Di­hydro­nium 3-nitro­benzene­sulfonate

The title compound, H₅O₂⁺·C₆H₄NO₅S^-, crystallized slowly over a period of several years. It is stable and the di­hydro­nium cation is well determined; all of the H-atom positions in the cation were refined. The strong hydrogen bond between the O atoms is nearly linear, with the H atom near the midpoint of the two O atoms. The refined O-H distances are 1.15 (2) and 1.27 (2) Å, respectively.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.036
• wR factor = 0.104
• Data-to-parameter ratio = 16.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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S1. Comment

In the title compound, dihydronium 3-nitrobenzenesulfonate, (I), water molecules are strongly hydrogen bonded with an O···O separation of 2.411 (2) Å, forming a dihydronium (H₅O₂⁺) cation. Each of the remaining H atoms in the cation participates in intermolecular hydrogen bonding with the sulfonate O atoms, and each sulfonate O atom acts as an acceptor, forming a three-dimensional network. There are a number of reports of dihydronium ions in the solid state. In the April 2002 release of the Cambridge Structural Database (Allen & Kennard, 1993), there are 36 occurrences in which the O···O separations are less than 2.6 Å between H₃O⁺ and H₂O pairs. Some early examples are: bis[chloro(1,2-propanediamine-N,N')cobalt] chloride hydrichloride hydronium (Saito & Iwasaki, 1962), and hydrogen chloride dihydrate (Lundgren & Olavssen, 1967).

In the current study, the data quality is sufficient to refine the dihydronium H-atom positions. The strong hydrogen bond between the waters is nearly linear, with the O—H···O angle equal to 177 (2)°. The hydrogen bonds between the ions are also nearly linear, with O—H···O angles in the range 174 (2)–179 (2)°. The central H atom in the cation has O—H distances of O1S—H1C = 1.15 (2) Å and O2S—H1C = 1.27 (2) Å. The dihydronium O atoms are pyramidal, with O1S 0.28 (2) Å out of the plane formed by atoms H1A, H1B, and H1, and O2S 0.32 (2) Å out of the the plane formed by atoms H2A, H2B, and H1C. The remaining cation O—H distances are O1S—H1A = 0.86 (2) Å, O1S—H1B = 0.83 (2) Å, O2S—H2A = 0.81 (2) Å and O2S—H2B = 0.81 (2) Å. The structure of the 3-nitrobenezenesulfonate anion has been reported in guandinium 3-nitrobenezenesulfonate (Russel & Ward, 1997) and in (2-p-benzoquinonediimine)decaaminediruthenium(II,III) pentakis(m-nitrobenzenesulfonate) pentahydrate (Joss et al., 1985). Here, the nitro moiety is twisted out of the benzene plane; the torsion angle C2—C3—N3—O3B is 20.2 (2)°. The orientation of the sulfonate is defined by the torsion angle C2—C1—S1—O1B of −104.6 (1)°. The room-temperature (295 K) cell is a = 7.945 (4) Å, b = 8.119 (4) Å, c = 9.389 (5) Å, α = 90.42 (1), β = 94.70 (1) and γ = 119.08°(1).

S2. Experimental

A Friedel Crafts substitution on PhCH₂CH₂Br with m-ClSO₂C₆H₄NO₂, AlCl₃ and CH₂Cl₂ was worked-up by hydrolysis, drying of the organic layer, and distillation. The yellow distillate (383 K, vac) contained several products, from which dihydronium 3-nitrobenzenesulfonate, (I), crystallized over a period of several years. Apparently, (I) was formed from the hydrolysis of unreacted sulfonyl chloride.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Displacement ellipsoid plot of dihydronium 3-nitrobenzene sulfonate, drawn at the 50% probability level.
	Fig. 2. Packing diagram viewed down the b axis. Dashed lines indicate hydrogen bonds.

dihydronium 3-nitrobenzenesulfonate

Crystal data

H5O2^+·C6H4NO5S^−	Z = 2
Mr = 239.20	F(000) = 248
Triclinic, P1	Dx = 1.540 Mg m^−3
a = 7.872 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.986 (2) Å	Cell parameters from 3195 reflections
c = 9.414 (2) Å	θ = 3.0–27.9°
α = 90.456 (5)°	µ = 0.33 mm^−1
β = 95.284 (5)°	T = 93 K
γ = 118.701 (5)°	Plate, yellow
V = 516.0 (1) Å^3	0.52 × 0.43 × 0.18 mm

Data collection

Bruker 1K CCD area-detector diffractometer	2433 independent reflections
Radiation source: sealed tube	2086 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scans	θmax = 28.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→10
Tmin = 0.845, Tmax = 0.943	k = −9→10
4192 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: diffmap
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0655P)^2 + 0.0567P] where P = (Fo^2 + 2Fc^2)/3
2433 reflections	(Δ/σ)max = 0.003
151 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

Experimental. Final cell refinement and decay correction applied after integration as part of merge process in SAINT v6.02 A.

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
C1	0.4772 (2)	0.7412 (2)	0.59702 (16)	0.0169 (3)
S1	0.46966 (5)	0.73880 (5)	0.78402 (4)	0.01761 (13)
O1A	0.37564 (18)	0.85010 (17)	0.81836 (13)	0.0257 (3)
O1B	0.36244 (18)	0.53895 (16)	0.81739 (12)	0.0254 (3)
O1C	0.67432 (16)	0.82819 (16)	0.84702 (12)	0.0226 (3)
C2	0.6480 (2)	0.7784 (2)	0.54137 (17)	0.0188 (3)
H2A	0.7585	0.7994	0.6006	0.023*
C3	0.6484 (2)	0.7832 (2)	0.39382 (17)	0.0193 (3)
N3	0.8314 (2)	0.82990 (19)	0.33401 (16)	0.0244 (3)
O3A	0.85094 (19)	0.88751 (17)	0.21244 (14)	0.0326 (3)
O3B	0.95581 (18)	0.80919 (19)	0.40894 (14)	0.0330 (3)
C4	0.4853 (2)	0.7485 (2)	0.30227 (18)	0.0234 (3)
H4A	0.4899	0.7526	0.2039	0.028*
C5	0.3152 (3)	0.7076 (3)	0.36067 (19)	0.0274 (4)
H5A	0.2035	0.6817	0.3009	0.033*
C6	0.3100 (2)	0.7050 (2)	0.50774 (18)	0.0232 (3)
H6A	0.1960	0.6793	0.5464	0.028*
O1S	−0.17062 (17)	0.18654 (17)	−0.03435 (13)	0.0217 (3)
H1SA	−0.238 (3)	0.171 (3)	0.035 (2)	0.028*
H1SB	−0.210 (3)	0.078 (3)	−0.070 (2)	0.028*
H1SC	−0.007 (3)	0.275 (3)	0.001 (2)	0.028*
O2S	0.17265 (18)	0.38120 (17)	0.04070 (13)	0.0225 (3)
H2SA	0.234 (3)	0.429 (3)	−0.026 (2)	0.029*
H2SB	0.221 (3)	0.318 (3)	0.074 (2)	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0202 (8)	0.0151 (7)	0.0151 (7)	0.0081 (6)	0.0029 (6)	0.0015 (5)
S1	0.0191 (2)	0.0167 (2)	0.0161 (2)	0.00755 (16)	0.00457 (14)	0.00130 (14)
O1A	0.0302 (6)	0.0280 (6)	0.0248 (6)	0.0175 (5)	0.0106 (5)	0.0023 (5)
O1B	0.0309 (7)	0.0187 (6)	0.0219 (6)	0.0073 (5)	0.0079 (5)	0.0035 (5)
O1C	0.0223 (6)	0.0244 (6)	0.0184 (6)	0.0097 (5)	−0.0008 (4)	−0.0013 (4)
C2	0.0179 (7)	0.0165 (7)	0.0206 (8)	0.0072 (6)	0.0019 (6)	−0.0007 (6)
C3	0.0206 (8)	0.0164 (7)	0.0207 (8)	0.0078 (6)	0.0079 (6)	0.0012 (6)
N3	0.0238 (7)	0.0188 (7)	0.0272 (8)	0.0065 (6)	0.0097 (6)	−0.0031 (6)
O3A	0.0404 (8)	0.0272 (6)	0.0296 (7)	0.0127 (6)	0.0210 (6)	0.0068 (5)
O3B	0.0215 (6)	0.0427 (8)	0.0341 (7)	0.0148 (6)	0.0052 (5)	−0.0048 (6)
C4	0.0303 (9)	0.0248 (8)	0.0172 (8)	0.0148 (7)	0.0039 (6)	0.0035 (6)
C5	0.0266 (9)	0.0379 (9)	0.0216 (9)	0.0192 (8)	−0.0009 (7)	0.0033 (7)
C6	0.0192 (8)	0.0291 (8)	0.0233 (9)	0.0129 (7)	0.0046 (6)	0.0041 (7)
O1S	0.0223 (6)	0.0221 (6)	0.0196 (6)	0.0097 (5)	0.0032 (5)	−0.0006 (5)
O2S	0.0232 (6)	0.0226 (6)	0.0207 (6)	0.0100 (5)	0.0044 (5)	0.0024 (5)

Geometric parameters (Å, º)

C1—C2	1.385 (2)	C4—C5	1.386 (2)
C1—C6	1.396 (2)	C4—H4A	0.9300
C1—S1	1.7669 (16)	C5—C6	1.389 (2)
S1—O1A	1.4539 (11)	C5—H5A	0.9300
S1—O1B	1.4564 (12)	C6—H6A	0.9300
S1—O1C	1.4729 (12)	O1S—H1SA	0.86 (2)
C2—C3	1.390 (2)	O1S—H1SB	0.83 (2)
C2—H2A	0.9300	O1S—H1SC	1.15 (2)
C3—C4	1.385 (2)	O2S—H1SC	1.27 (2)
C3—N3	1.472 (2)	O2S—H2SA	0.81 (2)
N3—O3B	1.2307 (18)	O2S—H2SB	0.81 (2)
N3—O3A	1.2320 (18)
C2—C1—C6	121.10 (14)	O3A—N3—C3	118.21 (14)
C2—C1—S1	119.68 (12)	C3—C4—C5	118.43 (15)
C6—C1—S1	119.21 (12)	C3—C4—H4A	120.8
O1A—S1—O1B	113.69 (7)	C5—C4—H4A	120.8
O1A—S1—O1C	112.33 (7)	C4—C5—C6	120.60 (15)
O1B—S1—O1C	111.42 (7)	C4—C5—H5A	119.7
O1A—S1—C1	106.37 (7)	C6—C5—H5A	119.7
O1B—S1—C1	106.74 (7)	C5—C6—C1	119.50 (15)
O1C—S1—C1	105.66 (7)	C5—C6—H6A	120.2
C1—C2—C3	117.68 (14)	C1—C6—H6A	120.2
C1—C2—H2A	121.2	H1SA—O1S—H1SB	105 (2)
C3—C2—H2A	121.2	H1SA—O1S—H1SC	111.6 (17)
C4—C3—C2	122.66 (15)	H1SB—O1S—H1SC	116.8 (17)
C4—C3—N3	119.25 (14)	H1SC—O2S—H2SA	112.1 (17)
C2—C3—N3	118.08 (14)	H1SC—O2S—H2SB	110.5 (17)
O3B—N3—O3A	123.99 (14)	H2SA—O2S—H2SB	104 (2)
O3B—N3—C3	117.79 (14)
C2—C1—S1—O1A	133.73 (12)	C4—C3—N3—O3B	−160.66 (14)
C6—C1—S1—O1A	−46.40 (14)	C2—C3—N3—O3B	20.2 (2)
C2—C1—S1—O1B	−104.56 (13)	C4—C3—N3—O3A	19.4 (2)
C6—C1—S1—O1B	75.32 (13)	C2—C3—N3—O3A	−159.66 (14)
C2—C1—S1—O1C	14.15 (14)	C2—C3—C4—C5	0.0 (2)
C6—C1—S1—O1C	−165.97 (12)	N3—C3—C4—C5	−179.02 (14)
C6—C1—C2—C3	1.6 (2)	C3—C4—C5—C6	1.1 (2)
S1—C1—C2—C3	−178.55 (11)	C4—C5—C6—C1	−1.0 (3)
C1—C2—C3—C4	−1.4 (2)	C2—C1—C6—C5	−0.4 (2)
C1—C2—C3—N3	177.69 (12)	S1—C1—C6—C5	179.67 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1SC···O2S	1.15 (2)	1.27 (2)	2.411 (2)	177 (2)
O1S—H1SA···O1A^i	0.86 (2)	1.79 (2)	2.643 (2)	177 (2)
O1S—H1SB···O1C^ii	0.83 (2)	1.87 (2)	2.696 (2)	174 (2)
O2S—H2SA···O1B^iii	0.81 (2)	1.85 (2)	2.656 (2)	177 (2)
O2S—H2SB···O1C^iv	0.81 (2)	1.85 (2)	2.663 (2)	179 (2)

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