Experimental
Crystal data
C10H9N2+·C16H9O8−·2H2O Mr = 522.46 Triclinic, ![[P \overline 1]](teximages/rz2388fi2.gif) a = 7.1955 (8) Å b = 8.935 (1) Å c = 9.8847 (11) Å α = 90.7920 (11)° β = 106.4850 (13)° γ = 107.1180 (15)° V = 579.09 (11) Å3 Z = 1 Mo Kα radiation μ = 0.12 mm−1 T = 296 K 0.23 × 0.21 × 0.19 mm
|
Data collection
Bruker APEXII area-detector diffractometer 2990 measured reflections 2050 independent reflections 1818 reflections with I > 2σ(I) Rint = 0.014
|
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1A⋯N1i | 0.92 (2) | 1.89 (2) | 2.814 (3) | 177 (4) | O4—H4A⋯O1W | 0.82 | 1.75 | 2.5657 (19) | 176 | O1W—H1W⋯O1ii | 0.83 | 1.86 | 2.642 (2) | 157 | O1W—H2W⋯O3iii | 0.84 | 2.03 | 2.841 (2) | 165 | O2—H2A⋯O2iv | 0.91 (2) | 1.54 (2) | 2.446 (3) | 173 (7) | C3—H3⋯O1v | 0.93 | 2.54 | 3.270 (2) | 135 | C13—H13⋯O2vi | 0.93 | 2.57 | 3.448 (2) | 159 | C9—H9⋯O2vii | 0.93 | 2.36 | 3.246 (2) | 160 | Symmetry codes: (i) -x+2, -y, -z; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1; (iv) -x, -y+1, -z; (v) -x+1, -y+1, -z; (vi) x+1, y, z; (vii) -x+1, -y, -z. | |
Data collection: APEX2 (Bruker, 2005
); cell refinement: SAINT (Bruker, 2005
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008
); software used to prepare material for publication: SHELXTL.
Supporting information
A mixture of 4,4'-bipyridine (0.078 g, 0.5 mmol), 4-4'-dicarboxybiphenyl-3-3'dicarboxylic acid (0.165 g; 0.5 mmol), water (10 mL) was stirred vigorously for 30 min and then sealed in a Teflon-lined stainless-steel autoclave (25 mL capacity). The autoclave was heated and maintained at 433K for 3 days, and then cooled to room temperature at 5Kh-1 to obtain colourless block crystals suitable for X-ray analysis.
Water H atoms were located in a difference Fourier map and refined with the O–H distance restrained to 0.84 Å and with Uiso(H) = 1.5 Ueq(O). The H atom bound to the N1 nitrogen atom in the cation and the carboxylic H atoms were refined with distance restraints of N–H = 0.90 Å and O–H = 0.90 Å, respectively. The H1A and H2A hydrogen atoms are disordered over two centrosymmetrically related positions and were therefore refined with site occupancies of 0.5. All other H atoms were placed at calculated positions and treated as riding on the parent atoms, with C–H = 0.93Å, and with Uiso(H) = 1.2 Ueq(C).
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
4-(4-Pyridyl)pyridinium 3',4,4'-tricarboxybiphenyl-3-carboxylate dihydrate
top Crystal data top C10H9N2+·C16H9O8−·2H2O | Z = 1 |
Mr = 522.46 | F(000) = 272 |
Triclinic, P1 | Dx = 1.498 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1955 (8) Å | Cell parameters from 2061 reflections |
b = 8.935 (1) Å | θ = 2.4–28.2° |
c = 9.8847 (11) Å | µ = 0.12 mm−1 |
α = 90.7920 (11)° | T = 296 K |
β = 106.4850 (13)° | Block, colourless |
γ = 107.1180 (15)° | 0.23 × 0.21 × 0.19 mm |
V = 579.09 (11) Å3 | |
Data collection top Bruker APEXII area-detector diffractometer | 1818 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.014 |
Graphite monochromator | θmax = 25.2°, θmin = 2.2° |
ϕ and ω scan | h = −7→8 |
2990 measured reflections | k = −10→9 |
2050 independent reflections | l = −11→11 |
Refinement top 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)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.112 | w = 1/[σ2(Fo2) + (0.0562P)2 + 0.2257P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2050 reflections | Δρmax = 0.32 e Å−3 |
180 parameters | Δρmin = −0.25 e Å−3 |
3 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.071 (9) |
Crystal data top C10H9N2+·C16H9O8−·2H2O | γ = 107.1180 (15)° |
Mr = 522.46 | V = 579.09 (11) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.1955 (8) Å | Mo Kα radiation |
b = 8.935 (1) Å | µ = 0.12 mm−1 |
c = 9.8847 (11) Å | T = 296 K |
α = 90.7920 (11)° | 0.23 × 0.21 × 0.19 mm |
β = 106.4850 (13)° | |
Data collection top Bruker APEXII area-detector diffractometer | 1818 reflections with I > 2σ(I) |
2990 measured reflections | Rint = 0.014 |
2050 independent reflections | |
Refinement top R[F2 > 2σ(F2)] = 0.039 | 3 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.32 e Å−3 |
2050 reflections | Δρmin = −0.25 e Å−3 |
180 parameters | |
Special details top Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.4881 (3) | 1.01415 (19) | 0.18864 (18) | 0.0405 (4) | |
H1 | 0.5318 | 1.1230 | 0.2095 | 0.049* | |
C2 | 0.4740 (2) | 0.94960 (17) | 0.05542 (16) | 0.0321 (4) | |
C3 | 0.4103 (3) | 0.78512 (18) | 0.03012 (17) | 0.0361 (4) | |
H3 | 0.4008 | 0.7393 | −0.0576 | 0.043* | |
C4 | 0.3611 (2) | 0.68843 (17) | 0.13133 (17) | 0.0333 (4) | |
C5 | 0.3102 (3) | 0.51258 (19) | 0.09704 (18) | 0.0397 (4) | |
C6 | 0.3725 (2) | 0.75584 (18) | 0.26291 (16) | 0.0344 (4) | |
C7 | 0.3003 (3) | 0.65386 (19) | 0.36673 (18) | 0.0389 (4) | |
C8 | 0.4384 (3) | 0.91911 (19) | 0.28990 (18) | 0.0407 (4) | |
H8 | 0.4490 | 0.9650 | 0.3779 | 0.049* | |
C9 | 0.9236 (3) | −0.1318 (2) | 0.19327 (19) | 0.0447 (4) | |
H9 | 0.8726 | −0.2254 | 0.1336 | 0.054* | |
C10 | 0.9232 (3) | −0.13691 (19) | 0.33220 (18) | 0.0412 (4) | |
H10 | 0.8722 | −0.2331 | 0.3647 | 0.049* | |
C11 | 0.9987 (2) | 0.00096 (18) | 0.42445 (17) | 0.0351 (4) | |
C12 | 1.0714 (3) | 0.1400 (2) | 0.3674 (2) | 0.0490 (5) | |
H12 | 1.1234 | 0.2355 | 0.4243 | 0.059* | |
C13 | 1.0666 (3) | 0.1367 (2) | 0.2273 (2) | 0.0524 (5) | |
H13 | 1.1151 | 0.2311 | 0.1914 | 0.063* | |
N1 | 0.9947 (2) | 0.00297 (17) | 0.14119 (15) | 0.0428 (4) | |
H1A | 0.997 (7) | 0.004 (5) | 0.049 (2) | 0.051* | 0.50 |
O1 | 0.4404 (2) | 0.44851 (15) | 0.14281 (16) | 0.0572 (4) | |
O3 | 0.1949 (2) | 0.51807 (15) | 0.33352 (14) | 0.0596 (4) | |
O4 | 0.3524 (3) | 0.72538 (16) | 0.49433 (14) | 0.0647 (5) | |
H4A | 0.3092 | 0.6627 | 0.5465 | 0.097* | |
O1W | 0.2145 (3) | 0.5413 (2) | 0.66452 (17) | 0.0799 (6) | |
H1W | 0.3004 | 0.5290 | 0.7356 | 0.120* | |
H2W | 0.1031 | 0.5241 | 0.6817 | 0.120* | |
O2 | 0.1336 (2) | 0.43770 (14) | 0.01377 (15) | 0.0520 (4) | |
H2A | 0.040 (8) | 0.490 (8) | 0.001 (8) | 0.078* | 0.50 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0520 (10) | 0.0255 (8) | 0.0388 (9) | 0.0025 (7) | 0.0159 (8) | −0.0015 (7) |
C2 | 0.0325 (8) | 0.0276 (8) | 0.0339 (8) | 0.0060 (6) | 0.0100 (6) | 0.0017 (6) |
C3 | 0.0467 (9) | 0.0279 (8) | 0.0327 (8) | 0.0081 (7) | 0.0141 (7) | −0.0006 (6) |
C4 | 0.0346 (8) | 0.0277 (8) | 0.0352 (8) | 0.0066 (6) | 0.0102 (6) | 0.0025 (6) |
C5 | 0.0549 (10) | 0.0293 (8) | 0.0396 (9) | 0.0115 (8) | 0.0231 (8) | 0.0057 (7) |
C6 | 0.0353 (8) | 0.0308 (8) | 0.0339 (8) | 0.0054 (6) | 0.0104 (7) | 0.0027 (6) |
C7 | 0.0447 (9) | 0.0324 (8) | 0.0376 (9) | 0.0063 (7) | 0.0152 (7) | 0.0023 (7) |
C8 | 0.0526 (10) | 0.0325 (8) | 0.0323 (9) | 0.0041 (7) | 0.0153 (7) | −0.0022 (7) |
C9 | 0.0530 (11) | 0.0371 (9) | 0.0421 (10) | 0.0122 (8) | 0.0135 (8) | −0.0016 (7) |
C10 | 0.0513 (10) | 0.0285 (8) | 0.0431 (10) | 0.0093 (7) | 0.0163 (8) | 0.0035 (7) |
C11 | 0.0373 (8) | 0.0286 (8) | 0.0391 (9) | 0.0092 (6) | 0.0119 (7) | 0.0039 (6) |
C12 | 0.0691 (13) | 0.0293 (9) | 0.0425 (10) | 0.0041 (8) | 0.0190 (9) | 0.0022 (7) |
C13 | 0.0714 (13) | 0.0379 (10) | 0.0451 (10) | 0.0079 (9) | 0.0226 (9) | 0.0093 (8) |
N1 | 0.0516 (9) | 0.0454 (8) | 0.0332 (8) | 0.0152 (7) | 0.0151 (7) | 0.0064 (6) |
O1 | 0.0725 (10) | 0.0442 (7) | 0.0666 (9) | 0.0307 (7) | 0.0254 (7) | 0.0142 (6) |
O3 | 0.0830 (10) | 0.0355 (7) | 0.0522 (8) | −0.0054 (7) | 0.0330 (7) | 0.0011 (6) |
O4 | 0.0976 (11) | 0.0443 (8) | 0.0368 (7) | −0.0065 (7) | 0.0266 (7) | 0.0019 (6) |
O1W | 0.0693 (10) | 0.0986 (13) | 0.0630 (10) | 0.0071 (9) | 0.0252 (8) | 0.0340 (9) |
O2 | 0.0599 (9) | 0.0273 (6) | 0.0601 (8) | 0.0046 (6) | 0.0146 (7) | −0.0086 (6) |
Geometric parameters (Å, º) top C1—C8 | 1.378 (2) | C9—N1 | 1.334 (2) |
C1—C2 | 1.395 (2) | C9—C10 | 1.375 (3) |
C1—H1 | 0.9300 | C9—H9 | 0.9300 |
C2—C3 | 1.400 (2) | C10—C11 | 1.392 (2) |
C2—C2i | 1.488 (3) | C10—H10 | 0.9300 |
C3—C4 | 1.385 (2) | C11—C12 | 1.392 (2) |
C3—H3 | 0.9300 | C11—C11ii | 1.489 (3) |
C4—C6 | 1.397 (2) | C12—C13 | 1.375 (3) |
C4—C5 | 1.514 (2) | C12—H12 | 0.9300 |
C5—O1 | 1.222 (2) | C13—N1 | 1.334 (2) |
C5—O2 | 1.277 (2) | C13—H13 | 0.9300 |
C6—C8 | 1.391 (2) | N1—H1A | 0.921 (18) |
C6—C7 | 1.484 (2) | O4—H4A | 0.8200 |
C7—O3 | 1.209 (2) | O1W—H1W | 0.8263 |
C7—O4 | 1.307 (2) | O1W—H2W | 0.8370 |
C8—H8 | 0.9300 | O2—H2A | 0.911 (19) |
| | | |
C8—C1—C2 | 121.02 (15) | C6—C8—H8 | 119.4 |
C8—C1—H1 | 119.5 | N1—C9—C10 | 122.24 (16) |
C2—C1—H1 | 119.5 | N1—C9—H9 | 118.9 |
C1—C2—C3 | 117.26 (15) | C10—C9—H9 | 118.9 |
C1—C2—C2i | 121.74 (17) | C9—C10—C11 | 120.39 (16) |
C3—C2—C2i | 121.00 (17) | C9—C10—H10 | 119.8 |
C4—C3—C2 | 122.24 (15) | C11—C10—H10 | 119.8 |
C4—C3—H3 | 118.9 | C10—C11—C12 | 116.23 (16) |
C2—C3—H3 | 118.9 | C10—C11—C11ii | 121.63 (18) |
C3—C4—C6 | 119.43 (14) | C12—C11—C11ii | 122.14 (18) |
C3—C4—C5 | 117.83 (14) | C13—C12—C11 | 120.36 (16) |
C6—C4—C5 | 122.62 (14) | C13—C12—H12 | 119.8 |
O1—C5—O2 | 122.14 (16) | C11—C12—H12 | 119.8 |
O1—C5—C4 | 119.75 (16) | N1—C13—C12 | 122.31 (17) |
O2—C5—C4 | 117.99 (15) | N1—C13—H13 | 118.8 |
C8—C6—C4 | 118.80 (15) | C12—C13—H13 | 118.8 |
C8—C6—C7 | 121.15 (14) | C13—N1—C9 | 118.47 (15) |
C4—C6—C7 | 119.90 (14) | C13—N1—H1A | 120 (3) |
O3—C7—O4 | 123.27 (16) | C9—N1—H1A | 121 (3) |
O3—C7—C6 | 122.33 (15) | C7—O4—H4A | 109.5 |
O4—C7—C6 | 114.33 (14) | H1W—O1W—H2W | 109.1 |
C1—C8—C6 | 121.24 (15) | C5—O2—H2A | 115 (5) |
C1—C8—H8 | 119.4 | | |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+2, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N1iii | 0.92 (2) | 1.89 (2) | 2.814 (3) | 177 (4) |
O4—H4A···O1W | 0.82 | 1.75 | 2.5657 (19) | 176 |
O1W—H1W···O1iv | 0.83 | 1.86 | 2.642 (2) | 157 |
O1W—H2W···O3v | 0.84 | 2.03 | 2.841 (2) | 165 |
O2—H2A···O2vi | 0.91 (2) | 1.54 (2) | 2.446 (3) | 173 (7) |
C3—H3···O1vii | 0.93 | 2.54 | 3.270 (2) | 135 |
C13—H13···O2viii | 0.93 | 2.57 | 3.448 (2) | 159 |
C9—H9···O2ix | 0.93 | 2.36 | 3.246 (2) | 160 |
Symmetry codes: (iii) −x+2, −y, −z; (iv) −x+1, −y+1, −z+1; (v) −x, −y+1, −z+1; (vi) −x, −y+1, −z; (vii) −x+1, −y+1, −z; (viii) x+1, y, z; (ix) −x+1, −y, −z. |
Experimental details
Crystal data |
Chemical formula | C10H9N2+·C16H9O8−·2H2O |
Mr | 522.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.1955 (8), 8.935 (1), 9.8847 (11) |
α, β, γ (°) | 90.7920 (11), 106.4850 (13), 107.1180 (15) |
V (Å3) | 579.09 (11) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.23 × 0.21 × 0.19 |
|
Data collection |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2990, 2050, 1818 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.599 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.112, 1.03 |
No. of reflections | 2050 |
No. of parameters | 180 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.25 |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N1i | 0.921 (18) | 1.894 (19) | 2.814 (3) | 177 (4) |
O4—H4A···O1W | 0.82 | 1.75 | 2.5657 (19) | 175.5 |
O1W—H1W···O1ii | 0.83 | 1.86 | 2.642 (2) | 157.0 |
O1W—H2W···O3iii | 0.84 | 2.03 | 2.841 (2) | 164.7 |
O2—H2A···O2iv | 0.911 (19) | 1.54 (2) | 2.446 (3) | 173 (7) |
C3—H3···O1v | 0.93 | 2.54 | 3.270 (2) | 135.4 |
C13—H13···O2vi | 0.93 | 2.57 | 3.448 (2) | 158.6 |
C9—H9···O2vii | 0.93 | 2.36 | 3.246 (2) | 159.6 |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y+1, −z+1; (iii) −x, −y+1, −z+1; (iv) −x, −y+1, −z; (v) −x+1, −y+1, −z; (vi) x+1, y, z; (vii) −x+1, −y, −z. |
Acknowledgements
The authors acknowledge the Chan Xue Yan Cooperative Special Project of Guangdong Province, the Ministry of Science and Technology (project No. 2007A090302046), the Project of Science and Technology of Guangdong Province (project No. 2007A020200002-4) and the Natural Science Foundation of Guangdong Province (No. 9151063101000037) for supporting this work.
References
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Wang, J.-J., Gou, L., Hu, H.-M., Han, Z.-X., Li, D.-S., Xue, G.-L., Yang, M.-L. & Shi, Q.-Z. (2007). Cryst. Growth Des. 7, 1514–1521. Web of Science CSD CrossRef CAS Google Scholar
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In recent years, research on coordination polymers has made considerable progress in the fields of supramolecular chemistry and crystal engineering, because of their intriguing structural motifs and functional properties, such as molecular adsorption, magnetism, and luminescence. In general, hydrogen bonding interactions between ligands are specific and directional. In this context, biphenyl-3,3',4,4'-tetracarboxylic acid and 4,4'-bipyridine are excellent candidates for the construction of three-dimensional network motifs (Wang et al., 2006; Wang et al., 2007; Yang et al., 2007). Recently, we obtained the title compound under hydrothermal conditions and report its crystal structure here.
The asymmetric unit of the title compound contains one half of a monoprotic 4-4'-bipyridinium cation, one half of a 3-3'-4-tricarboxybiphenyl-4'-carboxylato anion and a water molecule, with both cation and anion possessing crystallographically imposed centre of symmetry (Fig. 1). As a result, the H1A nitrogen-bound hydrogen atom in the cation and acidic H2A hydrogen atom in the anion are disordered over two positions with site occupancies of 0.5. Bond lengths and angles are unexceptional. In the crystal packing (Fig. 2), cations, anions and lattice water molecules are linked by intermolecular O—H···O, C—H···O and N—H···N hydrogen bonds (Table 1) into layers parallel to (2 1 0). The layers are further connected into a three-dimensional network by O—H···O hydrogen bonds involving the water molecules as H-donors and by weak π–π stacking interactions involving neighbouring benzene and pyridine rings, with centroid-to-centroid distances of 3.756 (5) Å.