2-Nitro-N-(4-pyridinio)benzene­sulfonamidate monohydrate

The title compound, C₁₁H₉N₃O₄S·H₂O, contains both an acid and a base centre and displays a zwitterionic structure. There are two independent mol­ecules and two water mol­ecules in the asymmetric unit. The dihedral angles between the benzene ring and the pyridinium ring are 109.7 (1) and 110.7 (1)°. The dihedral angles between the nitro group and the benzene ring are 116.1 (2) and 116.7 (1)°. The crystal structure is stabilized by N—H...O, O—H...N and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.032
• wR factor = 0.090
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   113.000
            Value of melting point given =     0.000
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.520
           From the CIF: _refine_ls_abs_structure_Flack_su    0.060
PLAT432_ALERT_2_C Short Inter X...Y Contact  O8     ..  C15     ..       3.01 Ang.
PLAT033_ALERT_4_C Flack Parameter Value Deviates from Zero .......       0.52
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT223_ALERT_4_C Large Solvent/Anion  H     Ueq(max)/Ueq(min) ...       3.23 Ratio
PLAT731_ALERT_1_C Bond    Calc     0.92(3), Rep   0.918(10) ......       3.00 su-Ra
              N1   -H1A     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.92(3), Rep   0.918(10) ......       3.00 su-Ra
              N1   -H1A     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     1.85(3), Rep   1.843(11) ......       2.73 su-Ra
              H1A  -O10     1.555   2.746
PLAT736_ALERT_1_C H...A   Calc     2.04(3), Rep   2.042(12) ......       2.50 su-Ra
              H10B -N2      1.555   2.656

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.54
           From the CIF: _reflns_number_total               4633
           Count of symmetry unique reflns         3073
           Completeness (_total/calc)            150.76%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1560
           Fraction of Friedel pairs measured     0.508
           Are heavy atom types Z>Si present        yes
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          9

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

S1. Comment

Organic pyridinium salts have been widely used in the construction of supramolecular architectures (Damiano et al., 2007). As part of our ongoing studies of supramolecular chemistry involving the pyridinium rings (Li et al., 2007), the structure of the title compound was determined by X-ray diffraction. There are two independent molecules and two independent water molecules in the unit cell. In the cations of the title compound the short C—N distance [N2—C1 = 1.367 (3) Å and N5—C12 = 1.365 (3) Å] indicate the slight conjugation of the sulfonamide N with the pyridinium ring (Allen et al., 1987).

The dihedral angles between the benzene ring and the pyridinium ring are 109.7 (1)° and 110.7 (1)° respectively. And the dihedral angles between the nitro group and the benzene ring are 116.1 (2)° and 116.7 (1)° respectively. The crystal structure is stabilized by N—H···O hydrogen bonds.

Related literature

For the uses of organic pyridinium salts, see: Damiano et al. (2007). For zwitterionic forms of N-arylbenzenesulfonamides, see: Li et al. (2007); Yu & Li (2007). For reference geometric data, see: Allen et al. (1987).

S2. Experimental

A solution of 2-nitrobenzenesulfonyl chloride (2.2 g, 10 mmol) in CH₂Cl₂ (10 ml) was added dropwise to a suspension of 4-aminopyridine (0.9 g, 10 mmol) in CH₂Cl₂ (10 ml) at room temperature with stirring. The reaction mixture was stirred overnight. The yellow solid obtained was washed with warm water to obtain the title compound in a yield of 55.7%. A colorless single crystal suitable for X-ray analysis was obtained by slow evaporation of an NaOH (10%) solution at room temperature over a period of a week.

S3. Refinement

The N-bound H atoms were located in a difference map and their coordinates were refined with U_iso(H) = 1.2U_eq(N). The C-bound H atoms were positioned geometrically (C—H = 0.93 Å) and refined as riding with U_iso(H) = 1.2U_eq(C). The Flack test results are ambiguous because of the presence of merohedral twin. The water O-bound H atoms were refined freely, but the O—H distances were restrained to 0.85 (1) Å, and the water HA···HB distance to 1.45 (1) Å.

Computing details

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

Fig. 1. View of the molecule of title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 35% probability level (arbitrary spheres for the H atoms).

2-Nitro-N-(4-pyridinio)benzenesulfonamidate monohydrate

Crystal data

C11H9N3O4S·H2O	F(000) = 616
Mr = 297.29	Dx = 1.557 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 4439 reflections
a = 8.7206 (17) Å	θ = 2.4–27.5°
b = 11.972 (2) Å	µ = 0.28 mm^−1
c = 12.743 (3) Å	T = 113 K
β = 107.65 (3)°	Block, colourless
V = 1267.8 (4) Å^3	0.14 × 0.10 × 0.04 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	4633 independent reflections
Radiation source: rotating anode	3587 reflections with I > 2σ(I)
Confocal monochromator	Rint = 0.033
ω scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	h = −11→11
Tmin = 0.962, Tmax = 0.989	k = −12→15
10348 measured reflections	l = −16→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.090	w = 1/[σ^2(Fo^2) + (0.0539P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.002
4633 reflections	Δρmax = 0.22 e Å^−3
385 parameters	Δρmin = −0.40 e Å^−3
9 restraints	Absolute structure: Flack (1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.52 (6)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S1	0.54299 (7)	0.49945 (5)	0.75574 (5)	0.01423 (14)
S2	1.01577 (7)	0.25356 (5)	0.35546 (5)	0.01307 (14)
O1	0.36887 (19)	0.49815 (17)	0.72910 (14)	0.0177 (4)
O2	0.6116 (2)	0.59540 (15)	0.71745 (16)	0.0187 (4)
O3	0.4219 (3)	0.29003 (18)	0.87441 (18)	0.0318 (5)
O4	0.2777 (2)	0.4008 (2)	0.94108 (18)	0.0326 (5)
O5	0.9524 (2)	0.15286 (15)	0.38857 (15)	0.0165 (4)
O6	1.1904 (2)	0.26159 (18)	0.38501 (16)	0.0182 (4)
O7	1.1373 (3)	0.46983 (18)	0.24125 (19)	0.0334 (5)
O8	1.2807 (2)	0.3638 (2)	0.16880 (18)	0.0371 (6)
N1	1.0324 (3)	0.2999 (2)	0.67719 (19)	0.0185 (5)
N2	0.5920 (2)	0.38299 (18)	0.71702 (19)	0.0146 (5)
N3	0.4050 (3)	0.3727 (2)	0.9245 (2)	0.0217 (5)
N4	0.5077 (3)	0.4240 (2)	0.43389 (18)	0.0179 (5)
N5	0.9564 (2)	0.36491 (18)	0.39696 (18)	0.0141 (5)
N6	1.1564 (3)	0.3888 (2)	0.18846 (19)	0.0230 (6)
C1	0.7414 (3)	0.3615 (2)	0.7078 (2)	0.0132 (5)
C2	0.7644 (3)	0.2549 (2)	0.6690 (2)	0.0167 (5)
H2	0.6813	0.2029	0.6537	0.020*
C3	0.9100 (3)	0.2265 (2)	0.6532 (2)	0.0188 (6)
H3	0.9231	0.1563	0.6259	0.023*
C4	1.0168 (3)	0.4019 (2)	0.7153 (2)	0.0179 (6)
H4	1.1030	0.4513	0.7304	0.021*
C5	0.8752 (3)	0.4350 (2)	0.7325 (2)	0.0169 (6)
H5	0.8672	0.5058	0.7604	0.020*
C6	0.6158 (3)	0.5053 (3)	0.9027 (2)	0.0148 (5)
C7	0.7441 (3)	0.5753 (2)	0.9531 (2)	0.0189 (6)
H7	0.7936	0.6156	0.9100	0.023*
C8	0.7996 (3)	0.5858 (2)	1.0674 (2)	0.0240 (6)
H8	0.8857	0.6329	1.0999	0.029*
C9	0.7271 (3)	0.5264 (3)	1.1326 (2)	0.0245 (7)
H9	0.7656	0.5325	1.2089	0.029*
C10	0.5978 (3)	0.4582 (2)	1.0843 (2)	0.0208 (6)
H10	0.5469	0.4197	1.1277	0.025*
C11	0.5441 (3)	0.4472 (2)	0.9712 (2)	0.0162 (6)
C12	0.8049 (3)	0.3782 (2)	0.4049 (2)	0.0120 (5)
C13	0.7734 (3)	0.4806 (2)	0.4510 (2)	0.0163 (6)
H13	0.8534	0.5347	0.4722	0.020*
C14	0.6264 (3)	0.4998 (2)	0.4642 (2)	0.0181 (5)
H14	0.6078	0.5669	0.4949	0.022*
C15	0.5302 (3)	0.3265 (2)	0.3884 (2)	0.0165 (5)
H15	0.4464	0.2752	0.3672	0.020*
C16	0.6767 (3)	0.3014 (2)	0.3725 (2)	0.0136 (5)
H16	0.6905	0.2339	0.3405	0.016*
C17	0.9459 (3)	0.2526 (2)	0.2084 (2)	0.0145 (5)
C18	0.8167 (3)	0.1850 (2)	0.1552 (2)	0.0179 (6)
H18	0.7672	0.1423	0.1967	0.021*
C19	0.7603 (3)	0.1799 (2)	0.0417 (2)	0.0229 (6)
H19	0.6723	0.1349	0.0080	0.027*
C20	0.8324 (3)	0.2406 (3)	−0.0223 (2)	0.0245 (7)
H20	0.7933	0.2365	−0.0987	0.029*
C21	0.9631 (3)	0.3074 (2)	0.0276 (2)	0.0195 (6)
H21	1.0141	0.3476	−0.0146	0.023*
C22	1.0173 (3)	0.3137 (2)	0.1415 (2)	0.0157 (6)
O9	0.2408 (2)	0.50194 (18)	0.48520 (16)	0.0183 (4)
O10	0.6923 (2)	0.74683 (18)	0.37557 (18)	0.0203 (4)
H1A	1.127 (3)	0.280 (3)	0.665 (3)	0.054 (11)*
H4A	0.411 (2)	0.441 (2)	0.444 (2)	0.021 (8)*
H9A	0.260 (3)	0.500 (3)	0.5558 (8)	0.047 (11)*
H9B	0.160 (2)	0.460 (2)	0.4517 (18)	0.024 (9)*
H10A	0.719 (4)	0.751 (4)	0.4468 (8)	0.11 (2)*
H10B	0.601 (2)	0.780 (3)	0.346 (2)	0.034 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0127 (3)	0.0152 (3)	0.0156 (3)	0.0016 (3)	0.0055 (2)	0.0026 (3)
S2	0.0098 (3)	0.0162 (3)	0.0138 (3)	0.0013 (3)	0.0044 (2)	0.0012 (3)
O1	0.0119 (8)	0.0220 (10)	0.0201 (10)	0.0049 (9)	0.0064 (7)	0.0009 (9)
O2	0.0242 (10)	0.0133 (9)	0.0209 (11)	0.0000 (8)	0.0102 (9)	0.0042 (8)
O3	0.0376 (12)	0.0285 (12)	0.0288 (13)	−0.0115 (10)	0.0095 (10)	−0.0019 (10)
O4	0.0157 (9)	0.0515 (15)	0.0329 (13)	−0.0051 (10)	0.0109 (9)	0.0064 (12)
O5	0.0194 (10)	0.0153 (9)	0.0158 (10)	0.0043 (8)	0.0067 (8)	0.0053 (8)
O6	0.0099 (8)	0.0269 (11)	0.0190 (10)	0.0008 (9)	0.0061 (7)	0.0016 (9)
O7	0.0378 (13)	0.0292 (13)	0.0329 (13)	−0.0111 (10)	0.0101 (11)	−0.0060 (10)
O8	0.0180 (10)	0.0689 (18)	0.0274 (13)	−0.0077 (11)	0.0114 (10)	0.0055 (12)
N1	0.0135 (11)	0.0249 (12)	0.0184 (12)	0.0064 (10)	0.0067 (9)	0.0022 (10)
N2	0.0116 (10)	0.0147 (11)	0.0196 (12)	0.0000 (9)	0.0078 (9)	−0.0001 (9)
N3	0.0209 (12)	0.0263 (14)	0.0176 (13)	−0.0040 (11)	0.0057 (10)	0.0071 (10)
N4	0.0148 (11)	0.0224 (13)	0.0179 (12)	0.0020 (10)	0.0072 (9)	0.0009 (10)
N5	0.0108 (10)	0.0177 (11)	0.0144 (11)	−0.0028 (9)	0.0046 (9)	−0.0035 (9)
N6	0.0193 (12)	0.0354 (15)	0.0146 (12)	−0.0067 (11)	0.0054 (10)	0.0064 (11)
C1	0.0123 (11)	0.0178 (13)	0.0100 (13)	0.0024 (10)	0.0042 (10)	0.0041 (10)
C2	0.0166 (11)	0.0179 (12)	0.0164 (13)	−0.0044 (12)	0.0062 (10)	0.0015 (12)
C3	0.0177 (13)	0.0173 (14)	0.0217 (15)	0.0033 (11)	0.0062 (11)	−0.0025 (11)
C4	0.0133 (12)	0.0214 (14)	0.0181 (14)	−0.0009 (11)	0.0035 (10)	0.0014 (12)
C5	0.0145 (12)	0.0147 (13)	0.0211 (15)	0.0009 (11)	0.0048 (11)	−0.0006 (11)
C6	0.0151 (12)	0.0134 (13)	0.0166 (13)	0.0032 (12)	0.0059 (10)	0.0000 (12)
C7	0.0206 (13)	0.0143 (13)	0.0224 (15)	−0.0036 (11)	0.0075 (12)	0.0006 (11)
C8	0.0252 (15)	0.0225 (15)	0.0224 (16)	−0.0067 (13)	0.0040 (13)	−0.0035 (12)
C9	0.0255 (14)	0.0278 (16)	0.0184 (15)	0.0041 (13)	0.0038 (12)	−0.0030 (12)
C10	0.0236 (14)	0.0239 (15)	0.0178 (15)	0.0041 (12)	0.0106 (12)	0.0047 (12)
C11	0.0103 (11)	0.0175 (13)	0.0217 (15)	0.0013 (10)	0.0062 (11)	0.0027 (11)
C12	0.0152 (12)	0.0125 (12)	0.0083 (12)	0.0024 (10)	0.0038 (10)	0.0017 (10)
C13	0.0168 (12)	0.0141 (13)	0.0183 (14)	−0.0048 (11)	0.0060 (11)	−0.0026 (11)
C14	0.0225 (13)	0.0147 (12)	0.0186 (13)	−0.0018 (12)	0.0087 (11)	−0.0020 (12)
C15	0.0136 (12)	0.0198 (13)	0.0173 (14)	0.0002 (11)	0.0066 (11)	−0.0031 (11)
C16	0.0093 (11)	0.0150 (12)	0.0173 (14)	−0.0026 (10)	0.0051 (10)	−0.0032 (11)
C17	0.0160 (12)	0.0150 (12)	0.0119 (13)	0.0007 (12)	0.0033 (10)	−0.0004 (11)
C18	0.0193 (13)	0.0163 (14)	0.0198 (15)	−0.0015 (12)	0.0084 (12)	0.0037 (12)
C19	0.0262 (15)	0.0190 (15)	0.0202 (15)	−0.0061 (13)	0.0022 (12)	0.0005 (12)
C20	0.0322 (15)	0.0275 (16)	0.0115 (14)	0.0032 (14)	0.0033 (12)	−0.0006 (13)
C21	0.0193 (13)	0.0221 (15)	0.0205 (15)	0.0031 (12)	0.0110 (12)	0.0049 (12)
C22	0.0118 (11)	0.0181 (14)	0.0172 (14)	0.0001 (11)	0.0045 (11)	0.0019 (11)
O9	0.0157 (9)	0.0210 (10)	0.0194 (11)	0.0003 (9)	0.0072 (8)	−0.0056 (10)
O10	0.0170 (9)	0.0221 (10)	0.0215 (11)	0.0022 (9)	0.0057 (8)	0.0043 (10)

Geometric parameters (Å, º)

S1—O2	1.4464 (19)	C6—C11	1.403 (3)
S1—O1	1.4521 (17)	C7—C8	1.394 (4)
S1—N2	1.581 (2)	C7—H7	0.9300
S1—C6	1.787 (3)	C8—C9	1.383 (4)
S2—O5	1.4416 (19)	C8—H8	0.9300
S2—O6	1.4568 (17)	C9—C10	1.377 (4)
S2—N5	1.578 (2)	C9—H9	0.9300
S2—C17	1.787 (3)	C10—C11	1.380 (4)
O3—N3	1.211 (3)	C10—H10	0.9300
O4—N3	1.237 (3)	C12—C16	1.409 (3)
O7—N6	1.221 (3)	C12—C13	1.421 (3)
O8—N6	1.221 (3)	C13—C14	1.362 (3)
N1—C4	1.336 (4)	C13—H13	0.9300
N1—C3	1.345 (3)	C14—H14	0.9300
N1—H1A	0.918 (10)	C15—C16	1.385 (3)
N2—C1	1.367 (3)	C15—H15	0.9300
N3—C11	1.478 (3)	C16—H16	0.9300
N4—C14	1.342 (3)	C17—C18	1.386 (4)
N4—C15	1.344 (3)	C17—C22	1.404 (3)
N4—H4A	0.913 (10)	C18—C19	1.380 (4)
N5—C12	1.365 (3)	C18—H18	0.9300
N6—C22	1.482 (3)	C19—C20	1.379 (4)
C1—C2	1.405 (4)	C19—H19	0.9300
C1—C5	1.419 (4)	C20—C21	1.380 (4)
C2—C3	1.387 (3)	C20—H20	0.9300
C2—H2	0.9300	C21—C22	1.385 (4)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.376 (3)	O9—H9A	0.864 (10)
C4—H4	0.9300	O9—H9B	0.867 (10)
C5—H5	0.9300	O10—H10A	0.867 (10)
C6—C7	1.389 (4)	O10—H10B	0.870 (10)
O2—S1—O1	116.08 (11)	C9—C8—C7	120.3 (3)
O2—S1—N2	114.62 (10)	C9—C8—H8	119.9
O1—S1—N2	106.27 (11)	C7—C8—H8	119.9
O2—S1—C6	105.68 (13)	C10—C9—C8	119.8 (3)
O1—S1—C6	105.03 (11)	C10—C9—H9	120.1
N2—S1—C6	108.55 (13)	C8—C9—H9	120.1
O5—S2—O6	116.29 (11)	C9—C10—C11	119.8 (3)
O5—S2—N5	114.48 (10)	C9—C10—H10	120.1
O6—S2—N5	106.33 (12)	C11—C10—H10	120.1
O5—S2—C17	105.23 (12)	C10—C11—C6	121.9 (3)
O6—S2—C17	105.61 (11)	C10—C11—N3	117.1 (2)
N5—S2—C17	108.33 (12)	C6—C11—N3	121.0 (2)
C4—N1—C3	121.3 (2)	N5—C12—C16	127.0 (2)
C4—N1—H1A	120 (2)	N5—C12—C13	116.4 (2)
C3—N1—H1A	119 (2)	C16—C12—C13	116.6 (2)
C1—N2—S1	123.21 (19)	C14—C13—C12	120.2 (2)
O3—N3—O4	124.9 (3)	C14—C13—H13	119.9
O3—N3—C11	119.3 (2)	C12—C13—H13	119.9
O4—N3—C11	115.9 (2)	N4—C14—C13	121.6 (3)
C14—N4—C15	120.7 (2)	N4—C14—H14	119.2
C14—N4—H4A	118.3 (19)	C13—C14—H14	119.2
C15—N4—H4A	121.0 (19)	N4—C15—C16	120.9 (2)
C12—N5—S2	123.16 (18)	N4—C15—H15	119.6
O7—N6—O8	125.8 (3)	C16—C15—H15	119.6
O7—N6—C22	118.2 (2)	C15—C16—C12	120.0 (2)
O8—N6—C22	115.9 (2)	C15—C16—H16	120.0
N2—C1—C2	116.3 (2)	C12—C16—H16	120.0
N2—C1—C5	127.2 (2)	C18—C17—C22	116.9 (2)
C2—C1—C5	116.5 (2)	C18—C17—S2	119.0 (2)
C3—C2—C1	120.6 (2)	C22—C17—S2	124.1 (2)
C3—C2—H2	119.7	C19—C18—C17	121.1 (2)
C1—C2—H2	119.7	C19—C18—H18	119.4
N1—C3—C2	120.3 (2)	C17—C18—H18	119.4
N1—C3—H3	119.8	C20—C19—C18	121.0 (3)
C2—C3—H3	119.8	C20—C19—H19	119.5
N1—C4—C5	121.1 (3)	C18—C19—H19	119.5
N1—C4—H4	119.5	C19—C20—C21	119.6 (3)
C5—C4—H4	119.5	C19—C20—H20	120.2
C4—C5—C1	120.2 (2)	C21—C20—H20	120.2
C4—C5—H5	119.9	C20—C21—C22	119.1 (3)
C1—C5—H5	119.9	C20—C21—H21	120.4
C7—C6—C11	117.3 (2)	C22—C21—H21	120.4
C7—C6—S1	119.3 (2)	C21—C22—C17	122.3 (2)
C11—C6—S1	123.3 (2)	C21—C22—N6	115.7 (2)
C6—C7—C8	120.9 (3)	C17—C22—N6	122.0 (2)
C6—C7—H7	119.6	H9A—O9—H9B	111.6 (16)
C8—C7—H7	119.6	H10A—O10—H10B	110.7 (16)
O2—S1—N2—C1	36.7 (2)	O4—N3—C11—C10	62.9 (3)
O1—S1—N2—C1	166.3 (2)	O3—N3—C11—C6	64.4 (4)
C6—S1—N2—C1	−81.2 (2)	O4—N3—C11—C6	−116.0 (3)
O5—S2—N5—C12	−36.0 (2)	S2—N5—C12—C16	−4.2 (4)
O6—S2—N5—C12	−165.8 (2)	S2—N5—C12—C13	175.7 (2)
C17—S2—N5—C12	81.0 (2)	N5—C12—C13—C14	−178.5 (2)
S1—N2—C1—C2	−178.07 (19)	C16—C12—C13—C14	1.4 (4)
S1—N2—C1—C5	1.5 (4)	C15—N4—C14—C13	−0.6 (4)
N2—C1—C2—C3	177.8 (2)	C12—C13—C14—N4	−0.4 (4)
C5—C1—C2—C3	−1.9 (4)	C14—N4—C15—C16	0.6 (4)
C4—N1—C3—C2	−0.8 (4)	N4—C15—C16—C12	0.4 (4)
C1—C2—C3—N1	1.4 (4)	N5—C12—C16—C15	178.5 (2)
C3—N1—C4—C5	0.7 (4)	C13—C12—C16—C15	−1.3 (4)
N1—C4—C5—C1	−1.2 (4)	O5—S2—C17—C18	18.6 (2)
N2—C1—C5—C4	−177.8 (3)	O6—S2—C17—C18	142.2 (2)
C2—C1—C5—C4	1.8 (4)	N5—S2—C17—C18	−104.2 (2)
O2—S1—C6—C7	−14.8 (2)	O5—S2—C17—C22	−159.0 (2)
O1—S1—C6—C7	−138.0 (2)	O6—S2—C17—C22	−35.5 (3)
N2—S1—C6—C7	108.6 (2)	N5—S2—C17—C22	78.1 (2)
O2—S1—C6—C11	161.6 (2)	C22—C17—C18—C19	−1.0 (4)
O1—S1—C6—C11	38.3 (3)	S2—C17—C18—C19	−178.8 (2)
N2—S1—C6—C11	−75.0 (2)	C17—C18—C19—C20	1.1 (4)
C11—C6—C7—C8	0.6 (4)	C18—C19—C20—C21	0.1 (4)
S1—C6—C7—C8	177.2 (2)	C19—C20—C21—C22	−1.2 (4)
C6—C7—C8—C9	−0.1 (4)	C20—C21—C22—C17	1.3 (4)
C7—C8—C9—C10	−1.1 (4)	C20—C21—C22—N6	−179.0 (2)
C8—C9—C10—C11	1.7 (4)	C18—C17—C22—C21	−0.2 (4)
C9—C10—C11—C6	−1.2 (4)	S2—C17—C22—C21	177.5 (2)
C9—C10—C11—N3	180.0 (2)	C18—C17—C22—N6	−179.9 (2)
C7—C6—C11—C10	0.0 (4)	S2—C17—C22—N6	−2.2 (4)
S1—C6—C11—C10	−176.4 (2)	O7—N6—C22—C21	116.6 (3)
C7—C6—C11—N3	178.8 (2)	O8—N6—C22—C21	−62.4 (3)
S1—C6—C11—N3	2.4 (4)	O7—N6—C22—C17	−63.7 (4)
O3—N3—C11—C10	−116.7 (3)	O8—N6—C22—C17	117.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O9	0.91 (1)	1.87 (1)	2.764 (3)	167 (3)
O9—H9A···O1	0.86 (1)	2.12 (1)	2.967 (3)	166 (3)
N1—H1A···O10^i	0.92 (1)	1.84 (1)	2.757 (3)	174 (4)
O9—H9B···N5^ii	0.87 (1)	2.04 (1)	2.901 (3)	170 (2)
O9—H9B···O6^ii	0.87 (1)	2.56 (2)	3.125 (3)	123 (2)
O10—H10A···O6^iii	0.87 (1)	2.05 (1)	2.914 (3)	174 (4)
O10—H10B···N2^iv	0.87 (1)	2.04 (1)	2.902 (3)	170 (3)

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