Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013939/bt6080sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013939/bt6080Isup2.hkl |
CCDC reference: 172216
4,4'-Bipyridine-2,2'-dicarboxylic acid was prepared according to literature procedures (Becker & Neumann, 1972; Rebek et al., 1985). Crystals were grown by slow evaporation of an aqueous solution at room temperature.
H atoms bound to C atoms were placed geometrically and refined using a riding model with an isotropic displacement parameter fixed at 1.2 times Ueq of the C atom to which they are attached. H atoms on O1A, N4 and the water molecules were located in difference Fourier maps and refined with an isotropic displacement parameter fixed at 1.2 times the atom to which they are bound and O—H and N—H distances restrained to be 0.88 (1) and 0.84 (1) Å, respectively. The H···H distances in the water molecules were also restrained to be 1.37 (2) Å to ensure a chemically reasonable H—O—H bond angle.
Data collection: R-AXIS PROCESS (Molecular Structure Corporation, 1997); cell refinement: R-AXIS PROCESS; data reduction: R-AXIS PROCESS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1993); software used to prepare material for publication: SHELXL97.
C12H8N2O4·2H2O | F(000) = 584 |
Mr = 280.24 | Dx = 1.513 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.520 (1) Å | Cell parameters from 3856 reflections |
b = 15.970 (2) Å | θ = 2.6–25.2° |
c = 9.670 (1) Å | µ = 0.12 mm−1 |
β = 110.77 (1)° | T = 130 K |
V = 1230.2 (2) Å3 | Block, colourless |
Z = 4 | 0.15 × 0.15 × 0.10 mm |
Rigaku R-AXIS IIc diffractometer | 1270 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.043 |
Graphite monochromator | θmax = 25.2°, θmin = 2.6° |
thin–slice ϕ scans | h = 0→10 |
3856 measured reflections | k = 0→19 |
2126 independent reflections | l = −11→10 |
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)] = 0.055 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.108 | w = 1/[σ2(Fo2) + (0.0246P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max = 0.003 |
2126 reflections | Δρmax = 0.22 e Å−3 |
200 parameters | Δρmin = −0.30 e Å−3 |
8 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.037 (2) |
C12H8N2O4·2H2O | V = 1230.2 (2) Å3 |
Mr = 280.24 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.520 (1) Å | µ = 0.12 mm−1 |
b = 15.970 (2) Å | T = 130 K |
c = 9.670 (1) Å | 0.15 × 0.15 × 0.10 mm |
β = 110.77 (1)° |
Rigaku R-AXIS IIc diffractometer | 1270 reflections with I > 2σ(I) |
3856 measured reflections | Rint = 0.043 |
2126 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 8 restraints |
wR(F2) = 0.108 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.22 e Å−3 |
2126 reflections | Δρmin = −0.30 e Å−3 |
200 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 6.9101 (0.0059) x - 8.2210 (0.0166) y + 0.2688 (0.0111) z = 2.3503 (0.0099) * -0.0062 (0.0020) C1 * 0.0073 (0.0020) C2 * -0.0027 (0.0021) C3 * -0.0031 (0.0019) N4 * 0.0041 (0.0020) C5 * 0.0007 (0.0021) C6 Rms deviation of fitted atoms = 0.0046 7.5155 (0.0048) x - 5.1418 (0.0180) y + 0.0841 (0.0109) z = 4.6511 (0.0095) * -0.0046 (0.0021) C1A * 0.0113 (0.0020) C2A * -0.0091 (0.0020) C3A * -0.0006 (0.0020) N4A * 0.0077 (0.0021) C5A * -0.0046 (0.0021) C6A Rms deviation of fitted atoms = 0.0072 Angle to previous plane (with approximate e.s.d.) = 49.82 (0.08) |
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 > σ(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 | ||
C1 | 0.2699 (4) | −0.50742 (17) | 0.1406 (3) | 0.0153 (7) | |
C2 | 0.1921 (4) | −0.44721 (17) | 0.0318 (3) | 0.0167 (7) | |
C3 | 0.1996 (4) | −0.45680 (18) | −0.1068 (3) | 0.0196 (7) | |
H3 | 0.1490 | −0.4158 | −0.1804 | 0.024* | |
N4 | 0.2767 (3) | −0.52267 (15) | −0.1407 (3) | 0.0187 (6) | |
H4 | 0.272 (4) | −0.5270 (19) | −0.2328 (15) | 0.022* | |
C5 | 0.3494 (4) | −0.58138 (18) | −0.0411 (3) | 0.0194 (7) | |
H5 | 0.4024 | −0.6278 | −0.0678 | 0.023* | |
C6 | 0.3481 (4) | −0.57530 (18) | 0.1005 (3) | 0.0193 (7) | |
H6 | 0.4006 | −0.6174 | 0.1712 | 0.023* | |
C7 | 0.0920 (4) | −0.37288 (17) | 0.0550 (4) | 0.0201 (7) | |
O1 | 0.0663 (3) | −0.31695 (12) | −0.0457 (2) | 0.0320 (6) | |
O2 | 0.0392 (2) | −0.37279 (12) | 0.1584 (2) | 0.0214 (5) | |
C1A | 0.2680 (4) | −0.50708 (18) | 0.2946 (3) | 0.0166 (7) | |
C2A | 0.3154 (4) | −0.43927 (17) | 0.3927 (3) | 0.0166 (7) | |
C3A | 0.3040 (4) | −0.44974 (18) | 0.5329 (3) | 0.0182 (7) | |
H3A | 0.3321 | −0.4035 | 0.5988 | 0.022* | |
N4A | 0.2560 (3) | −0.52076 (14) | 0.5794 (3) | 0.0196 (6) | |
C5A | 0.2140 (4) | −0.58539 (19) | 0.4865 (3) | 0.0215 (7) | |
H5A | 0.1807 | −0.6363 | 0.5189 | 0.026* | |
C6A | 0.2168 (4) | −0.58110 (18) | 0.3437 (4) | 0.0195 (7) | |
H6A | 0.1842 | −0.6282 | 0.2799 | 0.023* | |
C7A | 0.3865 (4) | −0.35780 (18) | 0.3627 (3) | 0.0188 (7) | |
O1A | 0.3838 (3) | −0.29998 (12) | 0.4557 (3) | 0.0311 (6) | |
H1A | 0.458 (3) | −0.2641 (15) | 0.455 (4) | 0.037* | |
O2A | 0.4433 (3) | −0.35072 (12) | 0.2629 (2) | 0.0220 (5) | |
O3 | 0.4464 (3) | −0.24391 (14) | −0.1605 (3) | 0.0322 (6) | |
H31 | 0.481 (3) | −0.2110 (16) | −0.212 (3) | 0.039* | |
H32 | 0.350 (2) | −0.2609 (19) | −0.213 (3) | 0.039* | |
O4 | 0.1072 (3) | −0.28403 (14) | −0.3433 (3) | 0.0286 (6) | |
H41 | 0.079 (4) | −0.277 (2) | −0.4352 (13) | 0.034* | |
H42 | 0.042 (3) | −0.2574 (17) | −0.311 (3) | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0146 (16) | 0.0175 (14) | 0.0137 (16) | −0.0048 (13) | 0.0049 (14) | −0.0027 (14) |
C2 | 0.0174 (16) | 0.0174 (14) | 0.0142 (16) | −0.0038 (13) | 0.0041 (14) | −0.0009 (13) |
C3 | 0.0217 (17) | 0.0201 (15) | 0.0160 (17) | 0.0007 (14) | 0.0054 (15) | 0.0021 (14) |
N4 | 0.0241 (15) | 0.0208 (13) | 0.0118 (14) | 0.0006 (12) | 0.0074 (13) | 0.0001 (12) |
C5 | 0.0242 (18) | 0.0152 (14) | 0.0220 (18) | −0.0001 (14) | 0.0121 (15) | −0.0007 (15) |
C6 | 0.0243 (17) | 0.0165 (15) | 0.0177 (17) | 0.0025 (14) | 0.0080 (14) | 0.0028 (14) |
C7 | 0.0215 (18) | 0.0173 (14) | 0.0188 (18) | −0.0006 (14) | 0.0038 (15) | 0.0000 (15) |
O1 | 0.0519 (16) | 0.0232 (11) | 0.0269 (13) | 0.0174 (12) | 0.0214 (13) | 0.0101 (11) |
O2 | 0.0243 (12) | 0.0243 (11) | 0.0185 (12) | 0.0030 (10) | 0.0113 (11) | −0.0005 (10) |
C1A | 0.0162 (16) | 0.0189 (14) | 0.0152 (17) | 0.0029 (14) | 0.0061 (15) | 0.0013 (14) |
C2A | 0.0159 (15) | 0.0154 (14) | 0.0176 (17) | −0.0015 (13) | 0.0050 (14) | −0.0003 (13) |
C3A | 0.0193 (16) | 0.0204 (15) | 0.0180 (17) | 0.0007 (14) | 0.0104 (14) | −0.0023 (14) |
N4A | 0.0239 (15) | 0.0200 (13) | 0.0159 (14) | 0.0022 (12) | 0.0085 (12) | 0.0028 (12) |
C5A | 0.0249 (18) | 0.0212 (15) | 0.0192 (17) | −0.0006 (15) | 0.0087 (15) | 0.0033 (15) |
C6A | 0.0218 (17) | 0.0178 (15) | 0.0162 (17) | −0.0014 (14) | 0.0035 (15) | −0.0019 (14) |
C7A | 0.0181 (17) | 0.0184 (15) | 0.0185 (18) | −0.0011 (14) | 0.0050 (15) | −0.0016 (14) |
O1A | 0.0469 (16) | 0.0189 (11) | 0.0359 (15) | −0.0129 (12) | 0.0250 (14) | −0.0090 (12) |
O2A | 0.0260 (12) | 0.0232 (11) | 0.0199 (12) | −0.0043 (10) | 0.0119 (11) | −0.0017 (10) |
O3 | 0.0335 (15) | 0.0336 (13) | 0.0290 (14) | −0.0066 (12) | 0.0104 (12) | 0.0044 (13) |
O4 | 0.0349 (15) | 0.0293 (12) | 0.0265 (13) | 0.0005 (11) | 0.0168 (12) | −0.0013 (12) |
C1—C6 | 1.397 (4) | C2A—C3A | 1.403 (4) |
C1—C2 | 1.405 (4) | C2A—C7A | 1.506 (4) |
C1—C1A | 1.495 (4) | C3A—N4A | 1.336 (4) |
C2—C3 | 1.373 (4) | C3A—H3A | 0.9500 |
C2—C7 | 1.524 (4) | N4A—C5A | 1.331 (4) |
C3—N4 | 1.341 (4) | C5A—C6A | 1.391 (4) |
C3—H3 | 0.9500 | C5A—H5A | 0.9500 |
N4—C5 | 1.330 (4) | C6A—H6A | 0.9500 |
N4—H4 | 0.88 (1) | C7A—O2A | 1.228 (3) |
C5—C6 | 1.376 (4) | C7A—O1A | 1.295 (3) |
C5—H5 | 0.9500 | O1A—H1A | 0.85 (1) |
C6—H6 | 0.9500 | O3—H31 | 0.85 (1) |
C7—O2 | 1.233 (4) | O3—H32 | 0.84 (1) |
C7—O1 | 1.282 (3) | O4—H41 | 0.84 (1) |
C1A—C6A | 1.400 (4) | O4—H42 | 0.84 (1) |
C1A—C2A | 1.401 (4) | ||
C6—C1—C2 | 117.9 (3) | C6A—C1A—C1 | 116.7 (3) |
C6—C1—C1A | 117.0 (3) | C2A—C1A—C1 | 125.1 (3) |
C2—C1—C1A | 125.0 (3) | C1A—C2A—C3A | 117.4 (3) |
C3—C2—C1 | 118.8 (3) | C1A—C2A—C7A | 125.2 (3) |
C3—C2—C7 | 116.9 (3) | C3A—C2A—C7A | 117.4 (3) |
C1—C2—C7 | 124.3 (3) | N4A—C3A—C2A | 124.1 (3) |
N4—C3—C2 | 121.5 (3) | N4A—C3A—H3A | 118.0 |
N4—C3—H3 | 119.3 | C2A—C3A—H3A | 118.0 |
C2—C3—H3 | 119.3 | C5A—N4A—C3A | 118.2 (3) |
C5—N4—C3 | 121.2 (3) | N4A—C5A—C6A | 122.4 (3) |
C5—N4—H4 | 121 (2) | N4A—C5A—H5A | 118.8 |
C3—N4—H4 | 117 (2) | C6A—C5A—H5A | 118.8 |
N4—C5—C6 | 120.3 (3) | C5A—C6A—C1A | 119.7 (3) |
N4—C5—H5 | 119.8 | C5A—C6A—H6A | 120.1 |
C6—C5—H5 | 119.8 | C1A—C6A—H6A | 120.1 |
C5—C6—C1 | 120.2 (3) | O2A—C7A—O1A | 126.1 (3) |
C5—C6—H6 | 119.9 | O2A—C7A—C2A | 121.9 (3) |
C1—C6—H6 | 119.9 | O1A—C7A—C2A | 112.0 (3) |
O2—C7—O1 | 127.0 (3) | C7A—O1A—H1A | 106 (2) |
O2—C7—C2 | 120.3 (3) | H31—O3—H32 | 108 (2) |
O1—C7—C2 | 112.6 (3) | H41—O4—H42 | 110 (2) |
C6A—C1A—C2A | 118.2 (3) | ||
C6—C1—C2—C3 | −1.4 (4) | C6—C1—C1A—C2A | 130.7 (3) |
C1A—C1—C2—C3 | −178.0 (3) | C2—C1—C1A—C2A | −52.7 (4) |
C6—C1—C2—C7 | 175.8 (3) | C6A—C1A—C2A—C3A | −1.6 (4) |
C1A—C1—C2—C7 | −0.8 (4) | C1—C1A—C2A—C3A | 179.3 (3) |
C1—C2—C3—N4 | 1.1 (4) | C6A—C1A—C2A—C7A | 174.9 (3) |
C7—C2—C3—N4 | −176.3 (3) | C1—C1A—C2A—C7A | −4.2 (5) |
C2—C3—N4—C5 | −0.1 (4) | C1A—C2A—C3A—N4A | 2.2 (5) |
C3—N4—C5—C6 | −0.5 (4) | C7A—C2A—C3A—N4A | −174.6 (3) |
N4—C5—C6—C1 | 0.2 (4) | C2A—C3A—N4A—C5A | −1.0 (5) |
C2—C1—C6—C5 | 0.8 (4) | C3A—N4A—C5A—C6A | −0.6 (5) |
C1A—C1—C6—C5 | 177.6 (3) | N4A—C5A—C6A—C1A | 1.0 (5) |
C3—C2—C7—O2 | 159.2 (3) | C2A—C1A—C6A—C5A | 0.1 (4) |
C1—C2—C7—O2 | −18.0 (4) | C1—C1A—C6A—C5A | 179.3 (3) |
C3—C2—C7—O1 | −17.8 (4) | C1A—C2A—C7A—O2A | −16.5 (5) |
C1—C2—C7—O1 | 165.0 (3) | C3A—C2A—C7A—O2A | 160.0 (3) |
C6—C1—C1A—C6A | −48.4 (4) | C1A—C2A—C7A—O1A | 165.4 (3) |
C2—C1—C1A—C6A | 128.2 (3) | C3A—C2A—C7A—O1A | −18.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N4Ai | 0.88 (1) | 1.78 (1) | 2.650 (4) | 172 (3) |
O1A—H1A···O1ii | 0.85 (1) | 1.59 (1) | 2.433 (3) | 168 (3) |
O3—H32···O4 | 0.84 (1) | 2.04 (1) | 2.875 (3) | 172 (3) |
O3—H31···O2iii | 0.85 (1) | 2.01 (1) | 2.854 (3) | 174 (3) |
O4—H41···O3iv | 0.84 (1) | 2.09 (1) | 2.916 (3) | 165 (3) |
O4—H42···O2Aiv | 0.84 (1) | 2.15 (2) | 2.942 (3) | 156 (3) |
C3—H3···O4 | 0.95 | 2.58 | 3.491 (4) | 161 |
C5A—H5A···O3v | 0.95 | 2.66 | 3.569 (4) | 161 |
Symmetry codes: (i) x, y, z−1; (ii) x+1/2, −y−1/2, z+1/2; (iii) x+1/2, −y−1/2, z−1/2; (iv) x−1/2, −y−1/2, z−1/2; (v) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C12H8N2O4·2H2O |
Mr | 280.24 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 130 |
a, b, c (Å) | 8.520 (1), 15.970 (2), 9.670 (1) |
β (°) | 110.77 (1) |
V (Å3) | 1230.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.15 × 0.15 × 0.10 |
Data collection | |
Diffractometer | Rigaku R-AXIS IIc diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3856, 2126, 1270 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.108, 0.94 |
No. of reflections | 2126 |
No. of parameters | 200 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.22, −0.30 |
Computer programs: R-AXIS PROCESS (Molecular Structure Corporation, 1997), R-AXIS PROCESS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Sheldrick, 1993), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H4···N4Ai | 0.88 (1) | 1.78 (1) | 2.650 (4) | 172 (3) |
O1A—H1A···O1ii | 0.85 (1) | 1.59 (1) | 2.433 (3) | 168 (3) |
O3—H32···O4 | 0.84 (1) | 2.04 (1) | 2.875 (3) | 172 (3) |
O3—H31···O2iii | 0.85 (1) | 2.01 (1) | 2.854 (3) | 174 (3) |
O4—H41···O3iv | 0.84 (1) | 2.09 (1) | 2.916 (3) | 165 (3) |
O4—H42···O2Aiv | 0.84 (1) | 2.15 (2) | 2.942 (3) | 156 (3) |
C3—H3···O4 | 0.95 | 2.58 | 3.491 (4) | 161.4 |
C5A—H5A···O3v | 0.95 | 2.66 | 3.569 (4) | 161.4 |
Symmetry codes: (i) x, y, z−1; (ii) x+1/2, −y−1/2, z+1/2; (iii) x+1/2, −y−1/2, z−1/2; (iv) x−1/2, −y−1/2, z−1/2; (v) −x+1/2, y−1/2, −z+1/2. |
4,4'-Bipyridine-2,2'-dicarboxylic acid, (I), crystallizes from aqueous solution as a dihydrate. Location in a difference Fourier map of H4 bound to N4 indicates that (I) is present in the crystal in a zwitterionic form. The bipyridine unit adopts a twisted conformation with the least-squares planes through the two pyridine rings forming an angle of 49.8 (1)° (Fig. 1).
Molecules of (I) are linked into infinite linear chains along [001] via hydrogen bonds between the pyridinium H4 atom and N4A in an adjacent bipyridine molecule (Table 1), with adjacent chains running in opposite directions. In addition, an extensive hydrogen-bond network lying roughly parallel to the (110) plane links molecules of (I) into a catemer arrangement (Fig. 2). A direct hydrogen bond exists between two carboxylic acid groups in adjacent molecules, and these groups are also hydrogen bonded via the two water molecules (Table 1). An equivalent catemer arrangement is adopted roughly parallel to the (110) plane, giving rise to two-dimensional `crinkled' sheets parallel to the (010) plane. These sheets are interdigitated, stacking along the [010] direction (Fig. 3). Between the sheets, several C—H···O contacts exist with geometries indicative of directional hydrogen-bond interactions (Table 1) (Desiraju & Steiner, 1999).
The observation that (I) crystallizes as a dihydrate may be rationalized by considering that the ratio of conventional hydrogen-bond donors (2) to hydrogen-bond acceptors (4) in (I) is mismatched (Desiraju, 1991). Incorporation of water molecules, with an inherent donor–acceptor ratio of 1:2, facilitates overall equalization of hydrogen-bond donor and acceptor functionality.