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The crystal structure of 4,4'-bi­pyridine-3,3'-di­carboxyl­ic acid dihydrate, C12H8N2O4·2H2O, has been determined at 130 (1) K. The mol­ecule exists in a zwitterionic form in the crystal and forms an extensive network of hydrogen bonds via the incorporated water mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013939/bt6080sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013939/bt6080Isup2.hkl
Contains datablock I

CCDC reference: 172216

Key indicators

  • Single-crystal X-ray study
  • T = 130 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.055
  • wR factor = 0.108
  • Data-to-parameter ratio = 10.6

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
DIFF_020 Alert A _diffrn_standards_interval_count and _diffrn_standards_interval_time are missing. Number of measurements between standards or time (min) between standards. DIFF_022 Alert A _diffrn_standards_decay_% is missing Percentage decrease in standards intensity.
Yellow Alert Alert Level C:
PLAT_731 Alert C Bond Calc 0.86(3), Rep 0.850(10) .... 3.00 s.u-Ratio O1A -H1A 1.555 1.555 PLAT_731 Alert C Bond Calc 0.85(3), Rep 0.850(10) .... 3.00 s.u-Ratio O3 -H31 1.555 1.555 PLAT_731 Alert C Bond Calc 0.84(3), Rep 0.840(10) .... 3.00 s.u-Ratio O4 -H42 1.555 1.555 PLAT_735 Alert C D-H Calc 0.86(3), Rep 0.850(10) .... 3.00 s.u-Ratio O1A -H1A 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(3), Rep 0.850(10) .... 3.00 s.u-Ratio O3 -H31 1.555 1.555 PLAT_735 Alert C D-H Calc 0.84(3), Rep 0.840(10) .... 3.00 s.u-Ratio O4 -H42 1.555 1.555 PLAT_736 Alert C H...A Calc 1.59(3), Rep 1.590(10) .... 3.00 s.u-Ratio H1A -O1 1.555 4.656 PLAT_736 Alert C H...A Calc 2.01(3), Rep 2.010(10) .... 3.00 s.u-Ratio H31 -O2 1.555 4.655
2 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
8 Alert Level C = Please check

Comment top

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.

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The asymmetric unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993).
[Figure 2] Fig. 2. The molecules of (I) linked by hydrogen bonds via water molecules into a catemer arrangement, projected onto (110). An equivalent arrangement is formed parallel to (110) (CAMERON; Watkin, 1996).
[Figure 3] Fig. 3. Projection onto the (001) plane showing the hydrogen-bonded sheets of (I) stacked along the [010] direction (CAMERON; Watkin et al., 1996).
4,4'-Bipyridine-2,2'-dicarboxylic acid dihydrate top
Crystal data top
C12H8N2O4·2H2OF(000) = 584
Mr = 280.24Dx = 1.513 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 8.520 (1) ÅCell parameters from 3856 reflections
b = 15.970 (2) Åθ = 2.6–25.2°
c = 9.670 (1) ŵ = 0.12 mm1
β = 110.77 (1)°T = 130 K
V = 1230.2 (2) Å3Block, colourless
Z = 40.15 × 0.15 × 0.10 mm
Data collection top
Rigaku R-AXIS IIc
diffractometer
1270 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.043
Graphite monochromatorθmax = 25.2°, θmin = 2.6°
thin–slice ϕ scansh = 010
3856 measured reflectionsk = 019
2126 independent reflectionsl = 1110
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055H 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 reflectionsΔρmax = 0.22 e Å3
200 parametersΔρmin = 0.30 e Å3
8 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.037 (2)
Crystal data top
C12H8N2O4·2H2OV = 1230.2 (2) Å3
Mr = 280.24Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.520 (1) ŵ = 0.12 mm1
b = 15.970 (2) ÅT = 130 K
c = 9.670 (1) Å0.15 × 0.15 × 0.10 mm
β = 110.77 (1)°
Data collection top
Rigaku R-AXIS IIc
diffractometer
1270 reflections with I > 2σ(I)
3856 measured reflectionsRint = 0.043
2126 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0558 restraints
wR(F2) = 0.108H atoms treated by a mixture of independent and constrained refinement
S = 0.94Δρmax = 0.22 e Å3
2126 reflectionsΔρmin = 0.30 e Å3
200 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2699 (4)0.50742 (17)0.1406 (3)0.0153 (7)
C20.1921 (4)0.44721 (17)0.0318 (3)0.0167 (7)
C30.1996 (4)0.45680 (18)0.1068 (3)0.0196 (7)
H30.14900.41580.18040.024*
N40.2767 (3)0.52267 (15)0.1407 (3)0.0187 (6)
H40.272 (4)0.5270 (19)0.2328 (15)0.022*
C50.3494 (4)0.58138 (18)0.0411 (3)0.0194 (7)
H50.40240.62780.06780.023*
C60.3481 (4)0.57530 (18)0.1005 (3)0.0193 (7)
H60.40060.61740.17120.023*
C70.0920 (4)0.37288 (17)0.0550 (4)0.0201 (7)
O10.0663 (3)0.31695 (12)0.0457 (2)0.0320 (6)
O20.0392 (2)0.37279 (12)0.1584 (2)0.0214 (5)
C1A0.2680 (4)0.50708 (18)0.2946 (3)0.0166 (7)
C2A0.3154 (4)0.43927 (17)0.3927 (3)0.0166 (7)
C3A0.3040 (4)0.44974 (18)0.5329 (3)0.0182 (7)
H3A0.33210.40350.59880.022*
N4A0.2560 (3)0.52076 (14)0.5794 (3)0.0196 (6)
C5A0.2140 (4)0.58539 (19)0.4865 (3)0.0215 (7)
H5A0.18070.63630.51890.026*
C6A0.2168 (4)0.58110 (18)0.3437 (4)0.0195 (7)
H6A0.18420.62820.27990.023*
C7A0.3865 (4)0.35780 (18)0.3627 (3)0.0188 (7)
O1A0.3838 (3)0.29998 (12)0.4557 (3)0.0311 (6)
H1A0.458 (3)0.2641 (15)0.455 (4)0.037*
O2A0.4433 (3)0.35072 (12)0.2629 (2)0.0220 (5)
O30.4464 (3)0.24391 (14)0.1605 (3)0.0322 (6)
H310.481 (3)0.2110 (16)0.212 (3)0.039*
H320.350 (2)0.2609 (19)0.213 (3)0.039*
O40.1072 (3)0.28403 (14)0.3433 (3)0.0286 (6)
H410.079 (4)0.277 (2)0.4352 (13)0.034*
H420.042 (3)0.2574 (17)0.311 (3)0.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0146 (16)0.0175 (14)0.0137 (16)0.0048 (13)0.0049 (14)0.0027 (14)
C20.0174 (16)0.0174 (14)0.0142 (16)0.0038 (13)0.0041 (14)0.0009 (13)
C30.0217 (17)0.0201 (15)0.0160 (17)0.0007 (14)0.0054 (15)0.0021 (14)
N40.0241 (15)0.0208 (13)0.0118 (14)0.0006 (12)0.0074 (13)0.0001 (12)
C50.0242 (18)0.0152 (14)0.0220 (18)0.0001 (14)0.0121 (15)0.0007 (15)
C60.0243 (17)0.0165 (15)0.0177 (17)0.0025 (14)0.0080 (14)0.0028 (14)
C70.0215 (18)0.0173 (14)0.0188 (18)0.0006 (14)0.0038 (15)0.0000 (15)
O10.0519 (16)0.0232 (11)0.0269 (13)0.0174 (12)0.0214 (13)0.0101 (11)
O20.0243 (12)0.0243 (11)0.0185 (12)0.0030 (10)0.0113 (11)0.0005 (10)
C1A0.0162 (16)0.0189 (14)0.0152 (17)0.0029 (14)0.0061 (15)0.0013 (14)
C2A0.0159 (15)0.0154 (14)0.0176 (17)0.0015 (13)0.0050 (14)0.0003 (13)
C3A0.0193 (16)0.0204 (15)0.0180 (17)0.0007 (14)0.0104 (14)0.0023 (14)
N4A0.0239 (15)0.0200 (13)0.0159 (14)0.0022 (12)0.0085 (12)0.0028 (12)
C5A0.0249 (18)0.0212 (15)0.0192 (17)0.0006 (15)0.0087 (15)0.0033 (15)
C6A0.0218 (17)0.0178 (15)0.0162 (17)0.0014 (14)0.0035 (15)0.0019 (14)
C7A0.0181 (17)0.0184 (15)0.0185 (18)0.0011 (14)0.0050 (15)0.0016 (14)
O1A0.0469 (16)0.0189 (11)0.0359 (15)0.0129 (12)0.0250 (14)0.0090 (12)
O2A0.0260 (12)0.0232 (11)0.0199 (12)0.0043 (10)0.0119 (11)0.0017 (10)
O30.0335 (15)0.0336 (13)0.0290 (14)0.0066 (12)0.0104 (12)0.0044 (13)
O40.0349 (15)0.0293 (12)0.0265 (13)0.0005 (11)0.0168 (12)0.0013 (12)
Geometric parameters (Å, º) top
C1—C61.397 (4)C2A—C3A1.403 (4)
C1—C21.405 (4)C2A—C7A1.506 (4)
C1—C1A1.495 (4)C3A—N4A1.336 (4)
C2—C31.373 (4)C3A—H3A0.9500
C2—C71.524 (4)N4A—C5A1.331 (4)
C3—N41.341 (4)C5A—C6A1.391 (4)
C3—H30.9500C5A—H5A0.9500
N4—C51.330 (4)C6A—H6A0.9500
N4—H40.88 (1)C7A—O2A1.228 (3)
C5—C61.376 (4)C7A—O1A1.295 (3)
C5—H50.9500O1A—H1A0.85 (1)
C6—H60.9500O3—H310.85 (1)
C7—O21.233 (4)O3—H320.84 (1)
C7—O11.282 (3)O4—H410.84 (1)
C1A—C6A1.400 (4)O4—H420.84 (1)
C1A—C2A1.401 (4)
C6—C1—C2117.9 (3)C6A—C1A—C1116.7 (3)
C6—C1—C1A117.0 (3)C2A—C1A—C1125.1 (3)
C2—C1—C1A125.0 (3)C1A—C2A—C3A117.4 (3)
C3—C2—C1118.8 (3)C1A—C2A—C7A125.2 (3)
C3—C2—C7116.9 (3)C3A—C2A—C7A117.4 (3)
C1—C2—C7124.3 (3)N4A—C3A—C2A124.1 (3)
N4—C3—C2121.5 (3)N4A—C3A—H3A118.0
N4—C3—H3119.3C2A—C3A—H3A118.0
C2—C3—H3119.3C5A—N4A—C3A118.2 (3)
C5—N4—C3121.2 (3)N4A—C5A—C6A122.4 (3)
C5—N4—H4121 (2)N4A—C5A—H5A118.8
C3—N4—H4117 (2)C6A—C5A—H5A118.8
N4—C5—C6120.3 (3)C5A—C6A—C1A119.7 (3)
N4—C5—H5119.8C5A—C6A—H6A120.1
C6—C5—H5119.8C1A—C6A—H6A120.1
C5—C6—C1120.2 (3)O2A—C7A—O1A126.1 (3)
C5—C6—H6119.9O2A—C7A—C2A121.9 (3)
C1—C6—H6119.9O1A—C7A—C2A112.0 (3)
O2—C7—O1127.0 (3)C7A—O1A—H1A106 (2)
O2—C7—C2120.3 (3)H31—O3—H32108 (2)
O1—C7—C2112.6 (3)H41—O4—H42110 (2)
C6A—C1A—C2A118.2 (3)
C6—C1—C2—C31.4 (4)C6—C1—C1A—C2A130.7 (3)
C1A—C1—C2—C3178.0 (3)C2—C1—C1A—C2A52.7 (4)
C6—C1—C2—C7175.8 (3)C6A—C1A—C2A—C3A1.6 (4)
C1A—C1—C2—C70.8 (4)C1—C1A—C2A—C3A179.3 (3)
C1—C2—C3—N41.1 (4)C6A—C1A—C2A—C7A174.9 (3)
C7—C2—C3—N4176.3 (3)C1—C1A—C2A—C7A4.2 (5)
C2—C3—N4—C50.1 (4)C1A—C2A—C3A—N4A2.2 (5)
C3—N4—C5—C60.5 (4)C7A—C2A—C3A—N4A174.6 (3)
N4—C5—C6—C10.2 (4)C2A—C3A—N4A—C5A1.0 (5)
C2—C1—C6—C50.8 (4)C3A—N4A—C5A—C6A0.6 (5)
C1A—C1—C6—C5177.6 (3)N4A—C5A—C6A—C1A1.0 (5)
C3—C2—C7—O2159.2 (3)C2A—C1A—C6A—C5A0.1 (4)
C1—C2—C7—O218.0 (4)C1—C1A—C6A—C5A179.3 (3)
C3—C2—C7—O117.8 (4)C1A—C2A—C7A—O2A16.5 (5)
C1—C2—C7—O1165.0 (3)C3A—C2A—C7A—O2A160.0 (3)
C6—C1—C1A—C6A48.4 (4)C1A—C2A—C7A—O1A165.4 (3)
C2—C1—C1A—C6A128.2 (3)C3A—C2A—C7A—O1A18.1 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N4Ai0.88 (1)1.78 (1)2.650 (4)172 (3)
O1A—H1A···O1ii0.85 (1)1.59 (1)2.433 (3)168 (3)
O3—H32···O40.84 (1)2.04 (1)2.875 (3)172 (3)
O3—H31···O2iii0.85 (1)2.01 (1)2.854 (3)174 (3)
O4—H41···O3iv0.84 (1)2.09 (1)2.916 (3)165 (3)
O4—H42···O2Aiv0.84 (1)2.15 (2)2.942 (3)156 (3)
C3—H3···O40.952.583.491 (4)161
C5A—H5A···O3v0.952.663.569 (4)161
Symmetry codes: (i) x, y, z1; (ii) x+1/2, y1/2, z+1/2; (iii) x+1/2, y1/2, z1/2; (iv) x1/2, y1/2, z1/2; (v) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H8N2O4·2H2O
Mr280.24
Crystal system, space groupMonoclinic, P21/n
Temperature (K)130
a, b, c (Å)8.520 (1), 15.970 (2), 9.670 (1)
β (°) 110.77 (1)
V3)1230.2 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.15 × 0.15 × 0.10
Data collection
DiffractometerRigaku R-AXIS IIc
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3856, 2126, 1270
Rint0.043
(sin θ/λ)max1)0.599
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.108, 0.94
No. of reflections2126
No. of parameters200
No. of restraints8
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N4Ai0.88 (1)1.78 (1)2.650 (4)172 (3)
O1A—H1A···O1ii0.85 (1)1.59 (1)2.433 (3)168 (3)
O3—H32···O40.84 (1)2.04 (1)2.875 (3)172 (3)
O3—H31···O2iii0.85 (1)2.01 (1)2.854 (3)174 (3)
O4—H41···O3iv0.84 (1)2.09 (1)2.916 (3)165 (3)
O4—H42···O2Aiv0.84 (1)2.15 (2)2.942 (3)156 (3)
C3—H3···O40.952.583.491 (4)161.4
C5A—H5A···O3v0.952.663.569 (4)161.4
Symmetry codes: (i) x, y, z1; (ii) x+1/2, y1/2, z+1/2; (iii) x+1/2, y1/2, z1/2; (iv) x1/2, y1/2, z1/2; (v) x+1/2, y1/2, z+1/2.
 

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