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4,4′-Bipyridine cocrystallizes with 3-hydroxy-2-naphthoic acid in a 1:2 ratio to give a centrosymmetric three-component supra­molecular adduct, namely 3-hydroxy-2-naphthoic acid–4,4′-bipyridine (2/1), C11H8O3·0.5C10H8N2, in which 4,4′-bipyridine is located on an inversion center. The pyridine–carboxylic acid heterosynthon generates an infinite one-dimensional hydrogen-bonded chain via π–π inter­actions between naphthyl and 4,4′-bipyridine groups. The one-dimensional chains are further assembled into a three-dimensional network by weak C—H...π inter­actions between pyridyl and naphthyl rings, and C—H...O inter­actions between 3-hydroxy-2-naphthoic acid mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106013461/av3011sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013461/av3011Isup2.hkl
Contains datablock I

CCDC reference: 601685

Comment top

Crystal engineering of organic molecules has been exploited in organic materials and even in active pharmaceutical ingredients (Desiraju, 2003; Almarsson & Zaworotko, 2004). Supramolecular synthons provide an effective strategy for synthesizing the specific organic supramolecular solids (Desiraju,1997). In particular, supramolecular heterosynthons have great advantages in designing the cocrystals of two or more components. For example, Bailey Walsh et al. (2003) inserted 4,4'-bipyridine between carboxylic acid moieties and utilized the pyridine–carboxylic acid heterosynthon to obtain several pharmaceutical cocrystals. Weak C—H···O interaction plays an important role in the heterosynthon. The pyridyl ring of 4,4'-bipyridine is also able to provide other weak interactions, such as ππ and C—H···π interactions. We have treated 4,4'-bipyridine with 3-hydroxy-2-naphthoic acid and obtained the crystalline supramolecular adduct (I), in which the pyridine–carboxylic acid heterosynthon generates a molecular complex which is engineered into a three-dimensional assembly by ππ and C—H···π interactions between pyridyl and naphthoic rings.

X-ray diffraction shows that the centrosymmetric three-component adduct is formed between 3-hydroxy-2-naphthoic acid and 4,4'-bipyridine in 2:1 ratio. The expected pyridine–carboxylic acid heterosynthon contains hydrogen-bonding [N1···O1 = 2.625 (2) A°] and C—H···O interaction (2.375 A°, 130.18°) between pyridyl ring and carboxylic acid group. The hydroxy group is involved in intramolecular hydrogen-bonding [O3···O2 = 2.557 (2) A°] with the carbonyl O atom (Table 2). The 4,4'-bipyridine molcule is located in the center of the adduct and on the inversion center, and the two pyridine rings are coplanar. Moreover, the naphthoic acid rings are parallel to the 4,4'-bipyridine molecule. The crystal packing of the adduct is controlled by two distinct weak interactions between the 4,4'-bipyridine and naphthoic acid rings. One naphthoic acid ring is involved in ππ interactions with a pyridyl ring at (x + 1, y, z) at a centroid–centroid distance of 3.630 Å (Table 3). Two adduct molecules connected together are parallel displaced and along a axis the adduct is linked into a one-dimensional infinite chain by face-to-face π stacking (Fig. 2). There also exists a point-to-face C15—H15···π interaction (H···centroid = 2.858 Å and C15—H15···π= 158°) between the CH group of a pyridyl ring and an adjacent naphthoic acid ring (−x, y − 1/2, 1/2 − z). Moreover, the hydroxy O atom is involved in C9—H9···O3 interactions (2.696 Å and 125.81°) with naphthoic acid rings related by (1 − x, y − 1/2, 1/2 − z). For the whole adduct molecule, the naphthoic acid rings lie in the end and pyridyl rings lie in the middle. Thus, each adduct molecule interacts with eight adjacent molecules in four directions, and each one-dimensional chain resulting from ππ interactions connects four chains through weak C—H ···π and C—H···O interactions into a three-dimensional assembly (Fig. 3), which exhibits intense photoluminescence at 534 nm upon photo-excitation at 365 nm. 3-Hydroxy-2-naphthoic acid exhibits luminescence at 524 nm upon excitation at 365 nm, which shows that the interactions between 3-hydroxy-2-naphthoic acid and 4,4'- bipyridine slightly affect the luminescent property. In conclusion, in the cocrystal 3-hydroxy-2-naphthoic acid interacts with 4,4'-bipyridine in four ways: O—H···N hydrogen-bonding, weak C—H···O, ππ stacking and C—H···π interactions. The four non-covalent interactions together with the C—H···O interactions between naphthoic acid molecules result in a three-dimensional supramolecular assembly. This result also demonstrates the fact that the pyridyl ring is an excellent cocrystal former.

Experimental top

A mixture of 3-hydroxy-2-naphthoic acid (0.075 g, 0.4 mmol) and 4,4'-bipyridine (0.032 g, 0.2 mmol) was stirred in enthanol (10 ml). The solution was kept in air and after several days yellow crystals were obtained with 70% yield.

Refinement top

All H atoms were constrained to ride on their parent atoms with Uiso(H) values of 1.2Ueq(parent atom) (C—H = 0.95 Å).

Computing details top

Data collection: CrystalClear (Rigaku Corporation, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. A plot of adduct (I) with 30% probability displacement ellipsoids. The dashed lines indicate hydrogen bonds.
[Figure 2] Fig. 2. The one-dimensional structure of (I) along axis. The dashed lines indicate hydrogen bonds or ππ interactions
[Figure 3] Fig. 3. The three-dimensional structure of (I), viewed along the a axis. The dotted lines indicate C—H···O(π) interactions
3-hydroxy-2-naphthoic–4,4'-bipyridine (2/1) top
Crystal data top
C11H8O3·0.5C10H8N2F(000) = 556
Mr = 266.27Dx = 1.367 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.999 (5) ÅCell parameters from 2304 reflections
b = 11.735 (7) Åθ = 2.9–27.4°
c = 12.393 (7) ŵ = 0.10 mm1
β = 98.799 (12)°T = 293 K
V = 1293.4 (13) Å3Prism, yellow
Z = 40.44 × 0.38 × 0.10 mm
Data collection top
Make and Model?? CCD
diffractometer
2934 independent reflections
Radiation source: fine-focus sealed tube1768 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
Detector resolution: 28.5714 pixels mm-1θmax = 27.4°, θmin = 2.3°
CCD_Profile_fitting scansh = 1111
Absorption correction: multi-scan
?
k = 1315
Tmin = 0.821, Tmax = 1.000l = 1515
9720 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.054H-atom parameters constrained
wR(F2) = 0.158 w = 1/[σ2(Fo2) + (0.0944P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max < 0.001
2934 reflectionsΔρmax = 0.27 e Å3
182 parametersΔρmin = 0.19 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.29 (2)
Crystal data top
C11H8O3·0.5C10H8N2V = 1293.4 (13) Å3
Mr = 266.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.999 (5) ŵ = 0.10 mm1
b = 11.735 (7) ÅT = 293 K
c = 12.393 (7) Å0.44 × 0.38 × 0.10 mm
β = 98.799 (12)°
Data collection top
Make and Model?? CCD
diffractometer
2934 independent reflections
Absorption correction: multi-scan
?
1768 reflections with I > 2σ(I)
Tmin = 0.821, Tmax = 1.000Rint = 0.042
9720 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.158H-atom parameters constrained
S = 0.96Δρmax = 0.27 e Å3
2934 reflectionsΔρmin = 0.19 e Å3
182 parameters
Special details top

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) top
xyzUiso*/Ueq
O10.15570 (12)0.05389 (12)0.22487 (10)0.0717 (4)
H10.06430.04620.19930.086*
O20.13676 (15)0.19441 (15)0.10344 (14)0.0983 (5)
O30.37149 (18)0.30019 (14)0.06488 (12)0.0971 (5)
H30.28120.27920.05450.117*
N10.12165 (14)0.01352 (13)0.13242 (11)0.0588 (4)
C10.21090 (19)0.13774 (17)0.17723 (15)0.0633 (5)
C20.37275 (17)0.16406 (15)0.21240 (14)0.0552 (4)
C30.4462 (2)0.24535 (16)0.15306 (15)0.0650 (5)
C40.5967 (2)0.26847 (18)0.18401 (17)0.0754 (6)
H40.64460.32250.14380.091*
C50.68033 (19)0.21370 (17)0.27386 (16)0.0685 (5)
C60.8378 (2)0.2340 (2)0.3060 (2)0.0927 (8)
H60.88860.28620.26570.111*
C70.9147 (2)0.1795 (3)0.3930 (3)0.1102 (10)
H71.01950.19310.41220.132*
C80.8438 (3)0.1035 (3)0.4555 (2)0.1070 (9)
H80.89920.06810.51800.128*
C90.6928 (2)0.0803 (2)0.42592 (19)0.0876 (7)
H90.64510.02730.46750.105*
C100.60855 (18)0.13392 (17)0.33503 (15)0.0646 (5)
C110.45347 (18)0.11116 (16)0.30113 (14)0.0598 (5)
H110.40420.05770.34110.072*
C120.16956 (19)0.07572 (18)0.04482 (17)0.0737 (6)
H120.10020.12520.01780.088*
C130.31515 (18)0.07213 (17)0.00897 (16)0.0692 (6)
H130.34360.11840.07160.083*
C140.22045 (19)0.05580 (17)0.16810 (16)0.0684 (5)
H140.18810.10160.23050.082*
C150.36796 (18)0.06393 (16)0.11825 (15)0.0651 (5)
H150.43440.11500.14640.078*
C160.41996 (15)0.00183 (13)0.02734 (12)0.0482 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0449 (6)0.0862 (10)0.0820 (9)0.0066 (6)0.0032 (6)0.0061 (7)
O20.0602 (8)0.1003 (12)0.1237 (12)0.0072 (7)0.0199 (8)0.0347 (9)
O30.0899 (10)0.0976 (12)0.0998 (11)0.0135 (9)0.0014 (8)0.0287 (9)
N10.0444 (7)0.0642 (10)0.0676 (9)0.0032 (6)0.0076 (6)0.0012 (7)
C10.0491 (9)0.0667 (12)0.0718 (11)0.0013 (8)0.0014 (8)0.0057 (9)
C20.0463 (8)0.0570 (10)0.0619 (10)0.0009 (7)0.0075 (8)0.0119 (8)
C30.0635 (10)0.0634 (12)0.0676 (11)0.0022 (9)0.0079 (9)0.0051 (9)
C40.0646 (11)0.0727 (13)0.0929 (14)0.0166 (10)0.0246 (11)0.0134 (11)
C50.0488 (9)0.0717 (12)0.0854 (13)0.0056 (8)0.0114 (9)0.0300 (10)
C60.0530 (11)0.1053 (19)0.1207 (18)0.0148 (11)0.0157 (12)0.0519 (15)
C70.0480 (11)0.141 (3)0.135 (2)0.0041 (14)0.0056 (14)0.072 (2)
C80.0687 (14)0.133 (2)0.1091 (19)0.0320 (15)0.0187 (14)0.0380 (17)
C90.0679 (12)0.1027 (18)0.0863 (15)0.0162 (11)0.0076 (11)0.0147 (12)
C100.0494 (9)0.0725 (13)0.0699 (11)0.0058 (8)0.0022 (8)0.0215 (9)
C110.0479 (8)0.0653 (11)0.0658 (11)0.0008 (8)0.0074 (8)0.0056 (8)
C120.0465 (9)0.0862 (14)0.0858 (14)0.0163 (9)0.0021 (9)0.0195 (11)
C130.0504 (9)0.0788 (14)0.0761 (12)0.0127 (8)0.0023 (8)0.0242 (9)
C140.0519 (9)0.0785 (13)0.0722 (12)0.0030 (9)0.0010 (8)0.0154 (9)
C150.0484 (8)0.0729 (12)0.0738 (12)0.0094 (8)0.0083 (8)0.0166 (9)
C160.0414 (7)0.0500 (9)0.0540 (9)0.0021 (6)0.0103 (6)0.0049 (7)
Geometric parameters (Å, º) top
O1—C11.286 (2)C7—C81.398 (4)
O1—H10.8400C7—H70.9500
O2—C11.240 (2)C8—C91.379 (3)
O3—C31.355 (2)C8—H80.9500
O3—H30.8400C9—C101.407 (3)
N1—C121.324 (2)C9—H90.9500
N1—C141.330 (2)C10—C111.420 (2)
C1—C21.487 (2)C11—H110.9500
C2—C111.370 (2)C12—C131.377 (3)
C2—C31.427 (3)C12—H120.9500
C3—C41.377 (3)C13—C161.379 (2)
C4—C51.401 (3)C13—H130.9500
C4—H40.9500C14—C151.379 (2)
C5—C101.421 (3)C14—H140.9500
C5—C61.432 (3)C15—C161.387 (2)
C6—C71.350 (4)C15—H150.9500
C6—H60.9500C16—C16i1.496 (3)
C1—O1—H1109.5C7—C8—H8120.2
C3—O3—H3109.5C8—C9—C10120.8 (3)
C12—N1—C14117.34 (14)C8—C9—H9119.6
O2—C1—O1123.16 (16)C10—C9—H9119.6
O2—C1—C2119.81 (17)C9—C10—C11122.5 (2)
O1—C1—C2117.01 (16)C9—C10—C5119.28 (18)
C11—C2—C3119.08 (15)C11—C10—C5118.21 (18)
C11—C2—C1121.08 (16)C2—C11—C10121.91 (18)
C3—C2—C1119.84 (16)C2—C11—H11119.0
O3—C3—C4118.45 (18)C10—C11—H11119.0
O3—C3—C2121.45 (16)N1—C12—C13123.12 (16)
C4—C3—C2120.09 (18)N1—C12—H12118.4
C3—C4—C5121.13 (19)C13—C12—H12118.4
C3—C4—H4119.4C12—C13—C16120.53 (17)
C5—C4—H4119.4C12—C13—H13119.7
C4—C5—C10119.57 (16)C16—C13—H13119.7
C4—C5—C6122.2 (2)N1—C14—C15122.69 (17)
C10—C5—C6118.2 (2)N1—C14—H14118.7
C7—C6—C5120.5 (2)C15—C14—H14118.7
C7—C6—H6119.7C14—C15—C16120.51 (15)
C5—C6—H6119.7C14—C15—H15119.7
C6—C7—C8121.5 (2)C16—C15—H15119.7
C6—C7—H7119.2C13—C16—C15115.80 (14)
C8—C7—H7119.2C13—C16—C16i121.91 (18)
C9—C8—C7119.6 (3)C15—C16—C16i122.29 (17)
C9—C8—H8120.2
Symmetry code: (i) x1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.841.792.625 (2)172
O3—H3···O20.841.812.557 (2)147

Experimental details

Crystal data
Chemical formulaC11H8O3·0.5C10H8N2
Mr266.27
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)8.999 (5), 11.735 (7), 12.393 (7)
β (°) 98.799 (12)
V3)1293.4 (13)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.44 × 0.38 × 0.10
Data collection
DiffractometerMake and Model?? CCD
diffractometer
Absorption correctionMulti-scan
Tmin, Tmax0.821, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
9720, 2934, 1768
Rint0.042
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.158, 0.96
No. of reflections2934
No. of parameters182
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.19

Computer programs: CrystalClear (Rigaku Corporation, 2000), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997).

Selected geometric parameters (Å, º) top
O1—C11.286 (2)N1—C121.324 (2)
O2—C11.240 (2)N1—C141.330 (2)
O3—C31.355 (2)
C12—N1—C14117.34 (14)O1—C1—C2117.01 (16)
O2—C1—O1123.16 (16)O3—C3—C4118.45 (18)
O2—C1—C2119.81 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N10.841.792.625 (2)172
O3—H3···O20.841.812.557 (2)147
The parameters for weak hydrogen bonds and ππ interaction top
D—H···AD—H(Å)H···A(Å)D···A(Å)D—H···A(°)Symmetry
C12—H12···O20.952.3753.075130
C9—H9···O30.952.6963.3421261 − x,y − 1/2,1/2 − z
C15—H15···Cg1a0.952.8583.755158-x,y − 1/2,1/2 − z
Cg1···Cg2b3.480c3.630d165ex + 1,y,z
Notes: (a) Cg1 = Ring C2–C5/C10/C11. (b) Cg(2)= Ring N1/C12/C13/C16/C15/C14. (c) Perpendicular distance of Cg1 on ring 2. (d) Distance between ring Centroids (Å). (e) Angle between the Cg1···Cg2 vector and normal to plane 2.
 

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