A whole zoo of hydrogen bonds in one crystal structure: tris­(isonicotinium) hydrogensulfate sulfate monohydrate

Depending on the reaction partner, the organic ditopic mol­ecule isonicotinic acid (Hina) can act either as a Brønsted acid or base. With sulfuric acid, the pyridine ring is protonated to become a pyridinium cation. Crystallization from ethanol affords the title compound tris­(4-carboxypyridinium) hydrogensulfate sulfate monohydrate, 3C₆H₆NO₂⁺·HSO₄⁻·SO₄²⁻·H₂O or [(H₂ina)₃(HSO₄)(SO₄)(H₂O)]. This solid contains 11 classical hydrogen bonds of very different flavour and nonclassical C—H...O contacts. All N—H and O—H donors find at least one acceptor within a suitable distance range, with one of the three pyridinium H atoms engaged in bifurcated N—H...O hydrogen bonds. The shortest hydrogen-bonding O...O distance is subtended by hydrogensulfate and sulfate anions, viz. 2.4752 (19) Å, and represents one of the shortest hydrogen bonds ever reported between these residues.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2009); program(s) used to solve structure: PLATON (Spek, 2009); program(s) used to refine structure: SHELXS2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2015).

Tris(4-carboxypyridinium) hydrogensulfate sulfate monohydrate

Crystal data

3C6H6NO2^+·HO4S^−·O4S^2^−·H2O	F(000) = 2416
Mr = 583.50	Dx = 1.638 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.951 (3) Å	Cell parameters from 4228 reflections
b = 11.7885 (18) Å	θ = 2.4–27.5°
c = 20.891 (4) Å	µ = 0.31 mm^−1
β = 105.625 (3)°	T = 100 K
V = 4731.8 (14) Å^3	Block, colourless
Z = 8	0.28 × 0.27 × 0.27 mm

Data collection

Bruker D8 goniometer with APEX CCD detector diffractometer	6845 independent reflections
Radiation source: microsource	5404 reflections with I > 2σ(I)
Multilayer optics monochromator	Rint = 0.063
/w scans	θmax = 30.2°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −28→27
Tmin = 0.623, Tmax = 0.746	k = −16→16
35239 measured reflections	l = −29→29

Refinement

Refinement on F^2	9 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.116	w = 1/[σ^2(Fo^2) + (0.0487P)^2 + 4.9842P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
6845 reflections	Δρmax = 0.51 e Å^−3
370 parameters	Δρmin = −0.56 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
S1	0.12011 (2)	0.66605 (3)	0.64692 (2)	0.01370 (10)
S2	0.38158 (2)	0.68524 (3)	0.55967 (2)	0.01295 (10)
O1	0.43434 (8)	0.37731 (11)	0.64455 (7)	0.0238 (3)
O2	0.40083 (8)	0.36973 (11)	0.53333 (7)	0.0210 (3)
H2	0.4044 (12)	0.4422 (14)	0.5356 (11)	0.025*
O3	0.23405 (8)	0.25122 (11)	0.68902 (7)	0.0234 (3)
O4	0.26037 (9)	0.26583 (11)	0.59142 (7)	0.0255 (3)
H4	0.2563 (13)	0.3392 (14)	0.5965 (12)	0.031*
O5	0.08490 (9)	0.36146 (11)	0.73034 (7)	0.0263 (3)
O6	0.08406 (8)	0.35221 (11)	0.62292 (7)	0.0190 (3)
H6	0.0861 (12)	0.4245 (13)	0.6266 (11)	0.023*
O7	0.07743 (7)	0.56994 (10)	0.61529 (7)	0.0197 (3)
O8	0.09884 (8)	0.71299 (11)	0.70275 (6)	0.0198 (3)
O9	0.19404 (7)	0.63968 (11)	0.66209 (7)	0.0205 (3)
O10	0.10480 (8)	0.76394 (11)	0.59579 (7)	0.0205 (3)
H10	0.1177 (12)	0.7472 (19)	0.5605 (9)	0.025*
O11	0.35396 (7)	0.76788 (10)	0.50441 (6)	0.0172 (3)
O12	0.41017 (7)	0.58692 (10)	0.53266 (6)	0.0180 (3)
O13	0.43568 (7)	0.74273 (10)	0.61154 (7)	0.0192 (3)
O14	0.32375 (7)	0.65188 (11)	0.58716 (7)	0.0191 (3)
O15	0.24056 (9)	0.47673 (12)	0.58955 (8)	0.0277 (3)
H1O	0.2218 (13)	0.514 (2)	0.6159 (11)	0.033*
H2O	0.2767 (11)	0.5208 (19)	0.5927 (12)	0.033*
N1	0.43030 (8)	−0.03301 (12)	0.59824 (8)	0.0162 (3)
H1N	0.4341 (11)	−0.1125 (13)	0.6011 (10)	0.019*
N2	0.26499 (9)	−0.14498 (13)	0.62201 (8)	0.0186 (3)
H2N	0.2701 (12)	−0.2190 (14)	0.6169 (11)	0.022*
N3	0.08556 (9)	−0.04953 (13)	0.68357 (8)	0.0187 (3)
H3N	0.0861 (12)	−0.1268 (13)	0.6855 (11)	0.022*
C1	0.41914 (10)	0.32400 (14)	0.59312 (9)	0.0150 (3)
C2	0.42136 (10)	0.19676 (14)	0.59313 (9)	0.0144 (3)
C3	0.41498 (10)	0.13498 (15)	0.53508 (9)	0.0170 (4)
H3	0.4072	0.1723	0.4934	0.020*
C4	0.42015 (10)	0.01831 (15)	0.53926 (9)	0.0176 (4)
H4A	0.4165	−0.0255	0.5003	0.021*
C5	0.43604 (10)	0.02422 (15)	0.65494 (9)	0.0170 (4)
H5	0.4430	−0.0156	0.6958	0.020*
C6	0.43178 (10)	0.14122 (15)	0.65383 (9)	0.0160 (3)
H6A	0.4359	0.1829	0.6936	0.019*
C7	0.24846 (10)	0.20984 (15)	0.64145 (9)	0.0161 (4)
C8	0.25418 (9)	0.08322 (15)	0.63380 (9)	0.0147 (3)
C9	0.25505 (10)	0.03596 (15)	0.57303 (9)	0.0157 (3)
H9	0.2518	0.0830	0.5354	0.019*
C10	0.26071 (10)	−0.08001 (15)	0.56820 (9)	0.0173 (4)
H10A	0.2616	−0.1138	0.5271	0.021*
C11	0.26340 (10)	−0.10231 (16)	0.68129 (10)	0.0197 (4)
H11	0.2659	−0.1515	0.7179	0.024*
C12	0.25815 (10)	0.01324 (15)	0.68862 (9)	0.0171 (4)
H12	0.2572	0.0447	0.7302	0.021*
C13	0.08430 (10)	0.30755 (15)	0.68092 (9)	0.0167 (4)
C14	0.08399 (10)	0.18012 (14)	0.68048 (9)	0.0153 (3)
C15	0.07360 (10)	0.11874 (15)	0.62185 (9)	0.0158 (3)
H15	0.0661	0.1568	0.5804	0.019*
C16	0.07433 (10)	0.00215 (15)	0.62448 (9)	0.0167 (4)
H16	0.0670	−0.0412	0.5849	0.020*
C17	0.09552 (12)	0.00712 (17)	0.74096 (10)	0.0237 (4)
H17	0.1033	−0.0332	0.7817	0.028*
C18	0.09452 (11)	0.12415 (16)	0.74086 (10)	0.0220 (4)
H18	0.1009	0.1654	0.7811	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0194 (2)	0.00870 (19)	0.0141 (2)	0.00012 (15)	0.00646 (17)	0.00099 (15)
S2	0.0181 (2)	0.00743 (18)	0.0138 (2)	−0.00006 (15)	0.00527 (16)	0.00094 (14)
O1	0.0394 (9)	0.0140 (6)	0.0194 (7)	−0.0011 (6)	0.0104 (6)	−0.0036 (5)
O2	0.0378 (9)	0.0075 (6)	0.0170 (6)	0.0011 (5)	0.0061 (6)	0.0010 (5)
O3	0.0310 (8)	0.0188 (7)	0.0215 (7)	0.0038 (6)	0.0091 (6)	−0.0043 (5)
O4	0.0424 (10)	0.0100 (6)	0.0302 (8)	0.0013 (6)	0.0206 (7)	0.0001 (6)
O5	0.0438 (10)	0.0158 (7)	0.0219 (7)	0.0015 (6)	0.0135 (7)	−0.0048 (5)
O6	0.0298 (8)	0.0096 (6)	0.0186 (6)	−0.0005 (5)	0.0083 (6)	−0.0001 (5)
O7	0.0231 (7)	0.0102 (6)	0.0254 (7)	−0.0020 (5)	0.0058 (6)	−0.0024 (5)
O8	0.0298 (8)	0.0145 (6)	0.0188 (7)	0.0012 (5)	0.0133 (6)	0.0003 (5)
O9	0.0194 (7)	0.0216 (7)	0.0204 (7)	0.0017 (5)	0.0053 (5)	−0.0021 (5)
O10	0.0383 (9)	0.0108 (6)	0.0158 (6)	0.0042 (5)	0.0131 (6)	0.0033 (5)
O11	0.0251 (7)	0.0116 (6)	0.0158 (6)	0.0050 (5)	0.0071 (5)	0.0037 (5)
O12	0.0259 (8)	0.0093 (6)	0.0210 (7)	0.0025 (5)	0.0101 (6)	0.0000 (5)
O13	0.0206 (7)	0.0121 (6)	0.0207 (7)	−0.0004 (5)	−0.0014 (5)	−0.0012 (5)
O14	0.0233 (7)	0.0144 (6)	0.0230 (7)	−0.0031 (5)	0.0122 (6)	0.0005 (5)
O15	0.0356 (9)	0.0135 (7)	0.0413 (9)	−0.0036 (6)	0.0231 (8)	−0.0025 (6)
N1	0.0175 (8)	0.0095 (7)	0.0212 (8)	−0.0010 (6)	0.0046 (6)	0.0008 (6)
N2	0.0207 (8)	0.0108 (7)	0.0226 (8)	−0.0013 (6)	0.0028 (6)	−0.0009 (6)
N3	0.0233 (9)	0.0094 (7)	0.0259 (8)	−0.0004 (6)	0.0110 (7)	0.0022 (6)
C1	0.0188 (9)	0.0106 (8)	0.0173 (8)	0.0010 (6)	0.0081 (7)	−0.0004 (6)
C2	0.0165 (9)	0.0100 (7)	0.0172 (8)	−0.0010 (6)	0.0055 (7)	0.0002 (6)
C3	0.0238 (10)	0.0131 (8)	0.0146 (8)	−0.0004 (7)	0.0057 (7)	−0.0005 (6)
C4	0.0215 (10)	0.0130 (8)	0.0184 (9)	−0.0021 (7)	0.0057 (7)	−0.0016 (7)
C5	0.0184 (9)	0.0145 (8)	0.0177 (8)	−0.0007 (7)	0.0040 (7)	0.0029 (7)
C6	0.0183 (9)	0.0154 (8)	0.0149 (8)	−0.0012 (7)	0.0056 (7)	0.0000 (6)
C7	0.0163 (9)	0.0124 (8)	0.0189 (9)	0.0005 (6)	0.0032 (7)	−0.0007 (6)
C8	0.0143 (9)	0.0125 (8)	0.0182 (8)	−0.0004 (6)	0.0056 (7)	−0.0007 (6)
C9	0.0177 (9)	0.0140 (8)	0.0161 (8)	0.0003 (7)	0.0058 (7)	0.0005 (6)
C10	0.0172 (9)	0.0154 (8)	0.0185 (8)	−0.0001 (7)	0.0031 (7)	−0.0037 (7)
C11	0.0198 (10)	0.0182 (9)	0.0198 (9)	−0.0011 (7)	0.0029 (7)	0.0051 (7)
C12	0.0181 (9)	0.0180 (9)	0.0154 (8)	−0.0013 (7)	0.0046 (7)	−0.0010 (7)
C13	0.0206 (10)	0.0130 (8)	0.0174 (8)	0.0007 (7)	0.0065 (7)	−0.0012 (6)
C14	0.0190 (9)	0.0115 (8)	0.0164 (8)	0.0005 (6)	0.0062 (7)	−0.0009 (6)
C15	0.0192 (9)	0.0123 (8)	0.0160 (8)	0.0005 (7)	0.0047 (7)	−0.0003 (6)
C16	0.0177 (9)	0.0142 (8)	0.0182 (9)	0.0007 (7)	0.0048 (7)	−0.0017 (7)
C17	0.0346 (12)	0.0186 (9)	0.0211 (9)	0.0004 (8)	0.0131 (8)	0.0040 (7)
C18	0.0357 (12)	0.0163 (9)	0.0168 (9)	0.0003 (8)	0.0118 (8)	−0.0003 (7)

Geometric parameters (Å, º)

S1—O8	1.4538 (13)	N3—H3N	0.911 (16)
S1—O9	1.4563 (14)	C1—C2	1.501 (2)
S1—O7	1.4637 (13)	C2—C3	1.391 (2)
S1—O10	1.5460 (13)	C2—C6	1.392 (2)
S2—O12	1.4699 (13)	C3—C4	1.380 (2)
S2—O13	1.4726 (14)	C3—H3	0.9500
S2—O14	1.4740 (14)	C4—H4A	0.9500
S2—O11	1.4977 (13)	C5—C6	1.382 (2)
O1—C1	1.211 (2)	C5—H5	0.9500
O2—C1	1.318 (2)	C6—H6A	0.9500
O2—H2	0.857 (16)	C7—C8	1.509 (2)
O3—C7	1.209 (2)	C8—C9	1.391 (2)
O4—C7	1.311 (2)	C8—C12	1.396 (2)
O4—H4	0.878 (16)	C9—C10	1.378 (2)
O5—C13	1.210 (2)	C9—H9	0.9500
O6—C13	1.320 (2)	C10—H10A	0.9500
O6—H6	0.855 (16)	C11—C12	1.378 (3)
O10—H10	0.867 (16)	C11—H11	0.9500
O15—H1O	0.864 (16)	C12—H12	0.9500
O15—H2O	0.876 (17)	C13—C14	1.502 (2)
N1—C4	1.338 (2)	C14—C18	1.388 (3)
N1—C5	1.341 (2)	C14—C15	1.389 (2)
N1—H1N	0.940 (15)	C15—C16	1.375 (2)
N2—C10	1.344 (2)	C15—H15	0.9500
N2—C11	1.345 (2)	C16—H16	0.9500
N2—H2N	0.888 (16)	C17—C18	1.380 (3)
N3—C17	1.340 (3)	C17—H17	0.9500
N3—C16	1.340 (2)	C18—H18	0.9500
O8—S1—O9	113.83 (8)	C6—C5—H5	120.1
O8—S1—O7	113.38 (8)	C5—C6—C2	118.57 (17)
O9—S1—O7	111.41 (8)	C5—C6—H6A	120.7
O8—S1—O10	102.95 (8)	C2—C6—H6A	120.7
O9—S1—O10	108.04 (8)	O3—C7—O4	125.91 (17)
O7—S1—O10	106.45 (8)	O3—C7—C8	121.84 (17)
O12—S2—O13	111.23 (8)	O4—C7—C8	112.25 (15)
O12—S2—O14	111.39 (8)	C9—C8—C12	120.02 (16)
O13—S2—O14	109.36 (8)	C9—C8—C7	120.85 (16)
O12—S2—O11	108.49 (7)	C12—C8—C7	119.13 (16)
O13—S2—O11	108.21 (8)	C10—C9—C8	119.06 (17)
O14—S2—O11	108.05 (8)	C10—C9—H9	120.5
C1—O2—H2	110.9 (16)	C8—C9—H9	120.5
C7—O4—H4	111.0 (16)	N2—C10—C9	119.49 (17)
C13—O6—H6	109.1 (15)	N2—C10—H10A	120.3
S1—O10—H10	111.6 (15)	C9—C10—H10A	120.3
H1O—O15—H2O	98 (2)	N2—C11—C12	119.57 (17)
C4—N1—C5	122.79 (15)	N2—C11—H11	120.2
C4—N1—H1N	119.9 (13)	C12—C11—H11	120.2
C5—N1—H1N	117.3 (13)	C11—C12—C8	118.82 (17)
C10—N2—C11	123.04 (16)	C11—C12—H12	120.6
C10—N2—H2N	116.3 (15)	C8—C12—H12	120.6
C11—N2—H2N	120.7 (15)	O5—C13—O6	124.80 (17)
C17—N3—C16	123.05 (16)	O5—C13—C14	121.98 (17)
C17—N3—H3N	117.4 (14)	O6—C13—C14	113.22 (15)
C16—N3—H3N	119.5 (14)	C18—C14—C15	120.24 (16)
O1—C1—O2	124.59 (16)	C18—C14—C13	118.05 (16)
O1—C1—C2	121.23 (16)	C15—C14—C13	121.71 (16)
O2—C1—C2	114.17 (15)	C16—C15—C14	119.19 (17)
C3—C2—C6	120.28 (16)	C16—C15—H15	120.4
C3—C2—C1	121.84 (16)	C14—C15—H15	120.4
C6—C2—C1	117.86 (16)	N3—C16—C15	119.24 (17)
C4—C3—C2	118.61 (17)	N3—C16—H16	120.4
C4—C3—H3	120.7	C15—C16—H16	120.4
C2—C3—H3	120.7	N3—C17—C18	119.91 (18)
N1—C4—C3	119.93 (17)	N3—C17—H17	120.0
N1—C4—H4A	120.0	C18—C17—H17	120.0
C3—C4—H4A	120.0	C17—C18—C14	118.36 (18)
N1—C5—C6	119.81 (17)	C17—C18—H18	120.8
N1—C5—H5	120.1	C14—C18—H18	120.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O12	0.86 (2)	1.71 (2)	2.5675 (18)	175 (2)
O4—H4···O15	0.88 (2)	1.65 (2)	2.5160 (19)	168 (2)
O6—H6···O7	0.86 (2)	1.73 (2)	2.5728 (18)	167 (2)
O10—H10···O11^i	0.87 (2)	1.61 (2)	2.4752 (19)	173 (2)
O15—H1O···O9	0.86 (2)	1.93 (2)	2.758 (2)	160 (2)
O15—H2O···O14	0.88 (2)	1.83 (2)	2.658 (2)	157 (2)
N1—H1N···O13^ii	0.94 (2)	1.72 (2)	2.6574 (19)	174 (2)
N2—H2N···O9^ii	0.89 (2)	2.60 (2)	3.128 (2)	119 (2)
N2—H2N···O14^ii	0.89 (2)	2.05 (2)	2.846 (2)	148 (2)
N3—H3N···O8^ii	0.91 (2)	1.93 (2)	2.830 (2)	171 (2)
N3—H3N···O10^ii	0.91 (2)	2.39 (2)	2.954 (2)	120 (2)
C17—H17···O1^iii	0.95	2.16	3.031 (2)	152

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