Promazinium picrate

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organic papers

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Yathirajanet al. _C

17H21N2S+C6H2N3O7 doi:10.1107/S1600536807008306 Acta Cryst.(2007). E63, o1432–o1434

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

Promazinium picrate

H. S. Yathirajan,aM. A. Ashok,a B. Narayana Acharaand Michael Bolteb*

a_{Department of Studies in Chemistry, University}

of Mysore, Manasagangotri, Mysore 570 006, India, andb

Institut fu¨r Anorganische Chemie, J. W. Goethe-Universita¨t Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 173 K

Mean(C–C) = 0.002 A˚ Disorder in main residue

Rfactor = 0.046

wRfactor = 0.128

Data-to-parameter ratio = 15.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 16 February 2007 Accepted 19 February 2007

In the title compound [systematic name: 3-(phenothiazin-10-yl)propanaminium 2,4,6-trinitrophenolate], C17H21N2S

+ -C6H2N3O7

, the dihedral angle between the two outer aromatic rings of the phenothiazine unit is 37.76 (6)_{. The}

crystal packing is stabilized by N—H O hydrogen bonds and several weak C—H O contacts.

Comment

Promazine hydrochloride (promazinium chloride) is an important antipsychotic drug (Tarasiewicz & Basinska, 1974). The organic cation contains a distinctive tricyclic aromatic ring system containing S and N atoms in the central ring. As part of our studies of these systems, we describe here the synthesis and structure of the title salt, (I) (Fig. 1), containing the promazinium cation, accompanied by picrate anions.

[image:1.610.241.423.371.482.2] [image:1.610.210.460.551.713.2]

The bond lengths and angles for (I) can be regarded as normal [Cambridge Structural Database, Version 5.28, November 2006 (Allen, 2002);MogulVersion 1.1 (Brunoet al.,

Figure 1

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2004)]. The dihedral angle between the two aromatic rings of the phenothiazine ring system is 37.76 (6)_{. Crystallographic}

studies of promazine (Falkenberg & Ringertz, 1967) and promazine hydrochloride, (II) (David et al., 1998) have been reported, but atomic coordinates (without standard uncer-tainties) are available only for the latter. A least-squares comparison of the promazinium cations of (I) and (II), fitting only the phenothiazine units (r.m.s. deviation 0.070A˚ ), is shown in Fig. 2. The cations differ only in two side-chain torsion angles. Whereas the conformation of N1—C1—C2— C3 is anticlinal in (I) (Table 1), it is antiperiplanar (166.3_{) in}

(II). On the other hand, C2—C3—N4—C6 is synclinal in (I), but anticlinal (76.7_{) in (II). The conformation of C1—C2—}

[image:2.610.47.295.73.303.2]

C3—N4 and C2—C3—N4—C5 is antiperiplanar in both structures. The crystal packing for (I) is stabilized by N— H O hydrogen bonds and several weak C—H O contacts (Table 2).

Experimental

Promazine hydrochloride (1.605 g, 0.05M) and picric acid (1.147 g, 0.05M) were mixed and stirred in a beaker. The precipitated bright brick-red salt was filtered off and washed thoroughly with doubly distilled water and dried over P2O5 in a vacuum desiccator. The

compound was recrystallized from ethanol by slow evaporation (m.p. 415–417 K), yielding red plates of (I).

Crystal data

C17H21N2S+C6H2N3O7

Mr= 513.52

Triclinic,P1

a= 10.0611 (6) A˚

b= 10.2518 (7) A˚

c= 11.9841 (8) A˚

= 85.649 (6)

= 78.414 (5)

= 82.040 (5) V= 1197.77 (13) A˚3

Z= 2

MoKradiation

= 0.19 mm1

T= 173 (2) K 0.420.360.19 mm

Data collection

Stoe IPDSII two-circle diffractometer

Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)

Tmin= 0.915,Tmax= 0.955

22432 measured reflections 5489 independent reflections 5037 reflections withI> 2(I)

Rint= 0.049

Refinement

R[F2> 2(F2)] = 0.046

wR(F2_{) = 0.128}

S= 1.04 5489 reflections 349 parameters

H atoms treated by a mixture of independent and constrained refinement

max= 0.78 e A˚

3

min=0.60 e A˚

3

Table 1

Selected torsion angles (_).

N1—C1—C2—C3 72.28 (15) C1—C2—C3—N4 161.37 (11)

[image:2.610.314.564.355.436.2]

C2—C3—N4—C6 50.38 (16) C2—C3—N4—C5 174.58 (12)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N4—H4 O31i

0.93 (2) 1.78 (2) 2.6735 (17) 162 (2) N4—H4 O362i 0.93 (2) 2.41 (2) 2.9804 (18) 119.8 (17) C2—H2B O322ii

0.99 2.53 3.280 (2) 132

C5—H5A O362i

0.98 2.46 3.008 (2) 115

C5—H5C O341 0.98 2.57 3.439 (2) 148 C6—H6B O341 0.98 2.50 3.389 (2) 150 C13—H13 O321ii

0.95 2.59 3.336 (3) 136

Symmetry codes: (i)xþ1;yþ1;zþ1; (ii)x1;y;z.

The N-bound H atom was located in a difference map. Its position andUisovalue were freely refined. The C-bound H atoms were found

in a difference map, repositioned in idealized locations (C—H = 0.95– 0.99 A˚ ) and refined as riding, with Uiso(H) = 1.2Ueq(C) or

1.5Ueq(methyl C). The O atoms of one of the picrate nitro groups are

disordered over two positions with site occupation factors of 0.662 (4) and 0.338 (4) (sum constrained to unity).

Data collection:X-AREA(Stoe & Cie, 2001); cell refinement: X-AREA; data reduction:X-AREA; program(s) used to solve structure:

SHELXS97(Sheldrick, 1997); program(s) used to refine structure:

SHELXL97 (Sheldrick, 1997); molecular graphics: XP in

SHELXTL-Plus(Sheldrick, 1991); software used to prepare material for publication:SHELXL97.

MAA thanks the University of Mysore for Research facil-ities.

References

Allen, F. H. (2002).Acta Cryst.B58, 380–388. Blessing, R. H. (1995).Acta Cryst.A51, 33–38.

Bruno, I. J., Cole, J. C., Kessler, M., Luo Jie, Motherwell, W. D. S., Purkis, L. H., Smith, B. R., Taylor, R., Cooper, R. I., Harris, S. E. & Orpen, A. G. (2004).J. Chem. Inf. Comput. Sci.44, 2133–2144.

David, W. I. F., Shankland, K. & Shankland, N. (1998).Chem. Commun.pp. 931–932.

Falkenberg, G. & Ringertz, H. (1967).Acta Cryst.23, 1111.

organic papers

Acta Cryst.(2007). E63, o1432–o1434 Yathirajanet al. _C

17H21N2S+C6H2N3O7

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Figure 2

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Sheldrick, G. M. (1991). SHELXTL-Plus. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Stoe & Cie (2001).X-AREA. Stoe & Cie, Darmstadt, Germany. Tarasiewicz, M. & Basinska, H. (1974).Talanta,21, 425–430.

organic papers

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Yathirajanet al. _C

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supporting information

sup-1 Acta Cryst. (2007). E63, o1432–o1434

supporting information

Acta Cryst. (2007). E63, o1432–o1434 [https://doi.org/10.1107/S1600536807008306]

Promazinium picrate

H. S. Yathirajan, M. A. Ashok, B. Narayana Achar and Michael Bolte

3-(phenothiazin-10-yl)propanaminium 2,4,6-trinitrophenolate

Crystal data

C17H21N2S+·C6H2N3O7−

Mr = 513.52

Triclinic, P1

Hall symbol: -P 1

a = 10.0611 (6) Å

b = 10.2518 (7) Å

c = 11.9841 (8) Å

α = 85.649 (6)°

β = 78.414 (5)°

γ = 82.040 (5)°

V = 1197.77 (13) Å3

Z = 2

F(000) = 536

Dx = 1.424 Mg m−3

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 21165 reflections

θ = 3.4–27.5°

µ = 0.19 mm−1

T = 173 K

Plate, red

0.42 × 0.36 × 0.19 mm

Data collection

Stoe IPDSII two-circle diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan

(MULABS; Spek, 2003; Blessing, 1995)

Tmin = 0.915, Tmax = 0.955

22432 measured reflections 5489 independent reflections 5037 reflections with I > 2σ(I)

Rint = 0.049

θmax = 27.6°, θmin = 3.4°

h = −13→13

k = −11→13

l = −15→15

Refinement

Refinement on F2

Least-squares matrix: full R[F2_{> 2}_σ₍_F2_{)] = 0.046}

wR(F2_{) = 0.128}

S = 1.04

5489 reflections 349 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2₍_F

o2) + (0.0689P)2 + 0.5434P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.78 e Å−3

Δρmin = −0.60 e Å−3

Extinction correction: SHELXL97,

Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2_θ_)]-1/4

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supporting information

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 (Å2₎

x y z Uiso*/Ueq Occ. (<1)

S1 0.35016 (4) 0.89530 (4) 0.10487 (3) 0.03213 (13)

N1 0.11730 (12) 0.74429 (11) 0.10612 (10) 0.0260 (3)

C1 0.03456 (15) 0.63790 (14) 0.10271 (14) 0.0296 (3)

H1A 0.0380 0.6188 0.0224 0.036*

H1B −0.0619 0.6668 0.1375 0.036*

C2 0.08684 (15) 0.51178 (14) 0.16718 (12) 0.0271 (3)

H2A 0.1000 0.5340 0.2429 0.033*

H2B 0.0180 0.4492 0.1792 0.033*

C3 0.22179 (15) 0.44706 (14) 0.10000 (12) 0.0278 (3)

H3A 0.2031 0.3996 0.0370 0.033*

H3B 0.2791 0.5164 0.0659 0.033*

N4 0.29959 (12) 0.35177 (12) 0.17290 (10) 0.0260 (3)

H4 0.325 (2) 0.401 (2) 0.2249 (19) 0.048 (6)*

C5 0.42412 (17) 0.28149 (17) 0.10129 (15) 0.0375 (4)

H5A 0.4789 0.3462 0.0566 0.056*

H5B 0.3964 0.2253 0.0496 0.056*

H5C 0.4786 0.2269 0.1507 0.056*

C6 0.21454 (17) 0.25458 (16) 0.24167 (15) 0.0361 (3)

H6A 0.1336 0.3018 0.2884 0.054*

H6B 0.2684 0.1995 0.2913 0.054*

H6C 0.1858 0.1987 0.1904 0.054*

C11 0.22132 (14) 0.86721 (13) 0.22512 (13) 0.0267 (3)

C12 0.11752 (14) 0.79291 (13) 0.21426 (12) 0.0250 (3)

C13 0.01890 (16) 0.76910 (15) 0.31119 (13) 0.0313 (3)

H13 −0.0535 0.7210 0.3056 0.038*

C14 0.02584 (18) 0.81543 (17) 0.41615 (14) 0.0384 (4)

H14 −0.0412 0.7974 0.4815 0.046*

C15 0.12980 (19) 0.88765 (16) 0.42602 (14) 0.0389 (4)

H15 0.1343 0.9183 0.4978 0.047*

C16 0.22693 (17) 0.91456 (14) 0.33007 (14) 0.0326 (3)

H16 0.2973 0.9652 0.3359 0.039*

C21 0.25000 (14) 0.90970 (14) −0.00247 (13) 0.0276 (3)

C22 0.14354 (14) 0.83110 (13) 0.00830 (12) 0.0251 (3)

C23 0.06887 (16) 0.84101 (15) −0.07948 (13) 0.0320 (3)

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supporting information

C24 0.10374 (18) 0.92163 (17) −0.17761 (14) 0.0368 (3)

H24 0.0542 0.9247 −0.2376 0.044*

C25 0.21004 (18) 0.99710 (18) −0.18793 (15) 0.0404 (4)

H25 0.2341 1.0511 −0.2550 0.048*

C26 0.28130 (16) 0.99331 (16) −0.09946 (15) 0.0360 (3)

H26 0.3517 1.0478 −0.1048 0.043*

O31 0.67586 (15) 0.51651 (16) 0.64962 (11) 0.0531 (4)

C31 0.62354 (15) 0.43194 (15) 0.60901 (13) 0.0299 (3)

C32 0.67401 (15) 0.38807 (16) 0.49367 (13) 0.0306 (3)

C33 0.61944 (15) 0.29822 (16) 0.44334 (12) 0.0313 (3)

H33 0.6579 0.2739 0.3676 0.038*

C34 0.50654 (15) 0.24307 (15) 0.50524 (12) 0.0283 (3)

C35 0.45079 (15) 0.27560 (15) 0.61632 (12) 0.0286 (3)

H35 0.3741 0.2364 0.6575 0.034*

C36 0.50737 (15) 0.36549 (15) 0.66702 (12) 0.0278 (3)

N32 0.79403 (15) 0.44125 (17) 0.42406 (12) 0.0426 (4)

N34 0.44353 (15) 0.15127 (14) 0.45179 (12) 0.0359 (3)

N36 0.44213 (15) 0.39407 (16) 0.78398 (11) 0.0381 (3)

O321 0.8150 (3) 0.5470 (2) 0.4339 (2) 0.0501 (6) 0.662 (4)

O322 0.8744 (2) 0.3563 (2) 0.35780 (18) 0.0531 (7) 0.662 (4)

O323 0.8729 (6) 0.4930 (7) 0.4678 (5) 0.0656 (16) 0.338 (4)

O324 0.7899 (5) 0.4747 (6) 0.3193 (4) 0.0668 (18) 0.338 (4)

O341 0.49221 (15) 0.12584 (15) 0.35180 (11) 0.0489 (3)

O342 0.34322 (15) 0.10399 (15) 0.50797 (12) 0.0516 (4)

O361 0.34491 (17) 0.3351 (2) 0.82934 (12) 0.0718 (6)

O362 0.48880 (18) 0.46888 (17) 0.83649 (12) 0.0633 (5)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

S1 0.02157 (19) 0.0360 (2) 0.0402 (2) −0.00729 (14) −0.00616 (14) −0.00374 (15)

N1 0.0283 (6) 0.0226 (5) 0.0296 (6) −0.0083 (4) −0.0088 (5) 0.0013 (4)

C1 0.0282 (7) 0.0255 (7) 0.0388 (8) −0.0094 (5) −0.0123 (6) 0.0023 (6)

C2 0.0280 (7) 0.0231 (6) 0.0305 (7) −0.0076 (5) −0.0043 (5) 0.0015 (5)

C3 0.0320 (7) 0.0278 (7) 0.0237 (6) −0.0056 (5) −0.0050 (5) 0.0013 (5)

N4 0.0288 (6) 0.0241 (6) 0.0253 (6) −0.0042 (5) −0.0046 (5) −0.0021 (4)

C5 0.0358 (8) 0.0344 (8) 0.0390 (8) 0.0026 (6) −0.0015 (7) −0.0089 (6)

C6 0.0376 (8) 0.0283 (7) 0.0423 (8) −0.0081 (6) −0.0091 (7) 0.0087 (6)

C11 0.0255 (6) 0.0207 (6) 0.0342 (7) −0.0004 (5) −0.0078 (5) −0.0028 (5)

C12 0.0238 (6) 0.0206 (6) 0.0303 (7) −0.0001 (5) −0.0061 (5) −0.0016 (5)

C13 0.0285 (7) 0.0274 (7) 0.0355 (8) −0.0019 (5) −0.0026 (6) 0.0019 (6)

C14 0.0417 (9) 0.0353 (8) 0.0319 (8) 0.0049 (7) 0.0010 (6) −0.0012 (6)

C15 0.0517 (10) 0.0314 (8) 0.0324 (8) 0.0075 (7) −0.0113 (7) −0.0076 (6)

C16 0.0381 (8) 0.0233 (7) 0.0394 (8) 0.0010 (6) −0.0158 (6) −0.0061 (6)

C21 0.0217 (6) 0.0253 (6) 0.0345 (7) −0.0023 (5) −0.0028 (5) −0.0022 (5)

C22 0.0236 (6) 0.0209 (6) 0.0301 (7) −0.0020 (5) −0.0044 (5) −0.0004 (5)

C23 0.0326 (7) 0.0297 (7) 0.0357 (8) −0.0052 (6) −0.0115 (6) 0.0020 (6)

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C25 0.0382 (8) 0.0398 (9) 0.0379 (8) −0.0027 (7) −0.0013 (7) 0.0114 (7)

C26 0.0276 (7) 0.0330 (8) 0.0440 (9) −0.0064 (6) −0.0001 (6) 0.0061 (6)

O31 0.0548 (8) 0.0749 (10) 0.0368 (6) −0.0398 (7) 0.0003 (6) −0.0155 (6)

C31 0.0272 (7) 0.0356 (8) 0.0291 (7) −0.0091 (6) −0.0075 (6) −0.0005 (6)

C32 0.0247 (7) 0.0396 (8) 0.0273 (7) −0.0083 (6) −0.0040 (5) 0.0046 (6)

C33 0.0283 (7) 0.0402 (8) 0.0249 (6) −0.0027 (6) −0.0055 (5) −0.0007 (6)

C34 0.0288 (7) 0.0313 (7) 0.0275 (7) −0.0047 (6) −0.0108 (6) −0.0012 (5)

C35 0.0273 (7) 0.0321 (7) 0.0272 (7) −0.0087 (6) −0.0057 (5) 0.0028 (5)

C36 0.0296 (7) 0.0321 (7) 0.0220 (6) −0.0065 (6) −0.0041 (5) −0.0005 (5)

N32 0.0344 (7) 0.0615 (10) 0.0321 (7) −0.0171 (7) −0.0010 (6) 0.0029 (6)

N34 0.0395 (7) 0.0372 (7) 0.0345 (7) −0.0044 (6) −0.0142 (6) −0.0050 (5)

N36 0.0380 (7) 0.0511 (8) 0.0261 (6) −0.0159 (6) −0.0003 (5) −0.0050 (6)

O321 0.0472 (14) 0.0453 (13) 0.0571 (14) −0.0238 (10) 0.0001 (11) 0.0086 (10)

O322 0.0436 (12) 0.0630 (14) 0.0444 (12) −0.0137 (10) 0.0174 (9) −0.0064 (10)

O323 0.050 (3) 0.086 (4) 0.068 (3) −0.043 (3) −0.011 (2) 0.010 (3)

O324 0.049 (3) 0.110 (4) 0.036 (2) −0.020 (3) 0.0064 (18) 0.015 (2)

O341 0.0511 (8) 0.0612 (8) 0.0389 (7) −0.0074 (6) −0.0129 (6) −0.0186 (6)

O342 0.0552 (8) 0.0590 (8) 0.0486 (7) −0.0322 (7) −0.0112 (6) −0.0048 (6)

O361 0.0588 (9) 0.1238 (16) 0.0381 (7) −0.0518 (10) 0.0127 (7) −0.0240 (8)

O362 0.0819 (11) 0.0740 (10) 0.0377 (7) −0.0469 (9) 0.0120 (7) −0.0231 (7)

Geometric parameters (Å, º)

S1—C11 1.7692 (15) C16—H16 0.9500

S1—C21 1.7728 (15) C21—C26 1.400 (2)

N1—C22 1.4207 (18) C21—C22 1.4075 (19)

N1—C12 1.4240 (18) C22—C23 1.400 (2)

N1—C1 1.4683 (17) C23—C24 1.399 (2)

C1—C2 1.539 (2) C23—H23 0.9500

C1—H1A 0.9900 C24—C25 1.385 (3)

C1—H1B 0.9900 C24—H24 0.9500

C2—C3 1.525 (2) C25—C26 1.390 (3)

C2—H2A 0.9900 C25—H25 0.9500

C2—H2B 0.9900 C26—H26 0.9500

C3—N4 1.5045 (18) O31—C31 1.2486 (19)

C3—H3A 0.9900 C31—C32 1.456 (2)

C3—H3B 0.9900 C31—C36 1.461 (2)

N4—C6 1.4942 (19) C32—C33 1.368 (2)

N4—C5 1.4958 (19) C32—N32 1.4697 (19)

N4—H4 0.93 (2) C33—C34 1.391 (2)

C5—H5A 0.9800 C33—H33 0.9500

C5—H5B 0.9800 C34—C35 1.383 (2)

C5—H5C 0.9800 C34—N34 1.4551 (19)

C6—H6A 0.9800 C35—C36 1.383 (2)

C6—H6B 0.9800 C35—H35 0.9500

C6—H6C 0.9800 C36—N36 1.4563 (19)

C11—C16 1.396 (2) N32—O321 1.151 (3)

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supporting information

C12—C13 1.398 (2) N32—O324 1.283 (5)

C13—C14 1.396 (2) N32—O322 1.302 (3)

C13—H13 0.9500 N34—O342 1.2328 (19)

C14—C15 1.391 (3) N34—O341 1.2330 (19)

C14—H14 0.9500 N36—O362 1.2232 (19)

C15—C16 1.389 (2) N36—O361 1.232 (2)

C15—H15 0.9500

C11—S1—C21 98.97 (7) C16—C15—H15 120.3

C22—N1—C12 117.85 (11) C14—C15—H15 120.3

C22—N1—C1 118.55 (12) C15—C16—C11 120.07 (15)

C12—N1—C1 118.00 (12) C15—C16—H16 120.0

N1—C1—C2 111.19 (11) C11—C16—H16 120.0

N1—C1—H1A 109.4 C26—C21—C22 120.58 (14)

C2—C1—H1A 109.4 C26—C21—S1 120.19 (12)

N1—C1—H1B 109.4 C22—C21—S1 119.16 (11)

C2—C1—H1B 109.4 C23—C22—C21 118.08 (13)

H1A—C1—H1B 108.0 C23—C22—N1 122.78 (13)

C3—C2—C1 110.57 (12) C21—C22—N1 119.13 (13)

C3—C2—H2A 109.5 C24—C23—C22 120.86 (14)

C1—C2—H2A 109.5 C24—C23—H23 119.6

C3—C2—H2B 109.5 C22—C23—H23 119.6

C1—C2—H2B 109.5 C25—C24—C23 120.45 (15)

H2A—C2—H2B 108.1 C25—C24—H24 119.8

N4—C3—C2 112.54 (11) C23—C24—H24 119.8

N4—C3—H3A 109.1 C24—C25—C26 119.54 (15)

C2—C3—H3A 109.1 C24—C25—H25 120.2

N4—C3—H3B 109.1 C26—C25—H25 120.2

C2—C3—H3B 109.1 C25—C26—C21 120.38 (15)

H3A—C3—H3B 107.8 C25—C26—H26 119.8

C6—N4—C5 110.27 (12) C21—C26—H26 119.8

C6—N4—C3 113.15 (12) O31—C31—C32 122.29 (14)

C5—N4—C3 110.50 (12) O31—C31—C36 126.20 (14)

C6—N4—H4 106.2 (14) C32—C31—C36 111.51 (13)

C5—N4—H4 109.7 (14) C33—C32—C31 125.16 (13)

C3—N4—H4 106.9 (14) C33—C32—N32 115.91 (14)

N4—C5—H5A 109.5 C31—C32—N32 118.93 (14)

N4—C5—H5B 109.5 C32—C33—C34 118.72 (14)

H5A—C5—H5B 109.5 C32—C33—H33 120.6

N4—C5—H5C 109.5 C34—C33—H33 120.6

H5A—C5—H5C 109.5 C35—C34—C33 121.37 (14)

H5B—C5—H5C 109.5 C35—C34—N34 119.00 (13)

N4—C6—H6A 109.5 C33—C34—N34 119.62 (13)

N4—C6—H6B 109.5 C36—C35—C34 119.57 (13)

H6A—C6—H6B 109.5 C36—C35—H35 120.2

N4—C6—H6C 109.5 C34—C35—H35 120.2

H6A—C6—H6C 109.5 C35—C36—N36 115.89 (13)

(9)

supporting information

C16—C11—C12 121.00 (14) N36—C36—C31 120.46 (13)

C16—C11—S1 119.72 (12) O323—N32—O324 117.0 (4)

C12—C11—S1 119.23 (11) O321—N32—O322 124.95 (19)

C13—C12—C11 118.18 (13) O321—N32—C32 121.09 (18)

C13—C12—N1 122.69 (13) O323—N32—C32 121.4 (3)

C11—C12—N1 119.13 (13) O324—N32—C32 117.4 (2)

C14—C13—C12 120.57 (15) O322—N32—C32 113.85 (16)

C14—C13—H13 119.7 O342—N34—O341 123.15 (14)

C12—C13—H13 119.7 O342—N34—C34 118.59 (13)

C15—C14—C13 120.68 (15) O341—N34—C34 118.25 (14)

C15—C14—H14 119.7 O362—N36—O361 121.77 (14)

C13—C14—H14 119.7 O362—N36—C36 120.07 (14)

C16—C15—C14 119.48 (15) O361—N36—C36 118.03 (14)

C22—N1—C1—C2 143.41 (13) C23—C24—C25—C26 −0.6 (3)

C12—N1—C1—C2 −63.50 (16) C24—C25—C26—C21 2.7 (3)

N1—C1—C2—C3 −72.28 (15) C22—C21—C26—C25 −1.8 (2)

C1—C2—C3—N4 161.37 (11) S1—C21—C26—C25 174.89 (13)

C2—C3—N4—C6 50.38 (16) O31—C31—C32—C33 −178.44 (17)

C2—C3—N4—C5 174.58 (12) C36—C31—C32—C33 1.3 (2)

C21—S1—C11—C16 −147.01 (12) O31—C31—C32—N32 2.4 (2)

C21—S1—C11—C12 35.43 (12) C36—C31—C32—N32 −177.84 (14)

C16—C11—C12—C13 0.8 (2) C31—C32—C33—C34 0.2 (2)

S1—C11—C12—C13 178.34 (10) N32—C32—C33—C34 179.31 (14)

C16—C11—C12—N1 −178.73 (13) C32—C33—C34—C35 −1.1 (2)

S1—C11—C12—N1 −1.20 (18) C32—C33—C34—N34 177.57 (14)

C22—N1—C12—C13 136.69 (14) C33—C34—C35—C36 0.5 (2)

C1—N1—C12—C13 −16.58 (19) N34—C34—C35—C36 −178.22 (13)

C22—N1—C12—C11 −43.79 (18) C34—C35—C36—N36 179.91 (14)

C1—N1—C12—C11 162.94 (13) C34—C35—C36—C31 1.2 (2)

C11—C12—C13—C14 −1.5 (2) O31—C31—C36—C35 177.76 (17)

N1—C12—C13—C14 178.01 (14) C32—C31—C36—C35 −2.0 (2)

C12—C13—C14—C15 0.9 (2) O31—C31—C36—N36 −0.9 (3)

C13—C14—C15—C16 0.5 (2) C32—C31—C36—N36 179.37 (14)

C14—C15—C16—C11 −1.2 (2) C33—C32—N32—O321 148.6 (2)

C12—C11—C16—C15 0.5 (2) C31—C32—N32—O321 −32.2 (3)

S1—C11—C16—C15 −176.99 (12) C33—C32—N32—O323 −160.1 (5)

C11—S1—C21—C26 147.76 (13) C31—C32—N32—O323 19.1 (5)

C11—S1—C21—C22 −35.51 (13) C33—C32—N32—O324 43.9 (4)

C26—C21—C22—C23 −1.2 (2) C31—C32—N32—O324 −136.9 (3)

S1—C21—C22—C23 −177.87 (11) C33—C32—N32—O322 −35.0 (2)

C26—C21—C22—N1 178.02 (13) C31—C32—N32—O322 144.19 (18)

S1—C21—C22—N1 1.30 (18) C35—C34—N34—O342 −0.9 (2)

C12—N1—C22—C23 −137.19 (14) C33—C34—N34—O342 −179.68 (15)

C1—N1—C22—C23 15.9 (2) C35—C34—N34—O341 178.16 (15)

C12—N1—C22—C21 43.67 (18) C33—C34—N34—O341 −0.6 (2)

C1—N1—C22—C21 −163.20 (13) C35—C36—N36—O362 177.37 (17)

(10)

supporting information

N1—C22—C23—C24 −175.93 (14) C35—C36—N36—O361 1.5 (2)

C22—C23—C24—C25 −2.4 (3) C31—C36—N36—O361 −179.72 (17)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N4—H4···O31i _{0.93 (2)} _{1.78 (2)} _{2.6735 (17)} _{162 (2)}

N4—H4···O362i _{0.93 (2)} _{2.41 (2)} _{2.9804 (18)} _{119.8 (17)}

C2—H2B···O322ii _0.99 _2.53 _{3.280 (2)} ₁₃₂

C5—H5A···O362i _0.98 _2.46 _{3.008 (2)} ₁₁₅

C5—H5C···O341 0.98 2.57 3.439 (2) 148

C6—H6B···O341 0.98 2.50 3.389 (2) 150

C13—H13···O321ii _0.95 _2.59 _{3.336 (3)} ₁₃₆