Diammonium biphenyl-4,4′-disulfonate

Abstract

In the title salt, 2NH₄ ⁺·C₁₂H₈O₆S₂ ²⁻, the dianion has crystallographic inversion symmetry. A three-dimensional framework is formed from primary hydrogen-bonded sheet structures comprising ammonium N—H⋯O_sulfonate inter­actions and is linked peripherally through the biphenyl residues of the anions. This open framework has 43 ų solvent-accessible voids.

Related literature

Biphenyl-4,4′-disulfonate clathrate structures may be found in: Russell et al. (1997 ▶); Swift, Pivovar et al. (1998 ▶); Swift, Reynolds & Ward (1998 ▶); Swift & Ward (2000 ▶); Pivovar et al. (2001 ▶).

Experimental

Crystal data

• 2NH₄ ⁺·C₁₂H₈O₆S₂ ²⁻

• M _r = 348.39

• Monoclinic,

• a = 14.778 (2) Å

• b = 7.4138 (12) Å

• c = 7.6647 (13) Å

• β = 96.667 (13)°

• V = 834.1 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 0.35 mm⁻¹

• T = 297 (2) K

• 0.40 × 0.30 × 0.11 mm

Data collection

• Rigaku AFC 7R four-circle diffractometer

• Absorption correction: ψ scan (TEXSAN for Windows; Molecular Structure Corporation, 1999 ▶) T _min = 0.874, T _max = 0.963

• 2129 measured reflections

• 1909 independent reflections

• 1030 reflections with I > 2σ(I)

• R _int = 0.037

• 3 standard reflections frequency: 150 min intensity decay: 1.6%

Refinement

• R[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 0.172

• S = 0.86

• 1909 reflections

• 116 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.39 e Å⁻³

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999 ▶); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O11i	0.91 (5)	1.96 (4)	2.861 (5)	172 (4)
N1—H12⋯O11ii	0.80 (5)	2.18 (5)	2.922 (5)	153 (5)
N1—H12⋯O13iii	0.80 (5)	2.45 (5)	2.955 (4)	122 (4)
N1—H13⋯O13	0.91 (6)	1.96 (6)	2.841 (5)	162 (4)
N1—H14⋯O12iv	0.88 (5)	1.97 (5)	2.848 (5)	174 (4)
C2—H2⋯O11	0.95	2.48	2.873 (6)	105
C6—H6⋯O12v	0.95	2.33	3.243 (6)	161

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

supplementary crystallographic information

Comment

The guanidinium salts of biphenyl-4,4'-disulfonic acid (BPDSH₂) form two-dimensional hydrogen-bonded open-framework structures in which the guanidinium cations form sheets connected by BPDS pillars. (Russell et al., 1997). These structures may accommodate various molecular guest species, commonly aromatic hydrocarbons, giving crystalline clathrates of the type (Gu⁺)₂ BPDS^2-. nG (where G = the guest species) (Swift, Pivovar et al., 1998; Swift, Reynolds & Ward, 1998; Swift & Ward, 2000; Pivovar et al., 2001). Because it was considered that the ammonium salt of BPDSH₂ might also have an open framework structure, we prepared crystals of anhydrous (NH₄⁺)₂ C₁₂H₈O₆S₂^2- (I) from an aqueous ammoniacal solution of the acid and the structure is reported here.

In (I), the planar anions have inversion symmetry coincident with crystallographic symmetry (Fig. 1). Each ammonium cation gives a total of five associations with sulfonate-O acceptors of the cation (Table 1) resulting in sheet structures which extend across the bc planes in the unit cell at a = 0. These sheets are linked across the a cell direction through the biphenyl residues of the BPDS anions, giving a three- dimensional framework structure (Fig. 2). There are 43 ų solvent accessible voids within the structure.

Experimental

Compound (I) was prepared by the room temperature interaction in a 2:1 stoichiometric ratio of ammonia as an aqueous solution with biphenyl-4,4'-disulfonic acid. Colourless crystal plates (m. p. >573 K) were obtained from the partial room temperature evaporation of this solution.

Refinement

The ammonium hydrogen atoms were located by difference methods and their positional and isotropic displacement parameters were refined. The aromatic H atoms were included in the refinement in calculated positions (C–H = 0.95 Å) using a riding model approximation, with U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

Molecular configuration and atom naming scheme for the BPDS anion in (I). Atoms of the inversion-related half of the compound are indicated by symmetry code (vi) (-x + 1, -y, -z + 1). The dashed lines represent the hydrogen bonds between the ammonium protons and the sulfonate-O acceptors.

Fig. 2.

A perspective view of the three-dimensional hydrogen-bonded framework structure of (I) with ammonium N–H–Osulfonate sheets interlinked by the biphenyl residues of the BPDS anions.

Crystal data

2N1H4+·C12H8O6S22–	F000 = 364
Mr = 348.39	Dx = 1.387 Mg m−3
Monoclinic, P21/c	Melting point > 573 K
Hall symbol: -P 2ybc	Mo Kα radiation λ = 0.71073 Å
a = 14.778 (2) Å	Cell parameters from 25 reflections
b = 7.4138 (12) Å	θ = 13.7–17.1º
c = 7.6647 (13) Å	µ = 0.35 mm−1
β = 96.667 (13)º	T = 297 (2) K
V = 834.1 (2) Å3	Plate, colourless
Z = 2	0.40 × 0.30 × 0.11 mm

Data collection

Rigaku AFC 7R four-circle diffractometer	Rint = 0.037
Radiation source: Rigaku rotating anode	θmax = 27.5º
Monochromator: graphite	θmin = 2.8º
T = 297(2) K	h = −8→19
ω–2θ scans	k = 0→9
Absorption correction: ψ scan(TEXSAN for Windows; Molecular Structure Corporation,1999)	l = −9→9
Tmin = 0.874, Tmax = 0.963	3 standard reflections
2129 measured reflections	every 150 min
1909 independent reflections	intensity decay: 1.6%
1030 reflections with I > 2σ(I)

Refinement

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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.172	w = 1/[σ2(Fo2) + (0.1P)2 + 0.8639P] where P = (Fo2 + 2Fc2)/3
S = 0.86	(Δ/σ)max < 0.001
1909 reflections	Δρmax = 0.30 e Å−3
116 parameters	Δρmin = −0.38 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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
S1	0.15898 (5)	0.00272 (12)	0.19165 (11)	0.0282 (2)
O11	0.15361 (18)	−0.1393 (4)	0.0601 (3)	0.0415 (8)
O12	0.14295 (19)	0.1783 (4)	0.1126 (4)	0.0458 (9)
O13	0.10228 (17)	−0.0332 (4)	0.3285 (3)	0.0442 (9)
C1	0.2732 (2)	0.0001 (5)	0.2931 (4)	0.0313 (9)
C2	0.3348 (3)	−0.1181 (8)	0.2409 (8)	0.079 (2)
C3	0.4233 (3)	−0.1161 (8)	0.3218 (8)	0.086 (2)
C4	0.4528 (2)	0.0004 (6)	0.4560 (5)	0.0383 (11)
C5	0.3888 (3)	0.1184 (8)	0.5045 (6)	0.0660 (18)
C6	0.3001 (3)	0.1182 (8)	0.4249 (7)	0.0664 (18)
N1	−0.0887 (3)	0.0292 (5)	0.2899 (5)	0.0376 (11)
H2	0.31710	−0.20180	0.14940	0.0940*
H3	0.46580	−0.19870	0.28270	0.1020*
H5	0.40600	0.20300	0.59550	0.0790*
H6	0.25740	0.20130	0.46240	0.0800*
H11	−0.107 (3)	0.055 (5)	0.175 (6)	0.039 (11)*
H12	−0.110 (3)	0.096 (7)	0.357 (6)	0.055 (15)*
H13	−0.027 (4)	0.035 (6)	0.299 (5)	0.055 (14)*
H14	−0.109 (3)	−0.076 (7)	0.323 (6)	0.053 (14)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0262 (4)	0.0305 (4)	0.0273 (4)	−0.0015 (4)	0.0011 (3)	0.0018 (4)
O11	0.0439 (16)	0.0432 (15)	0.0345 (13)	0.0003 (13)	−0.0073 (11)	−0.0066 (12)
O12	0.0426 (16)	0.0346 (15)	0.0595 (17)	0.0035 (12)	0.0030 (13)	0.0109 (13)
O13	0.0284 (13)	0.073 (2)	0.0313 (13)	−0.0046 (13)	0.0043 (10)	0.0096 (13)
C1	0.0245 (15)	0.0370 (17)	0.0324 (16)	−0.0007 (17)	0.0030 (12)	−0.0043 (18)
C2	0.042 (3)	0.089 (4)	0.097 (4)	0.024 (3)	−0.026 (3)	−0.067 (3)
C3	0.041 (3)	0.098 (4)	0.110 (4)	0.028 (3)	−0.023 (3)	−0.073 (4)
C4	0.0226 (17)	0.051 (2)	0.0404 (19)	−0.0011 (19)	0.0003 (14)	−0.010 (2)
C5	0.034 (2)	0.090 (4)	0.071 (3)	0.010 (2)	−0.006 (2)	−0.053 (3)
C6	0.031 (2)	0.090 (4)	0.075 (3)	0.016 (2)	−0.007 (2)	−0.054 (3)
N1	0.039 (2)	0.046 (2)	0.0285 (17)	0.0049 (16)	0.0073 (14)	0.0010 (16)

Geometric parameters (Å, °)

S1—O11	1.454 (3)	C2—C3	1.381 (7)
S1—O12	1.444 (3)	C3—C4	1.375 (7)
S1—O13	1.441 (3)	C4—C5	1.371 (6)
S1—C1	1.775 (3)	C4—C4i	1.477 (4)
N1—H14	0.88 (5)	C5—C6	1.380 (6)
N1—H11	0.91 (5)	C2—H2	0.9500
N1—H12	0.80 (5)	C3—H3	0.9500
N1—H13	0.91 (6)	C5—H5	0.9500
C1—C6	1.361 (6)	C6—H6	0.9500
C1—C2	1.357 (6)
O11—S1—O12	111.65 (17)	C1—C2—C3	119.6 (5)
O11—S1—O13	112.42 (16)	C2—C3—C4	123.0 (5)
O11—S1—C1	105.58 (16)	C3—C4—C5	115.8 (4)
O12—S1—O13	113.02 (17)	C4i—C4—C5	121.6 (4)
O12—S1—C1	107.17 (17)	C3—C4—C4i	122.7 (4)
O13—S1—C1	106.43 (15)	C4—C5—C6	122.0 (5)
H12—N1—H14	101 (5)	C1—C6—C5	120.6 (5)
H13—N1—H14	113 (4)	C1—C2—H2	120.00
H11—N1—H14	113 (4)	C3—C2—H2	120.00
H11—N1—H12	113 (4)	C4—C3—H3	118.00
H11—N1—H13	104 (4)	C2—C3—H3	119.00
H12—N1—H13	113 (4)	C4—C5—H5	119.00
C2—C1—C6	119.1 (4)	C6—C5—H5	119.00
S1—C1—C2	121.0 (3)	C5—C6—H6	120.00
S1—C1—C6	120.0 (3)	C1—C6—H6	120.00
O11—S1—C1—C2	0.7 (4)	C1—C2—C3—C4	0.6 (9)
O11—S1—C1—C6	−179.5 (3)	C2—C3—C4—C5	−0.9 (8)
O12—S1—C1—C2	−118.4 (4)	C2—C3—C4—C4i	178.9 (5)
O12—S1—C1—C6	61.4 (4)	C3—C4—C5—C6	0.8 (7)
O13—S1—C1—C2	120.4 (4)	C4i—C4—C5—C6	−179.0 (5)
O13—S1—C1—C6	−59.8 (4)	C3—C4—C4i—C3i	−180.0 (5)
S1—C1—C2—C3	179.6 (4)	C3—C4—C4i—C5i	0.2 (7)
C6—C1—C2—C3	−0.2 (8)	C5—C4—C4i—C3i	−0.2 (7)
S1—C1—C6—C5	−179.7 (4)	C5—C4—C4i—C5i	180.0 (5)
C2—C1—C6—C5	0.1 (7)	C4—C5—C6—C1	−0.5 (8)

Symmetry codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O11ii	0.91 (5)	1.96 (4)	2.861 (5)	172 (4)
N1—H12···O11iii	0.80 (5)	2.18 (5)	2.922 (5)	153 (5)
N1—H12···O13iv	0.80 (5)	2.45 (5)	2.955 (4)	122 (4)
N1—H13···O13	0.91 (6)	1.96 (6)	2.841 (5)	162 (4)
N1—H14···O12v	0.88 (5)	1.97 (5)	2.848 (5)	174 (4)
C2—H2···O11	0.95	2.48	2.873 (6)	105
C6—H6···O12vi	0.95	2.33	3.243 (6)	161

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