organic compounds
Acta Crystallographica Section E

Z=2
Mo K radiation
 = 0.18 mm1

Structure Reports
OnlineT = 100 (2) K
0.20  0.20  0.20 mm

Data collection

ISSN 1600-5368

1-[4-(Diaminomethyleneaminosulfonyl)phenyliminiomethyl]-2-naphtholate
N,N-dimethylformamide disolvate
Hoda El-Ghamry,a* Raafat Issa,a Kamal El-Baradie,a Keiko
Isagai,b Shigeyuki Masaokab and Ken SakaibaDepartment of Chemistry, Faculty of Science, Tanta University, Tanta, Egypt, andDepartment of Chemistry, Faculty of Science, Kyushu University, Hakozaki 6-10-1,
Higashi-ku, Fukuoka 812-8581, Japan
Correspondence e-mail: helghamrymo@yahoo.comb

Bruker SMART APEX CCDdetector diffractometer
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)
Tmin = 0.775, Tmax = 0.965

13950 measured reflections
5450 independent reflections
5190 reflections with I > 2(I)Rint = 0.026

Refinement
R[F 2 > 2(F 2)] = 0.036
wR(F 2) = 0.091
S = 1.08
5450 reflections
329 parameters
1 restraint

H-atom parameters constrainedmax = 0.47 e Å3
min = 0.22 e Å3
Absolute structure: Flack (1983),
2555 Friedel pairs
Flack parameter: 0.03 (6)Table 1
Received 23 May 2008; accepted 20 June 2008

Hydrogen-bond geometry (Å,  ).

Key indicators: single-crystal X-ray study; T = 100 K; mean (C–C) = 0.003 Å;
R factor = 0.037; wR factor = 0.091; data-to-parameter ratio = 16.6.

D—H  A

D—H

H  AD  A

D—H  A

N2—H2B  O2
N4—H4A  O3
N1—H1B  O2i
N1—H1A  O5ii
N2—H2A  O5ii

0.88
0.88
0.88
0.88
0.88

2.14
1.86
2.14
2.07
2.16

2.781 (2)2.560 (2)2.959 (2)2.874 (2)2.943 (2)

129
135
155
152
148

The asymmetric unit the title compound, C18H16N4O3S2C3H7NO, contains a molecule in a zwitterionic form with adeprotonated hydroxyl group and an iminium group, and two
dimethylformamide solvent molecules. The dihedral angles of
the guanidine group and the naphthyl ring system with respect
to the central benzene ring are 76.04 (7) and 3.45 (9) ,respectively. The conformation of the molecule may be
influenced, in part, by two intramolecular hydrogen bonds,
while in the crystal structure, intermolecular hydrogen bonds
form one-dimensional chains along [010].

Related literature
For related literature, see: Arestrup (1999); Bergant et al.
(1993); Boghaei et al. (2000); Esposito et al. (2000); Ganolkar(1985); Hao & Shen (2000); Jain & Chaturvedi (1977); Jeewoth
et al. (2000); Johnson et al. (1982); Kwiatkowski et al. (2003);
Lal (1979); Maki & Hashimato (1952); Papie et al. (1994);
Raman et al. (2003); Srinivasan et al. (1986); Wu & Lu (2003);
Tantaru et al. (2002).

Symmetry codes: (i) x; y  12; z þ 1; (ii) x þ 1; y þ 12; z þ 1.

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT(Bruker, 2004); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics: KENX
(Sakai, 2004); software used to prepare material for publication:
SHELXL97, TEXSAN (Molecular Structure Corporation, 2001),
KENX and ORTEPII (Johnson, 1976).

This work was supported by a Grant-in-Aid for Specially
Promoted Research (No. 18002016) from the Ministry of
Education, Culture, Sports, Science, and Technology of Japan.
HE acknowledges the Egyptian Channel System for thefinancial support to promote the joint research project
between Tanta and Kyushu Universities.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: LH2634).

References

Experimental
Crystal data
C18H16N4O3S2C3H7NO
Mr = 514.60
Monoclinic, P21
a = 8.5910 (11) Åo1350

El-Ghamry et al.

b = 9.9101 (12) Å
c = 15.1762 (19) Å = 106.327 (1)V = 1240.0 (3) Å3

Arestrup, F. M. (1999). Int. J. Antimicrob. Agents, 12, 279–285.
Bergant, F., Pacor, S., Ghosh, S., Chattopadhyay, S. K. & Sava, G. (1993). Anti
Cancer Drug Res. 13, 1011–1017.
Boghaei, D. M., Sabounchei, S. J. S. & Rayati, S. (2000). Synth. React. Inorg.
Met.-Org. Chem. 30, 1535–1545.
Bruker (2004). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.
Esposito, E. X., Baran, K., Kelly, K. & Madura, J. D. (2000). J. Mol. Graph.
Model. 18, 283–289.
Flack, H. D. (1983). Acta Cryst. A39, 876–881.
Ganolkar, M. C. (1985). Natl Acad. Sci. 8, 343–349.
Hao, Y. & Shen, H. (2000). Spectrochim. Acta A, 56, 1013–1020.
Jain, P. & Chaturvedi, K. (1977). J. Inorg. Nucl. Chem. 39, 901–903.
Jeewoth, T., Li Kam Wah, H., Bhowon, M. G., Ghoorohoo, D. & Babooram, K.
(2000). Synth. React. Inorg. Met.-Org. Chem. 30, 1023–1038.

doi:10.1107/S1600536808018710

Acta Cryst. (2008). E64, o1350–o1351

organic compounds
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee, USA.
Johnson, D. K., Murphy, T. B., Rose, N. J. & Goodwin, W. H. (1982). Inorg.
Chim. Acta, 67, 159–165.
Kwiatkowski, E., Romanowski, G., Nowicki, W., Kwiatkowski, M. & Suwinska,
K. (2003). Polyhedron, 22, 1009–1018.
Lal, K. (1979). J. Indian Chem. Soc. 56, 749–750.
Maki, T. & Hashimato, H. (1952). Bull. Chem. Soc. Jpn, 25, 411–413.
Molecular Structure Corporation (2001). TEXSAN. MSC, The Woodlands,
Texas, USA.

Acta Cryst. (2008). E64, o1350–o1351

Papie, S., Kaprivanae, N., Grabarie, Z. & Paracosterman, D. (1994). Dyes
Pigm. 25, 229–240.
Raman, N., Kulandai, S. A., Thangaraja, C. & Jeysubramanian, K. (2003).
Transition Met. Chem. 28, 29–36.
Sakai, K. (2004). KENX. Kyushu University, Japan.
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Srinivasan, K., Perrier, S. & Kochi, G. J. (1986). J. Mol. Catal. 36, 297–317.
Tantaru, G., Dorneau, V. & Stan, M. (2002). J. Pharm. Anal. 27, 827–832.
Wu, S. & Lu, S. (2003). J. Mol. Catal. A. 197, 51–59.

El-Ghamry et al.  C18H16N4O3S2C3H7NO

o1351

supplementary materials

supplementary materials
Acta Cryst. (2008). E64, o1350-o1351[ doi:10.1107/S1600536808018710 ]1-[4-(Diaminomethyleneaminosulfonyl)phenyliminiomethyl]-2-naphtholate N,N-dimethylformamide disolvate
H. El-Ghamry, R. Issa, K. El-Baradie, K. Isagai, S. Masaoka and K. Sakai
Comment
Schiff bases are considered a very important class of ligands as they easily form stable complexes with most transition metals.
Moreover, Schiff bases and their metal complexes are becoming increasingly important as biochemical (Johnson et al.,1982), analytical (Hao & Shen, 2000; Tantaru et al., 2002), industrial (Srinivasan et al., 1986) reagents and redox catalysts(Jeewoth et al., 2000; Boghaei et al., 2000; Wu & Lu, 2003; Kwiatkowski et al., 2003) as well as pigment dyes (Maki &Hashimato, 1952; Papie et al., 1994). What appears more important is that Schiff bases and their metal complexes are usefulin biological and pharmaceutical applications (Ganolkar, 1985; Bergant et al., 1993; Raman et al., 2003). Sulfonamides arealso the oldest class of antimicrobials and are still the drug of choice forroup and protonated amino group many diseases
such as cancer and tuberculosis (Arestrup, 1999; Esposito et al., 2000). A number of references are now available to showthat the condensation products of sulfonamides with aldehydes and ketones are also biologically active and have a goodability for complexation (Jain & Chaturvedi, 1977; Lal, 1979). In this paper, we report the synthesis and crystal structureof the title compound (I).
The asymmetric unit of (I) consists of one independent molecule of a zwitterion and two molecules of dimethylformamide. The oxygen atom attached to the naphthyl group (O3) is found to be a deprotonated form of hydroxyl group. The
imine unit connecting the naphthyl and phenyl groups is in a protonated form, giving an iminium unit. Two intramolecularhydrogen bonds (N4—H4A···O3 and N2—H2B···O2; Table 2) are formed to stabilize the conformation of the molecule.
Three intermolecular hydrogen bonds also take part in stabilizing the conformation together with the crystal packing of
the compound [N1—H1B···O2(i), N1—H1A···O5(ii), N2—H2A···O5(ii); symmetry operation (i): –x, y-0.5, 1-z, (ii): –x+1,
0.5+y, 1-z]. The guanidine unit, consisting of C1 and N1—N3 atoms, forms a planar geometry and is canted with respect tothe central phenyl ring at an angle of 76.04 (7) °. The C=N double bond character of the guanidine moiety is fully delocalized
over the unit as shown by the similar C—N distances within the unit. On the other hand, the naphthyl plane is declined only
by 3.45 (9) ° with regard to the phenyl ring. The iminium unit, consisting of atoms C8 and N4 [C8—N4 = 1.322 (2) Å], is
nearly coplanar to the naphthyl plane, as can be seen by the torsion angles about the C8—C9 axis, i.e., N4—C8—C9—C10= -1.0 (3) and N4—C8—C9—C18 = 178.27 (17) °. Good planarity is exhibited by the guanidine and phenyl moieties, while
the naphthyl moiety shows a deviation from the planar geometry, where the ten atom r.m.s deviation estimated in the bestplane calculation is 0.024 Å. No obvious stacking interaction is found in the crystal (see Fig. 2).
Experimental
Compound (I) was prepared as follows. A hot methanolic solution of 2-hydroxy-1-naphthaldehyde (0.9 mmol, 0.154 g) was
added to a methanolic solution of sulfaguanidine (0.9 mmol, 0.192 g). The resulting solution was then refluxed with stirringfor 2 h during which a yellow precipitate deposited. The precipitate was then filtered off from hot solution and then air-dried(yield: 85%). Analysis calculated for C18H16N4O3S: C, 58.69; H, 4.34; N, 15.21; S, 8.69% found: C, 59.16; H, 4.39; N,
14.94; S, 8.76%. IR (ν, cm-1): 3393 (m), 3316 (m), 3167 (w), 1614 (s), 1591 (s), 1580 (sh), 1540 (s),1514 (s), 1406 (m),sup-1

supplementary materials
1347 (m), 1316 (m), 1302 (w), 1295 (w), 1255 (s), 1175 (m), 1128 (s), 1092 (s), 1060 (s), 1042 (w), 1014 (m), 989 (w), 978(w), 966 (m), 964 (w), 835 (s), 822 (s), 811 (w), 743 (s), 727 (w), 686 (m), 608 (s), 558 (s), 539 (s), 475 (s), 432 (s), 409 (s).
A good quality single-crystal of (I) was prepared by vapour diffusion method as follow. Compound (I) was dissolved in aminimum amount of N,N-dimethylformamide and the solution was left in refrigerator in the presence of ether pool. Upon
leaving the solution for 3 days, it gradually raised its volume to give crystals suitable for X-ray diffraction analysis.
Refinement
All H atoms were placed in idealized positions (methyl C—H = 0.98 Å, aromatic C—H = 0.95 Å, and N—H = 0.88 Å), andincluded in the refinement in a riding-model approximation, with Uiso(H) = 1.5Ueq(methyl C) and Uiso(H) = 1.2Ueq(aromatic
C and N). In the final difference Fourier map, the highest peak was located 0.86 Å from atom C2. The deepest hole was
located 0.51 Å from atom S1.

FiguresFig. 1. The molecular structure of (I) showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. The solvent molecules are not shown.

Fig. 2. A stereoview for the crystal packing of (I).

1-[4-(Diaminomethyleneaminosulfonyl)phenyliminiomethyl]-2-naphtholate N,N-dimethylformamide disolvate
Crystal data
C18H16N4O3S·2C3H7NO

F000 = 544

Mr = 514.60

Dx = 1.378 Mg m−3

Monoclinic, P21
Hall symbol: P 2yb
a = 8.5910 (11) Åb = 9.9101 (12) Å
c = 15.1762 (19) Å
β = 106.327 (1)ºV = 1240.0 (3) Å3
Z=2

Mo Kα radiation
λ = 0.71073 Å
Cell parameters from 7706 reflections
θ = 2.5–28.3ºµ = 0.18 mm−1
T = 100 (2) K
Cube, yellow
0.20 × 0.20 × 0.20 mm

Data collection
Bruker SMART APEX CCD-detector diffractometer 5450 independent reflections
Radiation source: sealed tube
5190 reflections with I > 2σ(I)Rint = 0.026
Monochromator: graphite

sup-2

supplementary materials
T = 100(2) Kθmax = 27.1ºφ and ω scans

θmin = 2.5º

Absorption correction: multi-scan(SADABS; Sheldrick, 1996)
Tmin = 0.775, Tmax = 0.965
13950 measured reflections

h = −10→11k = −12→12
l = −19→19

Refinement
Refinement on F2
Least-squares matrix: fullR[F2 > 2σ(F2)] = 0.036

Hydrogen site location: inferred from neighbouringsites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0491P)2 + 0.3529P]

where P = (Fo2 + 2Fc2)/3wR(F2) = 0.091(Δ/σ)max = 0.001

S = 1.08

Δρmax = 0.47 e Å−35450 reflections

Δρmin = −0.22 e Å−3329 parameters
Extinction correction: none
1 restraint
Absolute structure: Flack (1983), 2555 Friedel pairs
Primary atom site location: structure-invariant direct
Flack parameter: −0.03 (6)methods
Secondary atom site location: difference Fourier map

Special details
Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it
was judged to be negligible, no decay correction was applied to the data.
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 ofcell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)
5.2137 (0.0068) x - 0.3949 (0.0103) y + 8.9719 (0.0123) z = 4.0913 (0.0088)* -0.0014 (0.0004) N1 * -0.0016 (0.0005) N2 * -0.0016 (0.0005) N3 * 0.0047 (0.0014) C1
Rms deviation of fitted atoms = 0.0027- 6.1727 (0.0045) x + 6.3206 (0.0058) y + 7.1057 (0.0101) z = 8.7939 (0.0072)
Angle to previous plane (with approximate e.s.d.) = 76.04 (0.07)* 0.0058 (0.0013) C2 * 0.0060 (0.0013) C3 * -0.0134 (0.0013) C4 * 0.0091 (0.0013) C5 * 0.0025 (0.0013) C6 * -0.0100 (0.0013)
C7 0.0707 (0.0027) N4 0.1033 (0.0034) C8
Rms deviation of fitted atoms = 0.0085- 6.1442 (0.0026) x + 6.5659 (0.0029) y + 6.2926 (0.0042) z = 8.2691 (0.0057)

sup-3

supplementary materials
Angle to previous plane (with approximate e.s.d.) = 3.45 (0.09)* 0.0103 (0.0013) N4 * -0.0338 (0.0015) C8 * -0.0052 (0.0016) C9 * 0.0523 (0.0016) C10 * 0.0115 (0.0016) C11 * -0.0294(0.0016) C12 * -0.0226 (0.0017) C13 * -0.0027 (0.0016) C14 * 0.0199 (0.0017) C15 * 0.0248 (0.0017) C16 * -0.0069 (0.0018) C17 *-0.0184 (0.0017) C18
Rms deviation of fitted atoms = 0.0240- 6.1272 (0.0029) x + 6.5698 (0.0029) y + 6.3590 (0.0070) z = 8.3630 (0.0094)
Angle to previous plane (with approximate e.s.d.) = 0.32 (0.06)* -0.0161 (0.0015) C9 * 0.0447 (0.0015) C10 * 0.0118 (0.0016) C11 * -0.0248 (0.0016) C12 * -0.0211 (0.0017) C13 * 0.0034(0.0016) C14 * 0.0230 (0.0017) C15 * 0.0202 (0.0017) C16 * -0.0161 (0.0016) C17 * -0.0248 (0.0016) C18 - 0.0128 (0.0027) N4 0.0526 (0.0025) C8 0.1229 (0.0022) O3
Rms deviation of fitted atoms = 0.0230
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 Rfactors(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)
S1
O1
O2
O3
O4
O5
N1
N2
N3
N4
N5
N6
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12

sup-4

x

y

z

Uiso*/Ueq−0.11893 (5)−0.24764 (16)−0.16593 (16)0.57291 (18)−0.0111 (3)0.72580 (19)0.1366 (2)0.0756 (2)−0.02653 (19)0.3407 (2)0.0840 (2)0.5259 (2)0.0599 (2)0.0195 (2)0.1424 (2)0.2502 (2)0.2327 (2)0.1098 (2)0.0047 (2)0.3396 (2)0.4473 (2)0.5652 (2)0.6790 (2)0.6721 (2)0.64754 (4)0.55840 (14)0.78608 (13)0.81413 (15)0.32634 (18)0.28022 (15)0.56994 (16)0.77841 (17)0.57624 (15)0.68157 (15)0.11583 (17)0.43169 (17)0.6446 (2)0.6549 (2)0.75172 (18)0.75575 (19)0.66596 (18)0.56887 (18)0.56322 (19)0.60541 (19)0.62620 (18)0.73244 (19)0.74704 (19)0.6666 (2)0.56177 (3)0.56814 (9)0.53549 (9)1.04536 (10)0.94460 (18)0.68340 (11)0.40154 (11)0.44614 (12)0.49661 (10)0.93727 (11)0.93544 (12)0.68153 (12)0.45009 (11)0.67283 (11)0.69345 (13)0.78083 (13)0.84865 (12)0.82732 (13)0.73931 (12)1.00860 (13)1.09660 (13)1.11006 (13)1.19945 (14)1.27010 (13)0.01452 (10)0.0193 (3)0.0194 (3)0.0256 (3)0.0650 (7)0.0285 (3)0.0206 (3)0.0218 (4)0.0165 (3)0.0182 (3)0.0260 (4)0.0219 (4)0.0163 (3)0.0152 (3)0.0186 (4)0.0190 (4)0.0169 (4)0.0183 (4)0.0180 (4)0.0184 (4)0.0176 (4)0.0197 (4)0.0222 (4)0.0224 (4)supplementary materials
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
H1A
H1B
H2A
H2B
H4A
H3
H4
H6
H7
H8
H11
H12
H14
H15
H16
H17
H19
H20A
H20B
H20C
H21A
H21B
H21C
H22
H23A
H23B
H23C
H24A
H24B
H24C

0.5510 (2)0.5425 (2)0.4250 (3)0.3137 (2)0.3208 (2)0.4381 (2)−0.0038 (3)0.1016 (3)0.1793 (4)0.5933 (3)0.5988 (3)0.3774 (3)0.19390.12970.13420.02740.41360.1522
0.3362
0.0983−0.0777
0.26320.76060.74990.61860.42010.23180.2449−0.0651
0.02850.07440.21390.14380.29430.1642
0.53850.65020.68070.51480.33180.40240.29830.56323 (19)0.4853 (2)0.3869 (2)0.3655 (2)0.4402 (2)0.54178 (19)0.2224 (2)0.0011 (2)0.1120 (3)0.3374 (2)0.4800 (2)0.4992 (3)0.60950.48140.81350.83140.74620.81450.8196
0.50700.49630.53390.81450.67870.50050.33470.29880.42240.21940.0114−0.0819−0.00400.18440.12430.02460.31020.5676
0.41530.48980.45100.59230.49961.26085 (13)1.33700 (13)1.32851 (15)1.24287 (15)
1.16690 (13)1.17358 (13)0.90039 (19)0.87992 (17)1.03111 (17)0.64427 (16)0.77380 (15)0.62885 (18)0.3691
0.4021
0.41280.47690.94560.64800.79460.87290.72441.0002
1.20901.32801.39501.3802
1.2366
1.10910.83770.81780.90750.87681.06491.0351
1.05780.58340.77130.80690.80570.57100.61580.66450.0191 (4)0.0223 (4)0.0248 (4)0.0236 (4)0.0221 (4)0.0179 (4)0.0373 (6)0.0332 (5)0.0470 (7)0.0282 (5)0.0324 (5)0.0399 (6)0.025*
0.025*
0.026*
0.026*
0.022*
0.022*
0.023*
0.022*
0.022*
0.022*
0.027*
0.027*
0.027*
0.030*
0.028*
0.026*
0.045*
0.050*
0.050*
0.050*
0.071*
0.071*
0.071*
0.034*
0.049*
0.049*
0.049*
0.060*
0.060*
0.060*

Atomic displacement parameters (Å2)
S1
O1

U11
0.0178 (2)0.0198 (7)U220.01154 (19)0.0192 (6)U33
0.01503 (19)0.0197 (6)U120.00018 (18)−0.0020 (5)U130.00590 (15)0.0066 (5)U230.00046 (17)0.0012 (5)sup-5

supplementary materials
O2
O3
O4
O5
N1
N2
N3
N4
N5
N6
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24

0.0234 (7)0.0315 (8)0.1020 (18)0.0310 (8)0.0297 (9)0.0305 (9)0.0235 (8)0.0199 (8)0.0352 (10)0.0219 (8)0.0196 (8)0.0180 (8)0.0251 (10)0.0226 (10)0.0209 (8)0.0240 (10)0.0194 (9)0.0191 (9)0.0195 (9)0.0230 (10)0.0202 (10)0.0206 (9)0.0210 (9)0.0258 (10)0.0316 (12)0.0238 (10)0.0228 (10)0.0193 (9)0.0469 (15)0.0371 (12)0.0679 (19)0.0337 (12)0.0342 (12)0.0348 (13)0.0159 (6)0.0220 (7)0.0211 (9)0.0228 (7)0.0127 (7)0.0127 (8)0.0120 (7)0.0150 (8)0.0159 (9)0.0188 (8)0.0152 (8)0.0146 (8)0.0147 (9)0.0135 (9)0.0140 (9)0.0139 (9)0.0153 (8)0.0155 (8)0.0153 (9)0.0161 (9)0.0189 (10)0.0251 (10)0.0173 (9)0.0237 (10)0.0230 (10)0.0198 (9)0.0209 (10)0.0163 (9)0.0264 (11)0.0213 (11)0.0395 (15)0.0260 (11)0.0307 (12)0.0313 (13)0.0193 (6)0.0236 (7)0.1044 (19)0.0381 (9)0.0241 (8)0.0286 (9)0.0153 (7)0.0192 (8)0.0279 (9)0.0255 (9)0.0130 (7)0.0130 (7)0.0177 (9)0.0227 (10)0.0170 (8)0.0180 (9)0.0206 (9)0.0211 (9)0.0187 (8)0.0212 (9)0.0270 (10)0.0193 (9)0.0197 (9)0.0166 (9)0.0224 (10)0.0292 (11)0.0206 (9)0.0190 (9)0.0488 (15)0.0470 (14)0.0297 (12)0.0275 (11)0.0328 (12)0.0472 (15)0.0038 (5)−0.0062 (6)0.0118 (10)0.0026 (6)0.0003 (7)−0.0008 (7)0.0010 (6)−0.0021 (6)−0.0014 (7)−0.0017 (7)0.0028 (8)0.0022 (8)−0.0017 (7)−0.0046 (7)0.0020 (7)−0.0004 (7)−0.0014 (7)0.0001 (7)0.0025 (7)0.0008 (7)−0.0025 (8)0.0025 (8)0.0060 (7)0.0067 (8)0.0065 (8)−0.0006 (8)−0.0007 (8)0.0046 (7)0.0044 (11)−0.0036 (9)−0.0226 (13)−0.0041 (9)−0.0030 (10)0.0062 (10)0.0067 (6)0.0079 (6)0.0820 (16)0.0202 (7)0.0154 (7)0.0189 (8)0.0076 (6)0.0045 (6)0.0104 (8)0.0076 (7)0.0030 (6)0.0044 (6)0.0087 (8)0.0095 (8)0.0071 (7)0.0077 (7)0.0078 (7)0.0064 (7)0.0063 (7)0.0083 (8)0.0060 (8)0.0022 (7)0.0070 (7)0.0046 (8)0.0119 (9)0.0105 (9)0.0032 (8)0.0067 (7)0.0305 (13)0.0210 (11)0.0070 (12)0.0127 (9)0.0105 (10)0.0011 (11)0.0021 (5)0.0012 (6)0.0082 (10)0.0000 (7)0.0010 (6)0.0002 (7)−0.0007 (6)−0.0006 (6)−0.0012 (6)−0.0011 (7)0.0020 (8)−0.0016 (8)0.0008 (7)−0.0034 (7)−0.0019 (7)0.0025 (7)0.0003 (7)−0.0013 (7)−0.0008 (7)−0.0031 (7)−0.0069 (8)−0.0069 (8)−0.0035 (8)−0.0033 (8)0.0048 (8)0.0015 (8)0.0002 (8)−0.0014 (7)0.0093 (11)−0.0056 (10)0.0037 (10)0.0000 (9)−0.0056 (10)−0.0024 (11)Geometric parameters (Å, °)
S1—O1
S1—O2
S1—N3
S1—C2
O3—C10O4—C19O5—C22
N1—C1
N2—C1
N3—C1
N4—C8
N4—C5

sup-6

1.4397 (14)1.4549 (14)1.5963 (16)1.7702 (17)1.289 (2)1.240 (3)1.261 (3)1.341 (2)1.336 (2)1.343 (2)1.322 (2)1.411 (2)N6—C22
N6—C23
N6—C24
N1—H1A
N1—H1BN2—H2AN2—H2B
N4—H4A
C3—H3
C4—H4
C6—H6
C7—H7

1.308 (3)1.445 (3)1.464 (3)0.88000.88000.88000.88000.88000.95000.95000.95000.9500supplementary materials
C2—C7
C2—C3
C3—C4
C4—C5
C5—C6
C6—C7
C8—C9
C9—C10C9—C18
C10—C11
C11—C12
C12—C13
C13—C14
C13—C18
C14—C15
C15—C16
C16—C17
C17—C18
N5—C19N5—C20N5—C211.389 (3)1.396 (3)1.388 (3)1.400 (3)1.398 (3)1.387 (3)1.410 (3)1.435 (3)1.457 (3)1.439 (3)1.351 (3)1.438 (3)1.409 (3)1.421 (3)1.383 (3)1.396 (3)1.385 (3)1.408 (3)1.320 (3)1.448 (3)1.453 (3)

C8—H8
C11—H11C12—H12C14—H14
C15—H15
C16—H16
C17—H17
C19—H19
C20—H20A
C20—H20B
C20—H20C
C21—H21A
C21—H21B
C21—H21C
C22—H22
C23—H23A
C23—H23B
C23—H23C
C24—H24A
C24—H24B
C24—H24C

0.95000.95000.95000.95000.95000.95000.95000.95000.98000.98000.98000.98000.98000.98000.95000.98000.98000.98000.98000.98000.9800O1—S1—O2
O1—S1—N3
O2—S1—N3
O1—S1—C2
O2—S1—C2
N3—S1—C2
C1—N1—H1A
C1—N1—H1B
H1A—N1—H1B
C1—N2—H2A
C1—N2—H2B
H2A—N2—H2B
C1—N3—S1
C8—N4—C5
C8—N4—H4A
C5—N4—H4A
C19—N5—C20
C19—N5—C21
C20—N5—C21
C22—N6—C23
C22—N6—C24
C23—N6—C24
N2—C1—N1
N2—C1—N3
N1—C1—N3
C7—C2—C3
C7—C2—S1
C3—C2—S1

115.99 (8)107.16 (8)113.33 (8)106.52 (8)106.42 (9)106.86 (8)
120.0
120.0
120.0
120.0
120.0
120.0
123.17 (13)124.29 (16)
117.9
117.9
122.4 (2)121.4 (2)116.0 (2)122.12 (19)120.95 (19)116.83 (19)116.84 (17)127.02 (17)116.14 (17)120.29 (16)119.38 (14)120.34 (14)C12—C11—H11
C10—C11—H11
C11—C12—C13
C11—C12—H12
C13—C12—H12
C14—C13—C18
C14—C13—C12
C18—C13—C12
C15—C14—C13
C15—C14—H14
C13—C14—H14
C14—C15—C16
C14—C15—H15
C16—C15—H15
C17—C16—C15
C17—C16—H16
C15—C16—H16
C16—C17—C18
C16—C17—H17
C18—C17—H17
C17—C18—C13
C17—C18—C9
C13—C18—C9
O4—C19—N5
O4—C19—H19
N5—C19—H19
N5—C20—H20A
N5—C20—H20B

119.4
119.4
122.34 (18)
118.8
118.8
120.20 (18)120.89 (18)118.90 (17)120.99 (19)
119.5
119.5
119.00 (19)
120.5
120.5
120.97 (19)
119.5
119.5
121.32 (18)
119.3
119.3
117.50 (17)123.51 (17)118.98 (17)123.8 (3)
118.1
118.1
109.5
109.5

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supplementary materials
C4—C3—C2
C4—C3—H3
C2—C3—H3
C3—C4—C5
C3—C4—H4
C5—C4—H4
C6—C5—C4
C6—C5—N4
C4—C5—N4
C7—C6—C5
C7—C6—H6
C5—C6—H6
C6—C7—C2
C6—C7—H7
C2—C7—H7
N4—C8—C9
N4—C8—H8
C9—C8—H8
C8—C9—C10
C8—C9—C18
C10—C9—C18
O3—C10—C9O3—C10—C11
C9—C10—C11
C12—C11—C10

119.58 (17)
120.2
120.2
120.20 (17)
119.9
119.9
119.83 (17)123.21 (16)116.94 (17)119.71 (16)
120.1
120.1
120.35 (17)
119.8
119.8
122.57 (17)
118.7
118.7
119.41 (17)120.43 (17)120.16 (17)122.53 (18)119.23 (18)118.24 (17)121.26 (18)

H20A—C20—H20B
N5—C20—H20C
H20A—C20—H20C
H20B—C20—H20C
N5—C21—H21A
N5—C21—H21B
H21A—C21—H21B
N5—C21—H21C
H21A—C21—H21C
H21B—C21—H21C
O5—C22—N6
O5—C22—H22
N6—C22—H22
N6—C23—H23A
N6—C23—H23B
H23A—C23—H23B
N6—C23—H23C
H23A—C23—H23C
H23B—C23—H23C
N6—C24—H24A
N6—C24—H24B
H24A—C24—H24B
N6—C24—H24C
H24A—C24—H24C
H24B—C24—H24C

109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
124.6 (2)
117.7
117.7
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5
109.5

O1—S1—N3—C1
O2—S1—N3—C1
C2—S1—N3—C1
S1—N3—C1—N2
S1—N3—C1—N1
O1—S1—C2—C7
O2—S1—C2—C7
N3—S1—C2—C7
O1—S1—C2—C3
O2—S1—C2—C3
N3—S1—C2—C3
C7—C2—C3—C4
S1—C2—C3—C4
C2—C3—C4—C5
C3—C4—C5—C6
C3—C4—C5—N4
C8—N4—C5—C6
C8—N4—C5—C4
C4—C5—C6—C7
N4—C5—C6—C7
C5—C6—C7—C2
C3—C2—C7—C6
S1—C2—C7—C6
C5—N4—C8—C9

156.25 (14)27.00 (17)−89.89 (16)−3.9 (3)177.04 (13)11.77 (17)136.09 (15)−102.53 (15)−168.26 (14)−43.94 (16)77.44 (16)0.2 (3)−179.79 (14)−2.0 (3)2.3 (3)−176.20 (17)
1.3 (3)179.76 (18)−0.8 (3)177.63 (17)−1.0 (3)
1.4 (3)−178.68 (14)−178.53 (17)C18—C9—C10—O3
C8—C9—C10—C11
C18—C9—C10—C11
O3—C10—C11—C12
C9—C10—C11—C12
C10—C11—C12—C13
C11—C12—C13—C14
C11—C12—C13—C18
C18—C13—C14—C15
C12—C13—C14—C15
C13—C14—C15—C16
C14—C15—C16—C17
C15—C16—C17—C18
C16—C17—C18—C13
C16—C17—C18—C9
C14—C13—C18—C17
C12—C13—C18—C17
C14—C13—C18—C9
C12—C13—C18—C9
C8—C9—C18—C17
C10—C9—C18—C17
C8—C9—C18—C13
C10—C9—C18—C13
C20—N5—C19—O4−176.40 (17)−176.88 (17)3.8 (3)177.77 (18)
−2.4 (3)−0.6 (3)−176.99 (18)
2.2 (3)0.1 (3)179.23 (18)−0.1 (3)0.7 (3)−1.3 (3)
1.2 (3)−177.82 (18)−0.6 (3)−179.77 (17)178.46 (17)−0.7 (3)−2.6 (3)176.74 (17)178.44 (16)−2.3 (3)−174.2 (2)sup-8

supplementary materials
N4—C8—C9—C10
N4—C8—C9—C18
C8—C9—C10—O3−1.0 (3)178.27 (17)2.9 (3)

C21—N5—C19—O4
C23—N6—C22—O5
C24—N6—C22—O5

0.8 (4)−0.3 (3)175.8 (2)Hydrogen-bond geometry (Å, °)D—H···A
N2—H2B···O2
N4—H4A···O3

D—H
0.88
0.88

H···A
2.14
1.86

D···A
2.781 (2)2.560 (2)

D—H···A
129
135

N1—H1B···O2i

0.88

2.14

2.959 (2)

155

ii

0.88

2.07

2.874 (2)

152

2.16

2.943 (2)148

N1—H1A···O5

ii

0.88
N2—H2A···O5
Symmetry codes: (i) −x, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+1.

sup-9

supplementary materials
Fig. 1

sup-10supplementary materials
Fig. 2

sup-11