Synthesis and characterization of four organic–inorganic salts: sulfates of 2-amino­pyridinium derivatives

Hybrid materials, fabricated by the combination of inorganic and organic components, have potential applications in chemistry and are endowed with the advantages of both building elements. There are several types of inter­molecular inter­actions present in these hybrid compounds, including electrostatic forces, π–π stacking and hydrogen-bonding inter­actions, the latter playing an important role in the construction of three-dimensional architectures and stabilizing supra­molecular crystal structures. Analysis of the inter­molecular inter­actions and their influence on packing modes therefore requires focused scientific attention. Four new organic–inorganic salts, namely 2-amino-4-methyl-3-nitro­pyridinium hydrogen sulfate, C₆H₈N₃O₂⁺·HSO₄⁻, bis­(2-amino-4-methyl-3-nitro­pyridinium) sulfate, 2C₆H₈N₃O₂⁺·SO₄²⁻, 2-amino-3-methyl­pyridinium hydrogen sulfate, C₆H₉N₂⁺·HSO₄⁻, and bis­(2-amino-3-methyl­pyridinium) sulfate monohydrate, 2C₆H₉N₂⁺·SO₄²⁻·H₂O, have been synthesized and characterized by X-ray diffraction. The crystal structures are stabilized by intra- and inter­molecular hydrogen bonds, as well as by weak π–π stacking and lp–π (lp is lone pair) inter­actions. Hirshfeld surface analysis was employed in order to study inter­molecular inter­actions.

Computing details

For all compounds, data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1997); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

(I) 2-Amino-4-methyl-3-nitropyridinium hydrogen sulfate

Crystal data

C6H8N3O2^+·HSO4^−	Z = 4
Mr = 251.22	F(000) = 520
Triclinic, P1	Dx = 1.667 Mg m^−3
a = 7.835 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.105 (3) Å	Cell parameters from 5835 reflections
c = 15.881 (4) Å	θ = 2.6–27.2°
α = 97.03 (3)°	µ = 0.34 mm^−1
β = 90.21 (3)°	T = 295 K
γ = 90.15 (3)°	Block, colourless
V = 1000.9 (6) Å^3	0.35 × 0.25 × 0.19 mm

Data collection

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4903 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3462 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.5°, θmin = 2.6°
ω scans	h = −10→10
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived Clark & Reid (1995)]	k = −11→10
Tmin = 0.906, Tmax = 0.941	l = −20→22
15737 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.057P)^2 + 0.482P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.140	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.36 e Å^−3
4903 reflections	Δρmin = −0.26 e Å^−3
308 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.053 (3)
Primary atom site location: structure-invariant direct methods

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. Refined as a 2-component twin.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.63763 (12)	0.46573 (9)	0.81181 (5)	0.0458 (2)
S2	1.14346 (11)	0.54496 (9)	0.68721 (5)	0.0445 (2)
O3	0.5457 (4)	0.4259 (3)	0.88454 (15)	0.0636 (7)
O4	0.8158 (4)	0.4193 (3)	0.81129 (18)	0.0691 (7)
O1	0.5657 (4)	0.3578 (4)	0.73207 (17)	0.0721 (8)
H1	0.4648	0.3803	0.7258	0.108*
N21	0.3552 (4)	0.8614 (3)	0.84691 (15)	0.0495 (7)
H21	0.3985	0.7722	0.8207	0.059*
O5	1.0629 (4)	0.6246 (4)	0.7708 (2)	0.0870 (10)
H5	0.9796	0.5699	0.7819	0.131*
N22	0.3759 (4)	0.7369 (3)	0.96753 (17)	0.0523 (7)
H22A	0.4171	0.6508	0.9375	0.063*
H22B	0.3630	0.7372	1.0213	0.063*
O23A	0.3168 (4)	0.9525 (4)	1.10498 (15)	0.0774 (9)
O2	0.6130 (4)	0.6373 (3)	0.79938 (18)	0.0759 (9)
N23	0.2206 (4)	1.0269 (4)	1.06112 (18)	0.0539 (7)
O13A	0.8016 (5)	−0.0149 (4)	0.39251 (16)	0.0867 (10)
N11	0.8537 (4)	0.1564 (3)	0.64549 (17)	0.0550 (7)
H11	0.8939	0.2523	0.6651	0.066*
C13	0.7522 (4)	−0.0329 (4)	0.53327 (19)	0.0410 (7)
N13	0.7042 (5)	−0.0655 (4)	0.44409 (19)	0.0594 (8)
C12	0.8215 (4)	0.1255 (4)	0.56154 (19)	0.0425 (7)
C22	0.3323 (4)	0.8688 (3)	0.93097 (18)	0.0394 (7)
N12	0.8551 (5)	0.2460 (3)	0.5147 (2)	0.0617 (8)
H12A	0.8957	0.3393	0.5381	0.074*
H12B	0.8362	0.2311	0.4610	0.074*
C23	0.2562 (4)	1.0166 (4)	0.97069 (18)	0.0405 (7)
O7	1.2457 (5)	0.6765 (4)	0.6604 (2)	0.0708 (12)	0.835 (7)
O13B	0.5732 (4)	−0.1418 (5)	0.4257 (2)	0.1027 (12)
O23B	0.0968 (4)	1.1049 (4)	1.0894 (2)	0.0868 (10)
C24	0.2142 (4)	1.1484 (4)	0.9254 (2)	0.0516 (8)
C14	0.7239 (4)	−0.1513 (4)	0.5877 (2)	0.0499 (8)
O6	1.0013 (6)	0.4936 (6)	0.6316 (2)	0.0904 (14)	0.835 (7)
O8	1.2358 (6)	0.4042 (5)	0.7044 (3)	0.0940 (15)	0.835 (7)
C25	0.2466 (5)	1.1272 (4)	0.8383 (2)	0.0612 (10)
H25	0.2211	1.2120	0.8059	0.073*
C15	0.7664 (5)	−0.1061 (5)	0.6734 (2)	0.0633 (10)
H15	0.7524	−0.1825	0.7120	0.076*
C26	0.3144 (6)	0.9846 (5)	0.8013 (2)	0.0634 (11)
H26	0.3335	0.9711	0.7431	0.076*
C16	0.8265 (6)	0.0453 (5)	0.6998 (2)	0.0660 (10)
H16	0.8500	0.0744	0.7572	0.079*
C41	0.6527 (6)	−0.3225 (4)	0.5612 (3)	0.0826 (14)
H41A	0.5303	−0.3177	0.5602	0.124*
H41B	0.6888	−0.3960	0.6008	0.124*
H41C	0.6936	−0.3631	0.5056	0.124*
C42	0.1419 (6)	1.3117 (4)	0.9643 (3)	0.0803 (13)
H42A	0.0224	1.2986	0.9750	0.120*
H42B	0.1571	1.3935	0.9260	0.120*
H42C	0.2001	1.3473	1.0167	0.120*
O8A	1.120 (3)	0.363 (2)	0.6936 (11)	0.065 (5)*	0.165 (7)
O6A	1.047 (2)	0.578 (2)	0.6174 (10)	0.050 (4)*	0.165 (7)
O7A	1.319 (2)	0.5916 (19)	0.6971 (10)	0.057 (5)*	0.165 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0540 (5)	0.0430 (4)	0.0417 (4)	0.0022 (4)	0.0057 (4)	0.0095 (3)
S2	0.0495 (5)	0.0424 (4)	0.0421 (4)	−0.0006 (4)	−0.0050 (4)	0.0072 (3)
O3	0.0776 (19)	0.0654 (15)	0.0508 (14)	−0.0042 (14)	0.0114 (13)	0.0185 (12)
O4	0.0546 (16)	0.0700 (16)	0.0829 (19)	0.0039 (13)	0.0018 (14)	0.0104 (14)
O1	0.0652 (18)	0.0897 (19)	0.0551 (16)	0.0173 (15)	−0.0074 (14)	−0.0166 (13)
N21	0.070 (2)	0.0436 (13)	0.0343 (13)	−0.0065 (14)	−0.0001 (14)	0.0025 (11)
O5	0.087 (2)	0.088 (2)	0.076 (2)	−0.0303 (17)	0.0261 (17)	−0.0286 (16)
N22	0.074 (2)	0.0421 (13)	0.0422 (14)	0.0050 (14)	0.0018 (14)	0.0110 (11)
O23A	0.107 (2)	0.0870 (19)	0.0392 (14)	0.0117 (18)	0.0034 (15)	0.0132 (13)
O2	0.099 (2)	0.0501 (14)	0.0839 (19)	0.0085 (14)	0.0216 (17)	0.0275 (13)
N23	0.0526 (18)	0.0587 (17)	0.0476 (17)	−0.0117 (14)	0.0067 (14)	−0.0042 (14)
O13A	0.132 (3)	0.094 (2)	0.0352 (14)	0.010 (2)	0.0008 (17)	0.0125 (13)
N11	0.069 (2)	0.0509 (15)	0.0436 (15)	−0.0042 (15)	−0.0005 (15)	−0.0021 (12)
C13	0.0392 (17)	0.0456 (16)	0.0374 (16)	0.0098 (13)	0.0006 (13)	0.0014 (12)
N13	0.063 (2)	0.0657 (18)	0.0463 (17)	0.0268 (16)	−0.0078 (16)	−0.0078 (14)
C12	0.0443 (18)	0.0440 (16)	0.0400 (17)	0.0078 (14)	0.0063 (14)	0.0083 (13)
C22	0.0459 (18)	0.0390 (15)	0.0337 (15)	−0.0086 (13)	−0.0047 (14)	0.0062 (12)
N12	0.080 (2)	0.0476 (15)	0.0604 (18)	0.0003 (16)	0.0094 (17)	0.0191 (13)
C23	0.0449 (18)	0.0400 (15)	0.0364 (16)	−0.0066 (13)	−0.0018 (14)	0.0046 (12)
O7	0.091 (3)	0.0554 (19)	0.070 (2)	−0.0150 (17)	0.0039 (19)	0.0236 (15)
O13B	0.060 (2)	0.141 (3)	0.091 (2)	0.015 (2)	−0.0280 (17)	−0.049 (2)
O23B	0.063 (2)	0.110 (2)	0.079 (2)	0.0046 (17)	0.0191 (16)	−0.0205 (17)
C24	0.0443 (19)	0.0438 (17)	0.067 (2)	−0.0071 (14)	−0.0127 (17)	0.0085 (15)
C14	0.0439 (19)	0.0447 (17)	0.062 (2)	0.0098 (14)	0.0115 (16)	0.0109 (15)
O6	0.094 (3)	0.105 (3)	0.069 (2)	−0.028 (3)	−0.029 (2)	−0.002 (2)
O8	0.079 (3)	0.075 (2)	0.139 (4)	0.022 (2)	0.007 (3)	0.057 (2)
C25	0.072 (3)	0.0489 (19)	0.067 (2)	−0.0049 (18)	−0.019 (2)	0.0267 (18)
C15	0.075 (3)	0.068 (2)	0.052 (2)	0.016 (2)	0.017 (2)	0.0278 (18)
C26	0.089 (3)	0.065 (2)	0.0392 (18)	−0.016 (2)	−0.0121 (19)	0.0205 (16)
C16	0.084 (3)	0.076 (2)	0.0383 (19)	0.010 (2)	0.0017 (19)	0.0088 (17)
C41	0.069 (3)	0.0459 (19)	0.131 (4)	−0.004 (2)	0.013 (3)	0.001 (2)
C42	0.070 (3)	0.049 (2)	0.120 (4)	0.006 (2)	−0.007 (3)	0.001 (2)

Geometric parameters (Å, º)

S1—O3	1.433 (3)	C13—N13	1.456 (4)
S1—O4	1.447 (3)	C13—C12	1.414 (4)
S1—O1	1.552 (3)	C13—C14	1.385 (4)
S1—O2	1.442 (2)	N13—O13B	1.213 (4)
S2—O5	1.542 (3)	C12—N12	1.325 (4)
S2—O7	1.438 (3)	C22—C23	1.417 (4)
S2—O6	1.447 (4)	N12—H12A	0.8600
S2—O8	1.407 (3)	N12—H12B	0.8600
S2—O8A	1.500 (17)	C23—C24	1.399 (4)
S2—O6A	1.391 (15)	C24—C25	1.397 (5)
S2—O7A	1.428 (16)	C24—C42	1.503 (5)
O1—H1	0.8200	C14—C15	1.404 (5)
N21—H21	0.8600	C14—C41	1.505 (5)
N21—C22	1.342 (4)	C25—H25	0.9300
N21—C26	1.343 (4)	C25—C26	1.342 (5)
O5—H5	0.8200	C15—H15	0.9300
N22—H22A	0.8600	C15—C16	1.331 (6)
N22—H22B	0.8600	C26—H26	0.9300
N22—C22	1.323 (4)	C16—H16	0.9300
O23A—N23	1.232 (4)	C41—H41A	0.9600
N23—C23	1.456 (4)	C41—H41B	0.9600
N23—O23B	1.216 (4)	C41—H41C	0.9600
O13A—N13	1.227 (4)	C42—H42A	0.9600
N11—H11	0.8600	C42—H42B	0.9600
N11—C12	1.349 (4)	C42—H42C	0.9600
N11—C16	1.338 (4)
O3—S1—O4	114.08 (18)	N12—C12—C13	127.0 (3)
O3—S1—O1	108.45 (18)	N21—C22—C23	115.7 (3)
O3—S1—O2	110.97 (16)	N22—C22—N21	117.4 (3)
O4—S1—O1	102.80 (16)	N22—C22—C23	126.8 (3)
O2—S1—O4	112.66 (18)	C12—N12—H12A	120.0
O2—S1—O1	107.25 (18)	C12—N12—H12B	120.0
O7—S2—O5	103.72 (18)	H12A—N12—H12B	120.0
O7—S2—O6	114.5 (2)	C22—C23—N23	117.7 (3)
O6—S2—O5	105.5 (2)	C24—C23—N23	120.4 (3)
O8—S2—O5	108.1 (2)	C24—C23—C22	121.9 (3)
O8—S2—O7	114.8 (2)	C23—C24—C42	124.6 (4)
O8—S2—O6	109.6 (3)	C25—C24—C23	117.2 (3)
O8A—S2—O5	101.7 (7)	C25—C24—C42	118.3 (3)
O6A—S2—O5	111.3 (7)	C13—C14—C15	116.7 (3)
O6A—S2—O8A	105.8 (10)	C13—C14—C41	124.7 (4)
O6A—S2—O7A	122.2 (9)	C15—C14—C41	118.6 (3)
O7A—S2—O5	103.1 (6)	C24—C25—H25	119.9
O7A—S2—O8A	111.0 (10)	C26—C25—C24	120.2 (3)
S1—O1—H1	109.5	C26—C25—H25	119.9
C22—N21—H21	118.0	C14—C15—H15	119.7
C22—N21—C26	123.9 (3)	C16—C15—C14	120.6 (3)
C26—N21—H21	118.0	C16—C15—H15	119.7
S2—O5—H5	109.5	N21—C26—H26	119.5
H22A—N22—H22B	120.0	C25—C26—N21	121.1 (3)
C22—N22—H22A	120.0	C25—C26—H26	119.5
C22—N22—H22B	120.0	N11—C16—H16	119.4
O23A—N23—C23	117.7 (3)	C15—C16—N11	121.3 (3)
O23B—N23—O23A	123.3 (3)	C15—C16—H16	119.4
O23B—N23—C23	119.0 (3)	C14—C41—H41A	109.5
C12—N11—H11	118.3	C14—C41—H41B	109.5
C16—N11—H11	118.3	C14—C41—H41C	109.5
C16—N11—C12	123.4 (3)	H41A—C41—H41B	109.5
C12—C13—N13	117.1 (3)	H41A—C41—H41C	109.5
C14—C13—N13	120.6 (3)	H41B—C41—H41C	109.5
C14—C13—C12	122.3 (3)	C24—C42—H42A	109.5
O13A—N13—C13	117.1 (3)	C24—C42—H42B	109.5
O13B—N13—O13A	124.6 (4)	C24—C42—H42C	109.5
O13B—N13—C13	118.3 (4)	H42A—C42—H42B	109.5
N11—C12—C13	115.8 (3)	H42A—C42—H42C	109.5
N12—C12—N11	117.2 (3)	H42B—C42—H42C	109.5
N21—C22—C23—N23	176.9 (3)	C22—N21—C26—C25	0.1 (6)
N21—C22—C23—C24	−2.4 (5)	C22—C23—C24—C25	1.5 (5)
N22—C22—C23—N23	−0.2 (5)	C22—C23—C24—C42	−176.6 (3)
N22—C22—C23—C24	−179.5 (3)	C23—C24—C25—C26	0.3 (5)
O23A—N23—C23—C22	31.3 (4)	O23B—N23—C23—C22	−147.2 (3)
O23A—N23—C23—C24	−149.4 (3)	O23B—N23—C23—C24	32.1 (5)
N23—C23—C24—C25	−177.8 (3)	C24—C25—C26—N21	−1.2 (6)
N23—C23—C24—C42	4.1 (5)	C14—C13—N13—O13A	−141.3 (3)
C13—C14—C15—C16	1.7 (6)	C14—C13—N13—O13B	37.9 (4)
N13—C13—C12—N11	175.6 (3)	C14—C13—C12—N11	−1.9 (5)
N13—C13—C12—N12	−3.3 (5)	C14—C13—C12—N12	179.2 (3)
N13—C13—C14—C15	−177.0 (3)	C14—C15—C16—N11	−2.3 (7)
N13—C13—C14—C41	3.3 (5)	C26—N21—C22—N22	179.0 (4)
C12—N11—C16—C15	0.8 (6)	C26—N21—C22—C23	1.6 (5)
C12—C13—N13—O13A	41.2 (4)	C16—N11—C12—C13	1.3 (5)
C12—C13—N13—O13B	−139.7 (3)	C16—N11—C12—N12	−179.6 (4)
C12—C13—C14—C15	0.5 (5)	C41—C14—C15—C16	−178.6 (4)
C12—C13—C14—C41	−179.2 (3)	C42—C24—C25—C26	178.6 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O8^i	0.82	1.84	2.655 (5)	173
O1—H1···O7A^i	0.82	2.15	2.812 (17)	137
N21—H21···O2	0.86	2.01	2.764 (4)	145
N21—H21···O7A^i	0.86	2.38	3.040 (15)	134
O5—H5···O4	0.82	1.87	2.680 (4)	171
N22—H22A···O3	0.86	2.16	3.013 (4)	169
N22—H22B···O3^ii	0.86	2.23	2.897 (4)	134
N22—H22B···O23A	0.86	2.09	2.667 (4)	124
N11—H11···O6	0.86	2.25	2.998 (6)	145
N11—H11···O8A	0.86	2.01	2.72 (2)	139
N12—H12A···O6	0.86	2.00	2.801 (5)	155
N12—H12B···O13A	0.86	2.17	2.721 (4)	122
N12—H12B···O7^iii	0.86	2.24	3.028 (5)	152
C25—H25···O8^iv	0.93	2.38	3.276 (5)	163
C25—H25···O8A^iv	0.93	2.42	3.316 (17)	163
C15—H15···O2^v	0.93	2.40	3.286 (4)	160
C26—H26···O13A^vi	0.93	2.46	3.244 (4)	142
C16—H16···O23A^ii	0.93	2.59	3.299 (4)	134

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

(II) Bis(2-amino-4-methyl-3-nitropyridinium) sulfate

Crystal data

2C6H8N3O2^+·SO4^2^−	F(000) = 840
Mr = 404.37	Dx = 1.540 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.557 (4) Å	Cell parameters from 1601 reflections
b = 13.632 (4) Å	θ = 2.5–28.6°
c = 12.211 (4) Å	µ = 0.24 mm^−1
β = 97.12 (3)°	T = 295 K
V = 1743.8 (10) Å^3	Block, colourless
Z = 4	0.60 × 0.41 × 0.26 mm

Data collection

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	2042 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1686 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.1°, θmin = 2.8°
ω scans	h = −14→14
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived Clark & Reid (1995)]	k = −14→18
Tmin = 0.917, Tmax = 0.955	l = −16→16
4844 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.041	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 0.714P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.120	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 0.22 e Å^−3
2042 reflections	Δρmin = −0.32 e Å^−3
125 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0042 (10)
Primary atom site location: structure-invariant direct methods

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.

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

	x	y	z	Uiso*/Ueq
S1	0.0000	0.50272 (4)	0.7500	0.0363 (2)
O11	0.11223 (11)	0.56597 (9)	0.78384 (9)	0.0432 (3)
O12	0.02621 (14)	0.44247 (10)	0.65665 (11)	0.0561 (4)
N1	0.26670 (13)	0.60819 (11)	0.63249 (11)	0.0394 (4)
H1	0.2169	0.5843	0.6764	0.047*
O3A	0.40140 (15)	0.47087 (12)	0.36468 (12)	0.0635 (4)
N3	0.36940 (14)	0.55646 (13)	0.36171 (12)	0.0447 (4)
O3B	0.34498 (18)	0.60392 (13)	0.27720 (11)	0.0731 (5)
N2	0.20494 (15)	0.48257 (12)	0.51249 (13)	0.0498 (4)
H2A	0.1563	0.4612	0.5588	0.060*
H2B	0.2083	0.4521	0.4512	0.060*
C3	0.35736 (15)	0.60566 (12)	0.46684 (13)	0.0360 (4)
C2	0.27430 (15)	0.56212 (13)	0.53545 (12)	0.0362 (4)
C6	0.33368 (18)	0.68972 (14)	0.66330 (15)	0.0457 (4)
H6	0.3246	0.7185	0.7309	0.055*
C4	0.42775 (16)	0.68808 (13)	0.49592 (15)	0.0425 (4)
C5	0.41376 (18)	0.73077 (14)	0.59838 (16)	0.0486 (5)
H5	0.4594	0.7870	0.6214	0.058*
C41	0.5217 (2)	0.73115 (17)	0.42627 (19)	0.0648 (6)
H41A	0.5773	0.6804	0.4058	0.097*
H41B	0.5714	0.7808	0.4676	0.097*
H41C	0.4765	0.7598	0.3610	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0422 (3)	0.0330 (3)	0.0352 (3)	0.000	0.0112 (2)	0.000
O11	0.0446 (7)	0.0493 (7)	0.0359 (6)	−0.0059 (6)	0.0060 (5)	−0.0039 (5)
O12	0.0642 (9)	0.0474 (8)	0.0615 (8)	−0.0105 (7)	0.0270 (7)	−0.0217 (7)
N1	0.0423 (8)	0.0440 (8)	0.0322 (7)	−0.0024 (6)	0.0055 (6)	0.0021 (6)
O3A	0.0673 (9)	0.0622 (10)	0.0602 (9)	0.0180 (8)	0.0047 (7)	−0.0150 (8)
N3	0.0404 (8)	0.0574 (10)	0.0374 (8)	−0.0031 (7)	0.0089 (6)	−0.0015 (7)
O3B	0.1030 (13)	0.0801 (11)	0.0375 (7)	−0.0059 (10)	0.0143 (8)	0.0092 (7)
N2	0.0563 (10)	0.0585 (10)	0.0358 (8)	−0.0212 (8)	0.0106 (7)	−0.0055 (7)
C3	0.0354 (8)	0.0393 (9)	0.0333 (7)	0.0016 (7)	0.0040 (6)	0.0029 (7)
C2	0.0370 (8)	0.0412 (9)	0.0297 (7)	0.0008 (7)	0.0010 (6)	0.0037 (7)
C6	0.0545 (11)	0.0412 (10)	0.0407 (9)	0.0020 (8)	0.0028 (8)	−0.0071 (8)
C4	0.0419 (9)	0.0367 (9)	0.0489 (10)	0.0005 (7)	0.0057 (7)	0.0077 (8)
C5	0.0541 (11)	0.0362 (9)	0.0542 (10)	−0.0045 (8)	0.0016 (9)	−0.0022 (8)
C41	0.0644 (13)	0.0617 (14)	0.0720 (14)	−0.0183 (11)	0.0236 (11)	0.0048 (12)

Geometric parameters (Å, º)

S1—O11^i	1.4820 (13)	N2—C2	1.319 (2)
S1—O11	1.4820 (13)	C3—C2	1.416 (2)
S1—O12^i	1.4591 (13)	C3—C4	1.369 (2)
S1—O12	1.4590 (13)	C6—H6	0.9300
N1—H1	0.8600	C6—C5	1.350 (3)
N1—C2	1.352 (2)	C4—C5	1.404 (3)
N1—C6	1.346 (2)	C4—C41	1.504 (3)
O3A—N3	1.214 (2)	C5—H5	0.9300
N3—O3B	1.218 (2)	C41—H41A	0.9600
N3—C3	1.468 (2)	C41—H41B	0.9600
N2—H2A	0.8600	C41—H41C	0.9600
N2—H2B	0.8600
O11—S1—O11^i	108.85 (11)	N1—C2—C3	115.60 (15)
O12^i—S1—O11^i	108.84 (7)	N2—C2—N1	118.45 (15)
O12—S1—O11	108.83 (7)	N2—C2—C3	125.94 (15)
O12^i—S1—O11	109.40 (8)	N1—C6—H6	119.2
O12—S1—O11^i	109.40 (8)	N1—C6—C5	121.58 (17)
O12—S1—O12^i	111.48 (12)	C5—C6—H6	119.2
C2—N1—H1	118.6	C3—C4—C5	117.22 (16)
C6—N1—H1	118.6	C3—C4—C41	123.26 (17)
C6—N1—C2	122.85 (15)	C5—C4—C41	119.46 (17)
O3A—N3—O3B	124.38 (16)	C6—C5—C4	119.62 (17)
O3A—N3—C3	117.84 (15)	C6—C5—H5	120.2
O3B—N3—C3	117.77 (16)	C4—C5—H5	120.2
H2A—N2—H2B	120.0	C4—C41—H41A	109.5
C2—N2—H2A	120.0	C4—C41—H41B	109.5
C2—N2—H2B	120.0	C4—C41—H41C	109.5
C2—C3—N3	116.93 (15)	H41A—C41—H41B	109.5
C4—C3—N3	119.91 (15)	H41A—C41—H41C	109.5
C4—C3—C2	123.12 (15)	H41B—C41—H41C	109.5
N1—C6—C5—C4	0.2 (3)	C3—C4—C5—C6	0.3 (3)
O3A—N3—C3—C2	−55.9 (2)	C2—N1—C6—C5	−0.2 (3)
O3A—N3—C3—C4	122.15 (19)	C2—C3—C4—C5	−0.9 (3)
N3—C3—C2—N1	178.99 (14)	C2—C3—C4—C41	176.33 (18)
N3—C3—C2—N2	−1.4 (3)	C6—N1—C2—N2	179.99 (16)
N3—C3—C4—C5	−178.87 (16)	C6—N1—C2—C3	−0.4 (2)
N3—C3—C4—C41	−1.6 (3)	C4—C3—C2—N1	1.0 (2)
O3B—N3—C3—C2	123.13 (19)	C4—C3—C2—N2	−179.46 (16)
O3B—N3—C3—C4	−58.8 (2)	C41—C4—C5—C6	−177.07 (18)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O11	0.86	1.83	2.675 (2)	165
N2—H2A···O12	0.86	1.95	2.790 (2)	166
N2—H2B···O11^ii	0.86	2.18	2.918 (2)	144
N2—H2B···O3A	0.86	2.42	2.918 (3)	117
C5—H5···O12^iii	0.93	2.26	3.168 (2)	166

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

(III) 2-Amino-3-methylpyridinium hydrogen sulfate

Crystal data

C6H9N2^+·HSO4^−	Z = 4
Mr = 206.22	F(000) = 432
Triclinic, P1	Dx = 1.510 Mg m^−3
a = 8.029 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.645 (4) Å	Cell parameters from 5715 reflections
c = 11.541 (4) Å	θ = 2.8–28.0°
α = 82.95 (3)°	µ = 0.34 mm^−1
β = 87.95 (3)°	T = 295 K
γ = 67.93 (3)°	Plank, colourless
V = 907.1 (6) Å^3	0.41 × 0.15 × 0.07 mm

Data collection

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	4467 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2889 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.5°, θmin = 2.6°
ω scans	h = −11→10
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived Clark & Reid (1995)]	k = −14→13
Tmin = 0.907, Tmax = 0.976	l = −15→15
19746 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.139	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 0.193P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
4467 reflections	Δρmax = 0.24 e Å^−3
239 parameters	Δρmin = −0.37 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
S2	0.01914 (8)	0.69762 (6)	0.29888 (5)	0.04795 (19)
S1	0.54773 (8)	0.68435 (6)	0.16433 (5)	0.04654 (18)
O12	0.6566 (2)	0.65348 (17)	0.06171 (14)	0.0553 (4)
O21	0.0772 (2)	0.82022 (17)	0.26289 (19)	0.0667 (5)
H21A	0.1743	0.7939	0.2298	0.100*
O11	0.5640 (2)	0.81267 (16)	0.20654 (17)	0.0587 (5)
H11A	0.6585	0.7901	0.2431	0.088*
O24	−0.1603 (2)	0.76257 (19)	0.34223 (16)	0.0639 (5)
O14	0.3587 (2)	0.7288 (2)	0.13688 (17)	0.0672 (5)
O13	0.6099 (2)	0.57557 (17)	0.25920 (14)	0.0587 (5)
O22	0.0269 (2)	0.63064 (17)	0.19637 (14)	0.0561 (4)
O23	0.1421 (2)	0.60922 (18)	0.38971 (15)	0.0686 (5)
N11	0.4358 (3)	0.3689 (2)	0.37549 (17)	0.0517 (5)
H11	0.3465	0.4452	0.3774	0.062*
N21	0.9474 (3)	0.35786 (19)	0.25743 (17)	0.0511 (5)
H21	0.8619	0.4367	0.2554	0.061*
C13	0.6205 (3)	0.1894 (2)	0.2702 (2)	0.0472 (5)
N22	0.9100 (3)	0.3721 (2)	0.05915 (18)	0.0663 (6)
H22A	0.8289	0.4524	0.0607	0.080*
H22B	0.9371	0.3378	−0.0059	0.080*
N12	0.3748 (3)	0.3853 (2)	0.18024 (18)	0.0592 (6)
H12A	0.2874	0.4615	0.1867	0.071*
H12B	0.3969	0.3540	0.1138	0.071*
C23	1.1284 (3)	0.1684 (2)	0.1620 (2)	0.0479 (5)
C24	1.2083 (3)	0.1088 (2)	0.2673 (2)	0.0567 (6)
H24	1.2970	0.0216	0.2721	0.068*
C22	0.9932 (3)	0.3011 (2)	0.1571 (2)	0.0468 (5)
C25	1.1625 (4)	0.1732 (3)	0.3683 (2)	0.0617 (7)
H25	1.2222	0.1319	0.4387	0.074*
C17	0.6648 (4)	0.1269 (3)	0.1581 (2)	0.0607 (7)
H17A	0.5670	0.1038	0.1354	0.091*
H17B	0.7719	0.0460	0.1686	0.091*
H17C	0.6840	0.1911	0.0982	0.091*
C12	0.4754 (3)	0.3160 (2)	0.2728 (2)	0.0453 (5)
C27	1.1760 (4)	0.1001 (3)	0.0522 (2)	0.0636 (7)
H27A	1.2263	0.1509	−0.0030	0.095*
H27B	1.0698	0.0969	0.0192	0.095*
H27C	1.2624	0.0089	0.0703	0.095*
C14	0.7143 (4)	0.1294 (3)	0.3713 (2)	0.0608 (7)
H14	0.8107	0.0465	0.3711	0.073*
C26	1.0286 (4)	0.2973 (3)	0.3608 (2)	0.0586 (7)
H26	0.9923	0.3414	0.4274	0.070*
C16	0.5294 (4)	0.3079 (3)	0.4754 (2)	0.0621 (7)
H16	0.4965	0.3485	0.5439	0.075*
C15	0.6697 (4)	0.1890 (3)	0.4759 (2)	0.0678 (8)
H15	0.7360	0.1470	0.5439	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0514 (4)	0.0537 (4)	0.0352 (3)	−0.0129 (3)	−0.0023 (3)	−0.0132 (3)
S1	0.0491 (3)	0.0506 (3)	0.0355 (3)	−0.0130 (3)	−0.0013 (2)	−0.0068 (2)
O12	0.0594 (10)	0.0645 (10)	0.0337 (9)	−0.0127 (8)	0.0044 (8)	−0.0111 (8)
O21	0.0654 (11)	0.0576 (10)	0.0785 (15)	−0.0219 (9)	0.0072 (10)	−0.0191 (10)
O11	0.0598 (10)	0.0485 (9)	0.0596 (12)	−0.0081 (7)	−0.0115 (9)	−0.0128 (8)
O24	0.0531 (10)	0.0852 (13)	0.0511 (11)	−0.0180 (9)	0.0055 (8)	−0.0266 (9)
O14	0.0484 (10)	0.0898 (13)	0.0592 (12)	−0.0201 (9)	−0.0038 (9)	−0.0108 (10)
O13	0.0760 (11)	0.0542 (10)	0.0393 (10)	−0.0188 (8)	−0.0006 (8)	0.0013 (8)
O22	0.0670 (10)	0.0652 (10)	0.0373 (9)	−0.0221 (8)	0.0003 (8)	−0.0192 (8)
O23	0.0768 (12)	0.0708 (12)	0.0374 (10)	−0.0019 (9)	−0.0075 (9)	−0.0108 (9)
N11	0.0660 (13)	0.0482 (11)	0.0377 (11)	−0.0159 (9)	−0.0007 (10)	−0.0112 (9)
N21	0.0656 (12)	0.0432 (10)	0.0377 (11)	−0.0116 (9)	0.0055 (9)	−0.0092 (8)
C13	0.0557 (14)	0.0451 (12)	0.0399 (13)	−0.0169 (10)	−0.0032 (11)	−0.0070 (10)
N22	0.0873 (16)	0.0519 (12)	0.0376 (12)	−0.0002 (11)	−0.0033 (11)	−0.0066 (9)
N12	0.0695 (13)	0.0526 (11)	0.0398 (12)	−0.0019 (10)	−0.0120 (10)	−0.0127 (9)
C23	0.0611 (14)	0.0417 (12)	0.0401 (13)	−0.0181 (10)	0.0062 (11)	−0.0076 (10)
C24	0.0667 (16)	0.0472 (13)	0.0468 (15)	−0.0122 (11)	0.0000 (12)	−0.0007 (11)
C22	0.0580 (14)	0.0464 (12)	0.0342 (12)	−0.0172 (11)	0.0036 (10)	−0.0061 (10)
C25	0.0794 (18)	0.0621 (16)	0.0379 (14)	−0.0213 (14)	−0.0061 (13)	0.0008 (12)
C17	0.0657 (16)	0.0612 (15)	0.0459 (15)	−0.0100 (12)	0.0012 (12)	−0.0174 (12)
C12	0.0550 (13)	0.0466 (12)	0.0356 (12)	−0.0192 (10)	−0.0021 (10)	−0.0082 (10)
C27	0.0858 (19)	0.0533 (14)	0.0456 (15)	−0.0171 (13)	0.0122 (13)	−0.0156 (12)
C14	0.0706 (16)	0.0525 (14)	0.0486 (15)	−0.0096 (12)	−0.0123 (13)	−0.0062 (12)
C26	0.0829 (18)	0.0623 (16)	0.0319 (13)	−0.0280 (14)	0.0033 (12)	−0.0084 (11)
C16	0.091 (2)	0.0644 (16)	0.0316 (13)	−0.0288 (15)	−0.0051 (13)	−0.0087 (11)
C15	0.091 (2)	0.0639 (17)	0.0414 (15)	−0.0211 (15)	−0.0182 (14)	−0.0011 (12)

Geometric parameters (Å, º)

S2—O21	1.550 (2)	N12—H12A	0.8600
S2—O24	1.4450 (18)	N12—H12B	0.8600
S2—O22	1.4423 (17)	N12—C12	1.326 (3)
S2—O23	1.4468 (19)	C23—C24	1.361 (3)
S1—O12	1.4425 (18)	C23—C22	1.417 (3)
S1—O11	1.5564 (18)	C23—C27	1.504 (3)
S1—O14	1.4442 (18)	C24—H24	0.9300
S1—O13	1.4430 (18)	C24—C25	1.392 (4)
O21—H21A	0.8200	C25—H25	0.9300
O11—H11A	0.8200	C25—C26	1.349 (4)
N11—H11	0.8600	C17—H17A	0.9600
N11—C12	1.351 (3)	C17—H17B	0.9600
N11—C16	1.352 (3)	C17—H17C	0.9600
N21—H21	0.8600	C27—H27A	0.9600
N21—C22	1.348 (3)	C27—H27B	0.9600
N21—C26	1.347 (3)	C27—H27C	0.9600
C13—C17	1.498 (3)	C14—H14	0.9300
C13—C12	1.415 (3)	C14—C15	1.405 (4)
C13—C14	1.362 (3)	C26—H26	0.9300
N22—H22A	0.8600	C16—H16	0.9300
N22—H22B	0.8600	C16—C15	1.341 (4)
N22—C22	1.327 (3)	C15—H15	0.9300
O24—S2—O21	102.57 (11)	C25—C24—H24	118.7
O24—S2—O23	112.14 (11)	N21—C22—C23	118.1 (2)
O22—S2—O21	107.66 (12)	N22—C22—N21	118.4 (2)
O22—S2—O24	114.21 (10)	N22—C22—C23	123.5 (2)
O22—S2—O23	112.21 (11)	C24—C25—H25	121.1
O23—S2—O21	107.24 (12)	C26—C25—C24	117.9 (2)
O12—S1—O11	107.83 (11)	C26—C25—H25	121.1
O12—S1—O14	111.58 (11)	C13—C17—H17A	109.5
O12—S1—O13	112.14 (10)	C13—C17—H17B	109.5
O14—S1—O11	103.25 (11)	C13—C17—H17C	109.5
O13—S1—O11	106.97 (11)	H17A—C17—H17B	109.5
O13—S1—O14	114.35 (12)	H17A—C17—H17C	109.5
S2—O21—H21A	109.5	H17B—C17—H17C	109.5
S1—O11—H11A	109.5	N11—C12—C13	118.3 (2)
C12—N11—H11	118.4	N12—C12—N11	118.0 (2)
C12—N11—C16	123.3 (2)	N12—C12—C13	123.7 (2)
C16—N11—H11	118.4	C23—C27—H27A	109.5
C22—N21—H21	118.3	C23—C27—H27B	109.5
C26—N21—H21	118.3	C23—C27—H27C	109.5
C26—N21—C22	123.3 (2)	H27A—C27—H27B	109.5
C12—C13—C17	119.4 (2)	H27A—C27—H27C	109.5
C14—C13—C17	122.8 (2)	H27B—C27—H27C	109.5
C14—C13—C12	117.8 (2)	C13—C14—H14	119.0
H22A—N22—H22B	120.0	C13—C14—C15	122.0 (2)
C22—N22—H22A	120.0	C15—C14—H14	119.0
C22—N22—H22B	120.0	N21—C26—C25	120.4 (2)
H12A—N12—H12B	120.0	N21—C26—H26	119.8
C12—N12—H12A	120.0	C25—C26—H26	119.8
C12—N12—H12B	120.0	N11—C16—H16	119.9
C24—C23—C22	117.6 (2)	C15—C16—N11	120.1 (2)
C24—C23—C27	123.3 (2)	C15—C16—H16	119.9
C22—C23—C27	119.1 (2)	C14—C15—H15	120.7
C23—C24—H24	118.7	C16—C15—C14	118.5 (2)
C23—C24—C25	122.6 (2)	C16—C15—H15	120.7
N11—C16—C15—C14	−1.0 (4)	C12—N11—C16—C15	0.2 (4)
C13—C14—C15—C16	0.6 (4)	C12—C13—C14—C15	0.5 (4)
C23—C24—C25—C26	2.6 (4)	C27—C23—C24—C25	−179.8 (3)
C24—C23—C22—N21	−2.5 (3)	C27—C23—C22—N21	177.2 (2)
C24—C23—C22—N22	177.4 (2)	C27—C23—C22—N22	−2.9 (4)
C24—C25—C26—N21	−2.2 (4)	C14—C13—C12—N11	−1.2 (3)
C22—N21—C26—C25	−0.5 (4)	C14—C13—C12—N12	179.3 (2)
C22—C23—C24—C25	−0.2 (4)	C26—N21—C22—N22	−177.0 (2)
C17—C13—C12—N11	178.7 (2)	C26—N21—C22—C23	2.9 (4)
C17—C13—C12—N12	−0.8 (4)	C16—N11—C12—C13	1.0 (4)
C17—C13—C14—C15	−179.4 (3)	C16—N11—C12—N12	−179.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O21—H21A···O14	0.82	1.77	2.575 (3)	168
O11—H11A···O24^i	0.82	1.80	2.607 (3)	169
N11—H11···O23	0.86	1.91	2.770 (3)	176
N21—H21···O13	0.86	2.01	2.829 (3)	159
N22—H22A···O12	0.86	2.07	2.924 (3)	174
N22—H22B···O22^ii	0.86	2.21	2.976 (3)	149
N12—H12A···O22	0.86	2.20	3.043 (3)	167
N12—H12B···O12^ii	0.86	2.10	2.906 (3)	155
C26—H26···O23^iii	0.93	2.36	3.249 (3)	159
C16—H16···O13^iii	0.93	2.52	3.437 (3)	170

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

(IV) Bis(2-amino-3-methylpyridinium) sulfate monohydrate

Crystal data

2C6H9N2^+·SO4^2^−·H2O	F(000) = 704
Mr = 332.38	Dx = 1.414 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.909 (4) Å	Cell parameters from 3026 reflections
b = 10.700 (4) Å	θ = 3.5–27.1°
c = 14.267 (4) Å	µ = 0.24 mm^−1
β = 110.34 (3)°	T = 295 K
V = 1561.5 (10) Å^3	Block, colourless
Z = 4	0.47 × 0.38 × 0.24 mm

Data collection

Rigaku Oxford Diffraction Xcalibur Atlas diffractometer	3627 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	2471 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 10.6249 pixels mm^-1	θmax = 29.3°, θmin = 3.0°
ω scans	h = −13→13
Absorption correction: analytical [CrysAlis PRO (Rigaku Oxford Diffraction, 2015), based on expressions derived Clark & Reid (1995)]	k = −10→13
Tmin = 0.920, Tmax = 0.956	l = −13→17
8806 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 0.366P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
3627 reflections	Δρmax = 0.17 e Å^−3
209 parameters	Δρmin = −0.35 e Å^−3
0 restraints

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.

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

	x	y	z	Uiso*/Ueq
S1	0.72531 (5)	0.29571 (5)	0.46286 (4)	0.04223 (16)
O1	0.62744 (12)	0.39662 (12)	0.45202 (10)	0.0483 (4)
O4	0.67656 (15)	0.21620 (15)	0.37315 (11)	0.0662 (5)
O3	0.73891 (16)	0.22195 (14)	0.55118 (11)	0.0594 (4)
N21	0.67255 (15)	0.64287 (15)	0.47175 (11)	0.0410 (4)
H21	0.6643	0.5633	0.4632	0.049*
O2	0.84963 (13)	0.35313 (14)	0.46971 (13)	0.0661 (5)
O1W	0.7618 (2)	0.12591 (18)	0.22015 (17)	0.0717 (5)
N11	0.41313 (18)	0.17852 (17)	0.29541 (12)	0.0521 (5)
H11	0.4949	0.1968	0.3204	0.063*
N22	0.89453 (15)	0.61269 (16)	0.52966 (13)	0.0516 (4)
H22A	0.8808	0.5337	0.5208	0.062*
H22B	0.9732	0.6409	0.5527	0.062*
N12	0.36908 (17)	0.38697 (17)	0.30324 (13)	0.0553 (5)
H12A	0.4517	0.4005	0.3302	0.066*
H12B	0.3148	0.4482	0.2927	0.066*
C23	0.8078 (2)	0.82167 (19)	0.52160 (14)	0.0443 (5)
C26	0.56326 (19)	0.7130 (2)	0.44841 (15)	0.0468 (5)
H26	0.4816	0.6749	0.4242	0.056*
C22	0.79406 (18)	0.69127 (18)	0.50771 (13)	0.0388 (4)
C13	0.1901 (2)	0.2416 (2)	0.23286 (14)	0.0493 (5)
C12	0.3255 (2)	0.2719 (2)	0.27786 (13)	0.0445 (5)
C25	0.5721 (2)	0.8377 (2)	0.46011 (16)	0.0544 (6)
H25	0.4972	0.8867	0.4444	0.065*
C24	0.6960 (2)	0.8922 (2)	0.49637 (16)	0.0546 (6)
H24	0.7030	0.9785	0.5036	0.066*
C27	0.9415 (2)	0.8768 (2)	0.56570 (19)	0.0685 (7)
H27A	0.9839	0.8436	0.6316	0.103*
H27B	0.9348	0.9660	0.5694	0.103*
H27C	0.9918	0.8562	0.5244	0.103*
C16	0.3790 (3)	0.0576 (2)	0.27570 (17)	0.0658 (7)
H16	0.4436	−0.0034	0.2892	0.079*
C17	0.0920 (2)	0.3434 (2)	0.20901 (18)	0.0659 (7)
H17A	0.0900	0.3799	0.2699	0.099*
H17B	0.0073	0.3101	0.1717	0.099*
H17C	0.1150	0.4062	0.1700	0.099*
C15	0.2520 (3)	0.0243 (3)	0.23659 (18)	0.0732 (7)
H15	0.2275	−0.0591	0.2247	0.088*
C14	0.1587 (3)	0.1193 (2)	0.21458 (16)	0.0627 (6)
H14	0.0709	0.0977	0.1861	0.075*
H1WA	0.746 (3)	0.166 (3)	0.261 (2)	0.099 (12)*
H1WB	0.759 (3)	0.177 (3)	0.177 (2)	0.095 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0335 (3)	0.0393 (3)	0.0549 (3)	−0.0003 (2)	0.0168 (2)	−0.0003 (2)
O1	0.0340 (7)	0.0388 (8)	0.0710 (9)	0.0019 (6)	0.0169 (6)	0.0020 (7)
O4	0.0582 (10)	0.0753 (11)	0.0661 (10)	0.0010 (8)	0.0230 (8)	−0.0241 (8)
O3	0.0675 (10)	0.0502 (9)	0.0609 (9)	0.0090 (8)	0.0228 (8)	0.0120 (7)
N21	0.0355 (8)	0.0400 (9)	0.0489 (9)	−0.0032 (7)	0.0165 (7)	−0.0028 (7)
O2	0.0366 (8)	0.0582 (10)	0.1082 (13)	−0.0027 (7)	0.0309 (8)	0.0041 (9)
O1W	0.0992 (15)	0.0568 (12)	0.0617 (12)	0.0058 (10)	0.0313 (11)	−0.0016 (10)
N11	0.0539 (11)	0.0579 (12)	0.0420 (10)	0.0042 (9)	0.0135 (8)	0.0007 (8)
N22	0.0348 (9)	0.0484 (10)	0.0696 (12)	−0.0014 (8)	0.0158 (8)	−0.0002 (9)
N12	0.0434 (10)	0.0512 (11)	0.0641 (11)	−0.0017 (9)	0.0094 (8)	0.0014 (9)
C23	0.0469 (11)	0.0444 (12)	0.0442 (11)	−0.0103 (10)	0.0192 (9)	−0.0023 (9)
C26	0.0327 (10)	0.0588 (14)	0.0499 (12)	0.0005 (10)	0.0154 (8)	0.0024 (10)
C22	0.0346 (10)	0.0446 (11)	0.0387 (10)	−0.0032 (9)	0.0149 (8)	0.0009 (8)
C13	0.0510 (12)	0.0586 (14)	0.0357 (11)	−0.0063 (11)	0.0117 (9)	−0.0012 (9)
C12	0.0469 (11)	0.0508 (13)	0.0344 (10)	0.0032 (10)	0.0123 (8)	0.0033 (9)
C25	0.0516 (13)	0.0539 (14)	0.0619 (14)	0.0133 (11)	0.0250 (10)	0.0087 (11)
C24	0.0705 (15)	0.0411 (12)	0.0591 (13)	0.0013 (11)	0.0312 (11)	0.0028 (10)
C27	0.0628 (15)	0.0621 (15)	0.0815 (17)	−0.0272 (13)	0.0261 (13)	−0.0129 (13)
C16	0.0914 (19)	0.0531 (15)	0.0548 (14)	0.0156 (14)	0.0281 (13)	0.0017 (11)
C17	0.0463 (13)	0.0798 (17)	0.0616 (14)	0.0017 (12)	0.0062 (11)	0.0001 (12)
C15	0.107 (2)	0.0537 (15)	0.0604 (15)	−0.0119 (16)	0.0312 (15)	−0.0092 (12)
C14	0.0704 (16)	0.0673 (16)	0.0490 (13)	−0.0161 (14)	0.0189 (11)	−0.0081 (11)

Geometric parameters (Å, º)

S1—O1	1.4882 (14)	C23—C27	1.494 (3)
S1—O4	1.4737 (16)	C26—H26	0.9300
S1—O3	1.4500 (16)	C26—C25	1.344 (3)
S1—O2	1.4609 (15)	C13—C12	1.428 (3)
N21—H21	0.8600	C13—C17	1.482 (3)
N21—C26	1.349 (2)	C13—C14	1.354 (3)
N21—C22	1.347 (2)	C25—H25	0.9300
O1W—H1WA	0.78 (3)	C25—C24	1.396 (3)
O1W—H1WB	0.82 (3)	C24—H24	0.9300
N11—H11	0.8600	C27—H27A	0.9600
N11—C12	1.345 (3)	C27—H27B	0.9600
N11—C16	1.349 (3)	C27—H27C	0.9600
N22—H22A	0.8600	C16—H16	0.9300
N22—H22B	0.8600	C16—C15	1.349 (4)
N22—C22	1.330 (2)	C17—H17A	0.9600
N12—H12A	0.8600	C17—H17B	0.9600
N12—H12B	0.8600	C17—H17C	0.9600
N12—C12	1.324 (3)	C15—H15	0.9300
C23—C22	1.410 (3)	C15—C14	1.395 (4)
C23—C24	1.371 (3)	C14—H14	0.9300
O4—S1—O1	107.42 (9)	N11—C12—C13	118.2 (2)
O3—S1—O1	109.77 (9)	N12—C12—N11	118.36 (19)
O3—S1—O4	109.73 (10)	N12—C12—C13	123.5 (2)
O3—S1—O2	111.01 (10)	C26—C25—H25	120.7
O2—S1—O1	108.52 (9)	C26—C25—C24	118.6 (2)
O2—S1—O4	110.32 (10)	C24—C25—H25	120.7
C26—N21—H21	118.4	C23—C24—C25	121.7 (2)
C22—N21—H21	118.4	C23—C24—H24	119.1
C22—N21—C26	123.26 (17)	C25—C24—H24	119.1
H1WA—O1W—H1WB	104 (3)	C23—C27—H27A	109.5
C12—N11—H11	118.4	C23—C27—H27B	109.5
C12—N11—C16	123.2 (2)	C23—C27—H27C	109.5
C16—N11—H11	118.4	H27A—C27—H27B	109.5
H22A—N22—H22B	120.0	H27A—C27—H27C	109.5
C22—N22—H22A	120.0	H27B—C27—H27C	109.5
C22—N22—H22B	120.0	N11—C16—H16	119.7
H12A—N12—H12B	120.0	N11—C16—C15	120.6 (2)
C12—N12—H12A	120.0	C15—C16—H16	119.7
C12—N12—H12B	120.0	C13—C17—H17A	109.5
C22—C23—C27	119.36 (19)	C13—C17—H17B	109.5
C24—C23—C22	117.78 (19)	C13—C17—H17C	109.5
C24—C23—C27	122.8 (2)	H17A—C17—H17B	109.5
N21—C26—H26	119.9	H17A—C17—H17C	109.5
C25—C26—N21	120.16 (19)	H17B—C17—H17C	109.5
C25—C26—H26	119.9	C16—C15—H15	121.1
N21—C22—C23	118.45 (17)	C16—C15—C14	117.7 (2)
N22—C22—N21	117.90 (18)	C14—C15—H15	121.1
N22—C22—C23	123.64 (17)	C13—C14—C15	123.0 (2)
C12—C13—C17	119.2 (2)	C13—C14—H14	118.5
C14—C13—C12	117.3 (2)	C15—C14—H14	118.5
C14—C13—C17	123.5 (2)
N21—C26—C25—C24	0.2 (3)	C27—C23—C22—N21	177.27 (18)
N11—C16—C15—C14	2.0 (4)	C27—C23—C22—N22	−1.6 (3)
C26—N21—C22—N22	178.88 (17)	C27—C23—C24—C25	−176.6 (2)
C26—N21—C22—C23	−0.1 (3)	C16—N11—C12—N12	177.62 (19)
C26—C25—C24—C23	−1.1 (3)	C16—N11—C12—C13	−2.3 (3)
C22—N21—C26—C25	0.4 (3)	C16—C15—C14—C13	−1.6 (4)
C22—C23—C24—C25	1.4 (3)	C17—C13—C12—N11	−177.54 (18)
C12—N11—C16—C15	−0.1 (3)	C17—C13—C12—N12	2.5 (3)
C12—C13—C14—C15	−0.8 (3)	C17—C13—C14—C15	179.4 (2)
C24—C23—C22—N21	−0.8 (3)	C14—C13—C12—N11	2.7 (3)
C24—C23—C22—N22	−179.67 (18)	C14—C13—C12—N12	−177.26 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N21—H21···O1	0.86	1.82	2.677 (2)	172
N11—H11···O4	0.86	1.87	2.727 (3)	173
N22—H22A···O2	0.86	2.05	2.897 (3)	168
N22—H22B···O2^i	0.86	2.07	2.812 (2)	145
N12—H12A···O1	0.86	2.09	2.881 (2)	152
N12—H12B···O1W^ii	0.86	2.06	2.890 (3)	162
C26—H26···O1^iii	0.93	2.57	3.127 (3)	119
O1W—H1WA···O4	0.78 (3)	2.07 (3)	2.824 (3)	161 (3)
O1W—H1WB···O3^iv	0.82 (3)	2.04 (3)	2.847 (3)	169 (3)

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