4,4'-Bipyridine-pyridine-3,5-dicarb-oxy-lic acid (3/4).

In the title compound, 3C(10)H(8)N(2)·4C(7)H(5)NO(4), the asymmetric unit contains two mol-ecules of pyridine-3,5-dicarb-oxy-lic acid and one mol-ecule of 4,4'-bipyridine in general positions together with one mol-ecule of 4,4'-bipyridine lying across a centre of inversion, thus giving a 4:3 molar ratio of pyridine-3,5-dicarb-oxy-lic acid to 4,4'-bipyridine. The dihedral angle between the bipyridine rings on general positions is 21.2 (2)°. These mol-ecular units are linked by O-H⋯N hydrogen bonds forming an extended two-dimensional framework in the crystal.

Related literature

For structures and properties of self-assembled supermolecular compounds, see: Lehn (1990 ▶). For hydrogen bonds and π–π stacking inter­actions in supermolecular compounds, see: Roesky & Andruh (2003 ▶). For related structures, see: Soleimannejad et al. (2009 ▶); Jiang et al. (2010 ▶).

Experimental

Crystal data

3C10H8N2·4C7H5NO4

M = 1137.04

Monoclinic,

a = 13.8461 (4) Å

b = 11.0564 (3) Å

c = 18.1060 (4) Å

β = 110.511 (1)°

V = 2596.09 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.14 × 0.12 × 0.05 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T min = 0.985, T max = 0.995

24265 measured reflections

5918 independent reflections

4086 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.118

S = 1.03

5918 reflections

379 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681102719X/bx2358sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102719X/bx2358Isup2.hkl

Supplementary material file. DOI: 10.1107/S160053681102719X/bx2358Isup3.cml

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

3C10H8N2·4C7H5NO4	F(000) = 1180
Mr = 1137.04	Dx = 1.455 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.8461 (4) Å	Cell parameters from 6026 reflections
b = 11.0564 (3) Å	θ = 2.3–27.4°
c = 18.1060 (4) Å	µ = 0.11 mm−1
β = 110.511 (1)°	T = 296 K
V = 2596.09 (12) Å3	Bar, colourless
Z = 2	0.14 × 0.12 × 0.05 mm

Bruker APEXII CCD area-detector diffractometer	5918 independent reflections
Radiation source: fine-focus sealed tube	4086 reflections with I > 2σ(I)
graphite	Rint = 0.031
phi and ω scans	θmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −17→17
Tmin = 0.985, Tmax = 0.995	k = −14→14
24265 measured reflections	l = −19→23

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.058P)2 + 0.3037P] where P = (Fo2 + 2Fc2)/3
5918 reflections	(Δ/σ)max = 0.001
379 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.22 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
O1	0.89232 (10)	0.36614 (11)	1.13048 (7)	0.0566 (4)
O2	0.91840 (11)	0.19752 (11)	1.20316 (7)	0.0556 (4)
H2	0.9475	0.2439	1.2395	0.083*
O3	0.74670 (12)	0.28184 (12)	0.82900 (7)	0.0623 (4)
O4	0.71741 (11)	0.08686 (12)	0.79668 (7)	0.0619 (4)
H4	0.7058	0.1124	0.7519	0.093*
O5	0.87147 (10)	0.21216 (11)	0.58878 (6)	0.0513 (3)
H5	0.8940	0.2100	0.6371	0.077*
O6	0.91991 (11)	0.01904 (12)	0.60066 (7)	0.0624 (4)
O7	0.79322 (9)	−0.10426 (10)	0.23327 (6)	0.0469 (3)
H7	0.7969	−0.1689	0.2123	0.070*
O8	0.84624 (11)	−0.21541 (11)	0.34327 (7)	0.0577 (4)
N1	0.75488 (11)	−0.01589 (13)	1.02110 (8)	0.0448 (4)
N2	0.76208 (10)	0.19983 (11)	0.34879 (7)	0.0357 (3)
N3	1.06273 (12)	0.77515 (15)	0.25843 (8)	0.0504 (4)
N4	0.83365 (12)	0.65049 (16)	−0.14945 (8)	0.0520 (4)
N5	0.51891 (10)	0.82688 (12)	0.16936 (7)	0.0391 (3)
C1	0.88290 (13)	0.25840 (16)	1.13706 (9)	0.0403 (4)
C2	0.82884 (12)	0.17824 (14)	1.06824 (9)	0.0360 (4)
C3	0.79903 (13)	0.06220 (15)	1.07946 (9)	0.0412 (4)
H3	0.8105	0.0371	1.1309	0.049*
C4	0.74003 (12)	0.02231 (15)	0.94810 (9)	0.0399 (4)
H4A	0.7118	−0.0317	0.9067	0.048*
C5	0.76425 (12)	0.13790 (15)	0.93021 (9)	0.0365 (4)
C6	0.80869 (12)	0.21694 (15)	0.99183 (9)	0.0387 (4)
H6	0.8249	0.2955	0.9819	0.046*
C7	0.74147 (13)	0.17741 (17)	0.84653 (9)	0.0435 (4)
C8	0.88248 (12)	0.10611 (15)	0.56092 (9)	0.0387 (4)
C9	0.84316 (11)	0.10225 (13)	0.47271 (8)	0.0326 (3)
C10	0.79689 (12)	0.20178 (14)	0.42774 (9)	0.0341 (3)
H10	0.7897	0.2724	0.4533	0.041*
C11	0.77338 (12)	0.09854 (14)	0.31231 (9)	0.0351 (4)
H11	0.7507	0.0980	0.2575	0.042*
C12	0.81732 (11)	−0.00551 (13)	0.35251 (8)	0.0333 (3)
C13	0.85226 (12)	−0.00289 (14)	0.43401 (9)	0.0353 (4)
H13	0.8818	−0.0715	0.4628	0.042*
C14	0.82183 (12)	−0.11939 (14)	0.30945 (9)	0.0365 (4)
C15	1.05291 (14)	0.66299 (18)	0.23018 (10)	0.0517 (5)
H15	1.0778	0.5997	0.2656	0.062*
C16	1.00790 (13)	0.63556 (17)	0.15141 (10)	0.0468 (4)
H16	1.0007	0.5554	0.1348	0.056*
C17	0.97328 (12)	0.72881 (15)	0.09689 (9)	0.0377 (4)
C18	0.92417 (12)	0.70293 (16)	0.01128 (9)	0.0380 (4)
C19	0.88180 (13)	0.58973 (16)	−0.01519 (9)	0.0444 (4)
H19	0.8830	0.5294	0.0209	0.053*
C20	0.83816 (14)	0.56738 (18)	−0.09498 (10)	0.0501 (5)
H20	0.8107	0.4911	−0.1115	0.060*
C21	0.87225 (15)	0.75957 (19)	−0.12476 (10)	0.0557 (5)
H21	0.8684	0.8187	−0.1622	0.067*
C22	0.91764 (14)	0.78877 (17)	−0.04623 (10)	0.0484 (4)
H22	0.9439	0.8660	−0.0317	0.058*
C23	0.98663 (14)	0.84544 (17)	0.12672 (10)	0.0505 (5)
H23	0.9666	0.9110	0.0926	0.061*
C24	1.02949 (15)	0.86454 (18)	0.20685 (11)	0.0553 (5)
H24	1.0354	0.9435	0.2256	0.066*
C25	0.48131 (13)	0.77880 (15)	0.09709 (9)	0.0407 (4)
H25	0.4599	0.6985	0.0919	0.049*
C26	0.47296 (12)	0.84300 (14)	0.02999 (9)	0.0376 (4)
H26	0.4469	0.8057	−0.0191	0.045*
C27	0.50350 (11)	0.96381 (14)	0.03536 (8)	0.0323 (3)
C28	0.54147 (13)	1.01290 (15)	0.11086 (9)	0.0438 (4)
H28	0.5624	1.0933	0.1180	0.053*
C29	0.54790 (13)	0.94206 (16)	0.17488 (9)	0.0444 (4)
H29	0.5740	0.9767	0.2248	0.053*

	U11	U22	U33	U12	U13	U23
O1	0.0855 (9)	0.0374 (7)	0.0412 (7)	−0.0112 (6)	0.0149 (6)	−0.0045 (6)
O2	0.0860 (9)	0.0441 (7)	0.0262 (6)	−0.0050 (6)	0.0065 (6)	−0.0053 (5)
O3	0.0973 (11)	0.0522 (9)	0.0348 (7)	−0.0113 (7)	0.0198 (7)	0.0069 (6)
O4	0.0973 (10)	0.0599 (9)	0.0235 (6)	−0.0126 (7)	0.0148 (6)	−0.0025 (6)
O5	0.0793 (9)	0.0441 (7)	0.0249 (6)	0.0074 (6)	0.0109 (6)	−0.0062 (5)
O6	0.1012 (10)	0.0483 (8)	0.0291 (6)	0.0213 (7)	0.0123 (6)	0.0055 (6)
O7	0.0818 (9)	0.0287 (6)	0.0277 (6)	−0.0007 (5)	0.0160 (6)	−0.0037 (5)
O8	0.0974 (10)	0.0319 (7)	0.0366 (7)	0.0155 (6)	0.0147 (7)	0.0028 (5)
N1	0.0630 (9)	0.0356 (8)	0.0315 (8)	−0.0053 (6)	0.0110 (7)	−0.0003 (6)
N2	0.0488 (8)	0.0287 (7)	0.0277 (7)	0.0007 (6)	0.0111 (6)	0.0008 (5)
N3	0.0596 (9)	0.0583 (10)	0.0293 (8)	0.0016 (8)	0.0105 (7)	−0.0065 (7)
N4	0.0595 (9)	0.0672 (11)	0.0277 (8)	0.0081 (8)	0.0129 (7)	−0.0009 (8)
N5	0.0472 (8)	0.0396 (8)	0.0284 (7)	0.0025 (6)	0.0104 (6)	0.0056 (6)
C1	0.0531 (10)	0.0393 (10)	0.0283 (8)	−0.0024 (8)	0.0141 (7)	−0.0041 (7)
C2	0.0427 (9)	0.0362 (9)	0.0284 (8)	0.0006 (7)	0.0114 (7)	−0.0014 (7)
C3	0.0583 (10)	0.0381 (9)	0.0255 (8)	0.0010 (8)	0.0125 (7)	0.0009 (7)
C4	0.0486 (9)	0.0390 (9)	0.0286 (8)	−0.0021 (7)	0.0092 (7)	−0.0044 (7)
C5	0.0425 (9)	0.0409 (9)	0.0250 (8)	−0.0014 (7)	0.0104 (7)	−0.0001 (7)
C6	0.0487 (9)	0.0363 (9)	0.0313 (9)	−0.0033 (7)	0.0141 (7)	0.0013 (7)
C7	0.0491 (10)	0.0525 (11)	0.0278 (9)	−0.0062 (8)	0.0119 (7)	0.0005 (8)
C8	0.0488 (9)	0.0392 (10)	0.0271 (8)	0.0020 (7)	0.0121 (7)	−0.0024 (7)
C9	0.0404 (8)	0.0315 (8)	0.0256 (8)	0.0001 (6)	0.0112 (6)	−0.0005 (6)
C10	0.0441 (9)	0.0297 (8)	0.0288 (8)	−0.0016 (7)	0.0131 (7)	−0.0032 (6)
C11	0.0473 (9)	0.0323 (8)	0.0241 (8)	−0.0019 (7)	0.0106 (6)	−0.0005 (6)
C12	0.0420 (8)	0.0290 (8)	0.0278 (8)	−0.0015 (6)	0.0110 (6)	−0.0020 (6)
C13	0.0464 (9)	0.0305 (8)	0.0267 (8)	0.0030 (7)	0.0100 (7)	0.0022 (6)
C14	0.0489 (9)	0.0304 (9)	0.0284 (8)	0.0010 (7)	0.0113 (7)	−0.0006 (6)
C15	0.0652 (12)	0.0530 (12)	0.0299 (9)	0.0009 (9)	0.0080 (8)	0.0027 (8)
C16	0.0588 (11)	0.0435 (10)	0.0340 (9)	−0.0013 (8)	0.0112 (8)	−0.0023 (8)
C17	0.0393 (8)	0.0444 (10)	0.0292 (8)	0.0030 (7)	0.0116 (7)	−0.0020 (7)
C18	0.0388 (8)	0.0477 (10)	0.0279 (8)	0.0066 (7)	0.0119 (7)	0.0006 (7)
C19	0.0513 (10)	0.0498 (11)	0.0298 (9)	0.0020 (8)	0.0114 (7)	0.0000 (7)
C20	0.0586 (11)	0.0560 (12)	0.0330 (9)	0.0013 (9)	0.0129 (8)	−0.0066 (8)
C21	0.0693 (13)	0.0634 (13)	0.0351 (10)	0.0069 (10)	0.0190 (9)	0.0098 (9)
C22	0.0583 (11)	0.0500 (11)	0.0370 (10)	0.0004 (8)	0.0166 (8)	0.0020 (8)
C23	0.0645 (11)	0.0435 (11)	0.0372 (10)	0.0082 (9)	0.0097 (8)	0.0006 (8)
C24	0.0693 (12)	0.0499 (11)	0.0409 (11)	0.0036 (9)	0.0119 (9)	−0.0121 (9)
C25	0.0529 (10)	0.0320 (9)	0.0353 (9)	−0.0008 (7)	0.0130 (8)	0.0026 (7)
C26	0.0496 (9)	0.0319 (9)	0.0276 (8)	−0.0005 (7)	0.0088 (7)	−0.0018 (7)
C27	0.0361 (8)	0.0317 (8)	0.0268 (8)	0.0015 (6)	0.0080 (6)	0.0016 (6)
C28	0.0607 (11)	0.0354 (9)	0.0306 (9)	−0.0111 (8)	0.0104 (8)	−0.0024 (7)
C29	0.0583 (10)	0.0442 (10)	0.0258 (8)	−0.0061 (8)	0.0086 (7)	−0.0013 (7)

O1—C1	1.209 (2)	C9—C13	1.386 (2)
O2—C1	1.310 (2)	C10—H10	0.9300
O2—H2	0.8200	C11—C12	1.383 (2)
O3—C7	1.206 (2)	C11—H11	0.9300
O4—C7	1.311 (2)	C12—C13	1.383 (2)
O4—H4	0.8200	C12—C14	1.494 (2)
O5—C8	1.3063 (19)	C13—H13	0.9300
O5—H5	0.8200	C15—C16	1.375 (2)
O6—C8	1.2049 (19)	C15—H15	0.9300
O7—C14	1.3056 (18)	C16—C17	1.391 (2)
O7—H7	0.8200	C16—H16	0.9300
O8—C14	1.2129 (19)	C17—C23	1.385 (2)
N1—C4	1.333 (2)	C17—C18	1.486 (2)
N1—C3	1.335 (2)	C18—C22	1.388 (2)
N2—C11	1.3370 (19)	C18—C19	1.394 (2)
N2—C10	1.3391 (19)	C19—C20	1.379 (2)
N3—C24	1.326 (2)	C19—H19	0.9300
N3—C15	1.330 (2)	C20—H20	0.9300
N4—C21	1.331 (2)	C21—C22	1.376 (2)
N4—C20	1.333 (2)	C21—H21	0.9300
N5—C29	1.328 (2)	C22—H22	0.9300
N5—C25	1.337 (2)	C23—C24	1.378 (2)
C1—C2	1.498 (2)	C23—H23	0.9300
C2—C6	1.380 (2)	C24—H24	0.9300
C2—C3	1.384 (2)	C25—C26	1.377 (2)
C3—H3	0.9300	C25—H25	0.9300
C4—C5	1.388 (2)	C26—C27	1.394 (2)
C4—H4A	0.9300	C26—H26	0.9300
C5—C6	1.380 (2)	C27—C28	1.391 (2)
C5—C7	1.500 (2)	C27—C27i	1.484 (3)
C6—H6	0.9300	C28—C29	1.376 (2)
C8—C9	1.496 (2)	C28—H28	0.9300
C9—C10	1.385 (2)	C29—H29	0.9300
C1—O2—H2	109.5	O8—C14—O7	124.97 (15)
C7—O4—H4	109.5	O8—C14—C12	121.98 (14)
C8—O5—H5	109.5	O7—C14—C12	113.00 (13)
C14—O7—H7	109.5	N3—C15—C16	123.54 (17)
C4—N1—C3	116.65 (14)	N3—C15—H15	118.2
C11—N2—C10	118.70 (13)	C16—C15—H15	118.2
C24—N3—C15	117.42 (15)	C15—C16—C17	119.38 (17)
C21—N4—C20	117.81 (15)	C15—C16—H16	120.3
C29—N5—C25	117.28 (13)	C17—C16—H16	120.3
O1—C1—O2	125.29 (15)	C23—C17—C16	116.58 (15)
O1—C1—C2	122.74 (15)	C23—C17—C18	122.40 (15)
O2—C1—C2	111.97 (14)	C16—C17—C18	121.02 (15)
C6—C2—C3	117.94 (15)	C22—C18—C19	116.55 (15)
C6—C2—C1	121.12 (15)	C22—C18—C17	122.44 (16)
C3—C2—C1	120.93 (14)	C19—C18—C17	121.01 (15)
N1—C3—C2	124.09 (15)	C20—C19—C18	119.88 (17)
N1—C3—H3	118.0	C20—C19—H19	120.1
C2—C3—H3	118.0	C18—C19—H19	120.1
N1—C4—C5	123.85 (15)	N4—C20—C19	122.77 (18)
N1—C4—H4A	118.1	N4—C20—H20	118.6
C5—C4—H4A	118.1	C19—C20—H20	118.6
C6—C5—C4	118.04 (14)	N4—C21—C22	122.94 (17)
C6—C5—C7	120.54 (15)	N4—C21—H21	118.5
C4—C5—C7	121.41 (14)	C22—C21—H21	118.5
C2—C6—C5	119.35 (15)	C21—C22—C18	120.04 (18)
C2—C6—H6	120.3	C21—C22—H22	120.0
C5—C6—H6	120.3	C18—C22—H22	120.0
O3—C7—O4	125.04 (15)	C24—C23—C17	120.18 (17)
O3—C7—C5	122.25 (16)	C24—C23—H23	119.9
O4—C7—C5	112.70 (15)	C17—C23—H23	119.9
O6—C8—O5	124.79 (15)	N3—C24—C23	122.84 (18)
O6—C8—C9	122.28 (15)	N3—C24—H24	118.6
O5—C8—C9	112.93 (14)	C23—C24—H24	118.6
C10—C9—C13	118.32 (14)	N5—C25—C26	122.83 (15)
C10—C9—C8	121.67 (14)	N5—C25—H25	118.6
C13—C9—C8	120.00 (13)	C26—C25—H25	118.6
N2—C10—C9	122.28 (14)	C25—C26—C27	120.19 (14)
N2—C10—H10	118.9	C25—C26—H26	119.9
C9—C10—H10	118.9	C27—C26—H26	119.9
N2—C11—C12	122.87 (14)	C28—C27—C26	116.31 (14)
N2—C11—H11	118.6	C28—C27—C27i	121.69 (17)
C12—C11—H11	118.6	C26—C27—C27i	122.00 (17)
C13—C12—C11	117.97 (14)	C29—C28—C27	119.75 (15)
C13—C12—C14	120.78 (14)	C29—C28—H28	120.1
C11—C12—C14	121.17 (13)	C27—C28—H28	120.1
C12—C13—C9	119.84 (14)	N5—C29—C28	123.63 (15)
C12—C13—H13	120.1	N5—C29—H29	118.2
C9—C13—H13	120.1	C28—C29—H29	118.2

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N5ii	0.82	1.80	2.5928 (17)	162.
O4—H4···N4iii	0.82	1.79	2.6037 (18)	172.
O5—H5···N3iv	0.82	1.78	2.5956 (17)	173.
O7—H7···N2iii	0.82	1.83	2.5862 (16)	152.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N5i	0.82	1.80	2.5928 (17)	162
O4—H4⋯N4ii	0.82	1.79	2.6037 (18)	172
O5—H5⋯N3iii	0.82	1.78	2.5956 (17)	173
O7—H7⋯N2ii	0.82	1.83	2.5862 (16)	152

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