2',6'-Bis(4-carb-oxy-phen-yl)-4,4'-bipyridin-1-ium nitrate 0.25-hydrate.

In the title compound, C(24)H(17)N(2)O(4) (+)·NO(3) (-)·0.25H(2)O, the central pyridine ring of the 2',6'-bis-(4-carb-oxy-phen-yl)-4,4'-bipyridin-1-ium cation is almost coplanar with one benzene ring [dihedral angle = 1.03 (5)°], while it makes dihedral angles of 9.59 (5)° with the other benzene ring and 13.66 (6)° with the pyridinium ring. In the crystal, N-H⋯O and O-H⋯O hydrogen bonds link the cations and nitrate anions into a sheet in the (302) plane. The crystal structure also exhibits π-π inter-actions between the central pyridine ring and the benzene rings of neighboring mol-ecules [centroid-centroid distance = 3.6756 (13) Å].

Related literature

For the properties and applications of mol­ecular-ionic crystals, see: Katrusiak & Szafrański (2006 ▶); Liao et al. (2008 ▶); Wang (2010 ▶).

Experimental

Crystal data

C24H17N2O4 +·NO3 −·0.25H2O

M = 463.91

Monoclinic,

a = 13.6978 (11) Å

b = 16.0688 (12) Å

c = 9.6354 (8) Å

β = 92.696 (1)°

V = 2118.5 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 293 K

0.25 × 0.21 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.973, T max = 0.978

11529 measured reflections

4158 independent reflections

2605 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.150

S = 1.04

4158 reflections

316 parameters

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811051506/bt5723sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811051506/bt5723Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811051506/bt5723Isup3.cml

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

C24H17N2O4+·NO3−·0.25H2O	F(000) = 962
Mr = 463.91	Dx = 1.454 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4158 reflections
a = 13.6978 (11) Å	θ = 1.0–26.0°
b = 16.0688 (12) Å	µ = 0.11 mm−1
c = 9.6354 (8) Å	T = 293 K
β = 92.696 (1)°	Block, colorless
V = 2118.5 (3) Å3	0.25 × 0.21 × 0.20 mm
Z = 4

Bruker APEXII CCD diffractometer	4158 independent reflections
Radiation source: fine-focus sealed tube	2605 reflections with I > 2σ(I)
graphite	Rint = 0.040
φ and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→16
Tmin = 0.973, Tmax = 0.978	k = −19→17
11529 measured reflections	l = −9→11

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.150	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0724P)2 + 0.0957P] where P = (Fo2 + 2Fc2)/3
4158 reflections	(Δ/σ)max < 0.001
316 parameters	Δρmax = 0.30 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.42765 (16)	0.78749 (14)	0.5913 (2)	0.0286 (5)
C2	0.46419 (18)	0.71363 (14)	0.5406 (3)	0.0334 (6)
H2	0.4404	0.6631	0.5715	0.040*
C3	0.53576 (18)	0.71478 (14)	0.4445 (3)	0.0337 (6)
H3	0.5597	0.6647	0.4117	0.040*
C4	0.57286 (16)	0.78937 (13)	0.3957 (2)	0.0258 (5)
C5	0.53495 (17)	0.86287 (14)	0.4469 (3)	0.0330 (6)
H5	0.5579	0.9135	0.4152	0.040*
C6	0.46397 (17)	0.86229 (14)	0.5438 (2)	0.0322 (6)
H6	0.4404	0.9123	0.5774	0.039*
C7	0.35134 (17)	0.78863 (14)	0.6971 (3)	0.0321 (6)
C8	0.65044 (16)	0.78741 (13)	0.2920 (2)	0.0254 (5)
C9	0.69124 (16)	0.85873 (14)	0.2365 (2)	0.0279 (5)
H9	0.6711	0.9110	0.2651	0.033*
C10	0.76210 (16)	0.85180 (13)	0.1382 (2)	0.0260 (5)
C11	0.78848 (16)	0.77208 (14)	0.0987 (2)	0.0273 (5)
H11	0.8352	0.7648	0.0327	0.033*
C12	0.74523 (16)	0.70341 (13)	0.1575 (2)	0.0249 (5)
C13	0.80567 (16)	0.92684 (13)	0.0741 (2)	0.0261 (5)
C14	0.7948 (2)	1.00598 (14)	0.1296 (3)	0.0438 (7)
H14	0.7611	1.0128	0.2104	0.053*
C15	0.8333 (2)	1.07395 (15)	0.0661 (3)	0.0460 (7)
H15	0.8248	1.1267	0.1033	0.055*
C16	0.89662 (18)	0.99033 (13)	−0.1044 (3)	0.0328 (6)
H16	0.9319	0.9856	−0.1842	0.039*
C17	0.85909 (17)	0.92067 (14)	−0.0450 (2)	0.0306 (6)
H17	0.8693	0.8688	−0.0844	0.037*
C18	0.76886 (16)	0.61666 (13)	0.1168 (2)	0.0247 (5)
C19	0.71249 (16)	0.55022 (14)	0.1607 (2)	0.0295 (5)
H19	0.6597	0.5606	0.2154	0.035*
C20	0.73369 (16)	0.46961 (14)	0.1246 (2)	0.0303 (6)
H20	0.6958	0.4262	0.1563	0.036*
C21	0.81127 (16)	0.45261 (13)	0.0410 (2)	0.0272 (5)
C22	0.86680 (18)	0.51865 (14)	−0.0048 (3)	0.0323 (6)
H22	0.9182	0.5083	−0.0622	0.039*
C23	0.84681 (16)	0.59942 (14)	0.0335 (2)	0.0301 (6)
H23	0.8857	0.6427	0.0036	0.036*
C24	0.83576 (16)	0.36588 (14)	0.0027 (2)	0.0286 (5)
N1	0.88275 (14)	1.06493 (12)	−0.0482 (2)	0.0337 (5)
H1	0.9064	1.1082	−0.0869	0.040*
N2	0.67797 (13)	0.71123 (10)	0.25346 (19)	0.0260 (4)
N3	0.99617 (14)	0.19689 (12)	−0.2573 (2)	0.0312 (5)
O2	0.31962 (13)	0.71380 (10)	0.72797 (19)	0.0456 (5)
H2A	0.2781	0.7176	0.7863	0.068*
O1	0.32181 (13)	0.85207 (11)	0.74803 (19)	0.0469 (5)
O4	0.89796 (12)	0.36227 (9)	−0.09689 (18)	0.0387 (5)
H4	0.9094	0.3135	−0.1148	0.058*
O3	0.80256 (12)	0.30430 (9)	0.05852 (18)	0.0350 (4)
O5	0.94948 (15)	0.21008 (10)	−0.14753 (19)	0.0496 (5)
O6	1.02518 (13)	0.25580 (11)	−0.32456 (19)	0.0451 (5)
O7	1.01033 (13)	0.12364 (10)	−0.28914 (18)	0.0428 (5)
O1W	0.5358 (6)	1.0131 (4)	0.1459 (10)	0.062 (2)	0.25
H1A	0.5359	0.9943	0.0556	0.092*	0.25
H1B	0.5683	1.0618	0.1548	0.092*	0.25

	U11	U22	U33	U12	U13	U23
C1	0.0288 (13)	0.0303 (13)	0.0272 (13)	0.0037 (10)	0.0056 (10)	0.0019 (10)
C2	0.0407 (14)	0.0244 (13)	0.0365 (15)	−0.0024 (10)	0.0156 (12)	0.0025 (10)
C3	0.0403 (14)	0.0224 (12)	0.0398 (15)	0.0029 (10)	0.0149 (12)	−0.0015 (10)
C4	0.0257 (12)	0.0270 (12)	0.0248 (13)	0.0015 (9)	0.0037 (10)	−0.0004 (9)
C5	0.0345 (14)	0.0245 (13)	0.0407 (15)	0.0012 (10)	0.0095 (12)	0.0001 (11)
C6	0.0363 (14)	0.0243 (13)	0.0367 (15)	0.0064 (10)	0.0100 (11)	−0.0032 (10)
C7	0.0315 (13)	0.0303 (14)	0.0351 (15)	0.0043 (11)	0.0084 (11)	0.0037 (11)
C8	0.0256 (12)	0.0234 (12)	0.0274 (13)	0.0015 (9)	0.0030 (10)	−0.0001 (9)
C9	0.0318 (13)	0.0221 (12)	0.0305 (13)	0.0007 (10)	0.0091 (10)	−0.0036 (10)
C10	0.0278 (12)	0.0246 (12)	0.0259 (13)	0.0004 (10)	0.0038 (10)	−0.0009 (9)
C11	0.0257 (12)	0.0264 (12)	0.0304 (13)	0.0010 (10)	0.0072 (10)	−0.0011 (10)
C12	0.0256 (12)	0.0243 (12)	0.0249 (13)	0.0010 (9)	0.0024 (10)	0.0010 (9)
C13	0.0268 (12)	0.0213 (12)	0.0305 (13)	0.0003 (9)	0.0051 (10)	0.0005 (9)
C14	0.0612 (18)	0.0250 (14)	0.0480 (17)	−0.0023 (12)	0.0325 (14)	−0.0033 (11)
C15	0.0628 (18)	0.0240 (14)	0.0538 (18)	−0.0013 (12)	0.0293 (15)	−0.0022 (12)
C16	0.0391 (14)	0.0277 (13)	0.0327 (14)	−0.0011 (11)	0.0119 (12)	−0.0005 (11)
C17	0.0363 (13)	0.0225 (12)	0.0333 (14)	0.0019 (10)	0.0063 (11)	−0.0026 (10)
C18	0.0258 (12)	0.0208 (12)	0.0276 (13)	−0.0004 (9)	0.0033 (10)	0.0023 (9)
C19	0.0273 (12)	0.0264 (13)	0.0361 (14)	0.0012 (10)	0.0134 (10)	0.0006 (10)
C20	0.0305 (13)	0.0223 (12)	0.0389 (15)	−0.0031 (10)	0.0098 (11)	0.0020 (10)
C21	0.0290 (12)	0.0229 (12)	0.0300 (13)	−0.0015 (10)	0.0047 (10)	−0.0012 (10)
C22	0.0329 (13)	0.0294 (13)	0.0357 (14)	0.0005 (11)	0.0147 (11)	−0.0011 (11)
C23	0.0327 (13)	0.0200 (12)	0.0384 (14)	−0.0020 (10)	0.0121 (11)	0.0021 (10)
C24	0.0282 (13)	0.0260 (13)	0.0321 (14)	−0.0001 (10)	0.0057 (11)	0.0004 (10)
N1	0.0399 (12)	0.0244 (11)	0.0380 (12)	−0.0038 (9)	0.0146 (10)	0.0045 (9)
N2	0.0272 (10)	0.0231 (10)	0.0278 (11)	0.0014 (8)	0.0043 (8)	−0.0005 (8)
N3	0.0333 (11)	0.0273 (11)	0.0338 (12)	−0.0033 (9)	0.0089 (9)	0.0009 (9)
O2	0.0508 (11)	0.0341 (10)	0.0541 (13)	0.0027 (8)	0.0271 (10)	0.0052 (9)
O1	0.0550 (12)	0.0346 (10)	0.0534 (13)	0.0088 (9)	0.0277 (10)	−0.0016 (9)
O4	0.0485 (10)	0.0250 (9)	0.0446 (11)	0.0010 (8)	0.0218 (9)	−0.0032 (8)
O3	0.0389 (10)	0.0240 (9)	0.0431 (11)	−0.0011 (7)	0.0141 (8)	0.0018 (7)
O5	0.0812 (14)	0.0267 (10)	0.0441 (12)	−0.0023 (9)	0.0370 (11)	−0.0029 (8)
O6	0.0528 (12)	0.0370 (10)	0.0466 (12)	−0.0102 (9)	0.0156 (9)	0.0122 (9)
O7	0.0522 (12)	0.0295 (10)	0.0482 (12)	0.0052 (8)	0.0181 (9)	−0.0051 (8)
O1W	0.069 (5)	0.023 (4)	0.093 (7)	0.006 (4)	−0.002 (5)	0.010 (4)

C1—C2	1.386 (3)	C15—N1	1.328 (3)
C1—C6	1.387 (3)	C15—H15	0.9300
C1—C7	1.495 (3)	C16—N1	1.333 (3)
C2—C3	1.380 (3)	C16—C17	1.369 (3)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.392 (3)	C17—H17	0.9300
C3—H3	0.9300	C18—C23	1.393 (3)
C4—C5	1.390 (3)	C18—C19	1.395 (3)
C4—C8	1.493 (3)	C19—C20	1.376 (3)
C5—C6	1.379 (3)	C19—H19	0.9300
C5—H5	0.9300	C20—C21	1.390 (3)
C6—H6	0.9300	C20—H20	0.9300
C7—O1	1.209 (3)	C21—C22	1.390 (3)
C7—O2	1.317 (3)	C21—C24	1.484 (3)
C8—N2	1.338 (3)	C22—C23	1.380 (3)
C8—C9	1.393 (3)	C22—H22	0.9300
C9—C10	1.392 (3)	C23—H23	0.9300
C9—H9	0.9300	C24—O3	1.224 (3)
C10—C11	1.389 (3)	C24—O4	1.314 (3)
C10—C13	1.492 (3)	N1—H1	0.8600
C11—C12	1.386 (3)	N3—O6	1.224 (2)
C11—H11	0.9300	N3—O7	1.234 (2)
C12—N2	1.341 (3)	N3—O5	1.279 (2)
C12—C18	1.488 (3)	O2—H2A	0.8200
C13—C14	1.390 (3)	O4—H4	0.8200
C13—C17	1.393 (3)	O1W—H1A	0.9210
C14—C15	1.370 (3)	O1W—H1B	0.9027
C14—H14	0.9300
C2—C1—C6	119.0 (2)	C13—C14—H14	119.8
C2—C1—C7	121.8 (2)	N1—C15—C14	120.4 (2)
C6—C1—C7	119.2 (2)	N1—C15—H15	119.8
C3—C2—C1	120.3 (2)	C14—C15—H15	119.8
C3—C2—H2	119.8	N1—C16—C17	120.1 (2)
C1—C2—H2	119.8	N1—C16—H16	119.9
C2—C3—C4	121.3 (2)	C17—C16—H16	119.9
C2—C3—H3	119.3	C16—C17—C13	120.6 (2)
C4—C3—H3	119.3	C16—C17—H17	119.7
C5—C4—C3	117.6 (2)	C13—C17—H17	119.7
C5—C4—C8	123.0 (2)	C23—C18—C19	118.2 (2)
C3—C4—C8	119.4 (2)	C23—C18—C12	121.34 (19)
C6—C5—C4	121.4 (2)	C19—C18—C12	120.5 (2)
C6—C5—H5	119.3	C20—C19—C18	121.2 (2)
C4—C5—H5	119.3	C20—C19—H19	119.4
C5—C6—C1	120.3 (2)	C18—C19—H19	119.4
C5—C6—H6	119.9	C19—C20—C21	120.5 (2)
C1—C6—H6	119.9	C19—C20—H20	119.7
O1—C7—O2	123.9 (2)	C21—C20—H20	119.7
O1—C7—C1	123.0 (2)	C22—C21—C20	118.6 (2)
O2—C7—C1	113.0 (2)	C22—C21—C24	120.3 (2)
N2—C8—C9	121.5 (2)	C20—C21—C24	121.1 (2)
N2—C8—C4	115.06 (19)	C23—C22—C21	120.9 (2)
C9—C8—C4	123.41 (19)	C23—C22—H22	119.5
C10—C9—C8	120.0 (2)	C21—C22—H22	119.5
C10—C9—H9	120.0	C22—C23—C18	120.5 (2)
C8—C9—H9	120.0	C22—C23—H23	119.7
C11—C10—C9	117.3 (2)	C18—C23—H23	119.7
C11—C10—C13	121.2 (2)	O3—C24—O4	123.5 (2)
C9—C10—C13	121.5 (2)	O3—C24—C21	123.8 (2)
C12—C11—C10	120.0 (2)	O4—C24—C21	112.65 (19)
C12—C11—H11	120.0	C15—N1—C16	121.6 (2)
C10—C11—H11	120.0	C15—N1—H1	119.2
N2—C12—C11	121.9 (2)	C16—N1—H1	119.2
N2—C12—C18	115.74 (19)	C8—N2—C12	119.23 (19)
C11—C12—C18	122.4 (2)	O6—N3—O7	123.2 (2)
C14—C13—C17	116.9 (2)	O6—N3—O5	119.81 (19)
C14—C13—C10	121.8 (2)	O7—N3—O5	117.02 (18)
C17—C13—C10	121.3 (2)	C7—O2—H2A	109.5
C15—C14—C13	120.5 (2)	C24—O4—H4	109.5
C15—C14—H14	119.8	H1A—O1W—H1B	110.5
C6—C1—C2—C3	0.1 (4)	C17—C13—C14—C15	1.6 (4)
C7—C1—C2—C3	−178.9 (2)	C10—C13—C14—C15	−178.2 (2)
C1—C2—C3—C4	−0.2 (4)	C13—C14—C15—N1	−0.9 (4)
C2—C3—C4—C5	−0.2 (4)	N1—C16—C17—C13	0.4 (4)
C2—C3—C4—C8	179.9 (2)	C14—C13—C17—C16	−1.4 (4)
C3—C4—C5—C6	0.7 (4)	C10—C13—C17—C16	178.4 (2)
C8—C4—C5—C6	−179.4 (2)	N2—C12—C18—C23	−170.8 (2)
C4—C5—C6—C1	−0.8 (4)	C11—C12—C18—C23	10.3 (3)
C2—C1—C6—C5	0.4 (4)	N2—C12—C18—C19	9.7 (3)
C7—C1—C6—C5	179.5 (2)	C11—C12—C18—C19	−169.2 (2)
C2—C1—C7—O1	176.2 (2)	C23—C18—C19—C20	0.8 (3)
C6—C1—C7—O1	−2.9 (4)	C12—C18—C19—C20	−179.7 (2)
C2—C1—C7—O2	−4.2 (4)	C18—C19—C20—C21	−1.1 (4)
C6—C1—C7—O2	176.7 (2)	C19—C20—C21—C22	0.1 (4)
C5—C4—C8—N2	−179.6 (2)	C19—C20—C21—C24	179.2 (2)
C3—C4—C8—N2	0.3 (3)	C20—C21—C22—C23	1.2 (4)
C5—C4—C8—C9	−0.5 (4)	C24—C21—C22—C23	−177.9 (2)
C3—C4—C8—C9	179.4 (2)	C21—C22—C23—C18	−1.5 (4)
N2—C8—C9—C10	0.3 (3)	C19—C18—C23—C22	0.4 (3)
C4—C8—C9—C10	−178.8 (2)	C12—C18—C23—C22	−179.1 (2)
C8—C9—C10—C11	0.6 (3)	C22—C21—C24—O3	166.1 (2)
C8—C9—C10—C13	178.5 (2)	C20—C21—C24—O3	−13.0 (4)
C9—C10—C11—C12	−0.5 (3)	C22—C21—C24—O4	−13.2 (3)
C13—C10—C11—C12	−178.5 (2)	C20—C21—C24—O4	167.7 (2)
C10—C11—C12—N2	−0.3 (3)	C14—C15—N1—C16	−0.1 (4)
C10—C11—C12—C18	178.5 (2)	C17—C16—N1—C15	0.4 (4)
C11—C10—C13—C14	−167.6 (2)	C9—C8—N2—C12	−1.1 (3)
C9—C10—C13—C14	14.5 (4)	C4—C8—N2—C12	178.05 (19)
C11—C10—C13—C17	12.6 (3)	C11—C12—N2—C8	1.2 (3)
C9—C10—C13—C17	−165.3 (2)	C18—C12—N2—C8	−177.77 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5i	0.86	1.84	2.697 (2)	171
O2—H2A···O3ii	0.82	1.93	2.728 (2)	163
O4—H4···O5	0.82	1.78	2.598 (2)	173
O1W—H1A···O1Wiii	0.92	2.14	2.963 (18)	149
O1W—H1B···O1iv	0.90	2.22	3.059 (8)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5i	0.86	1.84	2.697 (2)	171
O2—H2A⋯O3ii	0.82	1.93	2.728 (2)	163
O4—H4⋯O5	0.82	1.78	2.598 (2)	173
O1W—H1A⋯O1Wiii	0.92	2.14	2.963 (18)	149
O1W—H1B⋯O1iv	0.90	2.22	3.059 (8)	154

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