2-Amino-6-methyl-pyridinium 4-methyl-benzene-sulfonate.

In the asymmetric unit of the title salt, C6H9N2 (+)·C7H7O3S(-), there are two independent 2-amino-6-methyl-pyridinium cations and two independent 4-methyl-benzene-sulfonate anions. Both cations are protonated at their pyridine N atoms and their geometries reveal amine-imine tautomerism. In the 4-methyl-benzene-sulfonate anions, the carboxyl-ate groups are twisted out of the benzene ring planes by 88.4 (1) and 86.2 (2)°. In the crystal, the sulfonate O atoms of an anion inter-act with the protonated N atoms and the 2-amino groups of a cation via a pair of N-H⋯O hydrogen bonds, forming an R 2 (2)(8) ring motif. These motifs are connected via N-H⋯O hydrogen bonds, forming chains running along the a-axis direction. Within the chains there are weak C-H⋯O hydrogen bonds present. In addition, aromatic π-π stacking inter-actions [centroid-centroid distances = 3.771 (2), 3.599 (2), 3.599 (2) and 3.497 (2) Å] involving neighbouring chains are also observed.

Related literature

For crystal structures of related pyridine derivatives and their applications, see: Babu et al. (2014 ▶); Rajkumar et al. (2014 ▶); Jin et al. (2005 ▶). For unprotonated amino­pyridine derivatives, see: Anderson et al. (2005 ▶). For the structure of amino-methyl­pyridinium, see: Nahringbauer & Kvick (1977 ▶). For details of sulfonates, see: Onoda et al. (2001 ▶); Baskar Raj et al. (2003 ▶). For applications of benzene­sulfonic acid, see: Wang & Wei (2007 ▶). For simple organic–inorganic salts containing strong inter­molecular hydrogen bonds, see: Sethuram et al. (2013a ▶,b ▶); Shihabuddeen Syed et al. (2013 ▶); Showrilu et al. (2013 ▶); Huq et al. (2013 ▶). For bond-length data, see: Allen et al. (1987 ▶). For studies on the tautomeric forms of 2-amino­pyridine systems, see: Ishikawa et al. (2002 ▶). For graph-set analysis, see: Etter (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C6H9N2 +·C7H7O3S−

M = 280.35

Triclinic,

a = 7.5343 (2) Å

b = 13.6212 (5) Å

c = 13.9887 (5) Å

α = 106.307 (2)°

β = 97.946 (1)°

γ = 92.103 (2)°

V = 1360.31 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 293 K

0.35 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.920, T max = 0.953

32534 measured reflections

6237 independent reflections

4709 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.119

S = 1.06

6237 reflections

372 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.37 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814008587/su2726sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814008587/su2726Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814008587/su2726Isup3.cml

CCDC reference: 997539

Additional supporting information: crystallographic information; 3D view; checkCIF report

C6H9N2+·C7H7O3S−	Z = 4
Mr = 280.35	F(000) = 592
Triclinic, P1	Dx = 1.369 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5343 (2) Å	Cell parameters from 6237 reflections
b = 13.6212 (5) Å	θ = 2.0–28.1°
c = 13.9887 (5) Å	µ = 0.24 mm−1
α = 106.307 (2)°	T = 293 K
β = 97.946 (1)°	Block, colourless
γ = 92.103 (2)°	0.35 × 0.25 × 0.20 mm
V = 1360.31 (8) Å3

Bruker Kappa APEXII CCD diffractometer	6237 independent reflections
Radiation source: fine-focus sealed tube	4709 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and φ scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −9→9
Tmin = 0.920, Tmax = 0.953	k = −17→17
32534 measured reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.119	w = 1/[σ2(Fo2) + (0.0502P)2 + 0.655P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
6237 reflections	Δρmax = 0.33 e Å−3
372 parameters	Δρmin = −0.37 e Å−3
6 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0067 (10)

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.

	x	y	z	Uiso*/Ueq
C1	0.7573 (2)	0.33148 (14)	0.65370 (12)	0.0340 (4)
C2	0.6441 (3)	0.28156 (17)	0.56563 (15)	0.0510 (5)
H2	0.5822	0.2192	0.5594	0.061*
C3	0.6232 (3)	0.32433 (19)	0.48708 (16)	0.0568 (6)
H3	0.5472	0.2897	0.4279	0.068*
C4	0.7111 (3)	0.41650 (17)	0.49332 (15)	0.0450 (5)
C5	0.8219 (3)	0.46630 (18)	0.58213 (16)	0.0525 (5)
H5	0.8818	0.5293	0.5886	0.063*
C6	0.8455 (3)	0.42432 (17)	0.66170 (15)	0.0498 (5)
H6	0.9213	0.4590	0.7209	0.060*
C7	0.6848 (3)	0.4621 (2)	0.40658 (18)	0.0658 (7)
H7A	0.7653	0.4341	0.3602	0.099*
H7B	0.7093	0.5352	0.4315	0.099*
H7C	0.5630	0.4461	0.3727	0.099*
O1	0.63184 (18)	0.20570 (11)	0.73960 (10)	0.0473 (3)
O2	0.80180 (19)	0.36019 (11)	0.84663 (10)	0.0482 (3)
O3	0.95409 (17)	0.22525 (12)	0.74752 (10)	0.0487 (4)
S1	0.78890 (6)	0.27601 (4)	0.75373 (3)	0.03657 (13)
C14	0.1612 (2)	0.16545 (14)	0.35185 (12)	0.0335 (4)
C15	0.2427 (3)	0.07546 (17)	0.34413 (15)	0.0497 (5)
H15	0.2824	0.0416	0.2843	0.060*
C16	0.2656 (3)	0.03531 (17)	0.42480 (16)	0.0532 (5)
H16	0.3205	−0.0258	0.4186	0.064*
C17	0.2085 (3)	0.08433 (16)	0.51461 (14)	0.0427 (4)
C18	0.1255 (3)	0.17361 (18)	0.52060 (15)	0.0522 (5)
H18	0.0851	0.2074	0.5802	0.063*
C19	0.1007 (3)	0.21434 (16)	0.44031 (15)	0.0471 (5)
H19	0.0434	0.2746	0.4459	0.057*
C20	0.2366 (3)	0.0415 (2)	0.60338 (17)	0.0610 (6)
H20A	0.3489	0.0705	0.6450	0.092*
H20B	0.2384	−0.0317	0.5797	0.092*
H20C	0.1403	0.0584	0.6420	0.092*
O4	−0.01417 (17)	0.27792 (12)	0.25616 (11)	0.0496 (4)
O5	0.13593 (18)	0.13852 (11)	0.15948 (9)	0.0471 (3)
O6	0.30945 (17)	0.28838 (11)	0.27035 (10)	0.0453 (3)
S2	0.14592 (6)	0.22210 (4)	0.25238 (3)	0.03629 (13)
C21	0.5816 (2)	0.16145 (13)	0.08860 (13)	0.0327 (4)
C22	0.7160 (2)	0.14424 (14)	0.02675 (14)	0.0368 (4)
H22	0.8366	0.1588	0.0550	0.044*
C23	0.6682 (2)	0.10619 (15)	−0.07461 (14)	0.0407 (4)
H23	0.7569	0.0954	−0.1157	0.049*
C24	0.4871 (2)	0.08288 (14)	−0.11818 (14)	0.0392 (4)
H24	0.4556	0.0568	−0.1877	0.047*
C25	0.3584 (2)	0.09863 (13)	−0.05818 (13)	0.0340 (4)
C26	0.1613 (2)	0.07772 (16)	−0.09541 (15)	0.0452 (5)
H26A	0.1106	0.1403	−0.0996	0.068*
H26B	0.1047	0.0509	−0.0496	0.068*
H26C	0.1419	0.0285	−0.1609	0.068*
N3	0.40875 (19)	0.13737 (11)	0.04333 (11)	0.0325 (3)
N4	0.6161 (2)	0.19844 (15)	0.18808 (12)	0.0445 (4)
C8	0.3602 (2)	0.33977 (13)	0.91967 (13)	0.0334 (4)
C9	0.2264 (2)	0.35815 (15)	0.98204 (14)	0.0393 (4)
H9	0.1055	0.3440	0.9543	0.047*
C10	0.2761 (3)	0.39686 (16)	1.08322 (15)	0.0449 (5)
H10	0.1883	0.4085	1.1248	0.054*
C11	0.4573 (3)	0.41950 (16)	1.12590 (14)	0.0432 (4)
H11	0.4896	0.4463	1.1953	0.052*
C12	0.5854 (2)	0.40210 (13)	1.06520 (13)	0.0348 (4)
C13	0.7826 (3)	0.42082 (16)	1.10162 (15)	0.0460 (5)
H13A	0.8040	0.4713	1.1664	0.069*
H13B	0.8402	0.4453	1.0547	0.069*
H13C	0.8305	0.3580	1.1072	0.069*
N1	0.53289 (19)	0.36343 (11)	0.96397 (11)	0.0326 (3)
N2	0.3236 (2)	0.30260 (14)	0.82019 (13)	0.0449 (4)
H2A	0.2112 (15)	0.2825 (16)	0.7953 (15)	0.050 (6)*
H4B	0.531 (2)	0.2199 (16)	0.2235 (14)	0.050 (6)*
H4A	0.7276 (16)	0.2181 (17)	0.2166 (16)	0.058 (7)*
H2B	0.409 (2)	0.2798 (17)	0.7850 (15)	0.055 (7)*
H1A	0.619 (2)	0.3551 (17)	0.9244 (14)	0.051 (6)*
H3A	0.322 (2)	0.1430 (16)	0.0815 (13)	0.045 (6)*

	U11	U22	U33	U12	U13	U23
C1	0.0265 (8)	0.0429 (10)	0.0285 (8)	0.0011 (7)	0.0034 (6)	0.0043 (7)
C2	0.0497 (12)	0.0530 (12)	0.0423 (11)	−0.0155 (9)	−0.0094 (9)	0.0114 (10)
C3	0.0541 (13)	0.0694 (15)	0.0389 (11)	−0.0148 (11)	−0.0147 (9)	0.0157 (10)
C4	0.0383 (10)	0.0593 (12)	0.0387 (10)	0.0060 (9)	0.0052 (8)	0.0166 (9)
C5	0.0553 (13)	0.0522 (12)	0.0472 (12)	−0.0124 (10)	0.0042 (10)	0.0140 (10)
C6	0.0486 (11)	0.0569 (13)	0.0341 (10)	−0.0154 (10)	−0.0048 (8)	0.0050 (9)
C7	0.0627 (15)	0.0858 (18)	0.0588 (15)	0.0065 (13)	0.0054 (11)	0.0386 (14)
O1	0.0392 (7)	0.0579 (9)	0.0471 (8)	−0.0029 (6)	0.0109 (6)	0.0176 (7)
O2	0.0492 (8)	0.0618 (9)	0.0292 (7)	0.0042 (7)	0.0089 (6)	0.0047 (6)
O3	0.0341 (7)	0.0696 (10)	0.0431 (8)	0.0140 (6)	0.0050 (6)	0.0164 (7)
S1	0.0285 (2)	0.0514 (3)	0.0289 (2)	0.00414 (18)	0.00579 (16)	0.00929 (19)
C14	0.0279 (8)	0.0418 (10)	0.0281 (8)	0.0000 (7)	0.0043 (6)	0.0060 (7)
C15	0.0591 (13)	0.0552 (13)	0.0343 (10)	0.0181 (10)	0.0157 (9)	0.0065 (9)
C16	0.0624 (13)	0.0512 (12)	0.0461 (12)	0.0192 (10)	0.0076 (10)	0.0129 (10)
C17	0.0374 (10)	0.0538 (12)	0.0359 (10)	−0.0053 (8)	0.0003 (8)	0.0151 (9)
C18	0.0590 (13)	0.0651 (14)	0.0342 (10)	0.0124 (11)	0.0193 (9)	0.0106 (10)
C19	0.0527 (12)	0.0499 (12)	0.0413 (11)	0.0156 (9)	0.0171 (9)	0.0111 (9)
C20	0.0603 (14)	0.0771 (17)	0.0494 (13)	−0.0044 (12)	−0.0013 (10)	0.0302 (12)
O4	0.0337 (7)	0.0652 (9)	0.0513 (8)	0.0065 (6)	−0.0015 (6)	0.0226 (7)
O5	0.0446 (7)	0.0630 (9)	0.0281 (7)	−0.0099 (6)	0.0044 (5)	0.0064 (6)
O6	0.0335 (7)	0.0574 (9)	0.0437 (7)	−0.0099 (6)	0.0020 (6)	0.0163 (6)
S2	0.0269 (2)	0.0506 (3)	0.0298 (2)	−0.00331 (18)	0.00094 (16)	0.01147 (19)
C21	0.0292 (8)	0.0340 (9)	0.0360 (9)	0.0009 (7)	0.0005 (7)	0.0140 (7)
C22	0.0264 (8)	0.0400 (10)	0.0446 (10)	0.0042 (7)	0.0037 (7)	0.0140 (8)
C23	0.0367 (9)	0.0460 (11)	0.0420 (10)	0.0081 (8)	0.0109 (8)	0.0144 (9)
C24	0.0405 (10)	0.0438 (10)	0.0328 (9)	0.0034 (8)	0.0024 (7)	0.0117 (8)
C25	0.0330 (9)	0.0334 (9)	0.0367 (9)	−0.0004 (7)	−0.0012 (7)	0.0154 (7)
C26	0.0346 (10)	0.0527 (12)	0.0464 (11)	−0.0040 (8)	−0.0051 (8)	0.0177 (9)
N3	0.0269 (7)	0.0378 (8)	0.0345 (8)	0.0008 (6)	0.0036 (6)	0.0140 (6)
N4	0.0319 (8)	0.0622 (11)	0.0351 (9)	−0.0002 (8)	0.0003 (7)	0.0098 (8)
C8	0.0309 (8)	0.0348 (9)	0.0366 (9)	0.0069 (7)	0.0038 (7)	0.0139 (7)
C9	0.0303 (9)	0.0456 (11)	0.0445 (10)	0.0088 (7)	0.0074 (7)	0.0154 (8)
C10	0.0436 (10)	0.0532 (12)	0.0445 (11)	0.0133 (9)	0.0175 (9)	0.0185 (9)
C11	0.0497 (11)	0.0494 (11)	0.0316 (9)	0.0083 (9)	0.0052 (8)	0.0133 (8)
C12	0.0379 (9)	0.0333 (9)	0.0353 (9)	0.0038 (7)	0.0016 (7)	0.0149 (7)
C13	0.0397 (10)	0.0508 (12)	0.0457 (11)	−0.0001 (9)	−0.0040 (8)	0.0167 (9)
N1	0.0301 (7)	0.0365 (8)	0.0325 (8)	0.0055 (6)	0.0055 (6)	0.0116 (6)
N2	0.0328 (8)	0.0611 (11)	0.0365 (9)	0.0045 (8)	0.0028 (7)	0.0081 (8)

C1—C6	1.375 (3)	O6—S2	1.4497 (13)
C1—C2	1.380 (2)	C21—N4	1.325 (2)
C1—S1	1.7609 (18)	C21—N3	1.352 (2)
C2—C3	1.375 (3)	C21—C22	1.405 (3)
C2—H2	0.9300	C22—C23	1.357 (3)
C3—C4	1.372 (3)	C22—H22	0.9300
C3—H3	0.9300	C23—C24	1.401 (3)
C4—C5	1.378 (3)	C23—H23	0.9300
C4—C7	1.504 (3)	C24—C25	1.353 (3)
C5—C6	1.381 (3)	C24—H24	0.9300
C5—H5	0.9300	C25—N3	1.362 (2)
C6—H6	0.9300	C25—C26	1.493 (2)
C7—H7A	0.9600	C26—H26A	0.9600
C7—H7B	0.9600	C26—H26B	0.9600
C7—H7C	0.9600	C26—H26C	0.9600
O1—S1	1.4499 (14)	N3—H3A	0.894 (9)
O2—S1	1.4605 (14)	N4—H4B	0.876 (9)
O3—S1	1.4469 (13)	N4—H4A	0.876 (10)
C14—C15	1.375 (3)	C8—N2	1.325 (2)
C14—C19	1.378 (3)	C8—N1	1.347 (2)
C14—S2	1.7636 (18)	C8—C9	1.406 (3)
C15—C16	1.379 (3)	C9—C10	1.357 (3)
C15—H15	0.9300	C9—H9	0.9300
C16—C17	1.382 (3)	C10—C11	1.398 (3)
C16—H16	0.9300	C10—H10	0.9300
C17—C18	1.375 (3)	C11—C12	1.356 (3)
C17—C20	1.507 (3)	C11—H11	0.9300
C18—C19	1.380 (3)	C12—N1	1.360 (2)
C18—H18	0.9300	C12—C13	1.491 (3)
C19—H19	0.9300	C13—H13A	0.9600
C20—H20A	0.9600	C13—H13B	0.9600
C20—H20B	0.9600	C13—H13C	0.9600
C20—H20C	0.9600	N1—H1A	0.900 (9)
O4—S2	1.4485 (14)	N2—H2A	0.873 (10)
O5—S2	1.4582 (14)	N2—H2B	0.877 (10)
C6—C1—C2	119.11 (18)	O4—S2—C14	106.93 (8)
C6—C1—S1	120.76 (13)	O6—S2—C14	106.19 (8)
C2—C1—S1	120.13 (15)	O5—S2—C14	106.66 (8)
C3—C2—C1	119.76 (19)	N4—C21—N3	118.92 (16)
C3—C2—H2	120.1	N4—C21—C22	123.44 (16)
C1—C2—H2	120.1	N3—C21—C22	117.63 (16)
C4—C3—C2	122.01 (18)	C23—C22—C21	119.40 (16)
C4—C3—H3	119.0	C23—C22—H22	120.3
C2—C3—H3	119.0	C21—C22—H22	120.3
C3—C4—C5	117.70 (19)	C22—C23—C24	120.92 (17)
C3—C4—C7	120.99 (19)	C22—C23—H23	119.5
C5—C4—C7	121.3 (2)	C24—C23—H23	119.5
C4—C5—C6	121.2 (2)	C25—C24—C23	119.41 (17)
C4—C5—H5	119.4	C25—C24—H24	120.3
C6—C5—H5	119.4	C23—C24—H24	120.3
C1—C6—C5	120.25 (18)	C24—C25—N3	118.87 (16)
C1—C6—H6	119.9	C24—C25—C26	124.50 (17)
C5—C6—H6	119.9	N3—C25—C26	116.63 (16)
C4—C7—H7A	109.5	C25—C26—H26A	109.5
C4—C7—H7B	109.5	C25—C26—H26B	109.5
H7A—C7—H7B	109.5	H26A—C26—H26B	109.5
C4—C7—H7C	109.5	C25—C26—H26C	109.5
H7A—C7—H7C	109.5	H26A—C26—H26C	109.5
H7B—C7—H7C	109.5	H26B—C26—H26C	109.5
O3—S1—O1	113.06 (9)	C21—N3—C25	123.75 (15)
O3—S1—O2	111.56 (8)	C21—N3—H3A	119.2 (13)
O1—S1—O2	111.86 (8)	C25—N3—H3A	117.0 (13)
O3—S1—C1	107.19 (8)	C21—N4—H4B	121.1 (15)
O1—S1—C1	106.16 (8)	C21—N4—H4A	118.4 (16)
O2—S1—C1	106.52 (9)	H4B—N4—H4A	118 (2)
C15—C14—C19	119.43 (18)	N2—C8—N1	119.09 (16)
C15—C14—S2	120.43 (14)	N2—C8—C9	123.12 (16)
C19—C14—S2	120.03 (15)	N1—C8—C9	117.77 (16)
C14—C15—C16	120.19 (18)	C10—C9—C8	119.13 (17)
C14—C15—H15	119.9	C10—C9—H9	120.4
C16—C15—H15	119.9	C8—C9—H9	120.4
C15—C16—C17	121.08 (19)	C9—C10—C11	121.08 (18)
C15—C16—H16	119.5	C9—C10—H10	119.5
C17—C16—H16	119.5	C11—C10—H10	119.5
C18—C17—C16	117.94 (18)	C12—C11—C10	119.44 (18)
C18—C17—C20	120.96 (19)	C12—C11—H11	120.3
C16—C17—C20	121.1 (2)	C10—C11—H11	120.3
C17—C18—C19	121.60 (18)	C11—C12—N1	118.61 (17)
C17—C18—H18	119.2	C11—C12—C13	124.54 (17)
C19—C18—H18	119.2	N1—C12—C13	116.85 (16)
C14—C19—C18	119.74 (19)	C12—C13—H13A	109.5
C14—C19—H19	120.1	C12—C13—H13B	109.5
C18—C19—H19	120.1	H13A—C13—H13B	109.5
C17—C20—H20A	109.5	C12—C13—H13C	109.5
C17—C20—H20B	109.5	H13A—C13—H13C	109.5
H20A—C20—H20B	109.5	H13B—C13—H13C	109.5
C17—C20—H20C	109.5	C8—N1—C12	123.96 (15)
H20A—C20—H20C	109.5	C8—N1—H1A	118.4 (14)
H20B—C20—H20C	109.5	C12—N1—H1A	117.6 (14)
O4—S2—O6	112.84 (9)	C8—N2—H2A	115.9 (15)
O4—S2—O5	112.66 (8)	C8—N2—H2B	120.4 (15)
O6—S2—O5	111.06 (8)	H2A—N2—H2B	120 (2)
C6—C1—C2—C3	0.9 (3)	C15—C14—S2—O4	151.01 (16)
S1—C1—C2—C3	−178.58 (18)	C19—C14—S2—O4	−32.74 (18)
C1—C2—C3—C4	−0.5 (4)	C15—C14—S2—O6	−88.27 (17)
C2—C3—C4—C5	−0.4 (4)	C19—C14—S2—O6	87.97 (17)
C2—C3—C4—C7	−179.5 (2)	C15—C14—S2—O5	30.25 (18)
C3—C4—C5—C6	0.8 (3)	C19—C14—S2—O5	−153.50 (15)
C7—C4—C5—C6	179.9 (2)	N4—C21—C22—C23	−179.93 (18)
C2—C1—C6—C5	−0.5 (3)	N3—C21—C22—C23	1.0 (3)
S1—C1—C6—C5	178.96 (17)	C21—C22—C23—C24	−0.7 (3)
C4—C5—C6—C1	−0.3 (3)	C22—C23—C24—C25	0.0 (3)
C6—C1—S1—O3	−81.39 (18)	C23—C24—C25—N3	0.3 (3)
C2—C1—S1—O3	98.11 (17)	C23—C24—C25—C26	179.47 (17)
C6—C1—S1—O1	157.51 (16)	N4—C21—N3—C25	−179.79 (17)
C2—C1—S1—O1	−22.99 (19)	C22—C21—N3—C25	−0.7 (3)
C6—C1—S1—O2	38.15 (18)	C24—C25—N3—C21	0.0 (3)
C2—C1—S1—O2	−142.35 (17)	C26—C25—N3—C21	−179.21 (16)
C19—C14—C15—C16	−0.9 (3)	N2—C8—C9—C10	−179.67 (19)
S2—C14—C15—C16	175.40 (17)	N1—C8—C9—C10	−1.1 (3)
C14—C15—C16—C17	−0.3 (3)	C8—C9—C10—C11	0.6 (3)
C15—C16—C17—C18	1.0 (3)	C9—C10—C11—C12	−0.3 (3)
C15—C16—C17—C20	−178.9 (2)	C10—C11—C12—N1	0.4 (3)
C16—C17—C18—C19	−0.6 (3)	C10—C11—C12—C13	−178.58 (18)
C20—C17—C18—C19	179.3 (2)	N2—C8—N1—C12	179.90 (17)
C15—C14—C19—C18	1.2 (3)	C9—C8—N1—C12	1.3 (3)
S2—C14—C19—C18	−175.05 (16)	C11—C12—N1—C8	−0.9 (3)
C17—C18—C19—C14	−0.5 (3)	C13—C12—N1—C8	178.12 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2	0.90 (1)	1.88 (1)	2.772 (2)	171 (2)
N2—H2A···O3i	0.87 (1)	2.01 (1)	2.880 (2)	174 (2)
N2—H2B···O1	0.88 (1)	2.07 (1)	2.919 (2)	162 (2)
N3—H3A···O5	0.89 (1)	1.90 (1)	2.789 (2)	174 (2)
N4—H4A···O4ii	0.88 (1)	2.02 (1)	2.882 (2)	167 (2)
N4—H4B···O6	0.88 (1)	2.04 (1)	2.883 (2)	162 (2)
C22—H22···O5ii	0.93	2.58	3.455 (2)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2	0.90 (1)	1.88 (1)	2.772 (2)	171 (2)
N2—H2A⋯O3i	0.87 (1)	2.01 (1)	2.880 (2)	174 (2)
N2—H2B⋯O1	0.88 (1)	2.07 (1)	2.919 (2)	162 (2)
N3—H3A⋯O5	0.89 (1)	1.90 (1)	2.789 (2)	174 (2)
N4—H4A⋯O4ii	0.88 (1)	2.02 (1)	2.882 (2)	167 (2)
N4—H4B⋯O6	0.88 (1)	2.04 (1)	2.883 (2)	162 (2)
C22—H22⋯O5ii	0.93	2.58	3.455 (2)	157

Symmetry codes: (i) ; (ii) .