Different acid-base behaviour of a pyrazole and an isoxazole with organic acids: crystal and mol­ecular structures of the salt 3-(4-fluoro­phen­yl)-1H-pyrazolium 2,4,6-tri­nitro­phenolate and of the cocrystal 4-amino-N-(3,4-dimethyl-1,2-oxazol-5-yl)benzene­sulfonamide-3,5-di­nitro­benzoic acid (1/1)

Pyrazole and isoxazole rings differ only in the notional replacement of a potential hydrogen-bond-donor NH unit in pyrazole by a potential hydrogen-bond-acceptor O atom in isoxazole. It is thus of inter­est to compare the hydro­gen-bonding characteristics of these rings. (4-Fluoro­phen­yl)pyrazole undergoes protonation in the presence of 2,4,6-tri­nitro­phenol to yield the salt 3-(4-fluoro­phen­yl)-1H-pyrazolium 2,4,6-tri­nitro­phenolate, C₉H₈FN₂⁺·C₆H₂N₃O₇^-, (I), whereas there is no proton transfer between 4-amino-N-(3,4-dimethyl-1,2-oxazol-5-yl)benzene­sulfonamide and 3,5-di­nitro­benzoic acid, whose reaction gives the 1:1 cocrystal, C₁₁H₁₃N₃O₃S·C₇H₄N₂O₆, (II). The bond lengths in salt (I) provide evidence for aromatic-type delocalization in the pyrazolium ring and for extensive delocalization of the negative charge into the ring of the tri­nitro­phenolate anion. The O atoms of one of the nitro groups in the tri­nitro­phenolate anion are disordered over two sets of atomic sites having occupancies of 0.571 (6) and 0.429 (6), but all of the other substituents on the carbocyclic rings are fully ordered. The ions in salt (I) are linked by an extensive series of N-H...O hydrogen bonds to form a three-dimensional framework structure, and in cocrystal (II), the mol­ecular components are linked by a combination of O-H...N and N-H...O hydrogen bonds to form complex bilayers. Comparisons are made with some related compounds.

Computing details

For both compounds, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).

(I) 3-(4-Fluorophenyl)-1H-pyrazolium 2,4,6-trinitrophenolate

Crystal data

C9H8FN2^+·C6H2N3O7^−	F(000) = 800
Mr = 391.28	Dx = 1.630 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.8062 (7) Å	Cell parameters from 5289 reflections
b = 8.0061 (4) Å	θ = 3.4–32.9°
c = 17.6442 (12) Å	µ = 0.14 mm^−1
β = 107.009 (7)°	T = 298 K
V = 1594.81 (17) Å^3	Plate, colourless
Z = 4	0.32 × 0.26 × 0.18 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer	2749 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	Rint = 0.022
φ and ω scans	θmax = 27.6°, θmin = 3.4°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −15→14
Tmin = 0.811, Tmax = 0.975	k = −10→9
8339 measured reflections	l = −22→19
3682 independent reflections

Refinement

Refinement on F^2	3 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0585P)^2 + 0.5219P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3682 reflections	Δρmax = 0.24 e Å^−3
266 parameters	Δρmin = −0.27 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.45090 (15)	0.9297 (2)	0.64942 (10)	0.0442 (4)
H1	0.517 (2)	0.900 (3)	0.6826 (14)	0.053*
N2	0.42595 (13)	0.89427 (18)	0.57182 (8)	0.0351 (3)
H2	0.4737 (17)	0.830 (2)	0.5543 (12)	0.042*
C3	0.31937 (14)	0.9597 (2)	0.53368 (10)	0.0337 (4)
C4	0.27772 (17)	1.0378 (2)	0.59112 (12)	0.0470 (5)
H4	0.2060	1.0936	0.5827	0.056*
C5	0.36247 (19)	1.0166 (3)	0.66209 (13)	0.0517 (5)
H5	0.3588	1.0561	0.7109	0.062*
C21	0.26423 (14)	0.9447 (2)	0.44824 (10)	0.0340 (4)
C22	0.15299 (16)	1.0159 (3)	0.41447 (13)	0.0484 (5)
H22	0.1166	1.0746	0.4464	0.058*
C23	0.09641 (18)	1.0007 (3)	0.33485 (14)	0.0588 (6)
H23	0.0220	1.0478	0.3128	0.071*
C24	0.15166 (18)	0.9149 (3)	0.28859 (12)	0.0531 (5)
F24	0.09605 (12)	0.8956 (2)	0.21034 (8)	0.0848 (5)
C25	0.26152 (16)	0.8453 (2)	0.31890 (11)	0.0448 (4)
H25	0.2975	0.7886	0.2861	0.054*
C26	0.31796 (15)	0.8607 (2)	0.39906 (10)	0.0370 (4)
H26	0.3928	0.8142	0.4203	0.044*
C31	0.64472 (14)	0.6137 (2)	0.51076 (10)	0.0316 (4)
C32	0.73691 (14)	0.5783 (2)	0.58397 (10)	0.0335 (4)
C33	0.83668 (14)	0.4867 (2)	0.58817 (11)	0.0372 (4)
H33	0.8935	0.4694	0.6367	0.045*
C34	0.85189 (14)	0.4203 (2)	0.51957 (12)	0.0378 (4)
C35	0.76991 (15)	0.4458 (2)	0.44685 (11)	0.0376 (4)
H35	0.7819	0.4010	0.4012	0.045*
C36	0.67049 (14)	0.5379 (2)	0.44269 (10)	0.0337 (4)
O31	0.55522 (11)	0.70057 (17)	0.50515 (7)	0.0453 (3)
N32	0.72553 (13)	0.6379 (2)	0.65910 (9)	0.0420 (4)
O32	0.64110 (14)	0.7228 (2)	0.66069 (9)	0.0695 (5)
O33	0.79987 (14)	0.5978 (3)	0.72004 (9)	0.0797 (6)
N34	0.95594 (14)	0.3193 (2)	0.52412 (12)	0.0505 (4)
O34	1.03272 (13)	0.3075 (2)	0.58793 (12)	0.0700 (5)
O35	0.96177 (15)	0.2502 (2)	0.46356 (12)	0.0758 (5)
N36A	0.58888 (14)	0.5598 (2)	0.36370 (9)	0.0436 (4)	0.571 (6)
O36A	0.6285 (4)	0.5437 (8)	0.3059 (2)	0.0688 (12)	0.571 (6)
O37A	0.4858 (3)	0.5984 (7)	0.3557 (4)	0.0602 (13)	0.571 (6)
N36B	0.58888 (14)	0.5598 (2)	0.36370 (9)	0.0436 (4)	0.429 (6)
O36B	0.6010 (6)	0.4635 (8)	0.3109 (3)	0.0688 (12)	0.429 (6)
O37B	0.5094 (5)	0.6619 (7)	0.3499 (5)	0.0602 (13)	0.429 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0479 (9)	0.0516 (9)	0.0343 (8)	0.0060 (8)	0.0137 (7)	−0.0032 (7)
N2	0.0368 (8)	0.0377 (8)	0.0327 (8)	0.0047 (6)	0.0128 (6)	−0.0025 (6)
C3	0.0335 (8)	0.0287 (8)	0.0424 (10)	0.0003 (7)	0.0167 (7)	0.0014 (7)
C4	0.0455 (10)	0.0486 (11)	0.0536 (12)	0.0086 (9)	0.0251 (9)	−0.0028 (9)
C5	0.0601 (12)	0.0564 (12)	0.0461 (12)	0.0047 (10)	0.0273 (10)	−0.0096 (9)
C21	0.0306 (8)	0.0306 (8)	0.0420 (10)	−0.0005 (7)	0.0124 (7)	0.0036 (7)
C22	0.0369 (10)	0.0504 (11)	0.0593 (13)	0.0105 (8)	0.0164 (9)	0.0040 (9)
C23	0.0364 (10)	0.0731 (15)	0.0608 (14)	0.0152 (10)	0.0045 (9)	0.0116 (11)
C24	0.0437 (11)	0.0689 (14)	0.0398 (11)	−0.0008 (10)	0.0012 (8)	0.0094 (10)
F24	0.0633 (9)	0.1312 (14)	0.0455 (8)	0.0131 (8)	−0.0064 (6)	0.0065 (8)
C25	0.0424 (10)	0.0513 (11)	0.0413 (11)	0.0027 (9)	0.0131 (8)	0.0033 (8)
C26	0.0318 (8)	0.0412 (9)	0.0382 (10)	0.0040 (7)	0.0106 (7)	0.0042 (7)
C31	0.0294 (8)	0.0315 (8)	0.0351 (9)	0.0030 (6)	0.0113 (6)	0.0017 (7)
C32	0.0315 (8)	0.0351 (8)	0.0353 (9)	−0.0006 (7)	0.0120 (7)	0.0036 (7)
C33	0.0280 (8)	0.0363 (9)	0.0469 (10)	0.0002 (7)	0.0103 (7)	0.0104 (7)
C34	0.0283 (8)	0.0321 (8)	0.0575 (12)	0.0039 (7)	0.0194 (8)	0.0062 (8)
C35	0.0367 (9)	0.0337 (8)	0.0480 (11)	0.0008 (7)	0.0213 (8)	−0.0010 (7)
C36	0.0330 (8)	0.0335 (8)	0.0353 (9)	0.0015 (7)	0.0113 (7)	0.0003 (7)
O31	0.0401 (7)	0.0576 (8)	0.0362 (7)	0.0202 (6)	0.0081 (5)	−0.0028 (6)
N32	0.0384 (8)	0.0534 (9)	0.0344 (8)	0.0043 (7)	0.0111 (6)	0.0051 (7)
O32	0.0710 (11)	0.0965 (13)	0.0410 (9)	0.0406 (9)	0.0165 (7)	−0.0018 (8)
O33	0.0589 (10)	0.1370 (16)	0.0371 (8)	0.0312 (10)	0.0045 (7)	0.0060 (9)
N34	0.0355 (8)	0.0414 (9)	0.0811 (14)	0.0081 (7)	0.0272 (9)	0.0111 (9)
O34	0.0369 (8)	0.0721 (11)	0.0955 (14)	0.0185 (7)	0.0107 (8)	0.0124 (9)
O35	0.0672 (11)	0.0799 (12)	0.0924 (14)	0.0338 (9)	0.0423 (10)	0.0006 (10)
N36A	0.0422 (8)	0.0502 (9)	0.0388 (9)	0.0063 (7)	0.0123 (7)	−0.0062 (7)
O36A	0.063 (2)	0.110 (4)	0.0376 (11)	0.021 (2)	0.0213 (11)	0.000 (2)
O37A	0.0471 (15)	0.080 (3)	0.0460 (13)	0.0188 (19)	0.0016 (13)	−0.014 (2)
N36B	0.0422 (8)	0.0502 (9)	0.0388 (9)	0.0063 (7)	0.0123 (7)	−0.0062 (7)
O36B	0.063 (2)	0.110 (4)	0.0376 (11)	0.021 (2)	0.0213 (11)	0.000 (2)
O37B	0.0471 (15)	0.080 (3)	0.0460 (13)	0.0188 (19)	0.0016 (13)	−0.014 (2)

Geometric parameters (Å, º)

N1—N2	1.344 (2)	C26—H26	0.9300
N1—H1	0.86 (2)	C31—C32	1.453 (2)
N2—C3	1.347 (2)	C32—C33	1.371 (2)
N2—H2	0.88 (2)	C33—C34	1.381 (3)
C3—C4	1.397 (2)	C34—C35	1.378 (3)
C3—C21	1.462 (2)	C35—C36	1.370 (2)
C4—C5	1.366 (3)	C36—C31	1.455 (2)
C4—H4	0.9300	C31—O31	1.2447 (19)
C5—N1	1.327 (2)	C32—N32	1.452 (2)
C5—H5	0.9300	C34—N34	1.453 (2)
C21—C26	1.389 (2)	C36—N36A	1.455 (2)
C21—C22	1.395 (2)	C33—H33	0.9300
C22—C23	1.373 (3)	C35—H35	0.9300
C22—H22	0.9300	N32—O32	1.213 (2)
C23—C24	1.369 (3)	N32—O33	1.215 (2)
C23—H23	0.9300	N34—O34	1.225 (2)
C24—F24	1.353 (2)	N34—O35	1.223 (3)
C24—C25	1.369 (3)	N36A—O36A	1.248 (3)
C25—C26	1.381 (3)	N36A—O37A	1.223 (3)
C25—H25	0.9300
C5—N1—N2	109.49 (17)	C25—C26—C21	120.73 (16)
C5—N1—H1	129.2 (15)	C25—C26—H26	119.6
N2—N1—H1	121.3 (15)	C21—C26—H26	119.6
N1—N2—C3	108.72 (14)	O31—C31—C32	125.26 (15)
N1—N2—H2	120.5 (13)	O31—C31—C36	123.03 (15)
C3—N2—H2	130.5 (13)	C32—C31—C36	111.69 (14)
N2—C3—C4	106.69 (16)	C33—C32—N32	115.73 (15)
N2—C3—C21	123.52 (15)	C33—C32—C31	124.09 (16)
C4—C3—C21	129.79 (16)	N32—C32—C31	120.17 (14)
C5—C4—C3	106.89 (17)	C32—C33—C34	119.25 (16)
C5—C4—H4	126.6	C32—C33—H33	120.4
C3—C4—H4	126.6	C34—C33—H33	120.4
N1—C5—C4	108.21 (18)	C35—C34—C33	121.54 (16)
N1—C5—H5	125.9	C35—C34—N34	119.09 (17)
C4—C5—H5	125.9	C33—C34—N34	119.37 (17)
C26—C21—C22	118.41 (17)	C36—C35—C34	119.15 (17)
C26—C21—C3	122.48 (15)	C36—C35—H35	120.4
C22—C21—C3	119.11 (16)	C34—C35—H35	120.4
C23—C22—C21	121.08 (19)	C35—C36—N36A	115.66 (16)
C23—C22—H22	119.5	C35—C36—C31	124.27 (16)
C21—C22—H22	119.5	N36A—C36—C31	120.07 (14)
C24—C23—C22	118.70 (18)	O32—N32—O33	120.86 (17)
C24—C23—H23	120.7	O32—N32—C32	120.08 (15)
C22—C23—H23	120.7	O33—N32—C32	119.02 (16)
F24—C24—C25	118.3 (2)	O35—N34—O34	123.53 (18)
F24—C24—C23	119.46 (19)	O35—N34—C34	117.78 (19)
C25—C24—C23	122.25 (19)	O34—N34—C34	118.69 (19)
C24—C25—C26	118.81 (18)	O37A—N36A—O36A	122.0 (4)
C24—C25—H25	120.6	O37A—N36A—C36	120.0 (3)
C26—C25—H25	120.6	O36A—N36A—C36	118.0 (3)
C5—N1—N2—C3	0.1 (2)	N32—C32—C33—C34	177.64 (15)
N1—N2—C3—C4	−0.30 (19)	C31—C32—C33—C34	−1.0 (3)
N1—N2—C3—C21	−179.91 (15)	C32—C33—C34—C35	0.9 (3)
N2—C3—C4—C5	0.4 (2)	C32—C33—C34—N34	−178.34 (15)
C21—C3—C4—C5	179.98 (17)	C33—C34—C35—C36	−0.6 (3)
N2—N1—C5—C4	0.2 (2)	N34—C34—C35—C36	178.61 (15)
C3—C4—C5—N1	−0.4 (2)	C34—C35—C36—N36A	179.64 (15)
N2—C3—C21—C26	0.1 (3)	C34—C35—C36—C31	0.5 (3)
C4—C3—C21—C26	−179.45 (18)	O31—C31—C36—C35	178.05 (17)
N2—C3—C21—C22	179.46 (16)	C32—C31—C36—C35	−0.5 (2)
C4—C3—C21—C22	−0.1 (3)	O31—C31—C36—N36A	−1.1 (3)
C26—C21—C22—C23	1.3 (3)	C32—C31—C36—N36A	−179.68 (14)
C3—C21—C22—C23	−178.10 (18)	C33—C32—N32—O32	178.53 (17)
C21—C22—C23—C24	−0.4 (3)	C31—C32—N32—O32	−2.8 (3)
C22—C23—C24—F24	178.6 (2)	C33—C32—N32—O33	−3.4 (3)
C22—C23—C24—C25	−0.6 (4)	C31—C32—N32—O33	175.31 (18)
F24—C24—C25—C26	−178.46 (18)	C35—C34—N34—O35	−5.5 (3)
C23—C24—C25—C26	0.7 (3)	C33—C34—N34—O35	173.70 (18)
C24—C25—C26—C21	0.2 (3)	C35—C34—N34—O34	174.59 (17)
C22—C21—C26—C25	−1.2 (3)	C33—C34—N34—O34	−6.2 (3)
C3—C21—C26—C25	178.20 (16)	C35—C36—N36A—O37A	160.0 (3)
O31—C31—C32—C33	−177.73 (17)	C31—C36—N36A—O37A	−20.8 (4)
C36—C31—C32—C33	0.8 (2)	C35—C36—N36A—O36A	−22.4 (4)
O31—C31—C32—N32	3.7 (3)	C31—C36—N36A—O36A	156.8 (4)
C36—C31—C32—N32	−177.78 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O32	0.86 (2)	2.15 (2)	2.750 (2)	126 (2)
N1—H1···O36A^i	0.86 (2)	2.24 (2)	2.946 (4)	140 (2)
N1—H1···O36B^i	0.86 (2)	2.45 (2)	3.006 (6)	123 (2)
N2—H2···O31	0.883 (19)	1.800 (19)	2.677 (2)	172 (2)
N2—H2···O32	0.883 (19)	2.45 (2)	2.910 (2)	113.0 (16)
C22—H22···O35^ii	0.93	2.39	3.242 (3)	151
C26—H26···O31	0.93	2.25	3.151 (2)	162

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x−1, y+1, z.

(II) 4-Amino-N-(3,4-dimethyl-1,2-oxazol-5-yl)benzenesulfonamide–3,5-dinitrobenzoic acid (1/1)

Crystal data

C11H13N3O3S·C7H4N2O6	Z = 2
Mr = 479.43	F(000) = 496
Triclinic, P1	Dx = 1.566 Mg m^−3
a = 7.8189 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.6727 (5) Å	Cell parameters from 4665 reflections
c = 15.9304 (10) Å	θ = 3.3–29.3°
α = 96.439 (5)°	µ = 0.22 mm^−1
β = 94.458 (5)°	T = 298 K
γ = 107.477 (5)°	Plate, colourless
V = 1016.79 (11) Å^3	0.44 × 0.41 × 0.22 mm

Data collection

Agilent Xcalibur (Eos, Gemini) diffractometer	3286 reflections with I > 2σ(I)
Detector resolution: 16.0416 pixels mm^-1	Rint = 0.029
φ and ω scans	θmax = 27.6°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −10→10
Tmin = 0.796, Tmax = 0.952	k = −11→11
8229 measured reflections	l = −20→14
4476 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.130	w = 1/[σ^2(Fo^2) + (0.0562P)^2 + 0.2274P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
4476 reflections	Δρmax = 0.26 e Å^−3
312 parameters	Δρmin = −0.31 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C11	0.0863 (3)	0.2500 (3)	0.22330 (13)	0.0331 (5)
C12	0.1458 (3)	0.1343 (3)	0.26054 (14)	0.0357 (5)
H12	0.2169	0.1640	0.3129	0.043*
C13	0.0994 (3)	−0.0235 (3)	0.21983 (14)	0.0384 (5)
H13	0.1384	−0.1002	0.2454	0.046*
C14	−0.0055 (3)	−0.0705 (3)	0.14063 (14)	0.0365 (5)
C15	−0.0620 (3)	0.0477 (3)	0.10351 (14)	0.0412 (5)
H15	−0.1299	0.0193	0.0503	0.049*
C16	−0.0186 (3)	0.2050 (3)	0.14441 (14)	0.0386 (5)
H16	−0.0593	0.2814	0.1194	0.046*
N14	−0.0453 (3)	−0.2264 (3)	0.10036 (16)	0.0551 (6)
H141	−0.021 (4)	−0.298 (4)	0.1286 (19)	0.066*
H142	−0.126 (4)	−0.248 (3)	0.056 (2)	0.066*
S1	0.14181 (7)	0.44876 (7)	0.27622 (4)	0.03740 (17)
O1	0.1113 (2)	0.55430 (19)	0.21761 (11)	0.0489 (4)
O2	0.3125 (2)	0.4877 (2)	0.32574 (12)	0.0513 (5)
N1	−0.0098 (3)	0.4501 (2)	0.34254 (12)	0.0391 (5)
H1	−0.082 (3)	0.491 (3)	0.3273 (16)	0.047*
O21	0.0884 (2)	0.30401 (19)	0.43847 (10)	0.0422 (4)
N22	0.0219 (3)	0.2112 (2)	0.50365 (12)	0.0451 (5)
C23	−0.1429 (3)	0.2144 (3)	0.50733 (14)	0.0396 (5)
C24	−0.1958 (3)	0.3048 (2)	0.44689 (13)	0.0348 (5)
C25	−0.0470 (3)	0.3545 (2)	0.40695 (13)	0.0320 (5)
C26	−0.2531 (4)	0.1278 (3)	0.56999 (17)	0.0625 (8)
H26A	−0.3518	0.0384	0.5403	0.094*
H26B	−0.2993	0.2022	0.6032	0.094*
H26C	−0.1792	0.0868	0.6068	0.094*
C27	−0.3720 (3)	0.3375 (3)	0.43405 (18)	0.0537 (7)
H27A	−0.3929	0.3931	0.4859	0.081*
H27B	−0.4673	0.2359	0.4182	0.081*
H27C	−0.3692	0.4044	0.3898	0.081*
C31	0.3891 (3)	0.2031 (2)	0.76112 (13)	0.0309 (4)
C32	0.3955 (3)	0.0457 (2)	0.76450 (13)	0.0329 (5)
H32A	0.3381	−0.0382	0.7204	0.040*
C33	0.4888 (3)	0.0169 (2)	0.83484 (14)	0.0332 (5)
C34	0.5825 (3)	0.1383 (3)	0.90009 (14)	0.0344 (5)
H34	0.6476	0.1168	0.9463	0.041*
C35	0.5749 (3)	0.2934 (2)	0.89357 (13)	0.0327 (5)
C36	0.4776 (3)	0.3284 (3)	0.82656 (13)	0.0323 (5)
H36	0.4712	0.4334	0.8252	0.039*
C37	0.2815 (3)	0.2427 (3)	0.68944 (14)	0.0351 (5)
O31	0.2330 (2)	0.3625 (2)	0.69782 (11)	0.0523 (5)
O32	0.2466 (3)	0.1367 (2)	0.62014 (11)	0.0531 (5)
H32	0.182 (4)	0.169 (4)	0.581 (2)	0.080*
N33	0.4881 (3)	−0.1510 (2)	0.84299 (14)	0.0462 (5)
O33	0.4116 (3)	−0.2583 (2)	0.78483 (14)	0.0687 (6)
O34	0.5655 (3)	−0.1716 (2)	0.90861 (13)	0.0732 (6)
N35	0.6808 (3)	0.4275 (2)	0.95992 (12)	0.0426 (5)
O35	0.7720 (3)	0.3964 (2)	1.01676 (13)	0.0732 (6)
O36	0.6726 (3)	0.5629 (2)	0.95441 (13)	0.0725 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0356 (11)	0.0359 (11)	0.0303 (11)	0.0139 (9)	0.0040 (9)	0.0078 (8)
C12	0.0432 (12)	0.0385 (12)	0.0283 (11)	0.0176 (10)	−0.0001 (9)	0.0058 (9)
C13	0.0504 (13)	0.0389 (12)	0.0327 (12)	0.0223 (10)	0.0067 (10)	0.0081 (9)
C14	0.0392 (12)	0.0386 (12)	0.0311 (12)	0.0115 (10)	0.0082 (9)	0.0020 (9)
C15	0.0400 (12)	0.0550 (15)	0.0276 (12)	0.0158 (11)	−0.0036 (10)	0.0046 (10)
C16	0.0398 (12)	0.0494 (14)	0.0336 (12)	0.0210 (11)	0.0051 (10)	0.0143 (10)
N14	0.0672 (15)	0.0457 (13)	0.0466 (14)	0.0152 (11)	−0.0023 (11)	−0.0051 (10)
S1	0.0404 (3)	0.0322 (3)	0.0422 (3)	0.0134 (2)	0.0053 (2)	0.0102 (2)
O1	0.0624 (11)	0.0398 (9)	0.0540 (11)	0.0214 (8)	0.0169 (9)	0.0229 (8)
O2	0.0391 (9)	0.0450 (10)	0.0656 (12)	0.0108 (7)	−0.0038 (8)	0.0031 (8)
N1	0.0475 (11)	0.0404 (11)	0.0403 (11)	0.0265 (9)	0.0067 (9)	0.0144 (8)
O21	0.0517 (9)	0.0477 (9)	0.0347 (9)	0.0274 (8)	−0.0027 (7)	0.0093 (7)
N22	0.0647 (14)	0.0442 (11)	0.0292 (10)	0.0227 (10)	−0.0070 (9)	0.0099 (8)
C23	0.0539 (14)	0.0338 (12)	0.0272 (11)	0.0116 (10)	−0.0066 (10)	0.0017 (9)
C24	0.0417 (12)	0.0294 (11)	0.0299 (11)	0.0085 (9)	−0.0047 (9)	0.0037 (8)
C25	0.0436 (12)	0.0291 (10)	0.0249 (10)	0.0175 (9)	−0.0058 (9)	−0.0004 (8)
C26	0.077 (2)	0.0586 (17)	0.0458 (16)	0.0085 (14)	−0.0017 (14)	0.0223 (13)
C27	0.0454 (14)	0.0638 (17)	0.0552 (17)	0.0183 (12)	0.0037 (12)	0.0204 (13)
C31	0.0312 (11)	0.0339 (11)	0.0310 (11)	0.0136 (9)	0.0027 (9)	0.0098 (8)
C32	0.0356 (11)	0.0315 (11)	0.0324 (12)	0.0132 (9)	0.0007 (9)	0.0018 (8)
C33	0.0370 (11)	0.0281 (11)	0.0397 (12)	0.0155 (9)	0.0064 (9)	0.0106 (9)
C34	0.0389 (12)	0.0361 (12)	0.0333 (12)	0.0180 (9)	0.0013 (9)	0.0116 (9)
C35	0.0337 (11)	0.0343 (11)	0.0299 (11)	0.0123 (9)	−0.0025 (9)	0.0035 (8)
C36	0.0360 (11)	0.0309 (11)	0.0336 (11)	0.0141 (9)	0.0028 (9)	0.0102 (8)
C37	0.0382 (12)	0.0360 (12)	0.0328 (12)	0.0149 (9)	−0.0019 (9)	0.0072 (9)
O31	0.0664 (11)	0.0470 (10)	0.0504 (11)	0.0339 (9)	−0.0141 (9)	0.0043 (8)
O32	0.0754 (13)	0.0552 (11)	0.0341 (10)	0.0366 (10)	−0.0156 (9)	−0.0017 (8)
N33	0.0565 (13)	0.0334 (11)	0.0551 (14)	0.0214 (10)	0.0060 (11)	0.0130 (10)
O33	0.0911 (15)	0.0325 (10)	0.0772 (15)	0.0214 (10)	−0.0127 (12)	−0.0038 (9)
O34	0.1130 (17)	0.0516 (12)	0.0670 (14)	0.0421 (12)	−0.0082 (12)	0.0253 (10)
N35	0.0502 (12)	0.0380 (11)	0.0383 (11)	0.0163 (9)	−0.0092 (9)	0.0023 (8)
O35	0.0926 (15)	0.0579 (12)	0.0622 (13)	0.0308 (11)	−0.0433 (12)	−0.0049 (9)
O36	0.1039 (16)	0.0327 (10)	0.0714 (14)	0.0242 (10)	−0.0381 (12)	−0.0068 (8)

Geometric parameters (Å, º)

C11—C16	1.393 (3)	C26—H26A	0.9600
C11—C12	1.395 (3)	C26—H26B	0.9600
C11—S1	1.743 (2)	C26—H26C	0.9600
C12—C13	1.376 (3)	C27—H27A	0.9600
C12—H12	0.9300	C27—H27B	0.9600
C13—C14	1.398 (3)	C27—H27C	0.9600
C13—H13	0.9300	C31—C32	1.387 (3)
C14—N14	1.363 (3)	C31—C36	1.389 (3)
C14—C15	1.401 (3)	C31—C37	1.497 (3)
C15—C16	1.375 (3)	C32—C33	1.377 (3)
C15—H15	0.9300	C32—H32A	0.9300
C16—H16	0.9300	C33—C34	1.378 (3)
N14—H141	0.86 (3)	C34—C35	1.379 (3)
N14—H142	0.88 (3)	C34—H34	0.9300
S1—O2	1.4222 (17)	C35—C36	1.377 (3)
S1—O1	1.4334 (15)	C36—H36	0.9300
S1—N1	1.650 (2)	C37—O31	1.206 (2)
N1—C25	1.385 (3)	C37—O32	1.309 (3)
N1—H1	0.79 (2)	C33—N33	1.475 (3)
O21—N22	1.420 (2)	C35—N35	1.471 (3)
N22—C23	1.303 (3)	O32—H32	0.89 (3)
C23—C24	1.419 (3)	N33—O33	1.211 (3)
C23—C26	1.489 (3)	N33—O34	1.224 (3)
C24—C25	1.348 (3)	N35—O35	1.213 (2)
C24—C27	1.491 (3)	N35—O36	1.208 (2)
C25—O21	1.346 (2)
C16—C11—C12	119.6 (2)	C23—C26—H26A	109.5
C16—C11—S1	120.62 (16)	C23—C26—H26B	109.5
C12—C11—S1	119.78 (16)	H26A—C26—H26B	109.5
C13—C12—C11	120.0 (2)	C23—C26—H26C	109.5
C13—C12—H12	120.0	H26A—C26—H26C	109.5
C11—C12—H12	120.0	H26B—C26—H26C	109.5
C12—C13—C14	121.04 (19)	C24—C27—H27A	109.5
C12—C13—H13	119.5	C24—C27—H27B	109.5
C14—C13—H13	119.5	H27A—C27—H27B	109.5
N14—C14—C13	120.0 (2)	C24—C27—H27C	109.5
N14—C14—C15	121.8 (2)	H27A—C27—H27C	109.5
C13—C14—C15	118.2 (2)	H27B—C27—H27C	109.5
C16—C15—C14	121.1 (2)	C32—C31—C36	120.55 (18)
C16—C15—H15	119.5	C32—C31—C37	121.7 (2)
C14—C15—H15	119.5	C36—C31—C37	117.72 (18)
C15—C16—C11	120.02 (19)	C33—C32—C31	118.3 (2)
C15—C16—H16	120.0	C33—C32—H32A	120.8
C11—C16—H16	120.0	C31—C32—H32A	120.8
C14—N14—H141	118 (2)	C32—C33—C34	123.02 (19)
C14—N14—H142	112.8 (19)	C32—C33—N33	119.6 (2)
H141—N14—H142	125 (3)	C34—C33—N33	117.33 (19)
O2—S1—O1	120.11 (11)	C33—C34—C35	116.71 (19)
O2—S1—N1	107.53 (11)	C33—C34—H34	121.6
O1—S1—N1	103.19 (10)	C35—C34—H34	121.6
O2—S1—C11	108.66 (10)	C36—C35—C34	122.9 (2)
O1—S1—C11	109.45 (10)	C36—C35—N35	118.96 (18)
N1—S1—C11	107.09 (10)	C34—C35—N35	118.15 (18)
C25—N1—S1	125.92 (15)	C35—C36—C31	118.45 (19)
C25—N1—H1	118.1 (19)	C35—C36—H36	120.8
S1—N1—H1	113.8 (19)	C31—C36—H36	120.8
C25—O21—N22	106.43 (17)	O31—C37—O32	125.0 (2)
C23—N22—O21	106.02 (16)	O31—C37—C31	120.9 (2)
N22—C23—C24	112.5 (2)	O32—C37—C31	114.06 (18)
N22—C23—C26	120.0 (2)	C37—O32—H32	108 (2)
C24—C23—C26	127.5 (2)	O33—N33—O34	124.7 (2)
C25—C24—C23	102.63 (19)	O33—N33—C33	118.1 (2)
C25—C24—C27	129.9 (2)	O34—N33—C33	117.1 (2)
C23—C24—C27	127.4 (2)	O36—N35—O35	123.6 (2)
O21—C25—C24	112.40 (18)	O36—N35—C35	117.98 (18)
O21—C25—N1	116.08 (19)	O35—N35—C35	118.42 (19)
C24—C25—N1	131.48 (19)
C16—C11—C12—C13	−0.7 (3)	C27—C24—C25—O21	177.9 (2)
S1—C11—C12—C13	178.71 (17)	C23—C24—C25—N1	−178.5 (2)
C11—C12—C13—C14	0.8 (3)	C27—C24—C25—N1	0.1 (4)
C12—C13—C14—N14	178.0 (2)	S1—N1—C25—O21	25.9 (3)
C12—C13—C14—C15	0.2 (3)	S1—N1—C25—C24	−156.4 (2)
N14—C14—C15—C16	−179.1 (2)	C36—C31—C32—C33	1.1 (3)
C13—C14—C15—C16	−1.2 (3)	C37—C31—C32—C33	−176.31 (19)
C14—C15—C16—C11	1.3 (3)	C31—C32—C33—C34	−2.9 (3)
C12—C11—C16—C15	−0.4 (3)	C31—C32—C33—N33	176.00 (19)
S1—C11—C16—C15	−179.75 (17)	C32—C33—C34—C35	1.9 (3)
C16—C11—S1—O2	−149.50 (18)	N33—C33—C34—C35	−177.03 (19)
C12—C11—S1—O2	31.1 (2)	C33—C34—C35—C36	0.9 (3)
C16—C11—S1—O1	−16.6 (2)	C33—C34—C35—N35	−176.99 (19)
C12—C11—S1—O1	164.04 (17)	C34—C35—C36—C31	−2.6 (3)
C16—C11—S1—N1	94.62 (19)	N35—C35—C36—C31	175.27 (19)
C12—C11—S1—N1	−84.75 (19)	C32—C31—C36—C35	1.5 (3)
O2—S1—N1—C25	−58.4 (2)	C37—C31—C36—C35	179.07 (19)
O1—S1—N1—C25	173.70 (19)	C32—C31—C37—O31	158.1 (2)
C11—S1—N1—C25	58.2 (2)	C36—C31—C37—O31	−19.3 (3)
C25—O21—N22—C23	−0.9 (2)	C32—C31—C37—O32	−21.4 (3)
O21—N22—C23—C24	0.4 (2)	C36—C31—C37—O32	161.1 (2)
O21—N22—C23—C26	−180.0 (2)	C32—C33—N33—O33	3.5 (3)
N22—C23—C24—C25	0.1 (3)	C34—C33—N33—O33	−177.5 (2)
C26—C23—C24—C25	−179.4 (2)	C32—C33—N33—O34	−176.4 (2)
N22—C23—C24—C27	−178.6 (2)	C34—C33—N33—O34	2.6 (3)
C26—C23—C24—C27	1.9 (4)	C36—C35—N35—O36	2.7 (3)
N22—O21—C25—C24	1.0 (2)	C34—C35—N35—O36	−179.3 (2)
N22—O21—C25—N1	179.17 (18)	C36—C35—N35—O35	−177.0 (2)
C23—C24—C25—O21	−0.7 (2)	C34—C35—N35—O35	1.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O31^i	0.79 (2)	2.03 (2)	2.804 (3)	169 (2)
O32—H32···N22	0.89 (3)	1.83 (3)	2.719 (3)	172 (3)
N14—H141···O1^ii	0.86 (3)	2.39 (3)	3.232 (3)	167 (3)
N14—H142···O36^iii	0.87 (3)	2.29 (3)	3.072 (3)	149 (2)
C16—H16···O35^iv	0.93	2.50	3.383 (3)	160

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