Related literature

Acta Crystallogr Sect E Struct Rep Online

Acta Cryst. E

Acta Crystallographica Section E: Structure Reports Online

1600-5368

International Union of Crystallography

22412511

3297321

ds2171

10.1107/S1600536812003194

ACSEBH

S1600536812003194

Organic Papers

4,4′-Bipyridine–2-methoxybenzoic acid (1/2)

C₁₀H₈N₂·2C₈H₈O₃

Qian

Xiao-Yan

a*Liu

Feng-Zhi

aaSuzhou Industrial Park Centers for Disease Control and Prevention, Institute of Health Inspection and Supervision, 215021 Suzhou, Jiangsu, People’s Republic of China

Correspondence e-mail: xiaoyan.qian@live.cn

0132012

0422012

68Pt 3

e120300

o597o59712120122512012

2012

This is an open-access article distributed under the terms of the Creative Commons Attribution Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

A full version of this article is available from Crystallography Journals Online.

The asymmetric unit of the title compound, C₁₀H₈N₂·2C₈H₈O₃, contains two 2-methoxybenzoic acid molecules and one 4,4′-bipyridine molecule. The 4,4′-bipyridine molecule is disordered over two positions in a 1:1 ratio. In the crystal, the 2-methoxybenzoic acid and 4,4′-bipyridine molecules are connected by intermolecular O—H⋯N hydrogen bonds. The dihedral angle between the carboxy group and its attached ring is 26.823 (2)°.

Related literature

For the use and related structures of 2-methoxybenzoic acid in coordination chemistry, see: Vollano et al. (1984 ▶); Smith et al. (1986 ▶); Li (2005 ▶); Andrews et al. (2006 ▶); Ren et al. (2006 ▶); Zhao et al. (2008 ▶); Sharma et al. (2009 ▶).

Experimental <sec id="sec2.1.1"><title>Crystal data

C₁₀H₈N₂·2C₈H₈O₃

M _r = 460.47

Monoclinic,

a = 7.7090 (15) Å

b = 25.620 (5) Å

c = 6.3624 (13) Å

β = 112.08 (3)°

V = 1164.4 (4) Å³

Z = 2

Mo Kα radiation

μ = 0.09 mm⁻¹

T = 298 K

0.30 × 0.28 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.972, T _max = 0.977

5991 measured reflections

2060 independent reflections

1540 reflections with I > 2σ(I)

R _int = 0.088

Refinement

R[F ² > 2σ(F ²)] = 0.052

wR(F ²) = 0.154

S = 1.06

2060 reflections

172 parameters

9 restraints

H-atom parameters constrained

Δρ_max = 0.15 e Å⁻³

Δρ_min = −0.16 e Å⁻³

Data collection: <italic>APEX2</italic> (Bruker, 2005<xref ref-type="bibr" rid="bb2"> ▶</xref>); cell refinement: <italic>APEX2</italic>; data reduction: <italic>SAINT</italic> (Bruker, 2005<xref ref-type="bibr" rid="bb2"> ▶</xref>); program(s) used to solve structure: <italic>SHELXTL</italic> (Sheldrick, 2008<xref ref-type="bibr" rid="bb6"> ▶</xref>); program(s) used to refine structure: <italic>SHELXTL</italic>; molecular graphics: <italic>SHELXTL</italic>; software used to prepare material for publication: <italic>SHELXTL</italic>.</sec></sec><sec sec-type="supplementary-material"><title>Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812003194/ds2171sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812003194/ds2171Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812003194/ds2171Isup3.cml

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

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DS2171).

supplementary crystallographic information Comment

Bipyridine is a well known molecule often used as a linker in polymeric coordination complexes. 2-Methoxybenzoic acid is also sometimes used as a common ligand in coordination polymers (Vollano et al., 1984; Smith et al., 1986; Li, 2005; Andrews et al., 2006; Ren et al., 2006; Zhao et al., 2008; Sharma et al., 2009.). The title compound, (I), is a 1:2 cocrystal of the aforementioned linkers. Herewith we present its crystal structure. The asymmetric unit of the title compound (Fig. 1) contains two 2-methoxybenzoic acid molecules and one 4,4'-bipyridine molecule. The dihedral angle of carboxy group to its ring is 26.823 (2)°. The 4,4'-bipyridine molecule is disordered over two positions in a 1:1 ratio. In the crystal structure, the 2-methoxybenzoic acid and 4,4'-bipyridine are held together by intermolecular O—H···N hydrogen bonds.

Experimental

An ethanol solution (20 ml) of 2-methoxybenzoic acid (0.1 mmol) and 4,4'-bipyridine (0.1 mmol) was heated at 333 K for 2 h. Then the mixture was cooled to room temperature. After two weeks colorless crystals were obtained that were suitable for X-ray diffraction study.

FiguresFig. 1.

View of the title compound showing the atomic labeling and 30% probability displacement ellipsoids.

Fig. 2.

The O—H···N hydrogen bonds of (I). All H atoms have been omitted for clarity. The dashed lines indicate the O—H···N hydrogen bonds.

Crystal data

C₁₀H₈N₂·2C₈H₈O₃	F(000) = 484
M_r = 460.47	D_x = 1.313 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2567 reflections
a = 7.7090 (15) Å	θ = 2.4–23.4°
b = 25.620 (5) Å	µ = 0.09 mm⁻¹
c = 6.3624 (13) Å	T = 298 K
β = 112.08 (3)°	Block, colourless
V = 1164.4 (4) Å³	0.30 × 0.28 × 0.25 mm
Z = 2

Data collection

Bruker SMART APEXII CCD diffractometer	2060 independent reflections
Radiation source: fine-focus sealed tube	1540 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.088
ω scans	θ_max = 25.1°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→9
T_min = 0.972, T_max = 0.977	k = −30→29
5991 measured reflections	l = −7→7

Refinement

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.154	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0805P)² + 0.1072P] where P = (F_o² + 2F_c²)/3
2060 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.15 e Å⁻³
9 restraints	Δρ_min = −0.16 e Å⁻³

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.4229 (2)	0.58341 (6)	0.9083 (3)	0.0771 (5)
H1	0.3645	0.5715	0.9816	0.116*
C1	0.4341 (3)	0.65024 (7)	0.6614 (3)	0.0525 (5)
O2	0.1962 (2)	0.64201 (7)	0.8143 (3)	0.0791 (5)
C2	0.3393 (3)	0.68089 (7)	0.4708 (3)	0.0562 (5)
O3	0.1512 (2)	0.68604 (6)	0.4068 (2)	0.0717 (5)
C3	0.4378 (4)	0.70402 (9)	0.3514 (4)	0.0751 (7)
H3	0.3747	0.7242	0.2241	0.090*
C4	0.6271 (4)	0.69715 (11)	0.4209 (5)	0.0877 (8)
H4	0.6916	0.7131	0.3408	0.105*
C5	0.7227 (3)	0.66730 (11)	0.6053 (6)	0.0875 (8)
H5	0.8513	0.6627	0.6505	0.105*
C6	0.6260 (3)	0.64391 (9)	0.7248 (4)	0.0702 (6)
H6	0.6912	0.6235	0.8505	0.084*
C7	0.3370 (3)	0.62529 (8)	0.7980 (3)	0.0545 (5)
C8	0.0540 (4)	0.71555 (13)	0.2045 (4)	0.0945 (9)
H8A	0.0982	0.7509	0.2256	0.142*
H8B	−0.0779	0.7151	0.1734	0.142*
H8C	0.0767	0.7004	0.0793	0.142*
N1	0.2439 (3)	0.54252 (7)	0.1570 (3)	0.0661 (5)
C11	0.0512 (3)	0.50894 (7)	0.4279 (3)	0.0556 (5)
C9	0.3203 (7)	0.5048 (2)	0.3112 (9)	0.0635 (12)	0.50
H9	0.4362	0.4910	0.3277	0.076*	0.50
C10	0.2284 (7)	0.48633 (19)	0.4455 (9)	0.0616 (11)	0.50
H10	0.2804	0.4593	0.5474	0.074*	0.50
C12	−0.0112 (8)	0.5490 (2)	0.2734 (9)	0.0581 (18)*	0.50
H12	−0.1225	0.5658	0.2568	0.070*	0.50
C13	0.0872 (8)	0.5649 (3)	0.1426 (10)	0.063 (2)*	0.50
H13	0.0406	0.5923	0.0411	0.075*	0.50
C9'	0.2515 (7)	0.49348 (19)	0.2343 (9)	0.0625 (16)*	0.50
H9'	0.3280	0.4698	0.1990	0.075*	0.50
C10'	0.1531 (8)	0.4757 (2)	0.3634 (9)	0.0645 (16)*	0.50
H10'	0.1587	0.4407	0.4043	0.077*	0.50
C12'	0.0289 (8)	0.55892 (18)	0.3415 (9)	0.0554 (13)	0.50
H12'	−0.0516	0.5823	0.3710	0.066*	0.50
C13'	0.1266 (8)	0.57342 (19)	0.2127 (10)	0.0599 (14)	0.50
H13'	0.1112	0.6075	0.1585	0.072*	0.50

Atomic displacement parameters (Å2)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0796 (11)	0.0708 (10)	0.0986 (12)	0.0224 (8)	0.0536 (9)	0.0295 (9)
C1	0.0532 (11)	0.0469 (10)	0.0603 (11)	−0.0023 (8)	0.0247 (9)	−0.0035 (9)
O2	0.0730 (10)	0.0971 (12)	0.0823 (11)	0.0283 (8)	0.0465 (8)	0.0295 (9)
C2	0.0632 (12)	0.0525 (10)	0.0581 (11)	0.0013 (9)	0.0287 (9)	−0.0044 (9)
O3	0.0667 (9)	0.0895 (11)	0.0631 (9)	0.0218 (7)	0.0292 (7)	0.0171 (8)
C3	0.0904 (17)	0.0689 (14)	0.0751 (14)	−0.0069 (12)	0.0413 (13)	0.0071 (11)
C4	0.0878 (19)	0.0886 (17)	0.103 (2)	−0.0228 (14)	0.0550 (16)	0.0040 (15)
C5	0.0574 (13)	0.0915 (18)	0.121 (2)	−0.0166 (12)	0.0426 (14)	−0.0042 (17)
C6	0.0533 (12)	0.0671 (13)	0.0882 (15)	−0.0044 (10)	0.0244 (11)	0.0036 (11)
C7	0.0532 (11)	0.0563 (11)	0.0562 (11)	0.0063 (9)	0.0231 (9)	0.0015 (9)
C8	0.0963 (18)	0.126 (2)	0.0663 (14)	0.0422 (16)	0.0362 (13)	0.0282 (15)
N1	0.0785 (12)	0.0605 (10)	0.0678 (11)	−0.0008 (9)	0.0373 (9)	0.0010 (9)
C11	0.0683 (12)	0.0470 (10)	0.0550 (11)	−0.0013 (9)	0.0272 (9)	−0.0049 (8)
C9	0.054 (3)	0.076 (3)	0.060 (3)	0.003 (2)	0.022 (2)	−0.001 (2)
C10	0.059 (3)	0.067 (3)	0.059 (3)	0.013 (2)	0.022 (2)	0.018 (2)
C12'	0.072 (3)	0.042 (2)	0.055 (3)	−0.005 (2)	0.028 (2)	−0.010 (2)
C13'	0.083 (3)	0.043 (2)	0.054 (3)	−0.012 (2)	0.026 (3)	−0.002 (2)

Geometric parameters (Å, º)

O1—C7	1.316 (2)	N1—C9'	1.343 (5)
O1—H1	0.8200	N1—C9	1.345 (4)
C1—C6	1.389 (3)	N1—C13'	1.346 (5)
C1—C2	1.398 (3)	C11—C10'	1.325 (6)
C1—C7	1.488 (3)	C11—C12	1.377 (6)
O2—C7	1.207 (2)	C11—C12'	1.378 (5)
C2—O3	1.357 (2)	C11—C10	1.448 (4)
C2—C3	1.392 (3)	C11—C11ⁱ	1.490 (4)
O3—C8	1.437 (3)	C9—C10	1.382 (5)
C3—C4	1.368 (3)	C9—H9	0.9300
C3—H3	0.9300	C10—H10	0.9300
C4—C5	1.362 (4)	C12—C13	1.381 (7)
C4—H4	0.9300	C12—H12	0.9300
C5—C6	1.385 (4)	C13—H13	0.9300
C5—H5	0.9300	C9'—C10'	1.388 (6)
C6—H6	0.9300	C9'—H9'	0.9300
C8—H8A	0.9600	C10'—H10'	0.9300
C8—H8B	0.9600	C12'—C13'	1.357 (6)
C8—H8C	0.9600	C12'—H12'	0.9300
N1—C13	1.309 (6)	C13'—H13'	0.9300

C7—O1—H1	109.5	C10'—C11—C12	110.4 (4)
C6—C1—C2	118.00 (18)	C10'—C11—C12'	118.3 (3)
C6—C1—C7	119.65 (19)	C12—C11—C10	114.8 (3)
C2—C1—C7	122.34 (17)	C12'—C11—C10	112.0 (3)
O3—C2—C3	122.4 (2)	C10'—C11—C11ⁱ	120.4 (3)
O3—C2—C1	117.74 (17)	C12—C11—C11ⁱ	123.0 (3)
C3—C2—C1	119.9 (2)	C12'—C11—C11ⁱ	121.0 (3)
C2—O3—C8	117.29 (17)	C10—C11—C11ⁱ	122.1 (3)
C4—C3—C2	120.2 (2)	N1—C9—C10	120.8 (4)
C4—C3—H3	119.9	N1—C9—H9	119.6
C2—C3—H3	119.9	C10—C9—H9	119.6
C5—C4—C3	121.1 (2)	C9—C10—C11	120.2 (4)
C5—C4—H4	119.4	C9—C10—H10	119.9
C3—C4—H4	119.4	C11—C10—H10	119.9
C4—C5—C6	119.1 (2)	C11—C12—C13	121.7 (5)
C4—C5—H5	120.4	C11—C12—H12	119.1
C6—C5—H5	120.4	C13—C12—H12	119.1
C5—C6—C1	121.6 (2)	N1—C13—C12	122.0 (6)
C5—C6—H6	119.2	N1—C13—H13	119.0
C1—C6—H6	119.2	C12—C13—H13	119.0
O2—C7—O1	122.15 (18)	N1—C9'—C10'	124.5 (5)
O2—C7—C1	124.29 (18)	N1—C9'—H9'	117.7
O1—C7—C1	113.52 (17)	C10'—C9'—H9'	117.7
O3—C8—H8A	109.5	C11—C10'—C9'	119.4 (5)
O3—C8—H8B	109.5	C11—C10'—H10'	120.3
H8A—C8—H8B	109.5	C9'—C10'—H10'	120.3
O3—C8—H8C	109.5	C13'—C12'—C11	118.7 (4)
H8A—C8—H8C	109.5	C13'—C12'—H12'	120.6
H8B—C8—H8C	109.5	C11—C12'—H12'	120.6
C13—N1—C9'	110.4 (4)	N1—C13'—C12'	125.4 (4)
C13—N1—C9	120.3 (4)	N1—C13'—H13'	117.3
C9'—N1—C13'	113.3 (3)	C12'—C13'—H13'	117.3
C9—N1—C13'	112.6 (3)

C6—C1—C2—O3	178.65 (17)	C10'—C11—C12—C13	−28.0 (6)
C7—C1—C2—O3	−2.3 (3)	C12'—C11—C12—C13	88.6 (12)
C6—C1—C2—C3	−0.2 (3)	C10—C11—C12—C13	1.7 (7)
C7—C1—C2—C3	178.92 (18)	C11ⁱ—C11—C12—C13	179.7 (4)
C3—C2—O3—C8	1.7 (3)	C9'—N1—C13—C12	24.7 (7)
C1—C2—O3—C8	−177.1 (2)	C9—N1—C13—C12	−3.9 (8)
O3—C2—C3—C4	−179.2 (2)	C13'—N1—C13—C12	−77.4 (12)
C1—C2—C3—C4	−0.4 (3)	C11—C12—C13—N1	0.5 (9)
C2—C3—C4—C5	0.7 (4)	C13—N1—C9'—C10'	−23.9 (7)
C3—C4—C5—C6	−0.5 (4)	C9—N1—C9'—C10'	93.1 (9)
C4—C5—C6—C1	−0.1 (4)	C13'—N1—C9'—C10'	−1.4 (7)
C2—C1—C6—C5	0.4 (3)	C12—C11—C10'—C9'	28.7 (6)
C7—C1—C6—C5	−178.7 (2)	C12'—C11—C10'—C9'	7.6 (7)
C6—C1—C7—O2	151.7 (2)	C10—C11—C10'—C9'	−76.1 (7)
C2—C1—C7—O2	−27.4 (3)	C11ⁱ—C11—C10'—C9'	−178.2 (4)
C6—C1—C7—O1	−26.2 (3)	N1—C9'—C10'—C11	−3.8 (8)
C2—C1—C7—O1	154.75 (18)	C10'—C11—C12'—C13'	−6.4 (7)
C13—N1—C9—C10	4.8 (8)	C12—C11—C12'—C13'	−78.6 (12)
C9'—N1—C9—C10	−70.7 (8)	C10—C11—C12'—C13'	23.5 (7)
C13'—N1—C9—C10	26.7 (7)	C11ⁱ—C11—C12'—C13'	179.4 (5)
N1—C9—C10—C11	−2.5 (9)	C13—N1—C13'—C12'	89.0 (13)
C10'—C11—C10—C9	86.1 (8)	C9'—N1—C13'—C12'	2.6 (8)
C12—C11—C10—C9	−0.7 (7)	C9—N1—C13'—C12'	−27.3 (8)
C12'—C11—C10—C9	−23.2 (7)	C11—C12'—C13'—N1	1.2 (10)
C11ⁱ—C11—C10—C9	−178.8 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1ⁱⁱ	0.82	1.85	2.673 (2)	177

Symmetry code: (ii) x, y, z+1.

References

Andrews, P. C., Deacon, G. B., Junk, P. C., Kumar, I. & Silberstein, M. (2006). Dalton Trans. pp. 4852–4858.

Bruker (2005). APEX2, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.

Li, X. (2005). Z. Kristallogr. New Cryst. Struct. 220, 407–408.

Ren, N., Zhang, J. J., Xu, S. L., Zhang, H. Y., Wang, R. F. & Wang, S. P. (2006). Chin. J. Inorg. Chem. 22, 1905–1907.

Sharma, R. P., Singh, S., Singh, A. & Ferretti, V. (2009). J. Mol. Struct. 918, 188–193.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Smith, P. J., Day, R. O., Chandrasekhar, V. M., Holmes, J. & Holmes, R. R. (1986). Inorg. Chem. 25, 2495–2499.

Vollano, J. F., Day, R. O., Rau, D. N., Chandrasekhar, V. & Holmes, R. R. (1984). Inorg. Chem. 23, 3153–3160.

Zhao, N., Wang, S. P., Ma, R. X., Gao, Z. H., Wang, R. F. & Zhang, J. J. (2008). J. Alloys Compd, 463, 338–342.

Table 1Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1ⁱ	0.82	1.85	2.673 (2)	177

Symmetry code: (i) .