Tris(4-hydroxy-pyridinium) hydrogen sulfate-sulfate monohydrate.

In the crystal structure of the title salt, 3C(5)H(6)NO(+)·HSO(4) (-)·SO(4) (2-)·H(2)O, the hydrogen sulfate ion is linked to the sulfate ion by an O-H⋯O hydrogen bond. The hydrogen sulfate-sulfate anion is a hydrogen-bond acceptor for the three independent cations and the uncoordinated water mol-ecule, the hydrogen-bonding inter-actions giving rise to a three-dimensional hydrogen-bonded network. In the hydrogen sulfate-sulfate species, one of the sulfate groups is disordered in respect of its O atoms in a 2:1 ratio.

Related literature

For the crystal structure of bis­(4-hydroxy­pyridinium) sulfate monohydrate, see: Xu et al. (2009 ▶).

Experimental

Crystal data

3C5H6NO+·HSO4 −·SO4 2−·H2O

M = 499.47

Orthorhombic,

a = 10.5622 (3) Å

b = 19.6760 (7) Å

c = 20.2980 (7) Å

V = 4218.4 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.32 mm−1

T = 293 K

0.23 × 0.17 × 0.14 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.930, T max = 0.956

38906 measured reflections

4816 independent reflections

3031 reflections with I > 2σ(I)

R int = 0.064

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.133

S = 1.08

4816 reflections

359 parameters

151 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.31 e Å−3

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048545/xu2676sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809048545/xu2676Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

3C5H6NO+·HSO4−·SO42−·H2O	F(000) = 2080
Mr = 499.47	Dx = 1.573 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 21088 reflections
a = 10.5622 (3) Å	θ = 3.0–27.5°
b = 19.6760 (7) Å	µ = 0.32 mm−1
c = 20.2980 (7) Å	T = 293 K
V = 4218.4 (2) Å3	Prism, colorless
Z = 8	0.23 × 0.17 × 0.14 mm

Rigaku R-AXIS RAPID IP diffractometer	4816 independent reflections
Radiation source: fine-focus sealed tube	3031 reflections with I > 2σ(I)
graphite	Rint = 0.064
ω scan	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −13→13
Tmin = 0.930, Tmax = 0.956	k = −25→25
38906 measured reflections	l = −26→25

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0687P)2] where P = (Fo2 + 2Fc2)/3
4816 reflections	(Δ/σ)max = 0.001
359 parameters	Δρmax = 0.36 e Å−3
151 restraints	Δρmin = −0.31 e Å−3

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.47437 (6)	0.72762 (4)	0.42526 (3)	0.0411 (2)
S2	0.70661 (6)	0.53636 (3)	0.42933 (3)	0.03703 (19)
O1	0.3908 (3)	0.77692 (16)	0.45160 (13)	0.0526 (8)	0.67
O2	0.4603 (3)	0.66376 (14)	0.46657 (13)	0.0534 (7)	0.67
H2O	0.4899	0.6300	0.4455	0.080*	0.33
O3	0.6093 (2)	0.74804 (17)	0.43084 (14)	0.0526 (7)	0.67
O4	0.4463 (6)	0.7087 (3)	0.35765 (17)	0.057 (2)	0.67
O1'	0.4860 (6)	0.7986 (2)	0.4441 (3)	0.0619 (17)	0.33
O2'	0.3670 (5)	0.6974 (3)	0.4642 (3)	0.0687 (18)	0.33
O3'	0.5908 (4)	0.6914 (3)	0.4441 (3)	0.0594 (16)	0.33
O4'	0.4480 (10)	0.7201 (6)	0.3559 (3)	0.050 (4)	0.33
O5	0.79101 (16)	0.57990 (11)	0.46790 (8)	0.0564 (5)
O6	0.57405 (16)	0.55782 (10)	0.43845 (10)	0.0520 (5)
H6O	0.5716	0.6002	0.4464	0.078*	0.67
O7	0.71622 (18)	0.46548 (9)	0.45195 (9)	0.0516 (5)
O8	0.73894 (17)	0.53979 (11)	0.35927 (8)	0.0557 (5)
O9	0.61528 (17)	0.78290 (11)	0.76401 (9)	0.0525 (5)
O10	0.5361 (2)	0.61193 (12)	0.77445 (10)	0.0622 (6)
O11	0.92913 (18)	0.45490 (11)	0.76645 (9)	0.0516 (5)
O1W	0.8138 (3)	0.36629 (14)	0.37081 (11)	0.0745 (7)
N1	0.4461 (2)	0.79165 (14)	0.58566 (11)	0.0523 (6)
N2	0.6911 (2)	0.60986 (12)	0.59204 (11)	0.0477 (6)
N3	0.7757 (2)	0.44865 (13)	0.58375 (11)	0.0486 (6)
C1	0.3737 (3)	0.79553 (16)	0.63918 (13)	0.0526 (7)
H1	0.2866	0.8006	0.6346	0.063*
C2	0.4252 (2)	0.79225 (14)	0.70003 (12)	0.0442 (6)
H2	0.3740	0.7943	0.7372	0.053*
C3	0.5562 (2)	0.78579 (13)	0.70632 (11)	0.0377 (6)
C4	0.6297 (2)	0.78230 (13)	0.64949 (12)	0.0406 (6)
H4	0.7173	0.7782	0.6524	0.049*
C5	0.5724 (3)	0.78489 (14)	0.58982 (12)	0.0466 (7)
H5	0.6207	0.7820	0.5516	0.056*
C6	0.5672 (3)	0.59812 (15)	0.60013 (14)	0.0514 (7)
H6	0.5166	0.5892	0.5636	0.062*
C7	0.5147 (2)	0.59914 (15)	0.66110 (13)	0.0512 (7)
H7	0.4285	0.5912	0.6663	0.061*
C8	0.5901 (2)	0.61199 (14)	0.71564 (12)	0.0434 (6)
C9	0.7191 (2)	0.62398 (14)	0.70587 (13)	0.0449 (6)
H9	0.7718	0.6329	0.7415	0.054*
C10	0.7664 (3)	0.62247 (14)	0.64387 (13)	0.0461 (7)
H10	0.8522	0.6303	0.6371	0.055*
C11	0.6988 (2)	0.44270 (14)	0.63582 (13)	0.0466 (7)
H11	0.6123	0.4373	0.6293	0.056*
C12	0.7455 (2)	0.44448 (13)	0.69802 (12)	0.0402 (6)
H12	0.6915	0.4401	0.7339	0.048*
C13	0.8755 (2)	0.45294 (13)	0.70767 (11)	0.0367 (6)
C14	0.9534 (2)	0.45910 (14)	0.65243 (12)	0.0447 (6)
H14	1.0403	0.4647	0.6574	0.054*
C15	0.9007 (3)	0.45679 (15)	0.59115 (13)	0.0489 (7)
H15	0.9521	0.4609	0.5542	0.059*
H1N	0.415 (3)	0.7950 (17)	0.5474 (8)	0.082 (11)*
H2N	0.721 (3)	0.6063 (15)	0.5534 (7)	0.062 (9)*
H3N	0.747 (3)	0.4507 (18)	0.5449 (8)	0.088 (12)*
H1W	0.789 (3)	0.3988 (12)	0.3951 (14)	0.093 (13)*
H2W	0.848 (4)	0.3357 (14)	0.3939 (15)	0.115 (17)*
H9O	0.556 (2)	0.7852 (18)	0.7929 (14)	0.089 (13)*
H10O	0.592 (2)	0.6200 (17)	0.8044 (12)	0.076 (12)*
H11O	0.869 (2)	0.4553 (18)	0.7952 (13)	0.087 (12)*

	U11	U22	U33	U12	U13	U23
S1	0.0440 (4)	0.0531 (4)	0.0263 (3)	0.0036 (3)	−0.0035 (3)	−0.0001 (3)
S2	0.0342 (3)	0.0518 (4)	0.0250 (3)	−0.0001 (3)	−0.0003 (2)	0.0013 (3)
O1	0.0608 (19)	0.063 (2)	0.0335 (14)	0.0284 (16)	−0.0029 (14)	−0.0034 (14)
O2	0.0640 (19)	0.0522 (19)	0.0440 (16)	0.0061 (16)	0.0156 (14)	0.0115 (13)
O3	0.0423 (15)	0.063 (2)	0.0523 (17)	−0.0059 (15)	−0.0035 (13)	0.0008 (15)
O4	0.059 (4)	0.085 (4)	0.028 (3)	−0.009 (3)	−0.003 (3)	−0.006 (2)
O1'	0.086 (5)	0.048 (4)	0.052 (3)	0.000 (3)	−0.018 (3)	−0.006 (3)
O2'	0.054 (4)	0.107 (5)	0.045 (3)	−0.016 (4)	0.010 (3)	0.005 (3)
O3'	0.043 (3)	0.067 (4)	0.068 (4)	0.016 (3)	−0.017 (3)	−0.005 (3)
O4'	0.038 (6)	0.088 (7)	0.023 (6)	0.007 (5)	−0.001 (5)	−0.007 (5)
O5	0.0520 (11)	0.0785 (15)	0.0388 (10)	−0.0227 (10)	−0.0029 (8)	−0.0068 (10)
O6	0.0376 (10)	0.0588 (13)	0.0597 (12)	0.0082 (9)	0.0023 (9)	−0.0031 (10)
O7	0.0676 (12)	0.0504 (12)	0.0368 (10)	0.0132 (9)	−0.0048 (9)	0.0025 (8)
O8	0.0460 (10)	0.0943 (16)	0.0268 (9)	−0.0045 (10)	0.0017 (8)	0.0067 (9)
O9	0.0397 (10)	0.0872 (16)	0.0306 (10)	0.0037 (10)	−0.0050 (8)	0.0019 (9)
O10	0.0547 (13)	0.0897 (17)	0.0422 (11)	−0.0062 (12)	0.0121 (10)	−0.0051 (11)
O11	0.0415 (10)	0.0806 (15)	0.0326 (10)	−0.0052 (10)	−0.0041 (8)	−0.0032 (9)
O1W	0.1018 (19)	0.0718 (18)	0.0498 (13)	0.0291 (15)	0.0102 (13)	−0.0019 (12)
N1	0.0538 (14)	0.0726 (18)	0.0306 (12)	0.0034 (13)	−0.0085 (10)	0.0002 (11)
N2	0.0551 (15)	0.0519 (15)	0.0361 (12)	−0.0027 (11)	0.0071 (11)	0.0024 (11)
N3	0.0600 (15)	0.0511 (15)	0.0346 (12)	0.0046 (12)	−0.0121 (11)	0.0001 (10)
C1	0.0375 (14)	0.076 (2)	0.0438 (15)	0.0026 (14)	−0.0051 (12)	0.0008 (14)
C2	0.0378 (14)	0.0608 (18)	0.0339 (13)	0.0014 (12)	0.0016 (11)	−0.0008 (12)
C3	0.0383 (13)	0.0455 (16)	0.0292 (12)	0.0000 (11)	−0.0035 (10)	0.0012 (10)
C4	0.0366 (13)	0.0484 (16)	0.0369 (13)	0.0025 (11)	0.0035 (11)	−0.0019 (11)
C5	0.0537 (16)	0.0541 (18)	0.0320 (13)	0.0028 (13)	0.0066 (12)	−0.0020 (11)
C6	0.0482 (16)	0.0606 (19)	0.0453 (15)	−0.0073 (14)	−0.0031 (13)	−0.0012 (14)
C7	0.0413 (14)	0.064 (2)	0.0479 (16)	−0.0049 (14)	0.0012 (12)	−0.0013 (14)
C8	0.0452 (15)	0.0466 (16)	0.0384 (14)	0.0018 (12)	0.0048 (11)	0.0001 (12)
C9	0.0407 (14)	0.0531 (18)	0.0409 (14)	−0.0012 (12)	−0.0039 (11)	0.0020 (12)
C10	0.0414 (14)	0.0493 (17)	0.0476 (16)	−0.0043 (12)	0.0027 (12)	0.0052 (12)
C11	0.0386 (14)	0.0513 (18)	0.0498 (16)	0.0022 (12)	−0.0077 (12)	−0.0040 (13)
C12	0.0356 (13)	0.0473 (16)	0.0378 (13)	−0.0021 (11)	0.0023 (11)	−0.0016 (12)
C13	0.0367 (13)	0.0413 (15)	0.0321 (12)	−0.0008 (11)	−0.0009 (10)	−0.0014 (10)
C14	0.0375 (13)	0.0581 (18)	0.0386 (14)	−0.0031 (12)	0.0006 (11)	0.0020 (12)
C15	0.0572 (18)	0.0556 (18)	0.0340 (13)	−0.0003 (14)	0.0066 (12)	0.0031 (12)

S1—O1	1.416 (2)	N3—C11	1.338 (3)
S1—O4'	1.444 (5)	N3—C15	1.339 (4)
S1—O4	1.452 (3)	N3—H3N	0.847 (11)
S1—O1'	1.453 (4)	C1—C2	1.351 (3)
S1—O3'	1.473 (4)	C1—H1	0.9300
S1—O3	1.485 (2)	C2—C3	1.396 (3)
S1—O2'	1.505 (4)	C2—H2	0.9300
S1—O2	1.518 (3)	C3—C4	1.392 (3)
S2—O5	1.4633 (18)	C4—C5	1.355 (3)
S2—O8	1.4641 (17)	C4—H4	0.9300
S2—O7	1.4717 (19)	C5—H5	0.9300
S2—O6	1.4740 (18)	C6—C7	1.356 (4)
O2—H2O	0.8501	C6—H6	0.9300
O6—H6O	0.8501	C7—C8	1.386 (3)
O9—C3	1.328 (3)	C7—H7	0.9300
O9—H9O	0.860 (11)	C8—C9	1.397 (3)
O10—C8	1.323 (3)	C9—C10	1.355 (3)
O10—H10O	0.862 (11)	C9—H9	0.9300
O11—C13	1.321 (3)	C10—H10	0.9300
O11—H11O	0.863 (11)	C11—C12	1.356 (3)
O1W—H1W	0.847 (11)	C11—H11	0.9300
O1W—H2W	0.844 (11)	C12—C13	1.397 (3)
N1—C1	1.330 (3)	C12—H12	0.9300
N1—C5	1.343 (4)	C13—C14	1.396 (3)
N1—H1N	0.846 (11)	C14—C15	1.363 (3)
N2—C6	1.339 (3)	C14—H14	0.9300
N2—C10	1.342 (3)	C15—H15	0.9300
N2—H2N	0.848 (11)
O4'—S1—O1'	111.8 (5)	O9—C3—C4	117.8 (2)
O4—S1—O1'	120.8 (4)	O9—C3—C2	123.4 (2)
O4'—S1—O3'	111.4 (4)	C4—C3—C2	118.8 (2)
O1'—S1—O3'	109.1 (3)	C5—C4—C3	119.3 (2)
O1—S1—O3	112.58 (19)	C5—C4—H4	120.3
O4—S1—O3	109.7 (3)	C3—C4—H4	120.3
O4'—S1—O2'	109.1 (4)	N1—C5—C4	120.2 (2)
O1'—S1—O2'	107.8 (3)	N1—C5—H5	119.9
O3'—S1—O2'	107.5 (3)	C4—C5—H5	119.9
O1—S1—O2	107.29 (17)	N2—C6—C7	120.6 (3)
O4—S1—O2	106.8 (3)	N2—C6—H6	119.7
O3—S1—O2	106.03 (17)	C7—C6—H6	119.7
O5—S2—O8	110.52 (11)	C6—C7—C8	119.8 (2)
O5—S2—O7	110.23 (12)	C6—C7—H7	120.1
O8—S2—O7	109.31 (12)	C8—C7—H7	120.1
O5—S2—O6	110.11 (12)	O10—C8—C7	118.2 (2)
O8—S2—O6	109.29 (11)	O10—C8—C9	123.3 (2)
O7—S2—O6	107.32 (11)	C7—C8—C9	118.5 (2)
S1—O2—H2O	109.5	C10—C9—C8	119.2 (2)
S2—O6—H6O	109.5	C10—C9—H9	120.4
C3—O9—H9O	105 (2)	C8—C9—H9	120.4
C8—O10—H10O	110 (2)	N2—C10—C9	120.9 (3)
C13—O11—H11O	107 (2)	N2—C10—H10	119.5
H1w—O1w—H2W	110.3 (18)	C9—C10—H10	119.5
C1—N1—C5	121.7 (2)	N3—C11—C12	120.9 (2)
C1—N1—H1N	122 (2)	N3—C11—H11	119.6
C5—N1—H1N	117 (2)	C12—C11—H11	119.6
C6—N2—C10	121.0 (2)	C11—C12—C13	119.4 (2)
C6—N2—H2N	118 (2)	C11—C12—H12	120.3
C10—N2—H2N	121 (2)	C13—C12—H12	120.3
C11—N3—C15	121.3 (2)	O11—C13—C14	118.1 (2)
C11—N3—H3N	121 (2)	O11—C13—C12	123.5 (2)
C15—N3—H3N	117 (2)	C14—C13—C12	118.5 (2)
N1—C1—C2	120.9 (2)	C15—C14—C13	119.3 (2)
N1—C1—H1	119.6	C15—C14—H14	120.3
C2—C1—H1	119.6	C13—C14—H14	120.3
C1—C2—C3	119.1 (2)	N3—C15—C14	120.6 (2)
C1—C2—H2	120.4	N3—C15—H15	119.7
C3—C2—H2	120.4	C14—C15—H15	119.7
C5—N1—C1—C2	−0.5 (5)	O10—C8—C9—C10	179.4 (3)
N1—C1—C2—C3	1.0 (4)	C7—C8—C9—C10	−0.2 (4)
C1—C2—C3—O9	179.3 (3)	C6—N2—C10—C9	−0.3 (4)
C1—C2—C3—C4	−0.6 (4)	C8—C9—C10—N2	0.2 (4)
O9—C3—C4—C5	179.8 (2)	C15—N3—C11—C12	−0.3 (4)
C2—C3—C4—C5	−0.3 (4)	N3—C11—C12—C13	0.3 (4)
C1—N1—C5—C4	−0.5 (4)	C11—C12—C13—O11	−179.6 (3)
C3—C4—C5—N1	0.9 (4)	C11—C12—C13—C14	−0.2 (4)
C10—N2—C6—C7	0.4 (4)	O11—C13—C14—C15	179.6 (2)
N2—C6—C7—C8	−0.4 (5)	C12—C13—C14—C15	0.1 (4)
C6—C7—C8—O10	−179.3 (3)	C11—N3—C15—C14	0.2 (4)
C6—C7—C8—C9	0.4 (4)	C13—C14—C15—N3	−0.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O6	0.85	1.68	2.473 (3)	154
O6—H6o···O2	0.85	1.76	2.473 (3)	139
O9—H9o···O4i	0.86 (1)	1.76 (1)	2.612 (6)	174 (4)
O9—H9o···O4'i	0.86 (1)	1.72 (2)	2.569 (9)	172 (4)
O10—H10o···O1wii	0.86 (1)	1.70 (1)	2.554 (3)	172 (3)
O11—H11o···O8ii	0.86 (1)	1.73 (1)	2.591 (3)	173 (4)
O1w—H1w···O7	0.85 (1)	1.91 (1)	2.754 (3)	173 (4)
O1w—H2w···O3iii	0.84 (1)	1.93 (2)	2.749 (4)	162 (4)
N1—H1n···O1	0.85 (1)	1.99 (2)	2.798 (3)	159 (3)
N1—H1n···O1'	0.85 (1)	2.23 (3)	2.907 (6)	138 (3)
N2—H2n···O5	0.85 (1)	1.96 (1)	2.795 (3)	169 (3)
N3—H3n···O7	0.85 (1)	1.94 (1)	2.768 (3)	167 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2o⋯O6	0.85	1.68	2.473 (3)	154
O6—H6o⋯O2	0.85	1.76	2.473 (3)	139
O9—H9o⋯O4i	0.86 (1)	1.76 (1)	2.612 (6)	174 (4)
O9—H9o⋯O4′i	0.86 (1)	1.72 (2)	2.569 (9)	172 (4)
O10—H10o⋯O1wii	0.86 (1)	1.70 (1)	2.554 (3)	172 (3)
O11—H11o⋯O8ii	0.86 (1)	1.73 (1)	2.591 (3)	173 (4)
O1w—H1w⋯O7	0.85 (1)	1.91 (1)	2.754 (3)	173 (4)
O1w—H2w⋯O3iii	0.84 (1)	1.93 (2)	2.749 (4)	162 (4)
N1—H1n⋯O1	0.85 (1)	1.99 (2)	2.798 (3)	159 (3)
N1—H1n⋯O1′	0.85 (1)	2.23 (3)	2.907 (6)	138 (3)
N2—H2n⋯O5	0.85 (1)	1.96 (1)	2.795 (3)	169 (3)
N3—H3n⋯O7	0.85 (1)	1.94 (1)	2.768 (3)	167 (3)

Symmetry codes: (i) ; (ii) ; (iii) .