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Cocrystallization of 1,1′-(p-phenylene)dipyridin-4(1H)-one (4,4′-dpy) and terephthalic acid (tpa) affords the hydrogen-bonded 1:1 title complex, C16H12N2O2·C8H6O4. Both mol­ecules are symmetrically disposed about independent symmetry centers. Strong O—H...O hydrogen bonds between tpa carboxyl groups and 4,4′-dpy carbonyl groups produce one-dimensional zigzag infinite chains. Each chain is linked to four surrounding chains via weak C—H...O inter­actions, resulting in a three-dimensional mol­ecular framework.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106015174/gz3009sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106015174/gz3009Isup2.hkl
Contains datablock I

CCDC reference: 612457

Comment top

Derivatives of 4,4'-bipyridine (hereafter, 4,4'-bpy) have been widely studied as versatile building blocks in various branches of chemistry, including coordination polymers (Würthner et al., 2004), hydrogen-bonded adducts (Jayaraman et al., 2006), and metal-organic frameworks (Yaghi et al., 2003). Whenever 4,4'-bpy takes part in the formation of hydrogen-bonded adducts containing COOH groups, O—H···N hydrogen bonds are conventionally formed; this behaviour is attributed to the strong acid–base binary interactions (Du et al., 2005a,b). However, the structure of the hydrogen-bonded adduct 1-(4'-pyridyl)-pyridine-4-one–acetic acid indicated that pyridone can compete with pyridine to be a more effective hydrogen-bond acceptor (Goodgame et al., 2001). Surprisingly, there is no report on 1-[4-(4-oxo-1,4-dihydro-1-pyridyl)phenyl]pyridin-4(1H)-one (hereafter, 4,4'-dpy), an analogue of 4,4'-bpy with an extended rigid aromatic core. Therefore, this is the first report of the synthesis of 4,4'-dpy and its cocrystallization with terephthalic acid (hereafter, tpa) to form a hydrogen-bonded adduct, 4,4'-dpy.tpa, (I). This adduct may be useful in the field of crystal engineering and supramolecular chemistry.

X-ray crystal structure analysis shows that 4,4'-dpy cocrystallizes with tpa in a 1:1 molar ratio, consistent with the ratio of hydrogen-bond donor (OH) and acceptor (4,4'-dpy CO) sites. The asymmetric unit contains one-half molecule of both 4,4'-dpy and tpa. An inversion over centers of symmetry located at the center of the central 4,4'-dpy ring (1, 1/2, 1/2) and the center of the tpa ring (−1/2, 1/2, 0) generates the full molecule in both cases. The resulting structure is shown in Fig. 1, along with the atom-numbering scheme. The dihedral angle between the pyridone ring of 4,4'-dpy and the central tpa ring is 118.88 (4)°. The crystallographically equivalent terminal pyridone rings form dihedral angles of 46.73 (4)° with the central phenyl ring and atom O1 is essentially in the pyridone ring plane. For the tpa component, the two COOH groups adopt a trans-coplanar conformation in relation to the phenyl ring, and the O2/O3/C12 plane is at an angle of 15.04 (10)° to the C9/C10/C11 plane, primarily as a result of rotation around the C9—C12 vector since C12 is out of the C9/C10/C11 plane by only 0.043 (1) Å. No bond distances or angles of interest were noted.

As can be seen in Figs. 1 and 2, the 4,4'-dpy and tpa components are connected through strong O2—H2···O1 interactions, generating infinite one-dimensional zigzag chains parallel to the (104) plane. Within this plane, the chains are not interconnected, evidently because the tpa molecules are oriented nearly normal to (104), making their O3 acceptor atoms inaccessible to donors within the plane, as can be seen in Figs. 2 and 3; however, each chain is surrounded by, and hydrogen bonded to, four additional chains [two in front of and two behind (104)] via weak C8—H8···O3 interactions, as illustrated in Fig. 3. (Note that each of the four individual molecules shown in Fig. 3 represents a small section of a separate and distinct chain.) These four chains are symmetrically disposed about the central chain and C—H···O interactions link the chains into a three-dimensional framework. Shan et al. (2002) conducted a Cambridge Structural Database (Allen, 2002) survey of hydrogen-bond geometry in 4,4'-bpy.carboxylic acid adducts and reported an average H···A distance of 1.65 Å, DA distances ranging between 2.60 and 2.65 Å, and D—H···A angles in the range 165–180°. These values are similar to the hydrogen-bond geometry found in (I), as reported in Table 1.

In conclusion, this work indicates that 4,4'-dpy is potentially an excellent hydrogen-bond acceptor; notably, (I) represents the first utilization of these types of molecules in crystal engineering and supramolecular chemistry.

Experimental top

4,4'-dpy was prepared by a modified literature procedure (You & Twieg, 1999). 1, 4-Diflurobenzene (0.57 g, 5.0 mmol) and 4-hydroxypyridine (1.90 g, 20.0 mmol) were dissolved in N-methyl-2-pyrrolidone (NMP, 6 ml). Anhydrous K2CO3 (2.76 g, 20.0 mmol) was added, and the resulting mixture was heated to 423 K under argon overnight. After cooling to room temperature, the mixture was diluted with water and the precipitate was collected by vacuum filtration. Recrystallization from methanol/water gave 0.22 g of colorless 4, 4'-dpy (m.p. 480.3 K, yield 17%). RF = 0.24 (90/10, CH2Cl2/MeOH); 1H– MR (300 MHz, CD3OD): δ 8.15 (d, J = 7.2 Hz, 4H), 7.80 (s, 4H), 6.61 (d, J = 7.2 Hz, 4H); 13C NMR (75 MHz, CD3OD): δ 180.21, 141.08, 124.83, 117.80. Dilute solutions of 4,4'-dpy and tpa, both in CH3OH, were mixed and allowed to stand at room temperature until solvent evaporation produced colorless plate-shaped crystals of (I). 1H NMR (400 MHz, DMSO): δ 13.27 (broad, COOH), 8.02 (d, J = 7.6 Hz, 4H), 8.01 (s, 4H), 7.73 (s, 4H), 6.23 (d, J = 7.6 Hz, 4H); 13C NMR (100 MHz, DMSO): δ 178.1 (CO), 167.3 (COOH), 142.4, 140.3, 130.1, 124.6, 118.7; IR (KBr, cm−1): 1700, 1676, 1636, 1633.

Refinement top

The location of the hydroxy H atom was optimized by the circular Fourier method available in SHELXL97 (Sheldrick, 1997). All H atoms were treated as riding, with O—H and C—H distances of 0.82 and 0.93 Å, and with Uiso(H) values equal to 1.5 (hydroxy) or 1.2 times (all other H atoms) Ueq of the parent atom.

Computing details top

Data collection: APEXII (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SADABS (Bruker, 2005); program(s) used to solve structure: SIR92 (Burla et al., 1989); program(s) used to refine structure: LS in TEXSAN (Molecular Structure Corporation, 1997) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 and PLATON.

Figures top
[Figure 1] Fig. 1. The molecular structure and atom-numbering scheme for (I), with displacement ellipsoids drawn at the 50% probability level. The dashed line represents a hydrogen bond and the black circles denote inversion centers. [Symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) −1 − x, 1 − y, −z.]
[Figure 2] Fig. 2. Rows of hydrogen-bonded chains in (I), as viewed in the (104) plane; dashed lines represent hydrogen bonds. Within this plane, no C—H···O interactions occur.
[Figure 3] Fig. 3. C—H···O hydrogen bonding in (I), as viewed down [010]. The central chain interacts with four surrounding chains through C8—H8···O3 interactions at O3iii, O3iv, C8v, and C8vi. The trace of the (104) plane is vertical and only one molecule from each surrounding chain is shown for clarity. H atoms not involved in hydrogen bonding have also been omitted. [Symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) −1 − x, 1 − y, −z; (iii) 1/2 + x, 1/2 − y, 1/2 + z; (iv) 3/2 − x, 1/2 + y, 1/2 − z; (v) x − 1/2, 1/2 − y, z − 1/2; (vi) −x − 1/2, 1/2 + y, 1/2 − z.]
1-[4-(4-oxo-1,4-dihydro-1-pyridyl)phenyl]pyridin-4(1H)-one–terephthalic acid top
Crystal data top
C16H12N2O2·C8H6O4F(000) = 448
Mr = 430.40Dx = 1.493 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7275 reflections
a = 6.0931 (2) Åθ = 2.7–33.4°
b = 10.2759 (3) ŵ = 0.11 mm1
c = 15.2973 (5) ÅT = 100 K
β = 92.148 (1)°Prism, colorless
V = 957.12 (5) Å30.37 × 0.27 × 0.22 mm
Z = 2
Data collection top
Bruker Kappa-APEX-II CCD
diffractometer
3717 independent reflections
Radiation source: X-ray tube3183 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.026
ϕ and ω scansθmax = 33.4°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
h = 79
Tmin = 0.916, Tmax = 0.976k = 1515
17765 measured reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0683P)2 + 0.2721P]
where P = (Fo2 + 2Fc2)/3
3717 reflections(Δ/σ)max = 0.001
146 parametersΔρmax = 0.54 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C16H12N2O2·C8H6O4V = 957.12 (5) Å3
Mr = 430.40Z = 2
Monoclinic, P21/nMo Kα radiation
a = 6.0931 (2) ŵ = 0.11 mm1
b = 10.2759 (3) ÅT = 100 K
c = 15.2973 (5) Å0.37 × 0.27 × 0.22 mm
β = 92.148 (1)°
Data collection top
Bruker Kappa-APEX-II CCD
diffractometer
3717 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2005)
3183 reflections with I > 2σ(I)
Tmin = 0.916, Tmax = 0.976Rint = 0.026
17765 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.05Δρmax = 0.54 e Å3
3717 reflectionsΔρmin = 0.26 e Å3
146 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.20291 (12)0.22919 (7)0.22447 (5)0.01998 (15)
N10.67339 (12)0.39370 (7)0.38658 (5)0.01201 (14)
C10.34842 (14)0.28124 (8)0.27498 (5)0.01340 (16)
C20.33312 (14)0.41207 (8)0.30631 (6)0.01402 (16)
H2A0.21210.46250.28930.017*
C30.49242 (14)0.46418 (8)0.36056 (5)0.01330 (15)
H30.47770.54930.38020.016*
C40.69494 (14)0.26881 (8)0.35811 (6)0.01348 (15)
H40.81840.22130.37610.016*
C50.54117 (15)0.21185 (8)0.30420 (5)0.01373 (16)
H50.56140.12650.28600.016*
C60.83898 (13)0.44853 (8)0.44487 (5)0.01193 (15)
C70.92017 (14)0.57214 (8)0.42841 (5)0.01297 (15)
H70.86560.61960.38060.016*
C80.91669 (14)0.37565 (8)0.51623 (5)0.01330 (15)
H80.86030.29320.52670.016*
O20.10567 (12)0.36938 (7)0.16290 (4)0.01857 (15)
H20.00160.32460.18030.028*
O30.02102 (12)0.28640 (8)0.03302 (5)0.02296 (16)
C90.32276 (14)0.43267 (8)0.03862 (5)0.01234 (15)
C100.48400 (14)0.48530 (8)0.09047 (5)0.01413 (15)
H100.47340.47550.15090.017*
C110.33941 (14)0.44754 (8)0.05194 (5)0.01441 (16)
H110.23220.41250.08670.017*
C120.13364 (14)0.35616 (8)0.07740 (6)0.01425 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0210 (3)0.0153 (3)0.0227 (3)0.0000 (2)0.0115 (3)0.0022 (2)
N10.0114 (3)0.0108 (3)0.0137 (3)0.0005 (2)0.0023 (2)0.0008 (2)
C10.0147 (4)0.0125 (3)0.0127 (3)0.0007 (3)0.0025 (3)0.0012 (2)
C20.0131 (3)0.0132 (3)0.0155 (3)0.0016 (3)0.0031 (3)0.0002 (3)
C30.0130 (3)0.0118 (3)0.0150 (3)0.0020 (3)0.0015 (3)0.0004 (3)
C40.0136 (4)0.0110 (3)0.0156 (3)0.0011 (3)0.0021 (3)0.0004 (3)
C50.0158 (4)0.0114 (3)0.0138 (3)0.0008 (3)0.0022 (3)0.0004 (2)
C60.0101 (3)0.0123 (3)0.0133 (3)0.0001 (3)0.0012 (3)0.0010 (2)
C70.0129 (3)0.0126 (3)0.0132 (3)0.0000 (3)0.0020 (3)0.0011 (2)
C80.0132 (3)0.0113 (3)0.0152 (3)0.0007 (3)0.0015 (3)0.0010 (3)
O20.0201 (3)0.0198 (3)0.0154 (3)0.0043 (2)0.0044 (2)0.0002 (2)
O30.0196 (3)0.0286 (4)0.0205 (3)0.0103 (3)0.0016 (3)0.0029 (3)
C90.0115 (3)0.0116 (3)0.0139 (3)0.0007 (3)0.0009 (3)0.0002 (2)
C100.0144 (3)0.0155 (3)0.0125 (3)0.0002 (3)0.0002 (3)0.0001 (3)
C110.0137 (4)0.0161 (3)0.0135 (3)0.0014 (3)0.0014 (3)0.0009 (3)
C120.0127 (3)0.0139 (3)0.0160 (3)0.0012 (3)0.0015 (3)0.0010 (3)
Geometric parameters (Å, º) top
O1—C11.2719 (10)C6—C81.3921 (11)
N1—C41.3631 (11)C7—C8i1.3893 (11)
N1—C31.3660 (10)C7—H70.9300
N1—C61.4364 (10)C8—H80.9300
C1—C51.4312 (12)O2—C121.3196 (10)
C1—C21.4315 (12)O2—H20.8200
C2—C31.3627 (11)O3—C121.2168 (11)
C2—H2A0.9300C9—C111.3936 (11)
C3—H30.9300C9—C101.3947 (12)
C4—C51.3575 (11)C9—C121.4989 (12)
C4—H40.9300C10—C11ii1.3906 (12)
C5—H50.9300C10—H100.9300
C6—C71.3895 (11)C11—H110.9300
C4—N1—C3119.50 (7)C8—C6—N1119.08 (7)
C4—N1—C6119.59 (7)C8i—C7—C6119.60 (7)
C3—N1—C6120.89 (7)C8i—C7—H7120.2
O1—C1—C5121.69 (8)C6—C7—H7120.2
O1—C1—C2123.07 (8)C7i—C8—C6119.00 (8)
C5—C1—C2115.23 (7)C7i—C8—H8120.5
C3—C2—C1121.27 (8)C6—C8—H8120.5
C3—C2—H2A119.4C11—C9—C10119.75 (8)
C1—C2—H2A119.4C11—C9—C12118.50 (8)
C2—C3—N1121.19 (7)C10—C9—C12121.72 (7)
C2—C3—H3119.4C11ii—C10—C9120.11 (8)
N1—C3—H3119.4C11ii—C10—H10119.9
C5—C4—N1121.83 (8)C9—C10—H10119.9
C5—C4—H4119.1C10ii—C11—C9120.13 (8)
N1—C4—H4119.1C10ii—C11—H11119.9
C4—C5—C1120.97 (8)C9—C11—H11119.9
C4—C5—H5119.5O3—C12—O2123.99 (8)
C1—C5—H5119.5O3—C12—C9121.97 (8)
C7—C6—C8121.40 (7)O2—C12—C9114.02 (8)
C7—C6—N1119.51 (7)C12—O2—H2109.5
O1—C1—C2—C3179.84 (8)C3—N1—C6—C8132.99 (9)
C5—C1—C2—C30.43 (13)C8—C6—C7—C8i0.40 (14)
C1—C2—C3—N10.43 (13)N1—C6—C7—C8i178.78 (8)
C4—N1—C3—C20.25 (13)C7—C6—C8—C7i0.40 (14)
C6—N1—C3—C2179.00 (8)N1—C6—C8—C7i178.78 (8)
C3—N1—C4—C50.09 (13)C11—C9—C10—C11ii0.06 (14)
C6—N1—C4—C5178.86 (8)C12—C9—C10—C11ii178.10 (8)
N1—C4—C5—C10.11 (14)C10—C9—C11—C10ii0.06 (14)
O1—C1—C5—C4180.00 (8)C12—C9—C11—C10ii178.16 (8)
C2—C1—C5—C40.27 (13)C11—C9—C12—O314.71 (13)
C4—N1—C6—C7133.43 (9)C10—C9—C12—O3163.35 (9)
C3—N1—C6—C747.82 (12)C11—C9—C12—O2166.82 (8)
C4—N1—C6—C845.77 (12)C10—C9—C12—O215.11 (12)
Symmetry codes: (i) x+2, y+1, z+1; (ii) x1, y+1, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.821.712.5228 (10)175
C8—H8···O3iii0.932.473.1628 (11)132
Symmetry code: (iii) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H12N2O2·C8H6O4
Mr430.40
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)6.0931 (2), 10.2759 (3), 15.2973 (5)
β (°) 92.148 (1)
V3)957.12 (5)
Z2
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.37 × 0.27 × 0.22
Data collection
DiffractometerBruker Kappa-APEX-II CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2005)
Tmin, Tmax0.916, 0.976
No. of measured, independent and
observed [I > 2σ(I)] reflections
17765, 3717, 3183
Rint0.026
(sin θ/λ)max1)0.775
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.121, 1.05
No. of reflections3717
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.26

Computer programs: APEXII (Bruker, 2005), SAINT (Bruker, 2005), SAINT and SADABS (Bruker, 2005), SIR92 (Burla et al., 1989), LS in TEXSAN (Molecular Structure Corporation, 1997) and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and Mercury (Bruno et al., 2002), SHELXL97 and PLATON.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O10.821.712.5228 (10)175
C8—H8···O3i0.932.473.1628 (11)132
Symmetry code: (i) x+1/2, y+1/2, z+1/2.
 

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