0.409 (4)	0.390 (2)	0.2904 (16)	0.065 (6)*
C12	−0.1016 (3)	0.34838 (16)	0.35504 (13)	0.0477 (4)
H12	−0.161 (4)	0.262 (2)	0.3491 (15)	0.059 (6)*
C13	0.1318 (3)	0.39772 (15)	0.39777 (13)	0.0455 (4)
H13	0.240 (3)	0.3502 (19)	0.4211 (15)	0.055 (5)*
C14	0.2154 (3)	0.52060 (15)	0.40801 (11)	0.0381 (3)
H14	0.378 (3)	0.5589 (17)	0.4393 (13)	0.047 (5)*
C15	−0.3577 (3)	0.97768 (13)	0.27848 (12)	0.0382 (3)
C16	−0.3891 (4)	0.99242 (18)	0.18346 (15)	0.0527 (4)
H16	−0.291 (3)	0.9607 (18)	0.1424 (15)	0.050 (5)*
C17	−0.5632 (4)	1.0600 (2)	0.15643 (19)	0.0699 (6)
H17	−0.581 (4)	1.068 (2)	0.0958 (19)	0.077 (7)*
C18	−0.7007 (4)	1.11153 (19)	0.2227 (2)	0.0699 (7)
H18	−0.815 (5)	1.159 (2)	0.2032 (19)	0.087 (8)*
C19	−0.6636 (4)	1.09843 (16)	0.31741 (19)	0.0594 (5)
H19	−0.769 (4)	1.133 (2)	0.3657 (17)	0.072 (7)*
C20	−0.4926 (3)	1.03180 (14)	0.34607 (15)	0.0460 (4)
H20	−0.463 (4)	1.020 (2)	0.4122 (17)	0.068 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0400 (2)	0.03403 (19)	0.02939 (18)	0.00858 (14)	0.00133 (14)	0.00695 (13)
O1	0.0428 (6)	0.0469 (6)	0.0442 (6)	0.0002 (5)	−0.0078 (5)	0.0095 (5)
O2	0.0657 (8)	0.0497 (7)	0.0325 (6)	0.0252 (6)	0.0101 (5)	0.0084 (5)
O3	0.0450 (7)	0.0669 (8)	0.0447 (6)	0.0261 (6)	0.0045 (5)	0.0101 (6)
N1	0.0341 (6)	0.0297 (6)	0.0356 (6)	0.0049 (5)	0.0052 (5)	0.0079 (5)
N2	0.0432 (7)	0.0387 (7)	0.0341 (7)	0.0141 (5)	0.0066 (5)	0.0091 (5)
C1	0.0353 (7)	0.0319 (7)	0.0299 (7)	0.0061 (6)	0.0038 (5)	0.0081 (5)
C2	0.0345 (7)	0.0341 (7)	0.0352 (7)	0.0063 (6)	0.0061 (6)	0.0091 (6)
C3	0.0371 (7)	0.0340 (7)	0.0327 (7)	0.0098 (6)	0.0072 (6)	0.0065 (6)
C4	0.0446 (9)	0.0582 (10)	0.0415 (9)	0.0011 (8)	0.0115 (7)	0.0100 (8)
C5	0.0679 (12)	0.0703 (13)	0.0391 (9)	0.0050 (10)	0.0182 (9)	0.0153 (9)
C6	0.0657 (12)	0.0591 (11)	0.0336 (8)	0.0187 (9)	0.0019 (8)	0.0081 (8)
C7	0.0437 (10)	0.0666 (12)	0.0454 (10)	0.0059 (9)	−0.0013 (8)	0.0040 (8)
C8	0.0395 (8)	0.0578 (10)	0.0387 (8)	0.0049 (7)	0.0083 (7)	0.0083 (7)
C9	0.0353 (7)	0.0365 (7)	0.0277 (6)	0.0084 (6)	0.0070 (5)	0.0089 (5)
C10	0.0352 (8)	0.0487 (9)	0.0412 (8)	0.0093 (7)	0.0044 (6)	0.0143 (7)
C11	0.0392 (9)	0.0528 (10)	0.0440 (9)	−0.0039 (7)	0.0083 (7)	0.0071 (7)
C12	0.0613 (11)	0.0372 (8)	0.0458 (9)	0.0032 (8)	0.0192 (8)	0.0090 (7)
C13	0.0559 (10)	0.0408 (8)	0.0453 (9)	0.0185 (8)	0.0126 (8)	0.0130 (7)
C14	0.0386 (8)	0.0420 (8)	0.0357 (7)	0.0124 (6)	0.0061 (6)	0.0102 (6)
C15	0.0376 (8)	0.0278 (7)	0.0472 (8)	0.0055 (6)	0.0023 (6)	0.0076 (6)
C16	0.0586 (11)	0.0519 (10)	0.0504 (10)	0.0160 (9)	0.0049 (9)	0.0164 (8)
C17	0.0758 (15)	0.0623 (13)	0.0723 (14)	0.0162 (11)	−0.0125 (12)	0.0297 (11)
C18	0.0531 (11)	0.0428 (10)	0.114 (2)	0.0188 (9)	−0.0038 (12)	0.0217 (11)
C19	0.0490 (10)	0.0323 (8)	0.0959 (16)	0.0118 (7)	0.0120 (10)	0.0101 (9)
C20	0.0471 (9)	0.0294 (7)	0.0604 (11)	0.0065 (6)	0.0112 (8)	0.0063 (7)

Geometric parameters (Å, º)

S—O1	1.4305 (12)	C15—C16	1.378 (2)
S—O2	1.4444 (12)	C15—C20	1.390 (2)
S—C9	1.7653 (15)	C16—C17	1.389 (3)
S—C1	1.7843 (14)	C17—C18	1.378 (4)
O3—C2	1.2196 (18)	C18—C19	1.369 (3)
N1—C1	1.3022 (18)	C19—C20	1.376 (3)
N1—N2	1.3034 (17)	N2—H2	0.84 (2)
N2—C15	1.4022 (19)	C4—H4	0.94 (2)
C1—C2	1.476 (2)	C5—H5	0.99 (2)
C2—C3	1.491 (2)	C6—H6	0.96 (2)
C3—C8	1.380 (2)	C7—H7	0.96 (2)
C3—C4	1.386 (2)	C8—H8	0.96 (2)
C4—C5	1.381 (3)	C10—H10	0.939 (19)
C5—C6	1.372 (3)	C11—H11	0.91 (2)
C6—C7	1.374 (3)	C12—H12	0.97 (2)
C7—C8	1.387 (2)	C13—H13	0.94 (2)
C9—C14	1.383 (2)	C14—H14	0.971 (19)
C9—C10	1.386 (2)	C16—H16	0.91 (2)
C10—C11	1.379 (2)	C17—H17	0.87 (3)
C11—C12	1.382 (3)	C18—H18	0.94 (3)
C12—C13	1.373 (3)	C19—H19	1.01 (2)
C13—C14	1.380 (2)	C20—H20	0.97 (2)
O1—S—O2	117.51 (8)	C14—C9—S	119.17 (12)
O1—S—C9	109.01 (7)	C10—C9—S	119.13 (11)
O2—S—C9	108.36 (7)	C11—C10—C9	118.28 (15)
O1—S—C1	112.34 (7)	C11—C10—H10	121.6 (12)
O2—S—C1	106.18 (7)	C9—C10—H10	120.1 (12)
C9—S—C1	102.32 (7)	C10—C11—C12	120.68 (16)
C1—N1—N2	124.42 (13)	C10—C11—H11	117.3 (14)
N1—N2—C15	120.51 (13)	C12—C11—H11	121.9 (14)
N1—N2—H2	119.8 (13)	C13—C12—C11	120.18 (16)
C15—N2—H2	119.2 (13)	C13—C12—H12	120.3 (12)
N1—C1—C2	117.41 (12)	C11—C12—H12	119.5 (12)
N1—C1—S	125.87 (11)	C12—C13—C14	120.41 (16)
C2—C1—S	116.72 (10)	C12—C13—H13	122.0 (13)
O3—C2—C1	120.57 (13)	C14—C13—H13	117.6 (13)
O3—C2—C3	120.19 (13)	C13—C14—C9	118.78 (15)
C1—C2—C3	119.21 (12)	C13—C14—H14	122.6 (11)
C8—C3—C4	119.41 (15)	C9—C14—H14	118.6 (11)
C8—C3—C2	121.29 (14)	C16—C15—C20	120.74 (16)
C4—C3—C2	118.91 (14)	C16—C15—N2	122.33 (15)
C5—C4—C3	120.22 (17)	C20—C15—N2	116.93 (15)
C5—C4—H4	121.9 (13)	C15—C16—C17	118.2 (2)
C3—C4—H4	117.8 (13)	C15—C16—H16	118.7 (12)
C6—C5—C4	120.17 (17)	C17—C16—H16	123.0 (12)
C6—C5—H5	122.1 (14)	C18—C17—C16	121.2 (2)
C4—C5—H5	117.6 (14)	C18—C17—H17	122.0 (16)
C5—C6—C7	119.89 (17)	C16—C17—H17	116.8 (16)
C5—C6—H6	119.4 (14)	C19—C18—C17	119.90 (19)
C7—C6—H6	120.7 (14)	C19—C18—H18	120.3 (16)
C6—C7—C8	120.34 (18)	C17—C18—H18	119.7 (16)
C6—C7—H7	118.3 (14)	C18—C19—C20	120.1 (2)
C8—C7—H7	121.3 (14)	C18—C19—H19	120.2 (13)
C3—C8—C7	119.87 (16)	C20—C19—H19	119.6 (13)
C3—C8—H8	120.1 (12)	C19—C20—C15	119.81 (19)
C7—C8—H8	120.1 (12)	C19—C20—H20	122.2 (13)
C14—C9—C10	121.66 (14)	C15—C20—H20	118.0 (13)
S—C1—C2—O3	−17.82 (19)	N1—C1—C2—O3	162.97 (14)
S—C1—N1—N2	2.3 (2)	C9—S—C1—N1	115.97 (13)
O1—S—C1—N1	−127.27 (13)	C9—S—C1—C2	−63.16 (12)
O1—S—C1—C2	53.59 (13)	C1—N1—N2—C15	−179.00 (14)
O2—S—C1—N1	2.46 (15)	N2—N1—C1—C2	−178.53 (13)
O2—S—C1—C2	−176.68 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.84 (2)	1.98 (2)	2.668 (2)	138 (1)

(II) benzoyl(4-nitrophenylhydrazono)phenylsulfonylmethane

Crystal data

C20H15N3O5S	F(000) = 848
Mr = 409.41	Dx = 1.459 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.54178 Å
a = 14.8351 (7) Å	Cell parameters from 82 reflections
b = 6.0456 (5) Å	θ = 9–15°
c = 21.0161 (12) Å	µ = 1.89 mm^−1
β = 98.613 (6)°	T = 292 K
V = 1863.6 (2) Å^3	Prism, pale yellow
Z = 4	0.42 × 0.21 × 0.12 × 0.25 (radius) mm

Data collection

Kuma Diffraction KM-4 diffractometer	2943 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 74.9°, θmin = 3.9°
ω–2θ scans	h = −18→18
Absorption correction: ψ scan XEMP (Siemens, 1991)	k = −1→7
Tmin = 0.445, Tmax = 0.797	l = 0→26
4566 measured reflections	3 standard reflections every 100 reflections
3710 independent reflections	intensity decay: 5%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	All H-atom parameters refined
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.0759P)^2 + 1.2875P] where P = (Fo^2 + 2Fc^2)/3
S = 0.93	(Δ/σ)max = 0.007
3710 reflections	Δρmax = 0.33 e Å^−3
323 parameters	Δρmin = −0.49 e Å^−3
0 restraints	Extinction correction: SHELXL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0019 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S	0.51978 (4)	0.43082 (11)	0.10524 (3)	0.0542 (2)
O1	0.54900 (14)	0.2193 (4)	0.08498 (10)	0.0735 (6)
O2	0.53454 (12)	0.6212 (3)	0.06644 (9)	0.0676 (5)
O3	0.43199 (13)	0.1399 (3)	0.18090 (11)	0.0771 (6)
O4	0.11839 (18)	1.4824 (4)	−0.09700 (12)	0.0923 (7)
O5	0.01586 (17)	1.2996 (5)	−0.05798 (16)	0.1150 (10)
N1	0.33994 (14)	0.5617 (3)	0.07870 (9)	0.0517 (5)
N2	0.35991 (15)	0.7264 (4)	0.04234 (10)	0.0552 (5)
H2	0.417 (2)	0.749 (5)	0.0365 (14)	0.069 (9)*
N3	0.09448 (18)	1.3274 (4)	−0.06644 (12)	0.0730 (7)
C1	0.39941 (16)	0.4259 (4)	0.10873 (11)	0.0509 (5)
C2	0.37056 (18)	0.2459 (4)	0.14986 (12)	0.0556 (6)
C3	0.27397 (17)	0.1880 (4)	0.15439 (11)	0.0530 (6)
C4	0.2594 (2)	−0.0202 (5)	0.17955 (13)	0.0615 (6)
H4	0.310 (2)	−0.110 (5)	0.1917 (14)	0.074 (9)*
C5	0.1733 (2)	−0.0879 (6)	0.18735 (15)	0.0698 (8)
H5	0.166 (2)	−0.230 (6)	0.2067 (16)	0.085 (10)*
C6	0.1000 (2)	0.0499 (6)	0.17052 (17)	0.0788 (9)
H6	0.041 (3)	0.006 (6)	0.1763 (17)	0.098 (11)*
C7	0.1131 (2)	0.2566 (7)	0.14643 (19)	0.0857 (10)
H7	0.062 (3)	0.341 (7)	0.135 (2)	0.116 (14)*
C8	0.1993 (2)	0.3256 (5)	0.13822 (15)	0.0694 (8)
H8	0.204 (2)	0.472 (6)	0.1201 (16)	0.085 (10)*
C9	0.57342 (16)	0.4895 (4)	0.18383 (11)	0.0523 (6)
C10	0.5605 (2)	0.6971 (5)	0.20879 (14)	0.0642 (7)
H10	0.522 (2)	0.807 (6)	0.1847 (16)	0.085 (10)*
C11	0.6027 (2)	0.7464 (6)	0.27005 (16)	0.0764 (9)
H11	0.596 (3)	0.885 (6)	0.2880 (18)	0.097 (12)*
C12	0.6585 (2)	0.5934 (7)	0.30477 (15)	0.0775 (9)
H12	0.688 (2)	0.633 (6)	0.3481 (17)	0.090 (10)*
C13	0.6715 (2)	0.3889 (7)	0.27945 (15)	0.0776 (9)
H13	0.714 (3)	0.284 (7)	0.3027 (19)	0.107 (12)*
C14	0.6282 (2)	0.3330 (5)	0.21858 (14)	0.0646 (7)
H14	0.634 (2)	0.186 (6)	0.1968 (16)	0.089 (11)*
C15	0.29122 (16)	0.8694 (4)	0.01444 (10)	0.0506 (5)
C16	0.20005 (18)	0.8286 (5)	0.01620 (13)	0.0603 (6)
H16	0.183 (2)	0.707 (5)	0.0374 (15)	0.072 (9)*
C17	0.13536 (19)	0.9797 (5)	−0.01041 (14)	0.0642 (7)
H17	0.068 (2)	0.951 (5)	−0.0085 (15)	0.083 (10)*
C18	0.16369 (18)	1.1678 (5)	−0.03884 (12)	0.0574 (6)
C19	0.25361 (19)	1.2086 (5)	−0.04213 (12)	0.0570 (6)
H19	0.270 (2)	1.326 (5)	−0.0622 (15)	0.074 (9)*
C20	0.31822 (18)	1.0581 (4)	−0.01534 (11)	0.0547 (6)
H20	0.382 (2)	1.086 (5)	−0.0152 (14)	0.070 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0518 (3)	0.0619 (4)	0.0490 (3)	0.0081 (3)	0.0084 (2)	0.0018 (3)
O1	0.0783 (12)	0.0717 (13)	0.0711 (11)	0.0270 (10)	0.0135 (10)	−0.0134 (10)
O2	0.0567 (10)	0.0862 (14)	0.0606 (10)	0.0031 (9)	0.0110 (8)	0.0231 (10)
O3	0.0621 (11)	0.0665 (13)	0.0996 (15)	0.0106 (9)	0.0023 (10)	0.0291 (11)
O4	0.1032 (17)	0.0756 (15)	0.0944 (16)	0.0153 (13)	0.0021 (13)	0.0328 (13)
O5	0.0646 (14)	0.109 (2)	0.167 (3)	0.0208 (14)	0.0058 (15)	0.053 (2)
N1	0.0565 (11)	0.0523 (12)	0.0456 (9)	0.0025 (9)	0.0049 (8)	0.0021 (9)
N2	0.0523 (11)	0.0596 (13)	0.0540 (11)	0.0051 (10)	0.0092 (9)	0.0115 (10)
N3	0.0745 (16)	0.0693 (17)	0.0708 (14)	0.0135 (13)	−0.0036 (12)	0.0141 (13)
C1	0.0541 (13)	0.0500 (14)	0.0478 (11)	0.0027 (10)	0.0052 (9)	−0.0014 (10)
C2	0.0631 (15)	0.0473 (14)	0.0554 (13)	0.0044 (11)	0.0053 (11)	0.0037 (11)
C3	0.0597 (14)	0.0508 (14)	0.0487 (11)	0.0027 (11)	0.0083 (10)	0.0019 (10)
C4	0.0702 (17)	0.0561 (16)	0.0587 (14)	0.0035 (13)	0.0110 (12)	0.0045 (12)
C5	0.082 (2)	0.0640 (19)	0.0665 (16)	−0.0086 (15)	0.0206 (14)	0.0051 (14)
C6	0.0655 (18)	0.091 (2)	0.083 (2)	−0.0049 (17)	0.0221 (15)	0.0084 (18)
C7	0.0642 (18)	0.093 (3)	0.103 (2)	0.0136 (18)	0.0238 (17)	0.028 (2)
C8	0.0630 (16)	0.0644 (19)	0.0835 (19)	0.0126 (14)	0.0197 (14)	0.0198 (15)
C9	0.0475 (12)	0.0559 (14)	0.0530 (12)	0.0009 (10)	0.0058 (9)	0.0049 (11)
C10	0.0708 (17)	0.0566 (17)	0.0633 (15)	0.0043 (13)	0.0038 (13)	−0.0011 (13)
C11	0.090 (2)	0.071 (2)	0.0678 (17)	−0.0108 (17)	0.0102 (15)	−0.0112 (16)
C12	0.079 (2)	0.093 (3)	0.0573 (15)	−0.0178 (18)	0.0003 (14)	0.0023 (16)
C13	0.0726 (19)	0.087 (2)	0.0678 (17)	0.0028 (17)	−0.0072 (14)	0.0196 (17)
C14	0.0643 (16)	0.0612 (18)	0.0655 (15)	0.0081 (13)	0.0007 (12)	0.0075 (13)
C15	0.0540 (13)	0.0550 (14)	0.0424 (11)	0.0047 (11)	0.0063 (9)	0.0023 (10)
C16	0.0550 (14)	0.0622 (17)	0.0629 (14)	0.0017 (12)	0.0058 (11)	0.0141 (13)
C17	0.0538 (14)	0.0676 (18)	0.0700 (16)	0.0052 (13)	0.0050 (12)	0.0107 (14)
C18	0.0630 (15)	0.0573 (15)	0.0497 (12)	0.0094 (12)	0.0010 (10)	0.0042 (11)
C19	0.0677 (16)	0.0553 (16)	0.0477 (12)	0.0007 (12)	0.0073 (11)	0.0058 (11)
C20	0.0568 (14)	0.0582 (16)	0.0495 (12)	0.0008 (12)	0.0092 (10)	0.0036 (11)

Geometric parameters (Å, º)

S—O1	1.435 (2)	C12—C13	1.371 (5)
S—O2	1.4463 (19)	C13—C14	1.385 (4)
S—C9	1.759 (2)	C15—C16	1.381 (4)
S—C1	1.798 (2)	C15—C20	1.388 (3)
O3—C2	1.220 (3)	C16—C17	1.381 (4)
O4—N3	1.219 (3)	C17—C18	1.379 (4)
O5—N3	1.218 (3)	C18—C19	1.368 (4)
N1—C1	1.298 (3)	C19—C20	1.379 (4)
N1—N2	1.315 (3)	N2—H2	0.89 (3)
N2—C15	1.397 (3)	C4—H4	0.93 (3)
N3—C18	1.464 (3)	C5—H5	0.96 (4)
C1—C2	1.492 (3)	C6—H6	0.95 (4)
C2—C3	1.492 (4)	C7—H7	0.92 (4)
C3—C8	1.386 (4)	C8—H8	0.97 (4)
C3—C4	1.394 (4)	C10—H10	0.97 (3)
C4—C5	1.374 (4)	C11—H11	0.93 (4)
C5—C6	1.373 (5)	C12—H12	0.98 (4)
C6—C7	1.373 (5)	C13—H13	0.97 (4)
C7—C8	1.380 (4)	C14—H14	1.01 (4)
C9—C14	1.383 (4)	C16—H16	0.91 (3)
C9—C10	1.384 (4)	C17—H17	1.03 (3)
C10—C11	1.377 (4)	C19—H19	0.88 (3)
C11—C12	1.375 (5)	C20—H20	0.97 (3)
O1—S—O2	117.64 (12)	C14—C9—C10	121.6 (3)
O1—S—C9	110.13 (12)	C14—C9—S	120.3 (2)
O2—S—C9	106.46 (12)	C10—C9—S	118.0 (2)
O1—S—C1	110.08 (12)	C11—C10—C9	118.8 (3)
O2—S—C1	105.73 (11)	C11—C10—H10	119 (2)
C9—S—C1	106.11 (11)	C9—C10—H10	122 (2)
C1—N1—N2	124.4 (2)	C12—C11—C10	120.2 (3)
N1—N2—C15	119.9 (2)	C12—C11—H11	119 (2)
N1—N2—H2	120 (2)	C10—C11—H11	121 (2)
C15—N2—H2	120 (2)	C13—C12—C11	120.6 (3)
O5—N3—O4	123.0 (3)	C13—C12—H12	121 (2)
O5—N3—C18	118.8 (3)	C11—C12—H12	119 (2)
O4—N3—C18	118.3 (3)	C12—C13—C14	120.4 (3)
N1—C1—C2	120.7 (2)	C12—C13—H13	121 (2)
N1—C1—S	125.22 (19)	C14—C13—H13	119 (2)
C2—C1—S	114.10 (17)	C9—C14—C13	118.4 (3)
O3—C2—C3	119.4 (2)	C9—C14—H14	117 (2)
O3—C2—C1	115.9 (2)	C13—C14—H14	125 (2)
C3—C2—C1	124.7 (2)	C16—C15—C20	120.6 (2)
C8—C3—C4	118.1 (3)	C16—C15—N2	122.3 (2)
C8—C3—C2	125.7 (2)	C20—C15—N2	117.1 (2)
C4—C3—C2	116.1 (2)	C17—C16—C15	119.7 (3)
C5—C4—C3	120.9 (3)	C17—C16—H16	120.1 (19)
C5—C4—H4	121 (2)	C15—C16—H16	120.1 (19)
C3—C4—H4	118 (2)	C18—C17—C16	118.8 (3)
C6—C5—C4	120.2 (3)	C18—C17—H17	121.5 (18)
C6—C5—H5	121 (2)	C16—C17—H17	119.7 (18)
C4—C5—H5	119 (2)	C19—C18—C17	122.2 (2)
C5—C6—C7	119.8 (3)	C19—C18—N3	119.5 (3)
C5—C6—H6	121 (2)	C17—C18—N3	118.3 (3)
C7—C6—H6	119 (2)	C18—C19—C20	118.9 (3)
C6—C7—C8	120.4 (3)	C18—C19—H19	121 (2)
C6—C7—H7	117 (3)	C20—C19—H19	120 (2)
C8—C7—H7	123 (3)	C19—C20—C15	119.8 (2)
C7—C8—C3	120.6 (3)	C19—C20—H20	120.5 (18)
C7—C8—H8	117 (2)	C15—C20—H20	119.7 (18)
C3—C8—H8	123 (2)
S—C1—C2—O3	7.2 (3)	N1—C1—C2—O3	−173.3 (2)
S—C1—N1—N2	−1.6 (3)	C9—S—C1—N1	116.3 (2)
O1—S—C1—N1	−124.5 (2)	C9—S—C1—C2	−64.2 (2)
O1—S—C1—C2	54.9 (2)	C1—N1—N2—C15	−177.1 (2)
O2—S—C1—N1	3.5 (2)	N2—N1—C1—C2	179.0 (2)
O2—S—C1—C2	−177.04 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.89 (3)	1.91 (3)	2.642 (3)	139 (3)

(III) benzoylphenylphenylazophenylsulfonylmethane

Crystal data

C26H20N2O3S	F(000) = 920
Mr = 440.50	Dx = 1.281 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
a = 13.285 (3) Å	Cell parameters from 48 reflections
b = 16.577 (3) Å	θ = 5–13.5°
c = 11.421 (2) Å	µ = 0.17 mm^−1
β = 114.80 (3)°	T = 291 K
V = 2283.2 (8) Å^3	Prism, yellow
Z = 4	0.45 × 0.40 × 0.25 mm

Data collection

Siemens P3 diffractometer	Rint = 0.033
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 2.1°
Graphite monochromator	h = −1→17
ω–2θ scans	k = −21→1
6194 measured reflections	l = −14→13
5156 independent reflections	3 standard reflections every 97 reflections
3703 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.048	Hydrogen site location: difference Fourier map
wR(F^2) = 0.137	All H-atom parameters refined
S = 1.03	w = 1/[σ^2(Fo^2) + (0.079P)^2 + 0.2414P] where P = (Fo^2 + 2Fc^2)/3
5156 reflections	(Δ/σ)max = 0.010
366 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S	0.77738 (4)	0.02651 (3)	0.74760 (5)	0.04577 (15)
O1	0.69840 (15)	0.08997 (9)	0.71270 (17)	0.0732 (5)
O2	0.89159 (12)	0.04438 (10)	0.82594 (15)	0.0626 (4)
O3	0.57397 (11)	−0.06774 (9)	0.65845 (13)	0.0589 (4)
N1	0.83736 (11)	−0.10215 (8)	0.90155 (14)	0.0389 (3)
N2	0.83359 (12)	−0.15601 (9)	0.82408 (14)	0.0418 (3)
C1	0.74056 (14)	−0.04792 (10)	0.84734 (16)	0.0380 (4)
C2	0.63135 (14)	−0.09179 (11)	0.76617 (17)	0.0404 (4)
C3	0.59637 (14)	−0.16108 (11)	0.82221 (17)	0.0409 (4)
C4	0.50141 (17)	−0.20211 (13)	0.7430 (2)	0.0532 (5)
H4	0.462 (2)	−0.1800 (15)	0.657 (2)	0.070 (7)*
C5	0.4643 (2)	−0.26709 (15)	0.7884 (3)	0.0648 (6)
H5	0.401 (3)	−0.2908 (19)	0.726 (3)	0.101 (10)*
C6	0.5217 (2)	−0.29202 (15)	0.9134 (3)	0.0690 (6)
H6	0.495 (2)	−0.3372 (17)	0.950 (3)	0.086 (8)*
C7	0.6159 (2)	−0.25189 (15)	0.9943 (2)	0.0671 (6)
H7	0.6604 (19)	−0.2673 (15)	1.087 (2)	0.067 (7)*
C8	0.65351 (17)	−0.18620 (13)	0.9493 (2)	0.0526 (5)
H8	0.718 (2)	−0.1585 (14)	1.004 (2)	0.064 (6)*
C9	0.77133 (16)	−0.01932 (12)	0.60548 (18)	0.0467 (4)
C10	0.6799 (2)	−0.00950 (18)	0.4908 (2)	0.0690 (7)
H10	0.620 (2)	0.0189 (15)	0.488 (2)	0.072 (8)*
C11	0.6824 (3)	−0.0395 (3)	0.3803 (3)	0.0997 (11)
H11	0.624 (3)	−0.026 (2)	0.305 (4)	0.139 (14)*
C12	0.7730 (4)	−0.0784 (3)	0.3838 (3)	0.1096 (13)
H12	0.771 (4)	−0.098 (3)	0.315 (4)	0.156 (16)*
C13	0.8635 (3)	−0.0894 (2)	0.4973 (3)	0.0943 (10)
H13	0.919 (3)	−0.117 (2)	0.499 (3)	0.107 (11)*
C14	0.8642 (2)	−0.05863 (16)	0.6099 (2)	0.0643 (6)
H14	0.933 (2)	−0.0636 (14)	0.692 (2)	0.068 (7)*
C15	0.92878 (15)	−0.20690 (11)	0.86846 (18)	0.0434 (4)
C16	1.01770 (19)	−0.19859 (15)	0.9866 (3)	0.0684 (7)
H16	1.018 (2)	−0.1597 (17)	1.039 (3)	0.086 (9)*
C17	1.1068 (2)	−0.24943 (19)	1.0194 (4)	0.0961 (10)
H17	1.168 (3)	−0.244 (2)	1.094 (4)	0.128 (13)*
C18	1.1074 (3)	−0.30818 (19)	0.9368 (4)	0.0951 (10)
H18	1.169 (3)	−0.342 (2)	0.959 (4)	0.123 (12)*
C19	1.0196 (3)	−0.3179 (2)	0.8221 (3)	0.0932 (10)
H19	1.019 (3)	−0.362 (2)	0.769 (3)	0.118 (11)*
C20	0.9297 (2)	−0.26661 (16)	0.7858 (2)	0.0710 (7)
H20	0.868 (2)	−0.2681 (16)	0.689 (3)	0.082 (8)*
C21	0.73181 (15)	0.00269 (11)	0.95375 (18)	0.0420 (4)
C22	0.63161 (19)	0.03687 (15)	0.9363 (2)	0.0625 (6)
H22	0.571 (2)	0.0309 (15)	0.859 (2)	0.073 (8)*
C23	0.6231 (2)	0.08539 (17)	1.0294 (3)	0.0758 (7)
H23	0.556 (3)	0.1099 (19)	1.010 (3)	0.099 (9)*
C24	0.7141 (2)	0.10074 (19)	1.1407 (3)	0.0829 (8)
H24	0.704 (2)	0.1366 (18)	1.200 (3)	0.093 (9)*
C25	0.8141 (2)	0.0678 (2)	1.1585 (3)	0.0871 (9)
H25	0.882 (3)	0.077 (2)	1.244 (3)	0.134 (13)*
C26	0.82340 (19)	0.01890 (15)	1.0661 (2)	0.0611 (6)
H26	0.886 (2)	−0.0019 (15)	1.077 (2)	0.069 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0497 (3)	0.0342 (2)	0.0594 (3)	0.0002 (2)	0.0287 (2)	0.0040 (2)
O1	0.0960 (13)	0.0446 (8)	0.0970 (12)	0.0261 (8)	0.0582 (10)	0.0225 (8)
O2	0.0586 (9)	0.0634 (9)	0.0684 (9)	−0.0270 (7)	0.0292 (8)	−0.0103 (7)
O3	0.0423 (7)	0.0693 (10)	0.0542 (8)	−0.0019 (7)	0.0096 (6)	0.0180 (7)
N1	0.0334 (7)	0.0345 (7)	0.0473 (8)	0.0022 (6)	0.0155 (6)	−0.0024 (6)
N2	0.0442 (8)	0.0384 (8)	0.0433 (8)	0.0049 (6)	0.0188 (6)	0.0012 (6)
C1	0.0339 (8)	0.0333 (8)	0.0480 (9)	0.0029 (7)	0.0183 (7)	0.0020 (7)
C2	0.0327 (8)	0.0418 (9)	0.0457 (9)	0.0027 (7)	0.0155 (7)	0.0024 (7)
C3	0.0349 (9)	0.0424 (9)	0.0476 (9)	−0.0024 (7)	0.0193 (7)	−0.0013 (8)
C4	0.0478 (11)	0.0555 (11)	0.0552 (12)	−0.0104 (9)	0.0205 (9)	−0.0048 (10)
C5	0.0575 (13)	0.0616 (13)	0.0766 (15)	−0.0222 (11)	0.0294 (12)	−0.0100 (12)
C6	0.0703 (15)	0.0584 (14)	0.0856 (17)	−0.0166 (12)	0.0398 (13)	0.0066 (12)
C7	0.0639 (14)	0.0708 (15)	0.0657 (14)	−0.0076 (12)	0.0263 (12)	0.0186 (12)
C8	0.0437 (10)	0.0583 (12)	0.0527 (11)	−0.0086 (9)	0.0173 (9)	0.0078 (9)
C9	0.0456 (10)	0.0483 (10)	0.0480 (10)	0.0046 (8)	0.0214 (8)	0.0119 (8)
C10	0.0511 (13)	0.0963 (19)	0.0550 (13)	0.0118 (13)	0.0178 (11)	0.0234 (12)
C11	0.080 (2)	0.158 (3)	0.0497 (14)	0.006 (2)	0.0153 (14)	0.0118 (18)
C12	0.124 (3)	0.156 (4)	0.0555 (16)	0.010 (3)	0.0444 (19)	−0.008 (2)
C13	0.103 (2)	0.120 (3)	0.0787 (19)	0.038 (2)	0.0561 (18)	0.0107 (17)
C14	0.0576 (13)	0.0829 (16)	0.0582 (13)	0.0176 (12)	0.0299 (11)	0.0109 (12)
C15	0.0422 (9)	0.0396 (9)	0.0515 (10)	0.0068 (8)	0.0227 (8)	0.0009 (8)
C16	0.0508 (12)	0.0563 (13)	0.0781 (15)	0.0130 (10)	0.0073 (11)	−0.0171 (12)
C17	0.0547 (15)	0.083 (2)	0.118 (2)	0.0228 (14)	0.0035 (16)	−0.0114 (18)
C18	0.0776 (19)	0.0841 (19)	0.130 (3)	0.0428 (16)	0.050 (2)	0.0047 (19)
C19	0.111 (2)	0.091 (2)	0.089 (2)	0.0467 (18)	0.0524 (19)	−0.0083 (16)
C20	0.0840 (17)	0.0732 (15)	0.0567 (13)	0.0286 (13)	0.0302 (12)	−0.0071 (11)
C21	0.0383 (9)	0.0390 (9)	0.0529 (10)	0.0008 (7)	0.0232 (8)	−0.0013 (8)
C22	0.0435 (11)	0.0706 (15)	0.0708 (14)	0.0120 (10)	0.0215 (11)	−0.0105 (12)
C23	0.0604 (15)	0.0831 (17)	0.0940 (19)	0.0201 (13)	0.0424 (14)	−0.0161 (14)
C24	0.0783 (18)	0.099 (2)	0.0830 (17)	0.0086 (15)	0.0446 (15)	−0.0325 (16)
C25	0.0640 (16)	0.121 (3)	0.0722 (16)	0.0075 (16)	0.0242 (13)	−0.0398 (17)
C26	0.0428 (11)	0.0774 (15)	0.0608 (13)	0.0077 (11)	0.0195 (10)	−0.0189 (11)

Geometric parameters (Å, º)

S—O1	1.4197 (16)	C19—C20	1.381 (4)
S—O2	1.4323 (16)	C21—C26	1.375 (3)
S—C9	1.763 (2)	C21—C22	1.382 (3)
S—C1	1.8780 (18)	C22—C23	1.375 (3)
O3—C2	1.211 (2)	C23—C24	1.361 (4)
N1—N2	1.243 (2)	C24—C25	1.371 (4)
N1—C1	1.476 (2)	C25—C26	1.377 (3)
N2—C15	1.425 (2)	C4—H4	0.97 (2)
C1—C21	1.521 (2)	C5—H5	0.93 (3)
C1—C2	1.538 (2)	C6—H6	1.00 (3)
C2—C3	1.481 (3)	C7—H7	1.01 (2)
C3—C4	1.384 (3)	C8—H8	0.94 (2)
C3—C8	1.390 (3)	C10—H10	0.92 (3)
C4—C5	1.374 (3)	C11—H11	0.92 (4)
C5—C6	1.370 (4)	C12—H12	0.83 (5)
C6—C7	1.375 (4)	C13—H13	0.86 (3)
C7—C8	1.384 (3)	C14—H14	1.00 (2)
C9—C10	1.372 (3)	C16—H16	0.88 (3)
C9—C14	1.377 (3)	C17—H17	0.90 (4)
C10—C11	1.369 (4)	C18—H18	0.93 (4)
C11—C12	1.351 (5)	C19—H19	0.94 (4)
C12—C13	1.361 (5)	C20—H20	1.07 (3)
C13—C14	1.380 (4)	C22—H22	0.92 (2)
C15—C20	1.371 (3)	C23—H23	0.92 (3)
C15—C16	1.378 (3)	C24—H24	0.95 (3)
C16—C17	1.371 (3)	C25—H25	1.03 (4)
C17—C18	1.358 (4)	C26—H26	0.86 (3)
C18—C19	1.349 (5)
O1—S—O2	119.12 (11)	C11—C12—H12	118 (3)
O1—S—C9	108.54 (10)	C13—C12—H12	121 (3)
O2—S—C9	106.95 (9)	C12—C13—C14	119.7 (3)
O1—S—C1	107.90 (9)	C12—C13—H13	120 (2)
O2—S—C1	103.54 (8)	C14—C13—H13	121 (2)
C9—S—C1	110.63 (8)	C9—C14—C13	119.0 (2)
N2—N1—C1	111.78 (14)	C9—C14—H14	121.2 (14)
N1—N2—C15	114.04 (15)	C13—C14—H14	119.7 (14)
N1—C1—C21	110.25 (14)	C20—C15—C16	119.66 (19)
N1—C1—C2	113.63 (14)	C20—C15—N2	116.45 (18)
C21—C1—C2	111.94 (14)	C16—C15—N2	123.88 (17)
N1—C1—S	104.59 (11)	C17—C16—C15	119.5 (2)
C21—C1—S	104.41 (11)	C17—C16—H16	120.4 (19)
C2—C1—S	111.40 (12)	C15—C16—H16	120.0 (19)
O3—C2—C3	121.08 (16)	C18—C17—C16	120.5 (3)
O3—C2—C1	119.30 (16)	C18—C17—H17	118 (2)
C3—C2—C1	119.59 (15)	C16—C17—H17	122 (2)
C4—C3—C8	118.96 (18)	C19—C18—C17	120.3 (2)
C4—C3—C2	117.64 (17)	C19—C18—H18	120 (2)
C8—C3—C2	123.41 (17)	C17—C18—H18	120 (2)
C5—C4—C3	120.8 (2)	C18—C19—C20	120.3 (3)
C5—C4—H4	123.3 (15)	C18—C19—H19	119 (2)
C3—C4—H4	115.8 (15)	C20—C19—H19	121 (2)
C6—C5—C4	119.9 (2)	C15—C20—C19	119.6 (2)
C6—C5—H5	126.7 (19)	C15—C20—H20	120.5 (14)
C4—C5—H5	113.3 (19)	C19—C20—H20	119.1 (14)
C5—C6—C7	120.4 (2)	C26—C21—C22	118.43 (19)
C5—C6—H6	121.6 (16)	C26—C21—C1	121.30 (16)
C7—C6—H6	117.9 (16)	C22—C21—C1	120.19 (18)
C6—C7—C8	120.0 (2)	C23—C22—C21	121.0 (2)
C6—C7—H7	123.5 (14)	C23—C22—H22	119.3 (16)
C8—C7—H7	116.5 (14)	C21—C22—H22	119.4 (16)
C7—C8—C3	119.9 (2)	C24—C23—C22	120.2 (2)
C7—C8—H8	120.3 (14)	C24—C23—H23	122 (2)
C3—C8—H8	119.8 (14)	C22—C23—H23	117 (2)
C10—C9—C14	120.8 (2)	C23—C24—C25	119.3 (2)
C10—C9—S	120.53 (18)	C23—C24—H24	116.6 (18)
C14—C9—S	118.43 (16)	C25—C24—H24	123.9 (18)
C11—C10—C9	118.9 (3)	C24—C25—C26	120.9 (3)
C11—C10—H10	121.1 (16)	C24—C25—H25	120 (2)
C9—C10—H10	120.0 (16)	C26—C25—H25	119 (2)
C12—C11—C10	120.8 (3)	C21—C26—C25	120.1 (2)
C12—C11—H11	123 (3)	C21—C26—H26	118.5 (16)
C10—C11—H11	116 (3)	C25—C26—H26	121.3 (17)
C11—C12—C13	120.8 (3)
S—C1—C2—O3	−10.7 (2)	N1—C1—C2—O3	−128.47 (18)
S—C1—N1—N2	−82.95 (15)	C1—N1—N2—C15	176.09 (14)
O1—S—C1—N1	−168.74 (12)	N2—N1—C1—C21	165.33 (14)
O1—S—C1—C2	68.11 (14)	N2—N1—C1—C2	38.75 (19)
O1—S—C1—C21	−52.89 (14)	C9—S—C1—N1	72.67 (13)
O2—S—C1—N1	−41.60 (13)	C9—S—C1—C21	−171.48 (11)
O2—S—C1—C2	−164.75 (12)	C9—S—C1—C2	−50.48 (14)
O2—S—C1—C21	74.25 (13)	C21—C1—C2—O3	105.84 (19)

(IV) benzoyl(3-chlorophenylazo)phenyl(4-tolylsulfonyl)methane

Crystal data

C27H21ClN2O3S	F(000) = 1016
Mr = 488.97	Dx = 1.358 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.155 (2) Å	Cell parameters from 26 reflections
b = 9.542 (1) Å	θ = 4.7–12.0°
c = 18.822 (1) Å	µ = 0.28 mm^−1
β = 109.820 (9)°	T = 291 K
V = 2391.6 (4) Å^3	Prism, yellow
Z = 4	0.40 × 0.30 × 0.15 mm

Data collection

Siemens P3 diffractometer	Rint = 0.028
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 2.3°
Graphite monochromator	h = −1→18
ω–2θ scans	k = −1→12
6942 measured reflections	l = −24→23
5538 independent reflections	3 standard reflections every 97 reflections
3727 reflections with I > 2σ(I)	intensity decay: 3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	All H-atom parameters refined
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.0623P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.97	(Δ/σ)max = 0.012
5538 reflections	Δρmax = 0.29 e Å^−3
392 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (6)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S	0.23137 (3)	0.02032 (5)	0.47800 (2)	0.03974 (14)
Cl	−0.06658 (4)	0.16791 (9)	0.72742 (4)	0.0830 (2)
O1	0.26245 (10)	−0.05105 (16)	0.42286 (6)	0.0506 (4)
O2	0.13363 (10)	0.08395 (16)	0.45583 (7)	0.0553 (4)
O3	0.40690 (9)	−0.12803 (15)	0.58116 (7)	0.0468 (3)
N1	0.17671 (10)	−0.04286 (16)	0.59758 (7)	0.0363 (3)
N2	0.23786 (11)	0.02115 (16)	0.65142 (8)	0.0372 (3)
C1	0.22869 (12)	−0.11309 (19)	0.55117 (9)	0.0348 (4)
C2	0.33545 (13)	−0.16219 (19)	0.59869 (9)	0.0351 (4)
C3	0.34828 (13)	−0.25527 (19)	0.66508 (9)	0.0364 (4)
C4	0.44606 (14)	−0.2815 (2)	0.71244 (10)	0.0436 (4)
H4	0.4999 (16)	−0.236 (2)	0.7018 (11)	0.054 (6)*
C5	0.46517 (17)	−0.3717 (2)	0.77292 (11)	0.0528 (5)
H5	0.5305 (16)	−0.394 (2)	0.8019 (11)	0.051 (6)*
C6	0.38640 (17)	−0.4361 (3)	0.78711 (12)	0.0567 (6)
H6	0.3976 (15)	−0.498 (2)	0.8279 (12)	0.053 (6)*
C7	0.28894 (18)	−0.4101 (3)	0.74147 (13)	0.0602 (6)
H7	0.2336 (18)	−0.457 (2)	0.7515 (13)	0.069 (7)*
C8	0.26969 (15)	−0.3203 (2)	0.68092 (12)	0.0480 (5)
H8	0.2039 (19)	−0.302 (2)	0.6508 (13)	0.065 (7)*
C9	0.32184 (14)	0.1506 (2)	0.51941 (9)	0.0398 (4)
C10	0.41342 (14)	0.1429 (2)	0.50802 (10)	0.0425 (4)
H10	0.4243 (15)	0.066 (2)	0.4780 (11)	0.055 (6)*
C11	0.48377 (17)	0.2455 (2)	0.53719 (11)	0.0507 (5)
H11	0.5481 (18)	0.240 (2)	0.5288 (12)	0.071 (7)*
C12	0.46578 (18)	0.3560 (2)	0.57855 (12)	0.0562 (5)
C13	0.37261 (19)	0.3637 (2)	0.58787 (13)	0.0587 (6)
H13	0.3585 (16)	0.436 (2)	0.6169 (12)	0.063 (6)*
C14	0.30075 (17)	0.2623 (2)	0.55856 (12)	0.0500 (5)
H14	0.2345 (18)	0.261 (3)	0.5642 (13)	0.072 (7)*
C15	0.5471 (3)	0.4623 (4)	0.6134 (2)	0.0893 (10)
H151	0.592 (3)	0.471 (4)	0.589 (2)	0.141 (15)*
H152	0.519 (3)	0.550 (5)	0.614 (2)	0.143 (16)*
H153	0.575 (3)	0.453 (5)	0.667 (3)	0.155 (16)*
C16	0.19382 (13)	0.09395 (19)	0.69885 (9)	0.0358 (4)
C17	0.09258 (14)	0.0892 (2)	0.68991 (10)	0.0408 (4)
H17	0.0497 (14)	0.036 (2)	0.6536 (11)	0.046 (5)*
C18	0.05979 (14)	0.1672 (2)	0.73847 (10)	0.0450 (5)
C19	0.12447 (16)	0.2466 (2)	0.79556 (11)	0.0494 (5)
H19	0.0971 (16)	0.302 (2)	0.8282 (12)	0.057 (6)*
C20	0.22474 (17)	0.2491 (3)	0.80386 (12)	0.0561 (6)
H20	0.2686 (18)	0.306 (3)	0.8416 (14)	0.069 (7)*
C21	0.25988 (15)	0.1728 (2)	0.75542 (11)	0.0485 (5)
H21	0.3292 (16)	0.176 (2)	0.7595 (11)	0.056 (6)*
C22	0.16547 (13)	−0.2315 (2)	0.50542 (9)	0.0400 (4)
C23	0.21092 (18)	−0.3367 (2)	0.47738 (12)	0.0547 (5)
H23	0.2767 (19)	−0.336 (3)	0.4852 (13)	0.070 (7)*
C24	0.1547 (2)	−0.4438 (3)	0.43448 (15)	0.0704 (7)
H24	0.187 (2)	−0.512 (3)	0.4213 (15)	0.084 (9)*
C25	0.0530 (2)	−0.4470 (3)	0.41885 (15)	0.0742 (7)
H25	0.0158 (18)	−0.520 (3)	0.3933 (13)	0.072 (7)*
C26	0.00692 (19)	−0.3432 (3)	0.44578 (14)	0.0681 (7)
H26	−0.068 (2)	−0.342 (3)	0.4336 (13)	0.075 (7)*
C27	0.06226 (15)	−0.2354 (3)	0.48908 (12)	0.0503 (5)
H27	0.0340 (17)	−0.161 (2)	0.5075 (12)	0.063 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0377 (2)	0.0513 (3)	0.0297 (2)	0.0045 (2)	0.01081 (17)	0.0064 (2)
Cl	0.0455 (3)	0.1356 (7)	0.0759 (4)	0.0040 (4)	0.0311 (3)	−0.0242 (4)
O1	0.0572 (8)	0.0663 (9)	0.0315 (6)	−0.0074 (7)	0.0190 (6)	−0.0066 (6)
O2	0.0406 (7)	0.0688 (10)	0.0523 (8)	0.0128 (7)	0.0103 (6)	0.0222 (7)
O3	0.0367 (7)	0.0612 (9)	0.0476 (7)	0.0061 (6)	0.0208 (6)	0.0103 (6)
N1	0.0348 (7)	0.0440 (9)	0.0313 (7)	0.0068 (7)	0.0126 (6)	0.0016 (6)
N2	0.0369 (7)	0.0415 (8)	0.0350 (7)	0.0042 (7)	0.0145 (6)	0.0007 (7)
C1	0.0338 (8)	0.0419 (10)	0.0306 (8)	0.0043 (8)	0.0134 (7)	0.0006 (7)
C2	0.0356 (9)	0.0390 (10)	0.0329 (8)	0.0025 (8)	0.0146 (7)	−0.0038 (7)
C3	0.0367 (9)	0.0421 (10)	0.0321 (8)	0.0080 (8)	0.0138 (7)	0.0005 (7)
C4	0.0368 (10)	0.0517 (12)	0.0404 (9)	0.0041 (9)	0.0108 (8)	0.0015 (9)
C5	0.0479 (12)	0.0624 (14)	0.0418 (10)	0.0085 (11)	0.0072 (9)	0.0110 (10)
C6	0.0648 (14)	0.0647 (14)	0.0427 (10)	0.0180 (12)	0.0208 (10)	0.0184 (11)
C7	0.0551 (13)	0.0694 (15)	0.0666 (13)	0.0120 (12)	0.0345 (11)	0.0253 (12)
C8	0.0384 (10)	0.0574 (13)	0.0516 (11)	0.0096 (10)	0.0195 (9)	0.0156 (10)
C9	0.0425 (10)	0.0444 (10)	0.0347 (8)	0.0070 (8)	0.0160 (8)	0.0080 (8)
C10	0.0442 (10)	0.0494 (11)	0.0381 (9)	0.0033 (9)	0.0195 (8)	−0.0032 (9)
C11	0.0535 (12)	0.0567 (13)	0.0493 (11)	−0.0043 (10)	0.0272 (10)	−0.0044 (10)
C12	0.0701 (14)	0.0522 (13)	0.0525 (11)	−0.0088 (11)	0.0289 (11)	−0.0039 (10)
C13	0.0798 (16)	0.0425 (12)	0.0652 (13)	0.0041 (11)	0.0393 (13)	−0.0080 (11)
C14	0.0552 (12)	0.0481 (12)	0.0554 (11)	0.0117 (10)	0.0301 (10)	0.0050 (10)
C15	0.104 (3)	0.080 (2)	0.098 (2)	−0.041 (2)	0.053 (2)	−0.0347 (19)
C16	0.0373 (9)	0.0404 (10)	0.0310 (8)	0.0033 (8)	0.0132 (7)	0.0012 (7)
C17	0.0372 (9)	0.0525 (12)	0.0323 (8)	−0.0005 (9)	0.0113 (7)	−0.0061 (8)
C18	0.0405 (10)	0.0579 (12)	0.0407 (9)	0.0041 (9)	0.0191 (8)	0.0001 (9)
C19	0.0589 (13)	0.0527 (12)	0.0430 (10)	0.0035 (10)	0.0258 (10)	−0.0086 (9)
C20	0.0579 (13)	0.0640 (14)	0.0470 (11)	−0.0139 (11)	0.0183 (10)	−0.0215 (11)
C21	0.0392 (10)	0.0620 (13)	0.0452 (10)	−0.0054 (10)	0.0155 (8)	−0.0096 (10)
C22	0.0401 (9)	0.0482 (11)	0.0309 (8)	0.0003 (8)	0.0111 (7)	−0.0001 (8)
C23	0.0536 (13)	0.0589 (14)	0.0532 (12)	−0.0001 (11)	0.0203 (10)	−0.0162 (10)
C24	0.0808 (18)	0.0616 (16)	0.0695 (15)	−0.0077 (14)	0.0265 (14)	−0.0235 (13)
C25	0.0797 (19)	0.0681 (17)	0.0671 (15)	−0.0258 (15)	0.0150 (14)	−0.0181 (13)
C26	0.0509 (13)	0.0790 (18)	0.0676 (14)	−0.0162 (13)	0.0110 (12)	−0.0030 (14)
C27	0.0406 (10)	0.0596 (13)	0.0491 (11)	−0.0013 (10)	0.0131 (9)	−0.0006 (10)

Geometric parameters (Å, º)

S—O1	1.4297 (13)	C19—C20	1.374 (3)
S—O2	1.4372 (14)	C20—C21	1.384 (3)
S—C9	1.766 (2)	C22—C27	1.388 (3)
S—C1	1.8853 (17)	C22—C23	1.389 (3)
Cl—C18	1.7294 (19)	C23—C24	1.376 (3)
O3—C2	1.210 (2)	C24—C25	1.369 (4)
N1—N2	1.247 (2)	C25—C26	1.373 (4)
N1—C1	1.479 (2)	C26—C27	1.380 (3)
N2—C16	1.430 (2)	C4—H4	0.95 (2)
C1—C22	1.515 (3)	C5—H5	0.93 (2)
C1—C2	1.545 (2)	C6—H6	0.94 (2)
C2—C3	1.493 (2)	C7—H7	0.97 (2)
C3—C4	1.391 (2)	C8—H8	0.93 (2)
C3—C8	1.392 (3)	C10—H10	0.97 (2)
C4—C5	1.379 (3)	C13—H13	0.94 (2)
C5—C6	1.376 (3)	C14—H14	0.98 (2)
C6—C7	1.378 (3)	C15—H151	0.91 (4)
C7—C8	1.377 (3)	C15—H152	0.92 (4)
C9—C14	1.384 (3)	C15—H153	0.96 (4)
C9—C10	1.386 (3)	C11—H11	0.98 (2)
C10—C11	1.371 (3)	C17—H17	0.90 (2)
C11—C12	1.385 (3)	C19—H19	0.98 (2)
C12—C13	1.390 (3)	C20—H20	0.94 (3)
C12—C15	1.507 (4)	C21—H21	0.96 (2)
C13—C14	1.377 (3)	C23—H23	0.89 (2)
C16—C21	1.378 (3)	C24—H24	0.88 (3)
C16—C17	1.386 (2)	C25—H25	0.90 (2)
C17—C18	1.375 (3)	C26—H26	1.01 (3)
C18—C19	1.379 (3)	C27—H27	0.94 (2)
O1—S—O2	119.56 (8)	C14—C13—H13	118.2 (14)
O1—S—C9	107.48 (8)	C12—C13—H13	120.7 (14)
O2—S—C9	108.26 (9)	C13—C14—C9	119.40 (19)
O1—S—C1	107.23 (8)	C13—C14—H14	124.8 (15)
O2—S—C1	103.97 (8)	C9—C14—H14	115.8 (15)
C9—S—C1	110.14 (8)	C12—C15—H151	114 (2)
N2—N1—C1	110.76 (13)	C12—C15—H152	111 (3)
N1—N2—C16	114.57 (14)	H151—C15—H152	107 (3)
N1—C1—C22	110.93 (14)	C12—C15—H153	112 (3)
N1—C1—C2	112.35 (12)	H151—C15—H153	116 (4)
C22—C1—C2	112.09 (14)	H152—C15—H153	95 (3)
N1—C1—S	105.23 (11)	C21—C16—C17	120.96 (17)
C22—C1—S	104.04 (11)	C21—C16—N2	114.98 (15)
C2—C1—S	111.69 (11)	C17—C16—N2	124.06 (16)
O3—C2—C3	120.84 (15)	C18—C17—C16	118.02 (18)
O3—C2—C1	120.30 (15)	C18—C17—H17	121.1 (12)
C3—C2—C1	118.84 (14)	C16—C17—H17	120.9 (12)
C4—C3—C8	118.46 (17)	C17—C18—C19	122.07 (18)
C4—C3—C2	117.08 (16)	C17—C18—Cl	119.37 (15)
C8—C3—C2	124.43 (16)	C19—C18—Cl	118.55 (15)
C5—C4—C3	121.0 (2)	C20—C19—C18	119.03 (18)
C5—C4—H4	120.5 (12)	C20—C19—H19	122.1 (12)
C3—C4—H4	118.5 (12)	C18—C19—H19	118.9 (12)
C6—C5—C4	119.6 (2)	C19—C20—C21	120.3 (2)
C6—C5—H5	119.7 (13)	C19—C20—H20	119.2 (14)
C4—C5—H5	120.5 (13)	C21—C20—H20	120.5 (15)
C5—C6—C7	120.3 (2)	C16—C21—C20	119.66 (19)
C5—C6—H6	121.1 (13)	C16—C21—H21	119.3 (13)
C7—C6—H6	118.6 (13)	C20—C21—H21	121.0 (13)
C8—C7—C6	120.2 (2)	C27—C22—C23	119.00 (19)
C8—C7—H7	119.9 (14)	C27—C22—C1	121.36 (18)
C6—C7—H7	119.9 (14)	C23—C22—C1	119.62 (17)
C7—C8—C3	120.43 (19)	C24—C23—C22	120.6 (2)
C7—C8—H8	120.1 (14)	C24—C23—H23	117.6 (16)
C3—C8—H8	119.4 (14)	C22—C23—H23	121.8 (17)
C14—C9—C10	120.36 (19)	C25—C24—C23	119.9 (3)
C14—C9—S	121.46 (15)	C25—C24—H24	122.3 (19)
C10—C9—S	118.08 (15)	C23—C24—H24	117.6 (19)
C11—C10—C9	119.36 (19)	C24—C25—C26	120.1 (2)
C11—C10—H10	122.4 (12)	C24—C25—H25	120.8 (16)
C9—C10—H10	118.2 (12)	C26—C25—H25	119.0 (16)
C10—C11—C12	121.5 (2)	C25—C26—C27	120.7 (2)
C10—C11—H11	119.4 (14)	C25—C26—H26	121.3 (14)
C12—C11—H11	119.1 (14)	C27—C26—H26	118.1 (14)
C11—C12—C13	118.3 (2)	C26—C27—C22	119.7 (2)
C11—C12—C15	119.9 (2)	C26—C27—H27	123.7 (14)
C13—C12—C15	121.8 (2)	C22—C27—H27	116.6 (14)
C14—C13—C12	121.1 (2)
S—C1—C2—O3	−8.6 (2)	N1—C1—C2—O3	−126.60 (17)
S—C1—N1—N2	−89.33 (14)	C1—N1—N2—C16	179.20 (14)
O1—S—C1—N1	−168.62 (10)	N2—N1—C1—C22	158.76 (14)
O1—S—C1—C2	69.21 (13)	N2—N1—C1—C2	32.4 (2)
O1—S—C1—C22	−51.90 (13)	C9—S—C1—N1	74.72 (12)
O2—S—C1—N1	−41.08 (13)	C9—S—C1—C22	−168.55 (11)
O2—S—C1—C2	−163.25 (12)	C9—S—C1—C2	−47.45 (14)
O2—S—C1—C22	75.65 (13)	C22—C1—C2—O3	107.69 (19)