Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106015174/gz3009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106015174/gz3009Isup2.hkl |
CCDC reference: 612457
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 (C═O), 167.3 (COOH), 142.4, 140.3, 130.1, 124.6, 118.7; IR (KBr, cm−1): 1700, 1676, 1636, 1633.
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.
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.
C16H12N2O2·C8H6O4 | F(000) = 448 |
Mr = 430.40 | Dx = 1.493 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7275 reflections |
a = 6.0931 (2) Å | θ = 2.7–33.4° |
b = 10.2759 (3) Å | µ = 0.11 mm−1 |
c = 15.2973 (5) Å | T = 100 K |
β = 92.148 (1)° | Prism, colorless |
V = 957.12 (5) Å3 | 0.37 × 0.27 × 0.22 mm |
Z = 2 |
Bruker Kappa-APEX-II CCD diffractometer | 3717 independent reflections |
Radiation source: X-ray tube | 3183 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 33.4°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −7→9 |
Tmin = 0.916, Tmax = 0.976 | k = −15→15 |
17765 measured reflections | l = −23→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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H-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 parameters | Δρmax = 0.54 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C16H12N2O2·C8H6O4 | V = 957.12 (5) Å3 |
Mr = 430.40 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.0931 (2) Å | µ = 0.11 mm−1 |
b = 10.2759 (3) Å | T = 100 K |
c = 15.2973 (5) Å | 0.37 × 0.27 × 0.22 mm |
β = 92.148 (1)° |
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 = 0.976 | Rint = 0.026 |
17765 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.121 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.54 e Å−3 |
3717 reflections | Δρmin = −0.26 e Å−3 |
146 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.20291 (12) | 0.22919 (7) | 0.22447 (5) | 0.01998 (15) | |
N1 | 0.67339 (12) | 0.39370 (7) | 0.38658 (5) | 0.01201 (14) | |
C1 | 0.34842 (14) | 0.28124 (8) | 0.27498 (5) | 0.01340 (16) | |
C2 | 0.33312 (14) | 0.41207 (8) | 0.30631 (6) | 0.01402 (16) | |
H2A | 0.2121 | 0.4625 | 0.2893 | 0.017* | |
C3 | 0.49242 (14) | 0.46418 (8) | 0.36056 (5) | 0.01330 (15) | |
H3 | 0.4777 | 0.5493 | 0.3802 | 0.016* | |
C4 | 0.69494 (14) | 0.26881 (8) | 0.35811 (6) | 0.01348 (15) | |
H4 | 0.8184 | 0.2213 | 0.3761 | 0.016* | |
C5 | 0.54117 (15) | 0.21185 (8) | 0.30420 (5) | 0.01373 (16) | |
H5 | 0.5614 | 0.1265 | 0.2860 | 0.016* | |
C6 | 0.83898 (13) | 0.44853 (8) | 0.44487 (5) | 0.01193 (15) | |
C7 | 0.92017 (14) | 0.57214 (8) | 0.42841 (5) | 0.01297 (15) | |
H7 | 0.8656 | 0.6196 | 0.3806 | 0.016* | |
C8 | 0.91669 (14) | 0.37565 (8) | 0.51623 (5) | 0.01330 (15) | |
H8 | 0.8603 | 0.2932 | 0.5267 | 0.016* | |
O2 | −0.10567 (12) | 0.36938 (7) | 0.16290 (4) | 0.01857 (15) | |
H2 | −0.0016 | 0.3246 | 0.1803 | 0.028* | |
O3 | −0.02102 (12) | 0.28640 (8) | 0.03302 (5) | 0.02296 (16) | |
C9 | −0.32276 (14) | 0.43267 (8) | 0.03862 (5) | 0.01234 (15) | |
C10 | −0.48400 (14) | 0.48530 (8) | 0.09047 (5) | 0.01413 (15) | |
H10 | −0.4734 | 0.4755 | 0.1509 | 0.017* | |
C11 | −0.33941 (14) | 0.44754 (8) | −0.05194 (5) | 0.01441 (16) | |
H11 | −0.2322 | 0.4125 | −0.0867 | 0.017* | |
C12 | −0.13364 (14) | 0.35616 (8) | 0.07740 (6) | 0.01425 (16) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0210 (3) | 0.0153 (3) | 0.0227 (3) | 0.0000 (2) | −0.0115 (3) | −0.0022 (2) |
N1 | 0.0114 (3) | 0.0108 (3) | 0.0137 (3) | 0.0005 (2) | −0.0023 (2) | −0.0008 (2) |
C1 | 0.0147 (4) | 0.0125 (3) | 0.0127 (3) | −0.0007 (3) | −0.0025 (3) | 0.0012 (2) |
C2 | 0.0131 (3) | 0.0132 (3) | 0.0155 (3) | 0.0016 (3) | −0.0031 (3) | −0.0002 (3) |
C3 | 0.0130 (3) | 0.0118 (3) | 0.0150 (3) | 0.0020 (3) | −0.0015 (3) | −0.0004 (3) |
C4 | 0.0136 (4) | 0.0110 (3) | 0.0156 (3) | 0.0011 (3) | −0.0021 (3) | −0.0004 (3) |
C5 | 0.0158 (4) | 0.0114 (3) | 0.0138 (3) | 0.0008 (3) | −0.0022 (3) | −0.0004 (2) |
C6 | 0.0101 (3) | 0.0123 (3) | 0.0133 (3) | −0.0001 (3) | −0.0012 (3) | −0.0010 (2) |
C7 | 0.0129 (3) | 0.0126 (3) | 0.0132 (3) | 0.0000 (3) | −0.0020 (3) | 0.0011 (2) |
C8 | 0.0132 (3) | 0.0113 (3) | 0.0152 (3) | −0.0007 (3) | −0.0015 (3) | 0.0010 (3) |
O2 | 0.0201 (3) | 0.0198 (3) | 0.0154 (3) | 0.0043 (2) | −0.0044 (2) | −0.0002 (2) |
O3 | 0.0196 (3) | 0.0286 (4) | 0.0205 (3) | 0.0103 (3) | −0.0016 (3) | −0.0029 (3) |
C9 | 0.0115 (3) | 0.0116 (3) | 0.0139 (3) | −0.0007 (3) | −0.0009 (3) | −0.0002 (2) |
C10 | 0.0144 (3) | 0.0155 (3) | 0.0125 (3) | 0.0002 (3) | 0.0002 (3) | −0.0001 (3) |
C11 | 0.0137 (4) | 0.0161 (3) | 0.0135 (3) | 0.0014 (3) | 0.0014 (3) | −0.0009 (3) |
C12 | 0.0127 (3) | 0.0139 (3) | 0.0160 (3) | −0.0012 (3) | −0.0015 (3) | 0.0010 (3) |
O1—C1 | 1.2719 (10) | C6—C8 | 1.3921 (11) |
N1—C4 | 1.3631 (11) | C7—C8i | 1.3893 (11) |
N1—C3 | 1.3660 (10) | C7—H7 | 0.9300 |
N1—C6 | 1.4364 (10) | C8—H8 | 0.9300 |
C1—C5 | 1.4312 (12) | O2—C12 | 1.3196 (10) |
C1—C2 | 1.4315 (12) | O2—H2 | 0.8200 |
C2—C3 | 1.3627 (11) | O3—C12 | 1.2168 (11) |
C2—H2A | 0.9300 | C9—C11 | 1.3936 (11) |
C3—H3 | 0.9300 | C9—C10 | 1.3947 (12) |
C4—C5 | 1.3575 (11) | C9—C12 | 1.4989 (12) |
C4—H4 | 0.9300 | C10—C11ii | 1.3906 (12) |
C5—H5 | 0.9300 | C10—H10 | 0.9300 |
C6—C7 | 1.3895 (11) | C11—H11 | 0.9300 |
C4—N1—C3 | 119.50 (7) | C8—C6—N1 | 119.08 (7) |
C4—N1—C6 | 119.59 (7) | C8i—C7—C6 | 119.60 (7) |
C3—N1—C6 | 120.89 (7) | C8i—C7—H7 | 120.2 |
O1—C1—C5 | 121.69 (8) | C6—C7—H7 | 120.2 |
O1—C1—C2 | 123.07 (8) | C7i—C8—C6 | 119.00 (8) |
C5—C1—C2 | 115.23 (7) | C7i—C8—H8 | 120.5 |
C3—C2—C1 | 121.27 (8) | C6—C8—H8 | 120.5 |
C3—C2—H2A | 119.4 | C11—C9—C10 | 119.75 (8) |
C1—C2—H2A | 119.4 | C11—C9—C12 | 118.50 (8) |
C2—C3—N1 | 121.19 (7) | C10—C9—C12 | 121.72 (7) |
C2—C3—H3 | 119.4 | C11ii—C10—C9 | 120.11 (8) |
N1—C3—H3 | 119.4 | C11ii—C10—H10 | 119.9 |
C5—C4—N1 | 121.83 (8) | C9—C10—H10 | 119.9 |
C5—C4—H4 | 119.1 | C10ii—C11—C9 | 120.13 (8) |
N1—C4—H4 | 119.1 | C10ii—C11—H11 | 119.9 |
C4—C5—C1 | 120.97 (8) | C9—C11—H11 | 119.9 |
C4—C5—H5 | 119.5 | O3—C12—O2 | 123.99 (8) |
C1—C5—H5 | 119.5 | O3—C12—C9 | 121.97 (8) |
C7—C6—C8 | 121.40 (7) | O2—C12—C9 | 114.02 (8) |
C7—C6—N1 | 119.51 (7) | C12—O2—H2 | 109.5 |
O1—C1—C2—C3 | 179.84 (8) | C3—N1—C6—C8 | 132.99 (9) |
C5—C1—C2—C3 | −0.43 (13) | C8—C6—C7—C8i | 0.40 (14) |
C1—C2—C3—N1 | 0.43 (13) | N1—C6—C7—C8i | −178.78 (8) |
C4—N1—C3—C2 | −0.25 (13) | C7—C6—C8—C7i | −0.40 (14) |
C6—N1—C3—C2 | −179.00 (8) | N1—C6—C8—C7i | 178.78 (8) |
C3—N1—C4—C5 | 0.09 (13) | C11—C9—C10—C11ii | −0.06 (14) |
C6—N1—C4—C5 | 178.86 (8) | C12—C9—C10—C11ii | −178.10 (8) |
N1—C4—C5—C1 | −0.11 (14) | C10—C9—C11—C10ii | 0.06 (14) |
O1—C1—C5—C4 | 180.00 (8) | C12—C9—C11—C10ii | 178.16 (8) |
C2—C1—C5—C4 | 0.27 (13) | C11—C9—C12—O3 | −14.71 (13) |
C4—N1—C6—C7 | 133.43 (9) | C10—C9—C12—O3 | 163.35 (9) |
C3—N1—C6—C7 | −47.82 (12) | C11—C9—C12—O2 | 166.82 (8) |
C4—N1—C6—C8 | −45.77 (12) | C10—C9—C12—O2 | −15.11 (12) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x−1, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 1.71 | 2.5228 (10) | 175 |
C8—H8···O3iii | 0.93 | 2.47 | 3.1628 (11) | 132 |
Symmetry code: (iii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C16H12N2O2·C8H6O4 |
Mr | 430.40 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 6.0931 (2), 10.2759 (3), 15.2973 (5) |
β (°) | 92.148 (1) |
V (Å3) | 957.12 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.37 × 0.27 × 0.22 |
Data collection | |
Diffractometer | Bruker Kappa-APEX-II CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.916, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 17765, 3717, 3183 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.775 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.121, 1.05 |
No. of reflections | 3717 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 1.71 | 2.5228 (10) | 175 |
C8—H8···O3i | 0.93 | 2.47 | 3.1628 (11) | 132 |
Symmetry code: (i) x+1/2, −y+1/2, z+1/2. |
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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 C═O) 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, D—A 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.