4′-{[Benzoyl(4-nitro­phenyl­hydrazono)­methyl]­sulfonyl}acetanilide

The conformation of the title compound, C₂₂H₁₈N₄O₆S, is stabilized by a strong resonance-assisted intramolecular hydrogen bond linking the hydrazone moiety and the sulfonyl group. The resulting six-membered ring is practically planar. Short intramolecular contacts link oppositely charged atoms of the sulfonyl and β-carbonyl groups. The crystal packing is influenced by intermolecular hydrogen bonds involving the β-carbonyl O atoms and the N—H bonds of the terminal acet­amide moieties.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.056
• wR factor = 0.180
• Data-to-parameter ratio = 7.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



THETM_01  Alert A The value of sine(theta_max)/wavelength is less than 0.550
          Calculated sin(theta_max)/wavelength =    0.4976


 Alert Level B:



REFNR_01  Alert B Ratio of reflections to parameters is < 8 for a
          centrosymmetric structure
          sine(theta)/lambda                0.4976
          Proportion of unique data used    1.0000
          Ratio reflections to parameters   7.3054

Author response: Low ratio results either from the high photodynamic instabilty of the crystal or the presence of two molecules in the asymmetric unit. Crystals had been decaying heavily during the data collection. I would like to say that I really worked hard to get higher resolution data set. In fact, six crystals and data collections have been checked. The best one is reported in this paper. Merging data from several crystals didn't help to get to better results. The photodynamic instabilty is presumable responsible for the fact that only five X-ray structures of \a--phenylhydrazono--\b--ketosulfones have been published so far. All were photodynamically unstable. Structure of (I) is important because it has strongly electron-withdrawing nitro group bonded to the \a--phenylhydrazono ring. Preliminary experiments indicated that strong electron-withdrawing subsituents increased charge separation within the molecule, weakened the S---C1 bond and intensified the photodynamic activity. Therefore X-ray structure of (I) is a good starting point for modelling photodynamic decay.

 Alert Level C:



HYDTR_01  Alert C The hydrogen treatment should only be one of the following
          keywords
          *  refall
          *  refxyz
          *  refU
          *  noref
          *  undef
          *  constr
          *  none
          *  mixed
          Hydrogen treatment given as geom


 1 Alert Level A = Potentially serious problem

 1 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The present work is part of a project aimed at structural studies of modified β-ketosulfones. The investigated compounds have bactericidal and fungicidal activity (Zakrzewski & Kacała, 1998; Zakrzewski, 1999). In this paper, the X-ray structure of 4'-{[benzoyl(4-nitrophenylhydrazono)methyl]sulfonyl}acetanilide, (I), is reported. The title compound, (I), shows a high rate of the photodynamic decay. Freshly grown crystals decompose within approximately two weeks of being exposed to daylight.

The solid-state conformation of all five α-phenylhydrazono-β-ketosulfones reported in the scientific literature (Wolf, 1999, 2001a,b) are constrained either by strong intramolecular resonance-assisted hydrogen bonds (abbreviated hereafter RAHB) (Jeffrey, 1997) or by non-stereospecific electrostatic attraction of the oppositely charged sulfonyl S and β-carbonyl C atoms. Electron-withdrawing terminal substituents linked to the α-phenylhydrazone group restrict the electron-density transfer from the hydrazone moiety towards the positively charged S and β-carbonyl C atoms. This effect strengthens the RAHB and prompts the simultaneous intensification of the intramolecular electrostatic attraction (Wolf, 2001a, and references therein).

Compound (I) crystallizes in the triclinic space group P1. Two complete molecules are located in the asymmetric unit. A view with the atom-numbering is shown in Fig. 1. The superposition of both independent molecules clearly reveals the high similarity of their conformations (Fig. 2). The root-mean-square deviation calculated from the least-squares fit of all respective non-H atoms is 0.23 Å.

In both independent molecules, one of the sulfonyl double bonds (S1═O2 and S2═O8), the β-carbonyl groups and the phenylhydrazone moieties are approximately coplanar. According to Bertolasi et al. (Bertolasi, Gilli et al., 1994; Bertolasi, Nanni et al., 1994), their configuration may be defined as EZE. The three letters indicate, relatively to the C═N bond, the positions of the carbonyl C═O and sulfonyl S═O double bond, as well as the N—C bond bearing the phenyl ring.

Central fragments of both molecules are fixed by the strong intramolecular RAHB's. These bonds connect the hydrazone and sulfonyl groups. The six-membered RAHB rings in both asymmetric molecules are practically planar; the root-mean-square deviations from the O2/S1/C1/N1/N2/H2 and O8/S2/C23/N5/N6/H61 planes are 0.05 and 0.04 Å, respectively. The intramolecular N2···O2 and N6···O8 distances [2.620 (6) and 2.651 (7) Å, respectively] are much shorter than the sum of respective van der Waals radii, 3.07 Å (Bondi, 1964).

Large positive atomic charges are located on atoms S1, S2, C2 and C24 (1.32, 1.31, 0.51 and 0.50 e, respectively). All O atoms are negatively charged. The atomic charges of O1, O2 and O3 range between -0.53 and -0.71 e. The electrostatic potential derived atomic charges were calculated, with 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 CHELPG procedure of Breneman & Wiberg (1990). Electrostatic attraction of the oppositely loaded atoms generates intramolecular contacts beetwen S···O3 and O1···C2 pairs of atoms, details are summarized in Tables 2.

The bond-length distibution in (I) is close to that observed in all related compounds (Wolf, 1999, 2000, 2001a,b). In particular, the S1—C1 and S2—C23 bonds are longer [1.793 (6) and 1.783 (6) Å, respectively] than the conventional S—Csp² single bond, 1.751 Å (Allen et al., 1992). Similar bond elongation in all α-phenylhydrazono-β-ketosulfones was explained by the hyperconjugative (Juaristi & Cuevas, 1995; Graczyk & Mikołajczyk, 1994; Cramer, 1996) interactions involving σ(S—C1) – π*(C═O3) bonding and non-bonding atomic orbitals. Similar intramolecular interactions were also 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, 2001c).

In the crystal lattice, molecules of (I) form elongated centrosymmetric dimers, which are connected by the intermolecular hydrogen bonds involving the β-carbonyl O3 and O7 atoms, and the N3—H3 and N7—H71 bonds of the terminal acetamide moieties (Fig 3). According to Etter's graph-set terminology (Etter et al., 1990; Bernstein et al., 1995), these bond systems can be described as R²₂(20).

S2. Experimental

The title compound was synthesized by the reaction of p-acetanilide benzoylmethyl sulfone with 4-nitrophenyldiazonium chloride. The reactions was carried out in alkaline ethyl alcohol solution (Zakrzewski, 1996). The crystal used for data collection was obtained by vapour diffusion; the sample was dissolved in a 2:1 mixture of chloroform and isopropyl alcohol and equilibrated at room temperature against pure isopropyl alcohol for 15 d.

S3. Refinement

All H atoms were placed in calculated positions and were treated as riding on the adjacent N or C atom. They were refined with individual isotropic displacement parameters equal 1.2 times the value of the equivalent displacement parameters of the parent N or C atom.

Computing details

Data collection: KM-4 User's Guide (Kuma, 1991); cell refinement: KM-4 User's Guide); data reduction: DATAPROC (Gałdecki et al., 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SYBYL (Tripos, 1996) and XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. The molecular structures of both molecules present in the asymmetric unit of (I). The displacement ellipsoids are drawn at the 50% probability level. The intramolecular hydrogen bonds are indicated by a dashed line.
	Fig. 2. The superposition of of both molecules which are present in the asymmetric unit of (I). The second molecule is shown with dashed lines. The least-squares fit was based on all non-H atoms. The root-mean-square deviation was 0.23 Å.
	Fig. 3. The packing diagram showing centrosymmetric dimers linked by the intermolecular hydrogen bonds. Hydrogen bonds are indicated by a dashed line.

4^'-{[benzoyl(4-nitrophenylhydrazono)methyl]sulfonyl}acetanilide

Crystal data

C22H18N4O6S	Z = 4
Mr = 466.46	F(000) = 968
Triclinic, P1	Dx = 1.454 Mg m^−3
a = 7.461 (1) Å	Cu Kα radiation, λ = 1.54178 Å
b = 11.663 (2) Å	Cell parameters from 50 reflections
c = 24.621 (5) Å	θ = 5–25°
α = 94.31 (3)°	µ = 1.78 mm^−1
β = 90.88 (3)°	T = 293 K
γ = 94.01 (3)°	Ellipsoid, yellow
V = 2130.7 (6) Å^3	0.45 × 0.35 × 0.35 mm

Data collection

Kuma KM-4 diffractometer	2363 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.052
Graphite monochromator	θmax = 50.1°, θmin = 3.6°
ω–2θ scans	h = −7→7
Absorption correction: ψ scan (XEMP; Siemens, 1989)	k = −11→11
Tmin = 0.463, Tmax = 0.537	l = 0→24
4490 measured reflections	3 standard reflections every 100 reflections
4354 independent reflections	intensity decay: 46%

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)] = 0.056	Geom
wR(F^2) = 0.180	w = 1/[σ^2(Fo^2) + (0.104P)^2 + 0.8456P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
4354 reflections	Δρmax = 0.46 e Å^−3
596 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0027 (4)

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
S1	−0.0944 (3)	0.60069 (14)	0.68116 (6)	0.0575 (6)
O1	−0.2827 (6)	0.5861 (4)	0.66654 (17)	0.0666 (13)
O2	−0.0384 (7)	0.6916 (3)	0.72228 (16)	0.0742 (14)
O3	−0.0914 (6)	0.3731 (4)	0.62354 (16)	0.0643 (13)
O4	0.6041 (7)	0.6300 (4)	0.5047 (2)	0.0820 (15)
O5	0.2459 (10)	0.5814 (6)	1.0414 (2)	0.119 (2)
O6	0.3280 (9)	0.4135 (6)	1.0206 (2)	0.109 (2)
N1	0.0356 (6)	0.4633 (4)	0.75725 (19)	0.0456 (13)
N2	0.0577 (7)	0.5511 (4)	0.79382 (19)	0.0530 (14)
H2	0.0377	0.6192	0.7852	0.064*
N3	0.3134 (8)	0.6430 (4)	0.4794 (2)	0.0558 (15)
H3	0.2462	0.6503	0.4514	0.067*
N4	0.2675 (9)	0.5019 (7)	1.0084 (3)	0.0795 (19)
C1	−0.0260 (8)	0.4709 (5)	0.7074 (2)	0.0459 (16)
C2	−0.0470 (8)	0.3650 (5)	0.6715 (2)	0.0486 (16)
C3	−0.0097 (8)	0.2498 (5)	0.6899 (2)	0.0434 (16)
C4	−0.0593 (8)	0.2134 (6)	0.7407 (2)	0.0508 (17)
H4	−0.1106	0.2632	0.7663	0.061*
C5	−0.0307 (9)	0.1020 (6)	0.7522 (3)	0.0593 (19)
H5	−0.0623	0.0772	0.7860	0.071*
C6	0.0425 (9)	0.0280 (6)	0.7152 (3)	0.0630 (19)
H6	0.0594	−0.0469	0.7237	0.076*
C7	0.0918 (9)	0.0627 (6)	0.6651 (3)	0.0615 (19)
H7	0.1450	0.0124	0.6402	0.074*
C8	0.0622 (8)	0.1717 (6)	0.6523 (2)	0.0507 (17)
H8	0.0905	0.1942	0.6178	0.061*
C9	0.0302 (9)	0.6180 (5)	0.6232 (2)	0.0499 (17)
C10	0.2159 (10)	0.6329 (6)	0.6258 (3)	0.068 (2)
H10	0.2750	0.6373	0.6595	0.082*
C11	0.3144 (10)	0.6412 (6)	0.5792 (3)	0.070 (2)
H11	0.4392	0.6486	0.5813	0.084*
C12	0.2250 (9)	0.6385 (5)	0.5288 (2)	0.0472 (16)
C13	0.0403 (9)	0.6305 (5)	0.5270 (2)	0.0498 (17)
H13	−0.0194	0.6334	0.4937	0.060*
C14	−0.0581 (9)	0.6182 (5)	0.5731 (2)	0.0521 (17)
H14	−0.1830	0.6101	0.5708	0.063*
C15	0.4910 (11)	0.6373 (6)	0.4697 (3)	0.0595 (19)
C16	0.5390 (10)	0.6396 (7)	0.4099 (3)	0.078 (2)
H161	0.4318	0.6443	0.3884	0.094*
H162	0.5952	0.5705	0.3984	0.094*
H163	0.6203	0.7054	0.4052	0.094*
C17	0.1141 (8)	0.5338 (5)	0.8469 (2)	0.0438 (16)
C18	0.1098 (10)	0.6252 (6)	0.8848 (3)	0.069 (2)
H18	0.0714	0.6947	0.8745	0.083*
C19	0.1612 (10)	0.6158 (6)	0.9374 (3)	0.069 (2)
H19	0.1595	0.6786	0.9630	0.083*
C20	0.2148 (9)	0.5137 (6)	0.9520 (2)	0.0553 (18)
C21	0.2229 (9)	0.4203 (6)	0.9148 (3)	0.0586 (18)
H21	0.2640	0.3516	0.9253	0.070*
C22	0.1685 (9)	0.4305 (5)	0.8612 (2)	0.0543 (18)
H22	0.1691	0.3680	0.8355	0.065*
S2	0.3812 (3)	−0.12009 (15)	0.81709 (6)	0.0611 (6)
O7	0.1943 (6)	−0.1145 (4)	0.82986 (17)	0.0755 (15)
O8	0.4308 (8)	−0.2097 (4)	0.77737 (18)	0.0832 (16)
O9	0.4085 (6)	0.1102 (4)	0.87387 (17)	0.0671 (13)
O10	1.0833 (7)	−0.1345 (4)	0.9978 (2)	0.0764 (14)
O11	0.8034 (11)	−0.0880 (6)	0.4673 (2)	0.135 (3)
O12	0.7688 (11)	0.0883 (6)	0.4766 (2)	0.134 (3)
N5	0.5207 (7)	0.0236 (4)	0.7420 (2)	0.0518 (14)
N6	0.5450 (7)	−0.0623 (5)	0.7064 (2)	0.0608 (15)
H61	0.5225	−0.1319	0.7150	0.073*
N7	0.7917 (8)	−0.1397 (4)	1.02280 (19)	0.0546 (14)
H71	0.7247	−0.1418	1.0509	0.066*
N8	0.7684 (9)	−0.0056 (7)	0.4943 (2)	0.0769 (19)
C23	0.4591 (8)	0.0122 (5)	0.7907 (2)	0.0468 (16)
C24	0.4494 (8)	0.1188 (6)	0.8262 (3)	0.0502 (17)
C25	0.4944 (8)	0.2356 (5)	0.8072 (2)	0.0473 (16)
C26	0.4390 (8)	0.2672 (6)	0.7565 (2)	0.0522 (17)
H26	0.3802	0.2134	0.7313	0.063*
C27	0.4731 (10)	0.3798 (6)	0.7446 (3)	0.064 (2)
H27	0.4335	0.4019	0.7112	0.077*
C28	0.5634 (10)	0.4606 (6)	0.7802 (3)	0.0646 (19)
H28	0.5856	0.5361	0.7710	0.077*
C29	0.6208 (9)	0.4278 (6)	0.8300 (3)	0.0638 (19)
H29	0.6836	0.4812	0.8545	0.077*
C30	0.5854 (8)	0.3171 (6)	0.8431 (3)	0.0545 (18)
H30	0.6230	0.2960	0.8769	0.065*
C31	0.5068 (10)	−0.1310 (5)	0.8768 (2)	0.0505 (17)
C32	0.6882 (10)	−0.1437 (6)	0.8750 (3)	0.066 (2)
H32	0.7447	−0.1499	0.8416	0.079*
C33	0.7864 (9)	−0.1472 (6)	0.9224 (3)	0.0641 (19)
H33	0.9097	−0.1542	0.9212	0.077*
C34	0.7019 (9)	−0.1404 (5)	0.9721 (2)	0.0485 (16)
C35	0.5179 (9)	−0.1324 (5)	0.9734 (2)	0.0503 (17)
H35	0.4598	−0.1316	1.0066	0.060*
C36	0.4204 (9)	−0.1255 (5)	0.9263 (2)	0.0543 (17)
H36	0.2974	−0.1173	0.9275	0.065*
C37	0.9733 (11)	−0.1362 (6)	1.0328 (3)	0.0608 (18)
C38	1.0242 (10)	−0.1338 (7)	1.0928 (3)	0.079 (2)
H381	0.9173	−0.1360	1.1140	0.094*
H382	1.0974	−0.0645	1.1033	0.094*
H383	1.0902	−0.1995	1.0991	0.094*
C39	0.6077 (8)	−0.0420 (6)	0.6540 (2)	0.0509 (17)
C40	0.6573 (11)	−0.1351 (6)	0.6228 (3)	0.073 (2)
H40	0.6544	−0.2069	0.6371	0.087*
C41	0.7114 (11)	−0.1235 (7)	0.5706 (3)	0.076 (2)
H41	0.7464	−0.1869	0.5491	0.091*
C42	0.7132 (9)	−0.0178 (6)	0.5504 (2)	0.0550 (17)
C43	0.6705 (9)	0.0763 (6)	0.5816 (3)	0.0638 (19)
H43	0.6789	0.1484	0.5677	0.077*
C44	0.6137 (9)	0.0648 (6)	0.6349 (3)	0.0622 (19)
H44	0.5810	0.1283	0.6568	0.075*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0791 (14)	0.0563 (12)	0.0398 (10)	0.0141 (9)	−0.0028 (9)	0.0148 (8)
O1	0.062 (3)	0.081 (3)	0.062 (3)	0.018 (3)	0.004 (2)	0.028 (2)
O2	0.136 (4)	0.046 (3)	0.041 (3)	0.019 (3)	−0.012 (3)	0.000 (2)
O3	0.097 (4)	0.063 (3)	0.034 (3)	0.004 (3)	−0.016 (2)	0.009 (2)
O4	0.064 (3)	0.111 (4)	0.072 (3)	0.005 (3)	−0.019 (3)	0.017 (3)
O5	0.190 (7)	0.116 (5)	0.045 (3)	−0.003 (5)	−0.030 (4)	−0.008 (4)
O6	0.164 (6)	0.100 (5)	0.064 (4)	−0.001 (4)	−0.043 (4)	0.028 (3)
N1	0.050 (3)	0.049 (3)	0.038 (3)	0.004 (3)	0.000 (2)	0.004 (3)
N2	0.080 (4)	0.045 (3)	0.035 (3)	0.007 (3)	−0.007 (3)	0.005 (3)
N3	0.056 (4)	0.072 (4)	0.043 (4)	0.001 (3)	−0.011 (3)	0.025 (3)
N4	0.108 (6)	0.085 (5)	0.043 (4)	−0.016 (4)	−0.017 (4)	0.010 (4)
C1	0.054 (4)	0.054 (4)	0.032 (4)	0.005 (3)	0.000 (3)	0.015 (3)
C2	0.058 (4)	0.056 (4)	0.032 (4)	0.003 (3)	0.000 (3)	0.007 (3)
C3	0.048 (4)	0.047 (4)	0.035 (4)	−0.002 (3)	−0.012 (3)	0.007 (3)
C4	0.068 (5)	0.055 (5)	0.029 (4)	−0.002 (3)	−0.002 (3)	0.006 (3)
C5	0.075 (5)	0.062 (5)	0.040 (4)	−0.007 (4)	−0.014 (3)	0.014 (4)
C6	0.076 (5)	0.048 (4)	0.065 (5)	0.004 (4)	−0.018 (4)	0.009 (4)
C7	0.076 (5)	0.054 (5)	0.054 (5)	0.009 (4)	−0.009 (4)	−0.003 (4)
C8	0.058 (4)	0.061 (5)	0.032 (4)	0.001 (4)	−0.003 (3)	0.004 (3)
C9	0.060 (5)	0.055 (4)	0.036 (4)	0.002 (3)	−0.006 (3)	0.013 (3)
C10	0.073 (6)	0.087 (5)	0.042 (5)	−0.012 (4)	−0.020 (4)	0.013 (4)
C11	0.060 (5)	0.107 (6)	0.043 (5)	−0.010 (4)	−0.015 (4)	0.022 (4)
C12	0.056 (5)	0.047 (4)	0.040 (4)	0.000 (3)	−0.010 (3)	0.015 (3)
C13	0.063 (5)	0.052 (4)	0.036 (4)	0.006 (3)	−0.011 (3)	0.013 (3)
C14	0.058 (4)	0.057 (4)	0.043 (4)	0.009 (3)	−0.012 (4)	0.011 (3)
C15	0.062 (6)	0.055 (5)	0.062 (5)	−0.002 (4)	−0.009 (4)	0.015 (3)
C16	0.069 (5)	0.098 (6)	0.069 (5)	0.007 (4)	0.000 (4)	0.022 (4)
C17	0.059 (4)	0.045 (4)	0.027 (4)	−0.003 (3)	0.000 (3)	0.007 (3)
C18	0.114 (6)	0.046 (4)	0.047 (4)	0.009 (4)	−0.014 (4)	0.004 (4)
C19	0.113 (6)	0.058 (5)	0.036 (4)	0.000 (4)	−0.005 (4)	0.000 (4)
C20	0.068 (5)	0.065 (5)	0.031 (4)	−0.009 (4)	−0.008 (3)	0.005 (4)
C21	0.076 (5)	0.052 (4)	0.049 (4)	0.008 (4)	−0.005 (3)	0.014 (4)
C22	0.084 (5)	0.044 (4)	0.035 (4)	0.005 (4)	−0.002 (3)	0.005 (3)
S2	0.0821 (15)	0.0628 (12)	0.0382 (10)	−0.0079 (10)	−0.0039 (9)	0.0164 (9)
O7	0.066 (4)	0.102 (4)	0.058 (3)	−0.018 (3)	−0.005 (2)	0.035 (3)
O8	0.148 (5)	0.055 (3)	0.044 (3)	−0.010 (3)	−0.007 (3)	0.008 (2)
O9	0.096 (4)	0.076 (3)	0.031 (3)	0.012 (3)	0.013 (2)	0.011 (2)
O10	0.061 (3)	0.101 (4)	0.069 (3)	0.013 (3)	0.014 (3)	0.010 (3)
O11	0.239 (9)	0.117 (5)	0.052 (4)	0.044 (5)	0.047 (4)	−0.006 (4)
O12	0.231 (8)	0.105 (5)	0.073 (4)	0.015 (5)	0.047 (4)	0.034 (4)
N5	0.057 (3)	0.054 (4)	0.044 (4)	0.008 (3)	−0.011 (3)	0.001 (3)
N6	0.084 (4)	0.044 (3)	0.053 (4)	0.001 (3)	−0.001 (3)	0.006 (3)
N7	0.056 (4)	0.072 (4)	0.039 (3)	0.008 (3)	0.005 (3)	0.017 (3)
N8	0.094 (5)	0.093 (6)	0.045 (4)	0.012 (4)	0.013 (3)	0.004 (4)
C23	0.058 (4)	0.055 (4)	0.029 (4)	0.004 (3)	0.001 (3)	0.018 (3)
C24	0.047 (4)	0.065 (5)	0.040 (4)	0.005 (3)	0.000 (3)	0.005 (4)
C25	0.053 (4)	0.058 (4)	0.033 (4)	0.010 (3)	0.006 (3)	0.006 (3)
C26	0.062 (4)	0.061 (5)	0.035 (4)	0.008 (3)	−0.001 (3)	0.007 (3)
C27	0.089 (6)	0.066 (5)	0.040 (4)	0.016 (4)	0.005 (4)	0.012 (4)
C28	0.082 (5)	0.057 (5)	0.057 (5)	0.002 (4)	0.018 (4)	0.017 (4)
C29	0.061 (5)	0.063 (5)	0.064 (5)	−0.014 (4)	0.007 (4)	−0.003 (4)
C30	0.053 (4)	0.071 (5)	0.041 (4)	0.006 (4)	−0.003 (3)	0.007 (4)
C31	0.064 (5)	0.053 (4)	0.037 (4)	0.005 (3)	0.001 (3)	0.019 (3)
C32	0.075 (6)	0.093 (6)	0.034 (4)	0.020 (4)	0.011 (4)	0.017 (4)
C33	0.064 (5)	0.090 (5)	0.042 (4)	0.024 (4)	0.011 (4)	0.010 (4)
C34	0.061 (5)	0.051 (4)	0.035 (4)	0.007 (3)	0.003 (3)	0.011 (3)
C35	0.064 (5)	0.053 (4)	0.036 (4)	0.000 (3)	0.009 (3)	0.016 (3)
C36	0.061 (5)	0.065 (5)	0.039 (4)	−0.001 (3)	0.001 (4)	0.020 (3)
C37	0.067 (6)	0.061 (5)	0.057 (5)	0.006 (4)	0.008 (4)	0.018 (3)
C38	0.066 (5)	0.103 (6)	0.069 (5)	0.003 (4)	−0.010 (4)	0.028 (4)
C39	0.064 (5)	0.058 (5)	0.031 (4)	−0.001 (4)	−0.005 (3)	0.005 (4)
C40	0.114 (6)	0.051 (5)	0.054 (5)	0.015 (4)	0.008 (4)	0.001 (4)
C41	0.118 (7)	0.066 (6)	0.046 (5)	0.029 (5)	0.008 (4)	−0.001 (4)
C42	0.069 (5)	0.058 (5)	0.037 (4)	0.010 (4)	0.002 (3)	−0.005 (4)
C43	0.089 (6)	0.053 (5)	0.050 (5)	0.001 (4)	0.014 (4)	0.014 (4)
C44	0.083 (5)	0.050 (5)	0.053 (5)	0.008 (4)	0.012 (4)	−0.003 (4)

Geometric parameters (Å, º)

S1—O1	1.440 (5)	S2—O7	1.439 (5)
S1—O2	1.445 (4)	S2—O8	1.448 (5)
S1—C1	1.793 (6)	S2—C23	1.783 (6)
S1—C9	1.732 (6)	S2—C31	1.749 (6)
O3—C2	1.234 (6)	O9—C24	1.228 (7)
N1—N2	1.311 (6)	N5—N6	1.305 (7)
N1—C1	1.316 (7)	N5—C23	1.302 (7)
N2—C17	1.400 (7)	N6—C39	1.411 (8)
C1—C2	1.461 (8)	C23—C24	1.472 (8)
C2—C3	1.493 (8)	C24—C25	1.491 (8)
O5—N4	1.207 (8)	O11—N8	1.174 (7)
O6—N4	1.211 (8)	O12—N8	1.208 (8)
N4—C20	1.457 (8)	N8—C42	1.462 (8)
N3—C12	1.396 (8)	N7—C34	1.407 (8)
N3—C15	1.355 (8)	N7—C37	1.371 (8)
O4—C15	1.209 (8)	O10—C37	1.200 (8)
C15—C16	1.521 (9)	C37—C38	1.518 (9)
C3—C8	1.390 (8)	C25—C30	1.384 (8)
C3—C4	1.397 (8)	C25—C26	1.392 (8)
C4—C5	1.381 (8)	C26—C27	1.374 (8)
C5—C6	1.356 (9)	C27—C28	1.371 (9)
C6—C7	1.373 (9)	C28—C29	1.384 (9)
C7—C8	1.365 (8)	C29—C30	1.363 (8)
C9—C10	1.384 (9)	C31—C32	1.373 (9)
C9—C14	1.390 (8)	C31—C36	1.387 (8)
C10—C11	1.378 (9)	C32—C33	1.375 (9)
C11—C12	1.397 (8)	C33—C34	1.384 (9)
C12—C13	1.374 (8)	C34—C35	1.383 (8)
C13—C14	1.373 (8)	C35—C36	1.369 (8)
C17—C18	1.365 (8)	C39—C40	1.358 (9)
C17—C22	1.366 (8)	C39—C44	1.362 (8)
C18—C19	1.361 (9)	C40—C41	1.368 (9)
C19—C20	1.354 (9)	C41—C42	1.363 (9)
C20—C21	1.375 (9)	C42—C43	1.351 (9)
C21—C22	1.390 (8)	C43—C44	1.399 (9)
N2—H2	0.86	N6—H61	0.86
N3—H3	0.86	N7—H71	0.86
C4—H4	0.93	C26—H26	0.93
C5—H5	0.93	C27—H27	0.93
C6—H6	0.93	C28—H28	0.93
C7—H7	0.93	C29—H29	0.93
C8—H8	0.93	C30—H30	0.93
C10—H10	0.93	C32—H32	0.93
C11—H11	0.93	C33—H33	0.93
C13—H13	0.93	C35—H35	0.93
C14—H14	0.93	C36—H36	0.93
C16—H161	0.96	C38—H381	0.96
C16—H162	0.96	C38—H382	0.96
C16—H163	0.96	C38—H383	0.96
C18—H18	0.93	C40—H40	0.93
C19—H19	0.93	C41—H41	0.93
C21—H21	0.93	C43—H43	0.93
C22—H22	0.93	C44—H44	0.93
S1···O3	2.916 (4)	S2···O9	2.926 (5)
S1···N2	3.091 (5)	S2···N6	3.104 (6)
O1···C2	3.230 (7)	O7···C24	3.218 (8)
O2···C2	3.915 (7)	O8···C24	3.920 (8)
O1···N2	4.066 (7)	O7···N6	4.094 (7)
O2···N2	2.620 (6)	O8···N6	2.651 (7)
N2···C2	3.619 (8)	N6···C24	3.606 (9)
O1—S1—O2	117.4 (3)	O7—S2—O8	118.3 (3)
O1—S1—C1	109.3 (3)	O7—S2—C23	108.6 (3)
O1—S1—C9	109.2 (3)	O7—S2—C31	109.7 (3)
O2—S1—C1	105.2 (3)	O8—S2—C23	105.3 (3)
O2—S1—C9	109.2 (3)	O8—S2—C31	107.8 (3)
C1—S1—C9	105.5 (3)	C23—S2—C31	106.5 (3)
N2—N1—C1	123.8 (5)	N6—N5—C23	124.4 (5)
N1—N2—C17	119.9 (5)	N5—N6—C39	120.7 (6)
N1—C1—C2	117.6 (5)	S2—C23—N5	125.8 (5)
S1—C1—N1	124.7 (5)	S2—C23—C24	117.6 (5)
S1—C1—C2	117.6 (4)	N5—C23—C24	116.6 (5)
O3—C2—C1	117.8 (5)	O9—C24—C23	118.1 (6)
O3—C2—C3	119.4 (5)	O9—C24—C25	119.1 (6)
C1—C2—C3	122.8 (5)	C23—C24—C25	122.8 (5)
O5—N4—O6	122.6 (7)	O11—N8—O12	122.2 (7)
O5—N4—C20	117.8 (8)	O11—N8—C42	119.0 (7)
O6—N4—C20	119.5 (7)	O12—N8—C42	118.7 (7)
C12—N3—C15	128.7 (6)	C34—N7—C37	127.8 (6)
O4—C15—N3	124.0 (7)	O10—C37—N7	123.7 (7)
O4—C15—C16	121.7 (7)	O10—C37—C38	122.5 (7)
N3—C15—C16	114.3 (6)	N7—C37—C38	113.8 (6)
C8—C3—C4	118.9 (6)	C30—C25—C26	119.3 (6)
C8—C3—C2	117.5 (5)	C30—C25—C24	117.9 (6)
C4—C3—C2	123.3 (6)	C26—C25—C24	122.7 (6)
C5—C4—C3	118.8 (6)	C27—C26—C25	118.4 (6)
C6—C5—C4	121.3 (6)	C28—C27—C26	122.3 (6)
C5—C6—C7	120.5 (6)	C27—C28—C29	118.8 (6)
C8—C7—C6	119.5 (6)	C30—C29—C28	119.9 (6)
C7—C8—C3	121.0 (6)	C29—C30—C25	121.3 (6)
C10—C9—C14	119.3 (6)	C32—C31—C36	120.4 (6)
C10—C9—S1	121.4 (5)	C32—C31—S2	120.8 (5)
C14—C9—S1	119.4 (5)	C36—C31—S2	118.9 (5)
C11—C10—C9	121.0 (6)	C31—C32—C33	120.0 (6)
C10—C11—C12	119.4 (7)	C32—C33—C34	120.0 (6)
C13—C12—C11	119.2 (6)	C33—C34—C35	119.5 (6)
C13—C12—N3	117.4 (5)	C33—C34—N7	124.1 (6)
C11—C12—N3	123.4 (6)	C35—C34—N7	116.4 (5)
C14—C13—C12	121.5 (5)	C36—C35—C34	120.6 (6)
C13—C14—C9	119.5 (6)	C35—C36—C31	119.4 (6)
C18—C17—C22	120.6 (6)	C40—C39—C44	121.6 (6)
C18—C17—N2	116.8 (6)	C40—C39—N6	116.6 (6)
C22—C17—N2	122.5 (5)	C44—C39—N6	121.8 (6)
C19—C18—C17	120.8 (7)	C39—C40—C41	120.1 (7)
C20—C19—C18	119.0 (6)	C42—C41—C40	119.0 (7)
C19—C20—C21	121.8 (6)	C43—C42—C41	121.5 (6)
C19—C20—N4	119.5 (7)	C43—C42—N8	119.4 (7)
C21—C20—N4	118.6 (7)	C41—C42—N8	119.1 (6)
C20—C21—C22	118.7 (6)	C42—C43—C44	119.7 (6)
C17—C22—C21	119.1 (6)	C39—C44—C43	118.0 (6)
N1—N2—H2	120.0	N5—N6—H61	119.7
C17—N2—H2	120.0	C39—N6—H61	119.7
C15—N3—H3	115.6	C37—N7—H71	116.1
C12—N3—H3	115.6	C34—N7—H71	116.1
C5—C4—H4	120.6	C27—C26—H26	120.8
C3—C4—H4	120.6	C25—C26—H26	120.8
C6—C5—H5	119.4	C28—C27—H27	118.8
C4—C5—H5	119.4	C26—C27—H27	118.8
C5—C6—H6	119.7	C27—C28—H28	120.6
C7—C6—H6	119.7	C29—C28—H28	120.6
C8—C7—H7	120.3	C30—C29—H29	120.1
C6—C7—H7	120.3	C28—C29—H29	120.1
C7—C8—H8	119.5	C29—C30—H30	119.4
C3—C8—H8	119.5	C25—C30—H30	119.4
C11—C10—H10	119.5	C31—C32—H32	120.0
C9—C10—H10	119.5	C33—C32—H32	120.0
C10—C11—H11	120.3	C32—C33—H33	120.0
C12—C11—H11	120.3	C34—C33—H33	120.0
C14—C13—H13	119.3	C36—C35—H35	119.7
C12—C13—H13	119.3	C34—C35—H35	119.7
C13—C14—H14	120.2	C35—C36—H36	120.3
C9—C14—H14	120.2	C31—C36—H36	120.3
C15—C16—H161	109.5	C37—C38—H381	109.5
C15—C16—H162	109.5	C37—C38—H382	109.5
H161—C16—H162	109.5	H381—C38—H382	109.5
C15—C16—H163	109.5	C37—C38—H383	109.5
H161—C16—H163	109.5	H381—C38—H383	109.5
H162—C16—H163	109.5	H382—C38—H383	109.5
C19—C18—H18	119.6	C39—C40—H40	120.0
C17—C18—H18	119.6	C41—C40—H40	120.0
C20—C19—H19	120.5	C42—C41—H41	120.5
C18—C19—H19	120.5	C40—C41—H41	120.5
C20—C21—H21	120.6	C42—C43—H43	120.1
C22—C21—H21	120.6	C44—C43—H43	120.1
C17—C22—H22	120.5	C39—C44—H44	121.0
C21—C22—H22	120.5	C43—C44—H44	121.0
S1—C1—C2—O3	7.9 (8)	S2—C23—C24—O9	8.4 (8)
S1—C1—N1—N2	−1.3 (8)	S2—C23—N5—N6	−4.6 (9)
O1—S1—C1—C2	59.9 (5)	O7—S2—C23—C24	60.5 (5)
O1—S1—C1—N1	−117.4 (5)	O7—S2—C23—N5	−117.9 (5)
O2—S1—C1—C2	−173.2 (5)	O8—S2—C23—C24	−171.8 (5)
O2—S1—C1—N1	9.4 (6)	O8—S2—C23—N5	9.8 (6)
S1—C1—C2—C3	−174.7 (5)	S2—C23—C24—C25	−174.3 (4)
N1—C1—C2—O3	−174.5 (5)	N5—C23—C24—O9	−173.1 (6)
N1—C1—C2—C3	2.8 (9)	N5—C23—C24—C25	4.4 (9)
N2—N1—C1—C2	−178.7 (5)	N6—N5—C23—C24	177.0 (5)
C1—N1—N2—C17	176.2 (5)	C23—N5—N6—C39	178.2 (6)
C9—S1—C1—N1	124.9 (5)	C31—S2—C23—N5	124.1 (6)
C9—S1—C1—C2	−57.8 (5)	C31—S2—C23—C24	−57.5 (5)
C12—N3—C15—O4	−2.0 (11)	C34—N7—C37—O10	−1.0 (11)
C12—N3—C15—C16	177.4 (6)	C34—N7—C37—C38	178.7 (6)
O5—N4—C20—C19	6.5 (10)	O11—N8—C42—C41	2.8 (11)
O5—N4—C20—C21	−174.1 (7)	O11—N8—C42—C43	−179.2 (8)
O6—N4—C20—C19	−174.5 (7)	O12—N8—C42—C41	179.6 (8)
O6—N4—C20—C21	4.8 (10)	O12—N8—C42—C43	−2.4 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2	0.86	1.92	2.620 (6)	138
N3—H3···O3^i	0.86	2.15	2.993 (6)	166
N6—H61···O8	0.86	1.95	2.651 (7)	138
N7—H71···O9^ii	0.86	2.14	2.980 (7)	167

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y, −z+2.