Bis[2-(2,4-dinitro-benz-yl)pyridinium] biphenyl-4,4'-disulfonate trihydrate.

In the structure of the title salt, 2C(12)H(10)N(3)O(4) (+)·C(12)H(8)O(6)S(2) (2-)·3H(2)O, determined at 173 K, the biphenyl-4,4'-disulfonate dianions lie across crystallographic inversion centres with the sulfonate groups inter-acting head-to-head through centrosymmetric cyclic bis-(water)-bridged hydrogen-bonding associations [graph set R(4) (4)(11)], forming chains. The 2-(2,4-dinitro-benz-yl)pyridinium cations are linked to these chains through pyridinium-water N-H⋯O hydrogen bonds and a two-dimensional network is formed through water bridges between sulfonate and 2-nitro O atoms, while the structure also has weak cation-anion π-π aromatic ring inter-actions [minimum ring centroid separation = 3.8441 (13) Å].

Related literature

For structural data on 2-(2,4-dinitro­benz­yl)pyridine and related compounds, see Seff & Trueblood (1968 ▶); Scherl et al. (1996 ▶); Naumov et al. (2002 ▶, 2005 ▶). For bipyridine-4,4′-disulfonate compounds, see: Swift et al. (1998 ▶); Swift & Ward (1998 ▶); Holman & Ward (2000 ▶); Liao et al. (2001 ▶). For graph-set notation, see: Etter et al. (1990 ▶).

Experimental

Crystal data

2C12H10N3O4 +·C12H8O6S2 2−·3H2O

M = 886.83

Triclinic,

a = 8.3897 (3) Å

b = 10.6455 (4) Å

c = 11.7405 (5) Å

α = 97.879 (3)°

β = 96.926 (3)°

γ = 112.066 (4)°

V = 945.53 (7) Å3

Z = 1

Mo Kα radiation

μ = 0.23 mm−1

T = 173 K

0.30 × 0.25 × 0.15 mm

Data collection

Oxford Diffraction Gemini-S CCD-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.98, T max = 0.99

8964 measured reflections

3844 independent reflections

3441 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.104

S = 1.03

3844 reflections

296 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.30 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 1999 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810014819/ng2763sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810014819/ng2763Isup2.hkl

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

2C12H10N3O4+·C12H8O6S22−·3H2O	Z = 1
Mr = 886.83	F(000) = 460
Triclinic, P1	Dx = 1.557 Mg m−3
Hall symbol: -P 1	Melting point: 413 K
a = 8.3897 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.6455 (4) Å	Cell parameters from 5908 reflections
c = 11.7405 (5) Å	θ = 3.0–32.3°
α = 97.879 (3)°	µ = 0.23 mm−1
β = 96.926 (3)°	T = 173 K
γ = 112.066 (4)°	Prism, colourless
V = 945.53 (7) Å3	0.30 × 0.25 × 0.15 mm

Oxford Diffraction Gemini-S CCD-detector diffractometer	3844 independent reflections
Radiation source: Enhance (Mo) X-ray source	3441 reflections with I > 2σ(I)
graphite	Rint = 0.020
Detector resolution: 16.08 pixels mm-1	θmax = 26.5°, θmin = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.98, Tmax = 0.99	l = −14→14
8964 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0505P)2 + 0.4454P] where P = (Fo2 + 2Fc2)/3
3844 reflections	(Δ/σ)max = 0.001
296 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

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 esds 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O21	0.5436 (2)	0.07535 (18)	0.71892 (15)	0.0487 (6)
O22	0.51554 (19)	0.13704 (18)	0.55354 (14)	0.0460 (5)
O41	0.9552 (2)	0.10842 (19)	0.32892 (14)	0.0548 (6)
O42	1.2220 (2)	0.1865 (2)	0.41565 (15)	0.0627 (7)
N1	0.7507 (2)	0.15288 (18)	1.02586 (14)	0.0291 (5)
N21	0.6039 (2)	0.12314 (17)	0.63793 (15)	0.0319 (5)
N41	1.0680 (2)	0.15615 (18)	0.41645 (15)	0.0350 (5)
C2	0.8078 (2)	0.1261 (2)	0.92656 (16)	0.0276 (5)
C3	0.8089 (3)	−0.0026 (2)	0.89375 (18)	0.0348 (6)
C4	0.7505 (3)	−0.1008 (2)	0.9630 (2)	0.0403 (7)
C5	0.6935 (3)	−0.0690 (2)	1.06403 (19)	0.0400 (7)
C6	0.6954 (3)	0.0601 (2)	1.09439 (18)	0.0364 (7)
C11	0.9122 (2)	0.21211 (18)	0.74513 (16)	0.0256 (5)
C21	0.7921 (2)	0.16202 (18)	0.63956 (16)	0.0260 (5)
C31	0.8394 (2)	0.14506 (19)	0.53166 (17)	0.0278 (5)
C41	1.0145 (2)	0.17560 (19)	0.53089 (16)	0.0275 (5)
C51	1.1393 (2)	0.2235 (2)	0.63196 (17)	0.0303 (6)
C61	1.0871 (2)	0.2431 (2)	0.73779 (17)	0.0291 (6)
C71	0.8663 (3)	0.2446 (2)	0.86313 (17)	0.0318 (6)
S4A	0.60027 (6)	0.49714 (5)	0.81725 (4)	0.0279 (2)
O41A	0.71609 (19)	0.57569 (16)	0.92704 (12)	0.0391 (5)
O42A	0.51335 (19)	0.35151 (15)	0.81872 (14)	0.0412 (5)
O43A	0.4786 (2)	0.55635 (18)	0.77623 (13)	0.0436 (5)
C1A	0.9443 (2)	0.50258 (19)	0.54441 (16)	0.0272 (6)
C2A	0.7662 (3)	0.4645 (3)	0.51220 (19)	0.0576 (9)
C3A	0.6617 (3)	0.4658 (3)	0.59494 (19)	0.0531 (9)
C4A	0.7357 (2)	0.50677 (19)	0.71157 (16)	0.0263 (6)
C5A	0.9122 (3)	0.5469 (2)	0.74546 (18)	0.0399 (6)
C6A	1.0155 (3)	0.5444 (2)	0.66214 (19)	0.0409 (7)
O1W	0.7300 (2)	0.39624 (19)	1.07848 (14)	0.0422 (6)
O2W	0.4510 (4)	0.7847 (3)	0.7040 (3)	0.0475 (11)	0.500
H1	0.746 (4)	0.240 (3)	1.049 (2)	0.059 (8)*
H3	0.84830	−0.02380	0.82590	0.0420*
H4	0.75000	−0.18830	0.94090	0.0480*
H5	0.65440	−0.13420	1.11060	0.0480*
H6	0.65840	0.08380	1.16260	0.0440*
H31	0.75700	0.11440	0.46260	0.0330*
H51	1.25620	0.24210	0.62900	0.0360*
H61	1.17110	0.27820	0.80620	0.0350*
H71	0.96790	0.31920	0.91260	0.0380*
H72	0.77380	0.27800	0.85240	0.0380*
H2A	0.71510	0.43730	0.43320	0.0690*
H3A	0.54180	0.43900	0.57140	0.0640*
H5A	0.96300	0.57590	0.82450	0.0480*
H6A	1.13540	0.57160	0.68620	0.0490*
H11W	0.662 (4)	0.407 (3)	1.127 (3)	0.069 (9)*
H12W	0.719 (4)	0.441 (3)	1.031 (3)	0.062 (9)*
H21W	0.460 (5)	0.730 (4)	0.745 (4)	0.060 (10)*	0.500
H22W	0.515 (5)	0.860 (3)	0.755 (3)	0.065 (10)*	0.500

	U11	U22	U33	U12	U13	U23
O21	0.0343 (8)	0.0630 (11)	0.0535 (10)	0.0155 (8)	0.0225 (7)	0.0261 (8)
O22	0.0318 (8)	0.0596 (10)	0.0475 (9)	0.0198 (8)	0.0040 (7)	0.0119 (8)
O41	0.0577 (11)	0.0678 (12)	0.0295 (8)	0.0162 (9)	0.0131 (8)	0.0011 (8)
O42	0.0491 (10)	0.1108 (16)	0.0475 (10)	0.0453 (11)	0.0280 (8)	0.0225 (10)
N1	0.0249 (8)	0.0370 (10)	0.0239 (8)	0.0107 (7)	0.0051 (6)	0.0052 (7)
N21	0.0282 (9)	0.0288 (9)	0.0387 (9)	0.0105 (7)	0.0107 (7)	0.0053 (7)
N41	0.0446 (10)	0.0357 (9)	0.0341 (9)	0.0210 (8)	0.0187 (8)	0.0131 (8)
C2	0.0229 (9)	0.0318 (10)	0.0246 (9)	0.0074 (8)	0.0048 (7)	0.0042 (8)
C3	0.0401 (11)	0.0317 (11)	0.0320 (10)	0.0133 (9)	0.0092 (9)	0.0057 (8)
C4	0.0397 (12)	0.0326 (11)	0.0442 (12)	0.0116 (10)	−0.0008 (9)	0.0097 (9)
C5	0.0294 (11)	0.0508 (13)	0.0386 (12)	0.0104 (10)	0.0044 (9)	0.0236 (10)
C6	0.0273 (10)	0.0550 (14)	0.0270 (10)	0.0136 (10)	0.0067 (8)	0.0152 (9)
C11	0.0304 (10)	0.0207 (9)	0.0275 (9)	0.0096 (8)	0.0115 (7)	0.0068 (7)
C21	0.0253 (9)	0.0213 (9)	0.0334 (10)	0.0094 (7)	0.0102 (7)	0.0075 (7)
C31	0.0301 (10)	0.0254 (9)	0.0275 (9)	0.0106 (8)	0.0058 (7)	0.0054 (7)
C41	0.0331 (10)	0.0259 (9)	0.0287 (9)	0.0140 (8)	0.0134 (8)	0.0090 (8)
C51	0.0265 (10)	0.0333 (10)	0.0366 (11)	0.0141 (8)	0.0132 (8)	0.0116 (8)
C61	0.0286 (10)	0.0302 (10)	0.0286 (10)	0.0115 (8)	0.0051 (8)	0.0072 (8)
C71	0.0381 (11)	0.0269 (10)	0.0294 (10)	0.0106 (9)	0.0131 (8)	0.0034 (8)
S4A	0.0314 (3)	0.0369 (3)	0.0266 (2)	0.0204 (2)	0.0159 (2)	0.0132 (2)
O41A	0.0427 (8)	0.0521 (9)	0.0272 (7)	0.0214 (7)	0.0150 (6)	0.0081 (6)
O42A	0.0408 (8)	0.0418 (9)	0.0492 (9)	0.0168 (7)	0.0242 (7)	0.0205 (7)
O43A	0.0532 (9)	0.0702 (11)	0.0371 (8)	0.0471 (9)	0.0254 (7)	0.0254 (8)
C1A	0.0332 (10)	0.0285 (10)	0.0298 (10)	0.0170 (8)	0.0174 (8)	0.0136 (8)
C2A	0.0474 (14)	0.127 (2)	0.0247 (11)	0.0570 (16)	0.0166 (10)	0.0264 (13)
C3A	0.0385 (12)	0.113 (2)	0.0303 (11)	0.0483 (14)	0.0158 (10)	0.0256 (13)
C4A	0.0325 (10)	0.0283 (10)	0.0295 (9)	0.0187 (8)	0.0174 (8)	0.0129 (8)
C5A	0.0303 (10)	0.0487 (13)	0.0278 (10)	0.0045 (9)	0.0116 (8)	−0.0068 (9)
C6A	0.0241 (10)	0.0476 (13)	0.0370 (11)	0.0014 (9)	0.0144 (8)	−0.0061 (10)
O1W	0.0555 (10)	0.0677 (11)	0.0272 (8)	0.0456 (9)	0.0177 (7)	0.0154 (8)
O2W	0.0471 (19)	0.0426 (18)	0.0560 (15)	0.0206 (15)	0.0161 (15)	0.0066 (15)

S4A—O42A	1.4479 (16)	C21—C31	1.381 (3)
S4A—O43A	1.4558 (19)	C31—C41	1.382 (3)
S4A—C4A	1.7687 (19)	C41—C51	1.378 (3)
S4A—O41A	1.4481 (15)	C51—C61	1.381 (3)
O21—N21	1.214 (2)	C3—H3	0.9300
O22—N21	1.224 (2)	C4—H4	0.9300
O41—N41	1.213 (2)	C5—H5	0.9300
O42—N41	1.210 (3)	C6—H6	0.9300
O1W—H11W	0.88 (4)	C31—H31	0.9300
O1W—H12W	0.80 (3)	C51—H51	0.9300
O2W—H21W	0.82 (4)	C61—H61	0.9300
O2W—H22W	0.87 (3)	C71—H71	0.9700
N1—C6	1.342 (3)	C71—H72	0.9700
N1—C2	1.348 (2)	C1A—C2A	1.381 (3)
N21—C21	1.471 (3)	C1A—C6A	1.378 (3)
N41—C41	1.479 (3)	C1A—C1Ai	1.491 (3)
N1—H1	0.95 (3)	C2A—C3A	1.387 (4)
C2—C3	1.375 (3)	C3A—C4A	1.371 (3)
C2—C71	1.506 (3)	C4A—C5A	1.367 (3)
C3—C4	1.392 (3)	C5A—C6A	1.387 (3)
C4—C5	1.378 (3)	C2A—H2A	0.9300
C5—C6	1.365 (3)	C3A—H3A	0.9300
C11—C61	1.394 (3)	C5A—H5A	0.9300
C11—C71	1.512 (3)	C6A—H6A	0.9300
C11—C21	1.396 (3)
O43A—S4A—C4A	105.78 (9)	C2—C3—H3	120.00
O41A—S4A—C4A	106.12 (9)	C4—C3—H3	120.00
O41A—S4A—O42A	112.56 (9)	C5—C4—H4	120.00
O41A—S4A—O43A	113.37 (10)	C3—C4—H4	120.00
O42A—S4A—O43A	112.51 (10)	C6—C5—H5	121.00
O42A—S4A—C4A	105.74 (9)	C4—C5—H5	121.00
H11W—O1W—H12W	104 (3)	N1—C6—H6	120.00
H21W—O2W—H22W	97 (4)	C5—C6—H6	120.00
C2—N1—C6	123.13 (19)	C41—C31—H31	121.00
O21—N21—O22	123.47 (19)	C21—C31—H31	121.00
O22—N21—C21	118.33 (17)	C61—C51—H51	121.00
O21—N21—C21	118.17 (17)	C41—C51—H51	121.00
O42—N41—C41	118.02 (17)	C11—C61—H61	119.00
O41—N41—O42	123.59 (19)	C51—C61—H61	119.00
O41—N41—C41	118.38 (18)	H71—C71—H72	107.00
C6—N1—H1	117.1 (16)	C2—C71—H72	108.00
C2—N1—H1	119.8 (16)	C11—C71—H71	108.00
N1—C2—C3	118.39 (18)	C11—C71—H72	108.00
N1—C2—C71	114.88 (18)	C2—C71—H71	108.00
C3—C2—C71	126.73 (18)	C1Ai—C1A—C2A	121.47 (17)
C2—C3—C4	119.4 (2)	C1Ai—C1A—C6A	121.02 (18)
C3—C4—C5	120.3 (2)	C2A—C1A—C6A	117.51 (19)
C4—C5—C6	118.71 (19)	C1A—C2A—C3A	121.5 (2)
N1—C6—C5	120.0 (2)	C2A—C3A—C4A	119.8 (2)
C61—C11—C71	118.98 (18)	S4A—C4A—C5A	120.50 (15)
C21—C11—C71	124.29 (18)	C3A—C4A—C5A	119.8 (2)
C21—C11—C61	116.55 (17)	S4A—C4A—C3A	119.64 (17)
C11—C21—C31	123.34 (17)	C4A—C5A—C6A	120.1 (2)
N21—C21—C11	120.82 (16)	C1A—C6A—C5A	121.4 (2)
N21—C21—C31	115.84 (16)	C1A—C2A—H2A	119.00
C21—C31—C41	117.06 (17)	C3A—C2A—H2A	119.00
N41—C41—C51	119.43 (17)	C4A—C3A—H3A	120.00
C31—C41—C51	122.50 (17)	C2A—C3A—H3A	120.00
N41—C41—C31	118.07 (17)	C4A—C5A—H5A	120.00
C41—C51—C61	118.54 (17)	C6A—C5A—H5A	120.00
C11—C61—C51	121.97 (18)	C1A—C6A—H6A	119.00
C2—C71—C11	115.69 (17)	C5A—C6A—H6A	119.00
O43A—S4A—C4A—C5A	137.52 (17)	C61—C11—C21—C31	−1.2 (3)
O42A—S4A—C4A—C3A	73.2 (2)	C71—C11—C21—N21	−6.5 (3)
O41A—S4A—C4A—C3A	−167.09 (19)	C71—C11—C21—C31	173.82 (18)
O41A—S4A—C4A—C5A	16.81 (19)	C21—C11—C61—C51	−1.0 (3)
O42A—S4A—C4A—C5A	−102.95 (18)	C71—C11—C61—C51	−176.22 (18)
O43A—S4A—C4A—C3A	−46.4 (2)	N21—C21—C31—C41	−177.51 (17)
C6—N1—C2—C71	−179.2 (2)	C11—C21—C31—C41	2.2 (3)
C6—N1—C2—C3	0.2 (3)	C21—C31—C41—N41	179.06 (17)
C2—N1—C6—C5	−0.7 (3)	C21—C31—C41—C51	−1.2 (3)
O21—N21—C21—C11	−32.8 (3)	C31—C41—C51—C61	−0.8 (3)
O21—N21—C21—C31	146.90 (19)	N41—C41—C51—C61	178.96 (18)
O22—N21—C21—C31	−31.1 (3)	C41—C51—C61—C11	1.9 (3)
O22—N21—C21—C11	149.17 (19)	C6A—C1A—C2A—C3A	−1.1 (4)
O42—N41—C41—C31	178.02 (19)	C1Ai—C1A—C2A—C3A	178.3 (2)
O42—N41—C41—C51	−1.7 (3)	C2A—C1A—C6A—C5A	0.7 (3)
O41—N41—C41—C51	176.96 (19)	C1Ai—C1A—C6A—C5A	−178.72 (19)
O41—N41—C41—C31	−3.3 (3)	C2A—C1A—C1Ai—C2Ai	−180.0 (2)
N1—C2—C71—C11	−173.63 (18)	C2A—C1A—C1Ai—C6Ai	0.7 (3)
N1—C2—C3—C4	0.4 (3)	C6A—C1A—C1Ai—C2Ai	−0.7 (3)
C71—C2—C3—C4	179.8 (2)	C6A—C1A—C1Ai—C6Ai	180.0 (2)
C3—C2—C71—C11	7.0 (3)	C1A—C2A—C3A—C4A	0.6 (4)
C2—C3—C4—C5	−0.6 (4)	C2A—C3A—C4A—S4A	−175.7 (2)
C3—C4—C5—C6	0.1 (4)	C2A—C3A—C4A—C5A	0.4 (4)
C4—C5—C6—N1	0.5 (4)	S4A—C4A—C5A—C6A	175.26 (16)
C21—C11—C71—C2	88.6 (2)	C3A—C4A—C5A—C6A	−0.8 (3)
C61—C11—C71—C2	−96.6 (2)	C4A—C5A—C6A—C1A	0.3 (3)
C61—C11—C21—N21	178.55 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1W	0.95 (3)	1.71 (3)	2.655 (3)	175 (3)
O1W—H11W···O43Aii	0.88 (4)	1.84 (4)	2.716 (2)	175 (3)
O1W—H12W···O41A	0.80 (3)	2.01 (3)	2.806 (2)	172 (3)
O2W—H21W···O43A	0.82 (4)	1.99 (4)	2.761 (4)	155 (4)
O2W—H22W···O21iii	0.87 (3)	2.32 (3)	2.867 (2)	124 (3)
C2A—H2A···O2Wiv	0.93	2.46	3.195 (4)	136
C4—H4···O41Av	0.93	2.40	3.309 (3)	165
C5—H5···O42Avi	0.93	2.53	3.427 (3)	163
C5A—H5A···O41A	0.93	2.52	2.897 (3)	105
C5A—H5A···O1Wvii	0.93	2.58	3.232 (3)	128
C6—H6···O2Wii	0.93	2.44	3.316 (4)	156
C6—H6···O21vi	0.93	2.60	3.265 (3)	129
C71—H72···O21	0.97	2.46	2.799 (3)	100
C71—H72···O42A	0.97	2.59	3.558 (3)	176

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1W	0.95 (3)	1.71 (3)	2.655 (3)	175 (3)
O1W—H11W⋯O43Ai	0.88 (4)	1.84 (4)	2.716 (2)	175 (3)
O1W—H12W⋯O41A	0.80 (3)	2.01 (3)	2.806 (2)	172 (3)
O2W—H21W⋯O43A	0.82 (4)	1.99 (4)	2.761 (4)	155 (4)
O2W—H22W⋯O21ii	0.87 (3)	2.32 (3)	2.867 (2)	124 (3)

Symmetry codes: (i) ; (ii) .