In the title co-crystal, 2C
14H
10O
4·C
10H
8N
2, the diphenic acid molecules form a centrosymmetric dimeric pair, through strong O—H
O hydrogen bonds involving a carboxylic acid group from each molecule. In the crystal structure, the dimers are linked by C—H
O interactions to form layers parallel to the (001) plane. The adjacent layers are interlinked by bipyridine molecules, C
10H
8N
2, through O—H
N hydrogen bonds. The bipyridine molecule lies on a centre of symmetry.
Supporting information
CCDC reference: 217451
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.004 Å
- R factor = 0.036
- wR factor = 0.054
- Data-to-parameter ratio = 12.6
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Diphenic acid and 4,4'-bipyridine were obtained from Aldrich. Equimolar quantities of diphenic acid (27 mg) and 4,4'-bipyridine (15 mg) were dissolved in 15 ml of ethanol. The resulting solution was then set aside to crystallize at room temperature.
The C-bound H atoms were placed at their geometrically calculated positions, with C—H = 0.95 Å and in the riding model with Uiso(H) = 1.2Ueq(C). Attempts to place H2 at the calculated position resulted in a non-planar R22(8) ring formation, with an O—H···O angle of 133°. Hence, H1 and H2 were located from a difference Fourier map and both positional and isotropic displacement parameters were refined. H2 is involved in nearly symmetrical O—H···O hydrogen bonds with O···H distances of 1.33 (4) and 1.29 (4) Å, respectively.
Data collection: AFC Diffractometer Control (Molecular Structure Corporation, 1992); cell refinement: AFC Diffractometer Control; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.
Crystal data top
C28H20O8·C10H8N2 | Z = 1 |
Mr = 640.62 | F(000) = 334.00 |
Triclinic, P1 | Dx = 1.326 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.7107 Å |
a = 6.498 (2) Å | Cell parameters from 25 reflections |
b = 8.002 (7) Å | θ = 13.2–16.3° |
c = 16.208 (6) Å | µ = 0.09 mm−1 |
α = 99.45 (5)° | T = 298 K |
β = 100.93 (3)° | Block, colourless |
γ = 98.42 (5)° | 0.44 × 0.32 × 0.28 mm |
V = 802.4 (8) Å3 | |
Data collection top
AFC7R diffractometer | 1448 reflections with I > 2σ(I) |
Radiation source: X-ray tube | Rint = 0.016 |
Graphite monochromator | θmax = 25.0°, θmin = 2.2° |
ω/2–θ scans | h = −7→7 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→9 |
Tmin = 0.957, Tmax = 0.996 | l = −19→18 |
3049 measured reflections | 3 standard reflections every 250 reflections |
2830 independent reflections | intensity decay: −0.9% |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.036 | Weighting scheme based on measured s.u.'s w = 1/[(σ)2(Fo) + 0.00016(Fo)2] |
wR(F2) = 0.054 | (Δ/σ)max < 0.001 |
S = 1.31 | Δρmax = 0.30 e Å−3 |
2830 reflections | Δρmin = −0.27 e Å−3 |
225 parameters | |
Crystal data top
C28H20O8·C10H8N2 | γ = 98.42 (5)° |
Mr = 640.62 | V = 802.4 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 6.498 (2) Å | Mo Kα radiation |
b = 8.002 (7) Å | µ = 0.09 mm−1 |
c = 16.208 (6) Å | T = 298 K |
α = 99.45 (5)° | 0.44 × 0.32 × 0.28 mm |
β = 100.93 (3)° | |
Data collection top
AFC7R diffractometer | 1448 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.016 |
Tmin = 0.957, Tmax = 0.996 | 3 standard reflections every 250 reflections |
3049 measured reflections | intensity decay: −0.9% |
2830 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.054 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.31 | Δρmax = 0.30 e Å−3 |
2830 reflections | Δρmin = −0.27 e Å−3 |
225 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 1.1226 (3) | 0.6029 (2) | 0.3652 (1) | 0.0703 (6) | |
O2 | 0.8605 (3) | 0.4039 (2) | 0.2836 (1) | 0.0895 (7) | |
O3 | 0.8094 (3) | 0.3251 (2) | −0.0025 (1) | 0.0666 (6) | |
O4 | 0.8892 (3) | 0.5837 (2) | 0.0816 (1) | 0.0651 (6) | |
N1 | 0.7048 (4) | 0.6498 (3) | 0.5733 (1) | 0.0713 (8) | |
C1 | 0.9452 (4) | 0.5522 (3) | 0.3054 (1) | 0.0495 (7) | |
C2 | 0.8630 (3) | 0.6970 (3) | 0.2711 (1) | 0.0431 (6) | |
C3 | 0.9730 (4) | 0.8641 (3) | 0.3042 (1) | 0.0557 (7) | |
C4 | 0.8981 (4) | 1.0036 (3) | 0.2778 (2) | 0.0650 (8) | |
C5 | 0.7092 (5) | 0.9766 (3) | 0.2186 (2) | 0.0663 (9) | |
C6 | 0.5989 (4) | 0.8119 (3) | 0.1844 (1) | 0.0566 (7) | |
C7 | 0.6748 (3) | 0.6686 (3) | 0.2078 (1) | 0.0430 (6) | |
C8 | 0.5456 (3) | 0.4946 (3) | 0.1649 (1) | 0.0449 (6) | |
C9 | 0.3618 (4) | 0.4401 (3) | 0.1923 (1) | 0.0579 (8) | |
C10 | 0.2305 (4) | 0.2831 (4) | 0.1550 (2) | 0.0671 (9) | |
C11 | 0.2781 (4) | 0.1768 (3) | 0.0886 (2) | 0.0658 (8) | |
C12 | 0.4556 (4) | 0.2291 (3) | 0.0586 (1) | 0.0558 (7) | |
C13 | 0.5910 (3) | 0.3871 (3) | 0.0953 (1) | 0.0439 (6) | |
C14 | 0.7746 (3) | 0.4365 (3) | 0.0564 (1) | 0.0455 (7) | |
C15 | 0.5568 (5) | 0.7174 (4) | 0.6042 (2) | 0.083 (1) | |
C16 | 0.4722 (4) | 0.8523 (4) | 0.5777 (2) | 0.079 (1) | |
C17 | 0.5414 (4) | 0.9248 (3) | 0.5146 (1) | 0.0539 (7) | |
C18 | 0.6927 (5) | 0.8521 (4) | 0.4809 (2) | 0.083 (1) | |
C19 | 0.7694 (5) | 0.7169 (4) | 0.5118 (2) | 0.086 (1) | |
H1 | 1.177 (5) | 0.499 (4) | 0.388 (2) | 0.13 (1) | |
H2 | 0.973 (6) | 0.369 (4) | −0.038 (2) | 0.16 (1) | |
H3 | 1.1026 | 0.8829 | 0.3459 | 0.0669 | |
H4 | 0.9764 | 1.1171 | 0.3005 | 0.0780 | |
H5 | 0.6544 | 1.0721 | 0.2011 | 0.0795 | |
H6 | 0.4678 | 0.7955 | 0.1438 | 0.0679 | |
H7 | 0.3253 | 0.5124 | 0.2379 | 0.0695 | |
H8 | 0.1065 | 0.2486 | 0.1755 | 0.0806 | |
H9 | 0.1890 | 0.0682 | 0.0637 | 0.0789 | |
H10 | 0.4872 | 0.1564 | 0.0118 | 0.0669 | |
H11 | 0.5043 | 0.6699 | 0.6479 | 0.1002 | |
H12 | 0.3655 | 0.8955 | 0.6032 | 0.0953 | |
H13 | 0.7454 | 0.8947 | 0.4361 | 0.0995 | |
H14 | 0.8749 | 0.6697 | 0.4872 | 0.1037 | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.072 (1) | 0.058 (1) | 0.071 (1) | 0.0196 (9) | −0.0139 (9) | 0.0136 (9) |
O2 | 0.092 (1) | 0.041 (1) | 0.115 (2) | 0.0108 (10) | −0.028 (1) | 0.020 (1) |
O3 | 0.064 (1) | 0.066 (1) | 0.063 (1) | 0.0035 (9) | 0.0230 (9) | −0.0095 (9) |
O4 | 0.070 (1) | 0.052 (1) | 0.070 (1) | −0.0044 (9) | 0.0312 (9) | −0.0003 (9) |
N1 | 0.074 (2) | 0.074 (2) | 0.067 (1) | 0.028 (1) | 0.001 (1) | 0.021 (1) |
C1 | 0.056 (1) | 0.043 (1) | 0.050 (1) | 0.017 (1) | 0.009 (1) | 0.010 (1) |
C2 | 0.051 (1) | 0.040 (1) | 0.040 (1) | 0.012 (1) | 0.013 (1) | 0.0083 (10) |
C3 | 0.064 (2) | 0.045 (1) | 0.054 (1) | 0.008 (1) | 0.006 (1) | 0.009 (1) |
C4 | 0.088 (2) | 0.039 (1) | 0.064 (2) | 0.006 (1) | 0.010 (1) | 0.008 (1) |
C5 | 0.093 (2) | 0.043 (1) | 0.068 (2) | 0.023 (1) | 0.012 (2) | 0.020 (1) |
C6 | 0.067 (2) | 0.052 (1) | 0.052 (1) | 0.022 (1) | 0.005 (1) | 0.014 (1) |
C7 | 0.050 (1) | 0.041 (1) | 0.041 (1) | 0.012 (1) | 0.014 (1) | 0.0094 (10) |
C8 | 0.046 (1) | 0.047 (1) | 0.045 (1) | 0.013 (1) | 0.008 (1) | 0.018 (1) |
C9 | 0.054 (2) | 0.066 (2) | 0.057 (1) | 0.012 (1) | 0.018 (1) | 0.016 (1) |
C10 | 0.053 (2) | 0.077 (2) | 0.073 (2) | 0.000 (1) | 0.014 (1) | 0.030 (2) |
C11 | 0.059 (2) | 0.059 (2) | 0.070 (2) | −0.007 (1) | 0.002 (1) | 0.016 (1) |
C12 | 0.057 (2) | 0.049 (1) | 0.056 (1) | 0.005 (1) | 0.005 (1) | 0.008 (1) |
C13 | 0.044 (1) | 0.044 (1) | 0.042 (1) | 0.010 (1) | 0.004 (1) | 0.0094 (10) |
C14 | 0.047 (1) | 0.045 (1) | 0.041 (1) | 0.010 (1) | 0.004 (1) | 0.005 (1) |
C15 | 0.088 (2) | 0.107 (2) | 0.074 (2) | 0.037 (2) | 0.020 (2) | 0.050 (2) |
C16 | 0.075 (2) | 0.105 (2) | 0.081 (2) | 0.044 (2) | 0.029 (2) | 0.047 (2) |
C17 | 0.053 (1) | 0.064 (2) | 0.044 (1) | 0.015 (1) | 0.002 (1) | 0.013 (1) |
C18 | 0.110 (2) | 0.093 (2) | 0.074 (2) | 0.054 (2) | 0.044 (2) | 0.036 (2) |
C19 | 0.106 (2) | 0.089 (2) | 0.084 (2) | 0.051 (2) | 0.035 (2) | 0.025 (2) |
Geometric parameters (Å, º) top
O1—C1 | 1.321 (3) | C8—C9 | 1.389 (3) |
O1—H1 | 1.04 (3) | C8—C13 | 1.408 (3) |
O2—C1 | 1.197 (3) | C9—C10 | 1.383 (3) |
O3—C14 | 1.272 (2) | C9—H7 | 0.95 |
O3—H2 | 1.33 (4) | C10—C11 | 1.370 (4) |
O4—C14 | 1.256 (2) | C10—H8 | 0.95 |
N1—C15 | 1.309 (3) | C11—C12 | 1.372 (3) |
N1—C19 | 1.313 (3) | C11—H9 | 0.95 |
C1—C2 | 1.489 (3) | C12—C13 | 1.399 (3) |
C2—C3 | 1.388 (3) | C12—H10 | 0.95 |
C2—C7 | 1.402 (3) | C13—C14 | 1.486 (3) |
C3—C4 | 1.379 (3) | C15—C16 | 1.375 (4) |
C3—H3 | 0.95 | C15—H11 | 0.95 |
C4—C5 | 1.372 (3) | C16—C17 | 1.370 (3) |
C4—H4 | 0.95 | C16—H12 | 0.95 |
C5—C6 | 1.375 (3) | C17—C17i | 1.497 (4) |
C5—H5 | 0.95 | C17—C18 | 1.368 (3) |
C6—C7 | 1.393 (3) | C18—C19 | 1.382 (4) |
C6—H6 | 0.95 | C18—H13 | 0.95 |
C7—C8 | 1.498 (3) | C19—H14 | 0.95 |
| | | |
C1—O1—H1 | 111 (1) | C9—C10—C11 | 120.5 (2) |
C14—O3—H2 | 117 (1) | C9—C10—H8 | 119.7 |
C15—N1—C19 | 115.8 (2) | C11—C10—H8 | 119.8 |
O1—C1—O2 | 121.9 (2) | C10—C11—C12 | 119.3 (2) |
O1—C1—C2 | 113.2 (2) | C10—C11—H9 | 120.4 |
O2—C1—C2 | 124.9 (2) | C12—C11—H9 | 120.4 |
C1—C2—C3 | 119.0 (2) | C11—C12—C13 | 121.3 (2) |
C1—C2—C7 | 121.5 (2) | C11—C12—H10 | 119.3 |
C3—C2—C7 | 119.4 (2) | C13—C12—H10 | 119.3 |
C2—C3—C4 | 121.4 (2) | C8—C13—C12 | 119.6 (2) |
C2—C3—H3 | 119.3 | C8—C13—C14 | 122.7 (2) |
C4—C3—H3 | 119.3 | C12—C13—C14 | 117.7 (2) |
C3—C4—C5 | 119.2 (2) | O3—C14—O4 | 122.2 (2) |
C3—C4—H4 | 120.4 | O3—C14—C13 | 117.5 (2) |
C5—C4—H4 | 120.4 | O4—C14—C13 | 120.2 (2) |
C4—C5—C6 | 120.2 (2) | N1—C15—C16 | 124.3 (3) |
C4—C5—H5 | 119.9 | N1—C15—H11 | 117.8 |
C6—C5—H5 | 119.9 | C16—C15—H11 | 117.8 |
C5—C6—C7 | 121.6 (2) | C15—C16—C17 | 120.2 (3) |
C5—C6—H6 | 119.2 | C15—C16—H12 | 119.9 |
C7—C6—H6 | 119.2 | C17—C16—H12 | 119.9 |
C2—C7—C6 | 118.0 (2) | C16—C17—C17i | 122.1 (3) |
C2—C7—C8 | 124.6 (2) | C16—C17—C18 | 115.6 (2) |
C6—C7—C8 | 117.4 (2) | C17i—C17—C18 | 122.3 (3) |
C7—C8—C9 | 117.8 (2) | C17—C18—C19 | 120.3 (2) |
C7—C8—C13 | 124.4 (2) | C17—C18—H13 | 119.8 |
C9—C8—C13 | 117.7 (2) | C19—C18—H13 | 119.8 |
C8—C9—C10 | 121.6 (2) | N1—C19—C18 | 123.8 (3) |
C8—C9—H7 | 119.2 | N1—C19—H14 | 118.1 |
C10—C9—H7 | 119.2 | C18—C19—H14 | 118.1 |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H2···O4ii | 1.33 (4) | 1.29 (4) | 2.618 (3) | 171 (3) |
O1—H1···N1iii | 1.04 (3) | 1.65 (3) | 2.691 (4) | 172 (3) |
C4—H4···O2iv | 0.95 | 2.56 | 3.235 (4) | 128 |
C6—H6···O3v | 0.95 | 2.57 | 3.472 (4) | 158 |
C3—H3···O1 | 0.95 | 2.33 | 2.683 (4) | 101 |
C12—H10···O3 | 0.95 | 2.39 | 2.730 (4) | 100 |
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) −x+2, −y+1, −z+1; (iv) x, y+1, z; (v) −x+1, −y+1, −z. |
Experimental details
Crystal data |
Chemical formula | C28H20O8·C10H8N2 |
Mr | 640.62 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 6.498 (2), 8.002 (7), 16.208 (6) |
α, β, γ (°) | 99.45 (5), 100.93 (3), 98.42 (5) |
V (Å3) | 802.4 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.44 × 0.32 × 0.28 |
|
Data collection |
Diffractometer | AFC7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.957, 0.996 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3049, 2830, 1448 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.054, 1.31 |
No. of reflections | 2830 |
No. of parameters | 225 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.30, −0.27 |
Selected bond lengths (Å) topO1—C1 | 1.321 (3) | C7—C8 | 1.498 (3) |
O2—C1 | 1.197 (3) | C13—C14 | 1.486 (3) |
O3—C14 | 1.272 (2) | C15—C16 | 1.375 (4) |
O4—C14 | 1.256 (2) | C16—C17 | 1.370 (3) |
N1—C15 | 1.309 (3) | C17—C17i | 1.497 (4) |
N1—C19 | 1.313 (3) | C17—C18 | 1.368 (3) |
C1—C2 | 1.489 (3) | C18—C19 | 1.382 (4) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H2···O4ii | 1.33 (4) | 1.29 (4) | 2.618 (3) | 171 (3) |
O1—H1···N1iii | 1.04 (3) | 1.65 (3) | 2.691 (4) | 172 (3) |
C4—H4···O2iv | 0.95 | 2.56 | 3.235 (4) | 128 |
C6—H6···O3v | 0.95 | 2.57 | 3.472 (4) | 158 |
C3—H3···O1 | 0.95 | 2.33 | 2.683 (4) | 101 |
C12—H10···O3 | 0.95 | 2.39 | 2.730 (4) | 100 |
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) −x+2, −y+1, −z+1; (iv) x, y+1, z; (v) −x+1, −y+1, −z. |
The binding properties of the carboxyl groups of benzoic acid and its derivatives are interesting themes of structural chemistry (Lam et al., 2003). The diphenic acid (biphenyl-2,2'-dicarboxylic acid) is an extremely versatile building block for the purposes of crystal engineering. In the crystal structure of this compound, molecules form infinite chains, via R22(8) carboxylic acid pairs (Fronczek et al., 1987). The co-crystal structure of diphenic acid, diphenic acid-acridine (1/1) has been reported (Shaameri et al., 2001). Herein, we report the co-crystal structure of diphenic acid-4,4'-bipyridine (2/1), (I), which comprises two acid and one base molecule.
The asymmetric unit of (I) consists of one molecule of diphenic acid and a half molecule of 4,4'-bipyridine. The other diphenic acid molecule and the other half of the bipyridine molecule are generated by the symmetry operations (2 − x, 1 − y, −z) and (1 − x, 2 − y, 1 − z), respectively. In the diphenic acid, one of the carboxylic acid group shows normal C—O distances [O1—C1 = 1.321 (3) and O2—C1 = 1.197 (3) Å], while in the other these distances are nearly equal [C14—O3 = 1.272 (2) and C14—O4 = 1.256 (2) Å] indicating that it exists as COO− ion. However, no proton transfer from this carboxylic acid group to a N atom of the bipyridine is observed. Instead, the H+ ion is located at a distance of 1.33 (4) Å from O3 and 1.29 (4) Å from O4i indicating the formation of centrosymmetric diphenic acid dimer through strong O—H···O hydrogen bonds (Table 2). The dimers are linked through C4—H4···O2iii and C6—H6···O3iv interactions to form molecular layers parallel to the (0 0 1) plane. The adjacent layers are interlinked by the bipyridine molecules through O1—H1···N1ii hydrogen bonds. The symmetry codes are given in Table 2.