organic compounds
Redetermined structure of 4,4′-bipyridine–1,4-phenylenediacetic acid (1/1) co-crystal
aDepartment of Chemistry, Pandu College, Guwahati-781 012, Assam, India
*Correspondence e-mail: sanchay.bora@gmail.com
The 10H8N2·C10H10O4, consists of one half-molecule each of 4,4′-bipyridine and 1,4-phenylenediacetic acid: the complete molecules are generated by crystallographic inversion centres. The dihedral angle between the –CO2H group and the benzene ring in the diacid is 73.02 (7)°. In the crystal, the components are linked by O—H⋯N hydrogen bonds, generating [1-2-1] chains of alternating amine and carboxylic acid molecules. The chains are cross-linked by C—H⋯O interactions. This structure was previously incorrectly described as a (C10H10N2)2+·(C10H8O4)2− molecular salt [Jia et al. (2009). Acta Cryst. E65, o2490–o2490].
of the title 1:1 CCCDC reference: 1423417
1. Related literature
For the previous erroneous report of this structure as a molecular salt, see: Jia et al. (2009). For hydrogen-bonded co-crystals, see: Stahly (2009); Kavuru et al. (2010). For pharmaceutical co-crystals, see: Childs et al. (2009); Walsh et al. (2003). For a similar structure, see: Chinnakali et al. (1999).
2. Experimental
2.1. Crystal data
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2.2. Data collection
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2.3. Refinement
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Data collection: SMART (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 1423417
10.1107/S2056989015017569/hb7506sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2056989015017569/hb7506Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989015017569/hb7506Isup3.doc
Co-crystals represent a class of materials which contain two or more discrete molecular entities held together via non-covalent or supramolecular interactions in the π interactions. The resulting crystal structures can generate diverse physical and chemical properties such as solubility and stability that differ from the properties of the individual components. Crystal engineering plays an important role in the formation of co-crystals of desired properties so that they can find their applications in pharmaceutical industries (Childs et al., 2009 and Walsh et al., 2003). Herein, we report the supramolecular architecture of 1,4-phenylenediacetic acid and 4,4'-bipyridine formed via O—H···N hydrogen bridges and C—H···π interactions.
(Stahly, 2009). Due to their robust and directional nature, hydrogen bonds are extensively used as a tool to shape the structure of co-crystals (Kavuru et al., 2010). In this context, hydrogen bonds of varying strengths may be employed, ranging from strong O—H···O/N to weak C—H···The title compound can be prepared under hydrothermal condition using a mixture of 1,4-phenylenediacetic acid and 4,4'-bipyridine (1:1) in water. The acetic acid moiety involving C1, C2, O1 and O2 in 1,4-phenylenediacetic acid molecule makes dihedral angles of 73.04 (4)° and 2.06 (1)° with the phenyl and pyridyl ring planes respectively. These values are very close to those reported by Chinnakali et al. (1999). The dihedral angle between phenyl and planar pyridyl rings of 4,4'-bipyridine is found to be 73.21 (4)°. In the π interactions (C···π distance = 3.838 Å) between the methylene C—H and phenyl ring–π systems. These weak intermolecular forces together with the strong hydrogen bonds form the overall 3D supramolecular architecture.
the molecules are linked with one another through O1—H9···N1 hydrogen bonds with O···N distance of 2.637 (1) Å that extends in one direction leading to a supramolecular chain like structure. These zig-zag 1D chains are further connected via C—H···O bridges (C7—H6···O2 and C9—H7···O2 with C···O distances of 2.50 (1) Å and 2.45 (2) Å respectively) giving rise to a 2D layered structure in the solid state. In graph set notations (Bernstain et al., 1995), such 1D chains can be described as C22(20) where the subscripts and superscripts are the number of hydrogen bond donors and acceptors respectively. There are certain hydrogen bonded rings of descriptors R12(7), R44(16) and R44(30) which have periodic repetitions throughout the The adjacent layers are stacked in nearly parallel fashion by means of weak C—H···?
A mixture of 1,4-phenylenediacetic acid (1 mmol, 0.194 g) and 4,4?-bipyridine (1 mmol, 0.156 g) in water (10 ml) were placed in a 23 ml Teflon lined stainless steel reaction vessel. It was then heated to 393K for 24 hours at a heating rate of 5K min-1. On overnight standing, rectangular block shaped colourless crystals were obtained. The crystals were then filtered off, washed with water and dried in a vacuum desiccator over fused CaCl2. Yield: 71%.
Data collection: SMART (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids. | |
Fig. 2. A view of the O—H···N, C—H···O and C—H···π interactions observed in the crystal structure of the title compound. |
C10H8N2·C10H10O4 | V = 427.05 (8) Å3 |
Mr = 350.36 | Z = 1 |
Triclinic, P1 | F(000) = 184 |
a = 4.5577 (5) Å | Dx = 1.362 Mg m−3 |
b = 6.9806 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
c = 13.7995 (15) Å | µ = 0.10 mm−1 |
α = 99.508 (6)° | T = 296 K |
β = 94.297 (6)° | Rectangular block, colourless |
γ = 97.643 (7)° | 0.20 × 0.17 × 0.13 mm |
Bruker SMART CCD diffractometer | 1876 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
Graphite monochromator | θmax = 29.8°, θmin = 3.0° |
phi and ω scans | h = −6→6 |
8581 measured reflections | k = −9→9 |
2405 independent reflections | l = −19→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | All H-atom parameters refined |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0605P)2 + 0.0515P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2405 reflections | Δρmax = 0.19 e Å−3 |
155 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.061 (11) |
C10H8N2·C10H10O4 | γ = 97.643 (7)° |
Mr = 350.36 | V = 427.05 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 4.5577 (5) Å | Mo Kα radiation |
b = 6.9806 (8) Å | µ = 0.10 mm−1 |
c = 13.7995 (15) Å | T = 296 K |
α = 99.508 (6)° | 0.20 × 0.17 × 0.13 mm |
β = 94.297 (6)° |
Bruker SMART CCD diffractometer | 1876 reflections with I > 2σ(I) |
8581 measured reflections | Rint = 0.028 |
2405 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.123 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.19 e Å−3 |
2405 reflections | Δρmin = −0.16 e Å−3 |
155 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.8197 (2) | 0.45294 (13) | −0.18830 (6) | 0.0541 (3) | |
C1 | 0.7209 (2) | 0.60720 (15) | −0.21279 (8) | 0.0408 (3) | |
C2 | 0.5619 (3) | 0.71533 (19) | −0.13310 (10) | 0.0490 (3) | |
C3 | 0.7850 (2) | 0.86342 (15) | −0.06291 (8) | 0.0400 (3) | |
C4 | 0.9459 (3) | 0.80852 (16) | 0.01476 (9) | 0.0454 (3) | |
C5 | 0.8422 (3) | 1.05717 (17) | −0.07687 (8) | 0.0446 (3) | |
O2 | 0.7616 (3) | 0.66207 (15) | −0.28973 (7) | 0.0675 (3) | |
N1 | 0.8832 (2) | 0.73182 (15) | 0.32203 (7) | 0.0476 (3) | |
C6 | 0.8316 (3) | 0.67172 (18) | 0.40629 (9) | 0.0517 (3) | |
C7 | 0.6844 (3) | 0.77149 (18) | 0.47798 (9) | 0.0487 (3) | |
C8 | 0.5796 (2) | 0.94340 (15) | 0.46266 (7) | 0.0376 (2) | |
C10 | 0.7840 (3) | 0.8964 (2) | 0.30711 (10) | 0.0566 (3) | |
C9 | 0.6326 (3) | 1.00451 (19) | 0.37423 (9) | 0.0532 (3) | |
H9 | 0.927 (5) | 0.382 (3) | −0.2421 (15) | 0.104 (7)* | |
H3 | 0.908 (3) | 0.676 (2) | 0.0263 (11) | 0.061 (4)* | |
H4 | 0.731 (3) | 1.100 (2) | −0.1302 (11) | 0.055 (4)* | |
H6 | 0.660 (3) | 0.722 (2) | 0.5378 (12) | 0.067 (4)* | |
H1 | 0.462 (4) | 0.621 (2) | −0.0977 (12) | 0.065 (4)* | |
H8 | 0.822 (4) | 0.935 (2) | 0.2459 (13) | 0.073 (5)* | |
H7 | 0.560 (4) | 1.122 (3) | 0.3533 (13) | 0.081 (5)* | |
H2 | 0.412 (4) | 0.787 (3) | −0.1669 (12) | 0.071 (5)* | |
H5 | 0.902 (4) | 0.551 (3) | 0.4159 (12) | 0.071 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0764 (6) | 0.0483 (5) | 0.0463 (5) | 0.0272 (4) | 0.0173 (4) | 0.0141 (4) |
C1 | 0.0449 (6) | 0.0370 (5) | 0.0403 (5) | 0.0071 (4) | 0.0035 (4) | 0.0055 (4) |
C2 | 0.0434 (6) | 0.0489 (6) | 0.0549 (7) | 0.0115 (5) | 0.0119 (5) | 0.0025 (5) |
C3 | 0.0431 (5) | 0.0405 (5) | 0.0396 (5) | 0.0148 (4) | 0.0163 (4) | 0.0046 (4) |
C4 | 0.0580 (7) | 0.0363 (5) | 0.0467 (6) | 0.0141 (5) | 0.0146 (5) | 0.0116 (4) |
C5 | 0.0545 (7) | 0.0452 (6) | 0.0394 (5) | 0.0184 (5) | 0.0097 (5) | 0.0116 (4) |
O2 | 0.1023 (8) | 0.0630 (6) | 0.0502 (5) | 0.0351 (6) | 0.0215 (5) | 0.0232 (4) |
N1 | 0.0507 (6) | 0.0478 (5) | 0.0450 (5) | 0.0158 (4) | 0.0075 (4) | 0.0023 (4) |
C6 | 0.0643 (8) | 0.0439 (6) | 0.0511 (7) | 0.0221 (6) | 0.0096 (6) | 0.0075 (5) |
C7 | 0.0631 (7) | 0.0441 (6) | 0.0443 (6) | 0.0189 (5) | 0.0116 (5) | 0.0117 (5) |
C8 | 0.0370 (5) | 0.0374 (5) | 0.0379 (5) | 0.0073 (4) | 0.0026 (4) | 0.0045 (4) |
C10 | 0.0714 (9) | 0.0614 (8) | 0.0466 (7) | 0.0285 (6) | 0.0200 (6) | 0.0159 (6) |
C9 | 0.0691 (8) | 0.0515 (7) | 0.0490 (6) | 0.0284 (6) | 0.0181 (6) | 0.0166 (5) |
O1—C1 | 1.3051 (13) | C5—H4 | 0.972 (14) |
O1—H9 | 1.02 (2) | N1—C6 | 1.3264 (16) |
C1—O2 | 1.2056 (14) | N1—C10 | 1.3301 (16) |
C1—C2 | 1.5147 (16) | C6—C7 | 1.3820 (17) |
C2—C3 | 1.5108 (17) | C6—H5 | 0.964 (17) |
C2—H1 | 0.970 (16) | C7—C8 | 1.3906 (15) |
C2—H2 | 1.027 (17) | C7—H6 | 0.955 (16) |
C3—C4 | 1.3877 (16) | C8—C9 | 1.3850 (16) |
C3—C5 | 1.3908 (15) | C8—C8ii | 1.486 (2) |
C4—C5i | 1.3844 (18) | C10—C9 | 1.3810 (17) |
C4—H3 | 0.961 (15) | C10—H8 | 0.950 (18) |
C5—C4i | 1.3844 (18) | C9—H7 | 0.998 (19) |
C1—O1—H9 | 112.6 (12) | C3—C5—H4 | 120.1 (8) |
O2—C1—O1 | 123.26 (10) | C6—N1—C10 | 117.10 (10) |
O2—C1—C2 | 123.39 (11) | N1—C6—C7 | 123.47 (11) |
O1—C1—C2 | 113.30 (10) | N1—C6—H5 | 116.3 (10) |
C3—C2—C1 | 109.58 (9) | C7—C6—H5 | 120.2 (10) |
C3—C2—H1 | 110.0 (9) | C6—C7—C8 | 119.66 (11) |
C1—C2—H1 | 108.9 (10) | C6—C7—H6 | 119.0 (10) |
C3—C2—H2 | 109.4 (9) | C8—C7—H6 | 121.4 (10) |
C1—C2—H2 | 107.7 (9) | C9—C8—C7 | 116.53 (10) |
H1—C2—H2 | 111.2 (13) | C9—C8—C8ii | 121.59 (12) |
C4—C3—C5 | 118.28 (11) | C7—C8—C8ii | 121.88 (12) |
C4—C3—C2 | 121.06 (10) | N1—C10—C9 | 123.35 (12) |
C5—C3—C2 | 120.61 (10) | N1—C10—H8 | 115.3 (10) |
C5i—C4—C3 | 120.99 (10) | C9—C10—H8 | 121.3 (10) |
C5i—C4—H3 | 119.3 (9) | C10—C9—C8 | 119.89 (11) |
C3—C4—H3 | 119.7 (9) | C10—C9—H7 | 116.0 (11) |
C4i—C5—C3 | 120.73 (11) | C8—C9—H7 | 124.1 (11) |
C4i—C5—H4 | 119.2 (8) |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H9···N1iii | 1.02 (2) | 1.62 (2) | 2.6373 (13) | 176 (2) |
C7—H6···O2iv | 0.954 (16) | 2.504 (16) | 3.4196 (16) | 160.8 (11) |
C9—H7···O2v | 1.00 (2) | 2.45 (2) | 3.4205 (18) | 162.2 (16) |
Symmetry codes: (iii) −x+2, −y+1, −z; (iv) x, y, z+1; (v) −x+1, −y+2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H9···N1i | 1.02 (2) | 1.62 (2) | 2.6373 (13) | 176 (2) |
C7—H6···O2ii | 0.954 (16) | 2.504 (16) | 3.4196 (16) | 160.8 (11) |
C9—H7···O2iii | 1.00 (2) | 2.45 (2) | 3.4205 (18) | 162.2 (16) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) x, y, z+1; (iii) −x+1, −y+2, −z. |
Acknowledgements
Financial support from the Department of Science & Technology, India (under FASTRACK Grant No. SB/FT/CS-047/2013) is gratefully acknowledged. The authors also thank the USIC, Gauhati University, Guwahati (India), for providing the X-ray diffraction data.
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