Crystal structure of 4,4'-bipyridine-1,1'-diium naphthalene-2,6-di-sulfonate dihydrate.

The title hydrated mol-ecular organic salt, C10H10N2 (2+)·C10H6O6S2 (2-)·2H2O, crystallized with half a bipyridinium cation, half a naphthalene-2,6-di-sulfonate anion and a water mol-ecule in the asymmetric unit. The whole cation and anion are generated by inversion symmetry, the inversion centers being at the center of the bridging C-C bond of the cation, and at the center of the fused C-C bond of the naphthalene group of the anion. In the crystal, the anions and cations stack alternately along the a axis with π-π inter-actions [inter-centroid distance = 3.491 (1) Å]. The anions are linked via O-H⋯O(sulfonate) hydrogen bonds involving two inversion-related water mol-ecules, forming chains along [10-1]. These chains are bridged by bifurcated N-H⋯(O,O) hydrogen bonds, forming a three-dimensional framework structure. There are also C-H⋯O hydrogen bonds present, reinforcing the framework structure.

Related literature

For the use of 4,4′-bi­pyridine in the construction of metal-organic frameworks, see: Batten et al. (2012 ▶); Burd et al. (2012 ▶); Jeazet & Janiak (2012 ▶). For the use of naphthalene-2,6-di­sulfonate in the preparation of metal-organic frameworks, exploiting its different coordination modes, see: Zhao et al. (2013 ▶); Borodkin et al. (2013 ▶); Chen et al. (2001 ▶); Song et al. (2010 ▶); Pereira Silva et al. (2006 ▶).

Experimental

Crystal data

C10H10N2 2+·C10H6O6S2 2−·2H2O

M = 480.50

Monoclinic,

a = 7.4022 (2) Å

b = 10.9390 (3) Å

c = 12.6500 (4) Å

β = 99.908 (1)°

V = 1009.03 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.32 mm−1

T = 296 K

0.35 × 0.24 × 0.15 mm

Data collection

Bruker SMART BREEZE CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T min = 0.912, T max = 0.953

39553 measured reflections

2551 independent reflections

2340 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.103

S = 1.04

2551 reflections

153 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: APEX2 and SAINT (Bruker, 2012 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL2013 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681401784X/su2764sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401784X/su2764Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401784X/su2764Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S160053681401784X/su2764fig1.tif

A view of the mol­ecular structure of the title hydrated mol­ecular salt, with the atom labelling. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+1.] The inversion related water mol­ecule is not shown.

Click here for additional data file.

a . DOI: 10.1107/S160053681401784X/su2764fig2.tif

A view along the a axis of the crystal packing of the title compound, showing the hydrogen bonds as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonds have been omitted for clarity).

CCDC reference: 1006095

Additional supporting information: crystallographic information; 3D view; checkCIF report

C10H10N22+·C10H6O6S22−·2H2O	F(000) = 500
Mr = 480.50	Dx = 1.581 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.4022 (2) Å	Cell parameters from 39513 reflections
b = 10.9390 (3) Å	θ = 2.5–28.5°
c = 12.6500 (4) Å	µ = 0.32 mm−1
β = 99.908 (1)°	T = 296 K
V = 1009.03 (5) Å3	Plate, colourless
Z = 2	0.35 × 0.24 × 0.15 mm

Bruker SMART BREEZE CCD diffractometer	2551 independent reflections
Radiation source: fine-focus sealed X-ray tube	2340 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.033
ω–scans	θmax = 28.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −9→9
Tmin = 0.912, Tmax = 0.953	k = −14→14
39553 measured reflections	l = −16→16

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)] = 0.035	Hydrogen site location: mixed
wR(F2) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0614P)2 + 0.3867P] where P = (Fo2 + 2Fc2)/3
2551 reflections	(Δ/σ)max < 0.001
153 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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.

	x	y	z	Uiso*/Ueq
S1	0.21510 (4)	−0.06706 (3)	0.18311 (2)	0.02743 (12)
O1	0.14850 (17)	0.05494 (9)	0.15242 (9)	0.0398 (3)
O2	0.06807 (15)	−0.14963 (10)	0.19836 (9)	0.0421 (3)
O3	0.33036 (17)	−0.11776 (14)	0.11235 (9)	0.0513 (3)
C1	0.55029 (19)	0.16047 (12)	0.64530 (11)	0.0305 (3)
H1	0.5516	0.2306	0.6870	0.037*
C2	0.45657 (18)	0.15973 (11)	0.54200 (10)	0.0291 (3)
H2	0.3943	0.2295	0.5138	0.035*
C3	0.45389 (16)	0.05348 (10)	0.47790 (10)	0.0230 (2)
C4	0.35783 (17)	0.05061 (11)	0.37022 (10)	0.0254 (2)
H4	0.2972	0.1200	0.3400	0.030*
C5	0.35503 (17)	−0.05470 (11)	0.31137 (10)	0.0254 (3)
N1	0.30960 (19)	0.21624 (13)	0.91922 (12)	0.0454 (3)
H3	0.2627	0.1463	0.8994	0.054*
C6	0.46027 (17)	0.43924 (12)	0.98236 (11)	0.0282 (3)
C7	0.3717 (2)	0.41942 (15)	0.87696 (13)	0.0412 (3)
H7	0.3633	0.4821	0.8267	0.049*
C8	0.2972 (2)	0.30668 (18)	0.84798 (14)	0.0493 (4)
H8	0.2375	0.2935	0.7780	0.059*
C10	0.3922 (3)	0.23110 (15)	1.01926 (15)	0.0479 (4)
H10	0.3989	0.1662	1.0673	0.057*
C11	0.4686 (2)	0.34212 (14)	1.05306 (12)	0.0398 (3)
H11	0.5261	0.3519	1.1239	0.048*
O1W	0.23786 (19)	0.96590 (12)	0.89658 (11)	0.0447 (3)
H1A	0.126 (4)	0.958 (2)	0.8846 (19)	0.058 (7)*
H1B	0.275 (3)	0.940 (2)	0.957 (2)	0.061 (7)*

	U11	U22	U33	U12	U13	U23
S1	0.03049 (19)	0.02730 (19)	0.02227 (18)	−0.00197 (11)	−0.00176 (12)	−0.00094 (10)
O1	0.0471 (6)	0.0292 (5)	0.0372 (6)	−0.0022 (4)	−0.0096 (5)	0.0062 (4)
O2	0.0435 (6)	0.0385 (6)	0.0391 (6)	−0.0158 (4)	−0.0076 (4)	0.0034 (4)
O3	0.0470 (7)	0.0765 (9)	0.0290 (5)	0.0134 (6)	0.0025 (5)	−0.0100 (5)
C1	0.0381 (7)	0.0221 (6)	0.0293 (6)	0.0007 (5)	0.0005 (5)	−0.0037 (5)
C2	0.0352 (6)	0.0200 (5)	0.0301 (6)	0.0036 (5)	−0.0003 (5)	0.0002 (5)
C3	0.0241 (5)	0.0198 (5)	0.0246 (6)	−0.0009 (4)	0.0024 (4)	0.0014 (4)
C4	0.0269 (6)	0.0217 (5)	0.0259 (6)	−0.0003 (4)	0.0002 (4)	0.0024 (4)
C5	0.0270 (6)	0.0258 (6)	0.0219 (6)	−0.0028 (4)	0.0001 (4)	0.0006 (4)
N1	0.0439 (7)	0.0390 (7)	0.0573 (8)	−0.0149 (6)	0.0200 (6)	−0.0172 (6)
C6	0.0250 (6)	0.0320 (7)	0.0291 (6)	−0.0030 (5)	0.0085 (5)	−0.0050 (5)
C7	0.0474 (9)	0.0421 (8)	0.0324 (7)	−0.0079 (6)	0.0019 (6)	−0.0050 (6)
C8	0.0510 (9)	0.0537 (10)	0.0417 (8)	−0.0144 (8)	0.0037 (7)	−0.0167 (7)
C10	0.0582 (10)	0.0366 (8)	0.0531 (10)	−0.0097 (7)	0.0217 (8)	0.0011 (7)
C11	0.0468 (8)	0.0393 (8)	0.0336 (7)	−0.0079 (6)	0.0081 (6)	0.0003 (6)
O1W	0.0425 (7)	0.0486 (7)	0.0417 (7)	−0.0014 (5)	0.0037 (5)	0.0042 (5)

S1—O3	1.4489 (12)	N1—C10	1.317 (2)
S1—O1	1.4523 (11)	N1—C8	1.331 (3)
S1—O2	1.4525 (11)	N1—H3	0.8595
S1—C5	1.7735 (12)	C6—C11	1.383 (2)
C1—C2	1.3700 (18)	C6—C7	1.398 (2)
C1—C5i	1.4136 (17)	C6—C6ii	1.491 (2)
C1—H1	0.9300	C7—C8	1.375 (2)
C2—C3	1.4154 (17)	C7—H7	0.9300
C2—H2	0.9300	C8—H8	0.9300
C3—C3i	1.420 (2)	C10—C11	1.376 (2)
C3—C4	1.4244 (17)	C10—H10	0.9300
C4—C5	1.3698 (17)	C11—H11	0.9300
C4—H4	0.9300	O1W—H1A	0.82 (3)
C5—C1i	1.4135 (17)	O1W—H1B	0.82 (3)
O3—S1—O1	113.29 (8)	C1i—C5—S1	117.70 (9)
O3—S1—O2	112.23 (8)	C10—N1—C8	121.70 (14)
O1—S1—O2	112.29 (7)	C10—N1—H3	119.2
O3—S1—C5	106.32 (7)	C8—N1—H3	119.1
O1—S1—C5	107.01 (6)	C11—C6—C7	117.33 (13)
O2—S1—C5	105.01 (6)	C11—C6—C6ii	121.33 (16)
C2—C1—C5i	120.06 (11)	C7—C6—C6ii	121.33 (16)
C2—C1—H1	120.0	C8—C7—C6	119.63 (15)
C5i—C1—H1	120.0	C8—C7—H7	120.2
C1—C2—C3	120.41 (11)	C6—C7—H7	120.2
C1—C2—H2	119.8	N1—C8—C7	120.56 (15)
C3—C2—H2	119.8	N1—C8—H8	119.7
C2—C3—C3i	119.52 (14)	C7—C8—H8	119.7
C2—C3—C4	121.43 (11)	N1—C10—C11	120.35 (16)
C3i—C3—C4	119.05 (13)	N1—C10—H10	119.8
C5—C4—C3	119.78 (11)	C11—C10—H10	119.8
C5—C4—H4	120.1	C10—C11—C6	120.44 (15)
C3—C4—H4	120.1	C10—C11—H11	119.8
C4—C5—C1i	121.17 (11)	C6—C11—H11	119.8
C4—C5—S1	120.87 (9)	H1A—O1W—H1B	107 (2)
C5i—C1—C2—C3	−0.1 (2)	O1—S1—C5—C1i	−174.50 (11)
C1—C2—C3—C3i	1.3 (2)	O2—S1—C5—C1i	65.99 (12)
C1—C2—C3—C4	−179.84 (12)	C11—C6—C7—C8	0.2 (2)
C2—C3—C4—C5	−178.61 (12)	C6ii—C6—C7—C8	−178.78 (17)
C3i—C3—C4—C5	0.3 (2)	C10—N1—C8—C7	0.3 (3)
C3—C4—C5—C1i	−1.51 (19)	C6—C7—C8—N1	−0.4 (3)
C3—C4—C5—S1	172.51 (9)	C8—N1—C10—C11	0.1 (3)
O3—S1—C5—C4	132.64 (12)	N1—C10—C11—C6	−0.3 (3)
O1—S1—C5—C4	11.27 (13)	C7—C6—C11—C10	0.1 (2)
O2—S1—C5—C4	−108.24 (12)	C6ii—C6—C11—C10	179.13 (16)
O3—S1—C5—C1i	−53.13 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O1iii	0.82 (3)	2.01 (3)	2.8293 (18)	176 (2)
O1W—H1B···O3iv	0.82 (3)	2.04 (3)	2.8484 (18)	172 (2)
N1—H3···O2v	0.86	2.55	3.0212 (18)	116
N1—H3···O1Wvi	0.86	1.98	2.7948 (19)	157
C1—H1···O1vii	0.93	2.51	3.1946 (17)	130
C10—H10···O1viii	0.93	2.60	3.294 (2)	132
C11—H11···O2ix	0.93	2.47	3.2036 (19)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O1i	0.82 (3)	2.01 (3)	2.8293 (18)	176 (2)
O1W—H1B⋯O3ii	0.82 (3)	2.04 (3)	2.8484 (18)	172 (2)
N1—H3⋯O2iii	0.86	2.55	3.0212 (18)	116
N1—H3⋯O1W iv	0.86	1.98	2.7948 (19)	157
C1—H1⋯O1v	0.93	2.51	3.1946 (17)	130
C10—H10⋯O1vi	0.93	2.60	3.294 (2)	132
C11—H11⋯O2vii	0.93	2.47	3.2036 (19)	136

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