organic compounds
4,4′-([4,4′-Bipyridine]-1,1′-diium-1,1′-diyl)dibenzoate dihydrate
aPO Box 5800, MS 1411, Sandia National Laboratories, Albuquerque, NM 87185-1411, USA, bPO Box 5800, MS 1415, Sandia National Laboratories, Albuquerque, NM 87185-1415, USA, and cThe Molecular Foundry, Lawrence Berkeley National Laboratory, One Cyclotron Road, Berkeley, CA 94720, USA
*Correspondence e-mail: marodri@sandia.gov
We report here the synthesis of a neutral viologen derivative, C24H16N2O4·2H2O. The non-solvent portion of the structure (Z-Lig) is a zwitterion, consisting of two positively charged pyridinium cations and two negatively charged carboxylate anions. The carboxylate group is almost coplanar [dihedral angle = 2.04 (11)°] with the benzene ring, whereas the dihedral angle between pyridine and benzene rings is 46.28 (5)°. The Z-Lig molecule is positioned on a center of inversion (Fig. 1). The presence of the twofold axis perpendicular to the c-glide plane in C2/c generates a screw-axis parallel to the b axis that is shifted from the origin by 1/4 in the a and c directions. This screw-axis replicates the molecule (and solvent water molecules) through space. The Z-Lig molecule links to adjacent molecules via O—H⋯O hydrogen bonds involving solvent water molecules as well as intermolecular C—H⋯O interactions. There are also π–π interactions between benzene rings on adjacent molecules.
Keywords: crystal structure; zwitterion; hydrogen bonding; bipyridinium; π–π stacking.
CCDC reference: 1485598
Structure description
The title compound, C24H16N2O4·2H2O, (Fig. 1), includes both the ligand molecule 4,4′-([4,4′-bipyridine]-1,1′-diium-1,1′-diyl)dibenzoate (Z-Lig) and two solvent water molecules. The Z-Lig molecule is of great interest due to its zwitterionic properties. have been used for the construction of coordination polymers with built-in charged surfaces. Such polymers could be employed in gas sorption, separation, and electrochemical applications (e.g. see Aulakh et al., 2015).
The Z-Lig molecule is positioned on a center of inversion (Fig. 1). The presence of the twofold axis perpendicular to the c-glide plane in C2/c generates a screw-axis parallel to the b axis that is shifted from the origin by 1/4 in the a and c directions. This screw-axis replicates the molecule (and solvent water molecules) through space. The solvent water molecules serve to link the Z-Lig molecules via hydrogen bonding to neighboring Z-Lig molecules. The hydrogen bonding of the Z-Lig molecules is complex (Table 1 and Fig. 2). The carboxylate group, with atoms O2 and O3, forms a bond to a neighboring Z-Lig molecule via O2⋯H11 and O3⋯H12 bonds. Note that these bonds link to atoms C11 and C12 that are part of the same neighboring molecule. This is illustrated by the O2 and O3 atoms showing linkage to these same H11 and H12 atoms, respectively, along the backbone of the Z-Lig molecule [distances of 3.0641 (15) Å for O3⋯C12 and 3.3980 (16) Å for O2⋯C11, Fig. 2]. This linkage demands that some of the Z-Lig molecules link at near 90° orientations to one another. This bonding is more easily accommodated by the tilt of the inner (pyridyl) rings of the Z-Lig molecule about the N atoms above and below the plane formed by the carboxylate and the outer (benzene) rings.
The carboxylate O2 atom is hydrogen bonded to the solvent water molecule. Each O2 atom interacts with both the H1A and H1B atoms of different solvent water molecules, as shown in Fig. 2. The simultaneous bonding of O2 to two water molecules designates it as a bifurcated acceptor. The O3 atom of the carboxylate does not directly interact with the solvent water molecule; instead it makes linkages to atoms H8 and H4 of neighboring molecules. Note that these O3⋯H8 and O3⋯H4 bonds are not to the same neighboring molecule. There is another interaction between the O1 atom to the H9 atom located near the midway point along the Z-Lig backbone. A packing diagram of Z-Lig molecules shown in Fig. 3 highlights the linking of molecules via the solvent water molecule, as well as the bonding of the carboxylate to the neighboring molecule via the linkage with both O2⋯H11 and O3⋯H12. Fig. 4 illustrates an important π–π stacking interaction between Z-Lig molecules related via (1 − x, y, − z), in which the centroid–centroid distance is 3.514 (2) Å.
Similar structures to Z-Lig have been published by Gutov et al. (2009) for a hexahydrate as well as a protonated form of Z-Lig with Cl− counter-ions and solvent water. An Eu-based metal–organic framework compound synthesized with Z-Lig has been documented by Liu et al. (2015). For a related structure with similar C—H⋯O intermolecular interactions, see Fun et al. (2010).
Synthesis and crystallization
The title compound, Z-Lig, was synthesized in a two-step process as detailed below.
Step one: synthesis of H2L. A mixture of 1,1′-bis(2,4-dinitrophenyl)-4,4′-bipyridinium dichloride (1.00 g, 1.8 mmol) and 4-aminobenzoic acid (0.51 g, 3.7 mmol) in 20 ml of ethanol was stirred and heated at 368 K overnight. The reaction was cooled to room temperature, followed by addition of 50 ml of dichloromethane. The intermediate product was collected by filtration, then further triturated using dichloromethane to obtain 536 mg (64%) of the final product hereafter known as H2L (the protonated version of the title compound, with two chloride anions balancing the overall charge) as a light-brown solid.
1H NMR (500 MHz, [D6]DMSO): δ 8.09–8.11 (d, J = 8.0 Hz, 4H 4 × CHAr), 8.31–8.32 (d, J = 8.0 Hz, 4H 4 × CHAr), 9.01–9.10 (d, J = 6.0 Hz, 4H 4 × CHAr), 9.74–9.75 (d, J = 6.0 Hz, 4H 4 × CHAr) p.p.m.
Step two: Synthesis of the title compound Z-Lig. The reaction mixture containing Co(NO3)2.6H2O (0.0045 g, 0.0154 mmol) and the above product H2L (0.003 g, 0.0075 mmol) in 0.75 ml DMF, 0.75 ml H2O and 1 drop concentrated HNO3 was placed in a convection oven at 348 K for 24 h (heating rate 1.5 K/min and cooling rate of 1 K min−1), yielding large orange rod-shaped single crystals (70%).
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2
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Structural data
CCDC reference: 1485598
10.1107/S2414314616009664/pk4006sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S2414314616009664/pk4006Isup2.hkl
Supporting information file. DOI: 10.1107/S2414314616009664/pk4006Isup3.cml
Data collection: APEX2 (Bruker, 2014); cell
APEX2 (Bruker, 2014); data reduction: SAINT in APEX2 (Bruker, 2014); program(s) used to solve structure: SHELXS (Sheldrick, 2008) in APEX2 (Bruker, 2014); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008) and Materials Studio (Accelrys, 2013); software used to prepare material for publication: APEX2 (Bruker, 2014).C24H16N2O4·2H2O | F(000) = 904 |
Mr = 432.43 | Dx = 1.493 Mg m−3 |
Monoclinic, C2/c | Cu Kα radiation, λ = 1.54178 Å |
a = 19.1437 (6) Å | Cell parameters from 200 reflections |
b = 7.6420 (3) Å | θ = 4.7–74.4° |
c = 13.2619 (4) Å | µ = 0.90 mm−1 |
β = 97.369 (1)° | T = 100 K |
V = 1924.14 (11) Å3 | Block, orange |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
CMOS area detector diffractometer | 1782 reflections with I > 2σ(I) |
Radiation source: microfocus | Rint = 0.038 |
ω and φ scans | θmax = 74.4°, θmin = 4.7° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −23→23 |
Tmin = 0.86, Tmax = 0.91 | k = −9→9 |
9869 measured reflections | l = −16→14 |
1933 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.041 | Hydrogen site location: mixed |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.1P)2 + 0.5868P] where P = (Fo2 + 2Fc2)/3 |
1933 reflections | (Δ/σ)max = 0.009 |
153 parameters | Δρmax = 0.26 e Å−3 |
2 restraints | Δρmin = −0.38 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.78102 (5) | 1.70456 (15) | 0.67740 (8) | 0.0281 (3) | |
H1A | 0.7441 (9) | 1.649 (3) | 0.6973 (15) | 0.040 (5)* | |
H1B | 0.7896 (11) | 1.788 (2) | 0.7251 (14) | 0.042 (6)* | |
O2 | 0.66644 (5) | 1.49477 (13) | 0.70827 (8) | 0.0257 (3) | |
O3 | 0.58676 (5) | 1.70850 (12) | 0.67687 (7) | 0.0196 (3) | |
N1 | 0.38723 (5) | 1.04952 (14) | 0.56125 (8) | 0.0137 (3) | |
C1 | 0.60486 (7) | 1.55138 (17) | 0.67957 (9) | 0.0168 (3) | |
C2 | 0.54808 (7) | 1.41649 (17) | 0.64604 (9) | 0.0149 (3) | |
C3 | 0.56309 (6) | 1.23826 (18) | 0.64965 (10) | 0.0163 (3) | |
H3 | 0.6097 | 1.2000 | 0.6721 | 0.020* | |
C4 | 0.51070 (7) | 1.11543 (17) | 0.62088 (10) | 0.0161 (3) | |
H4 | 0.5209 | 0.9937 | 0.6233 | 0.019* | |
C5 | 0.44304 (6) | 1.17558 (17) | 0.58849 (9) | 0.0140 (3) | |
C6 | 0.42649 (7) | 1.35231 (17) | 0.58328 (9) | 0.0161 (3) | |
H6 | 0.3799 | 1.3903 | 0.5604 | 0.019* | |
C7 | 0.47989 (7) | 1.47252 (17) | 0.61249 (9) | 0.0162 (3) | |
H7 | 0.4697 | 1.5942 | 0.6095 | 0.019* | |
C8 | 0.34121 (7) | 1.07409 (17) | 0.47631 (9) | 0.0164 (3) | |
H8 | 0.3465 | 1.1719 | 0.4337 | 0.020* | |
C9 | 0.28684 (7) | 0.95821 (17) | 0.45133 (9) | 0.0167 (3) | |
H9 | 0.2546 | 0.9765 | 0.3916 | 0.020* | |
C10 | 0.27881 (6) | 0.81375 (16) | 0.51321 (9) | 0.0136 (3) | |
C11 | 0.32705 (6) | 0.79378 (17) | 0.60111 (10) | 0.0162 (3) | |
H11 | 0.3230 | 0.6971 | 0.6450 | 0.019* | |
C12 | 0.38017 (7) | 0.91350 (17) | 0.62417 (9) | 0.0163 (3) | |
H12 | 0.4121 | 0.9006 | 0.6847 | 0.020* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0223 (6) | 0.0283 (6) | 0.0353 (6) | −0.0051 (4) | 0.0098 (5) | −0.0033 (4) |
O2 | 0.0163 (5) | 0.0204 (6) | 0.0395 (6) | −0.0046 (4) | 0.0005 (4) | −0.0017 (4) |
O3 | 0.0243 (5) | 0.0157 (5) | 0.0185 (5) | −0.0052 (4) | 0.0019 (4) | −0.0006 (3) |
N1 | 0.0114 (5) | 0.0150 (6) | 0.0149 (5) | −0.0022 (4) | 0.0027 (4) | −0.0008 (4) |
C1 | 0.0170 (6) | 0.0193 (7) | 0.0146 (6) | −0.0040 (5) | 0.0045 (5) | −0.0007 (5) |
C2 | 0.0168 (6) | 0.0170 (7) | 0.0116 (6) | −0.0040 (5) | 0.0052 (5) | −0.0015 (4) |
C3 | 0.0130 (6) | 0.0194 (7) | 0.0168 (6) | −0.0013 (5) | 0.0031 (5) | −0.0017 (5) |
C4 | 0.0161 (7) | 0.0154 (6) | 0.0171 (6) | −0.0016 (5) | 0.0028 (5) | −0.0015 (5) |
C5 | 0.0132 (6) | 0.0174 (7) | 0.0118 (6) | −0.0045 (5) | 0.0026 (4) | −0.0008 (4) |
C6 | 0.0147 (6) | 0.0176 (7) | 0.0161 (6) | −0.0006 (5) | 0.0027 (5) | 0.0001 (5) |
C7 | 0.0192 (7) | 0.0158 (7) | 0.0142 (6) | −0.0016 (5) | 0.0047 (5) | −0.0001 (5) |
C8 | 0.0165 (6) | 0.0166 (6) | 0.0159 (6) | −0.0026 (5) | 0.0016 (5) | 0.0027 (5) |
C9 | 0.0153 (6) | 0.0189 (7) | 0.0152 (6) | −0.0023 (5) | −0.0012 (5) | 0.0030 (5) |
C10 | 0.0110 (6) | 0.0154 (7) | 0.0151 (6) | 0.0000 (5) | 0.0034 (5) | −0.0007 (5) |
C11 | 0.0163 (6) | 0.0152 (6) | 0.0169 (6) | −0.0019 (5) | 0.0010 (5) | 0.0029 (5) |
C12 | 0.0151 (6) | 0.0175 (7) | 0.0156 (6) | −0.0013 (5) | −0.0002 (5) | 0.0016 (5) |
O1—H1A | 0.892 (16) | C5—C6 | 1.3869 (19) |
O1—H1B | 0.898 (16) | C6—C7 | 1.3919 (18) |
O2—C1 | 1.2674 (16) | C6—H6 | 0.9500 |
O3—C1 | 1.2490 (17) | C7—H7 | 0.9500 |
N1—C12 | 1.3506 (17) | C8—C9 | 1.3743 (18) |
N1—C8 | 1.3513 (16) | C8—H8 | 0.9500 |
N1—C5 | 1.4495 (15) | C9—C10 | 1.3957 (18) |
C1—C2 | 1.5226 (17) | C9—H9 | 0.9500 |
C2—C3 | 1.3916 (19) | C10—C11 | 1.3996 (17) |
C2—C7 | 1.3916 (18) | C10—C10i | 1.480 (2) |
C3—C4 | 1.3908 (17) | C11—C12 | 1.3730 (17) |
C3—H3 | 0.9500 | C11—H11 | 0.9500 |
C4—C5 | 1.3895 (18) | C12—H12 | 0.9500 |
C4—H4 | 0.9500 | ||
H1A—O1—H1B | 101.9 (19) | C5—C6—H6 | 120.9 |
C12—N1—C8 | 121.05 (11) | C7—C6—H6 | 120.9 |
C12—N1—C5 | 119.11 (10) | C2—C7—C6 | 120.75 (12) |
C8—N1—C5 | 119.76 (11) | C2—C7—H7 | 119.6 |
O3—C1—O2 | 125.50 (12) | C6—C7—H7 | 119.6 |
O3—C1—C2 | 117.22 (11) | N1—C8—C9 | 120.27 (12) |
O2—C1—C2 | 117.28 (12) | N1—C8—H8 | 119.9 |
C3—C2—C7 | 119.56 (12) | C9—C8—H8 | 119.9 |
C3—C2—C1 | 121.07 (11) | C8—C9—C10 | 120.33 (11) |
C7—C2—C1 | 119.37 (11) | C8—C9—H9 | 119.8 |
C4—C3—C2 | 120.84 (12) | C10—C9—H9 | 119.8 |
C4—C3—H3 | 119.6 | C9—C10—C11 | 117.73 (11) |
C2—C3—H3 | 119.6 | C9—C10—C10i | 121.10 (14) |
C5—C4—C3 | 118.19 (12) | C11—C10—C10i | 121.17 (14) |
C5—C4—H4 | 120.9 | C12—C11—C10 | 120.24 (11) |
C3—C4—H4 | 120.9 | C12—C11—H11 | 119.9 |
C6—C5—C4 | 122.38 (12) | C10—C11—H11 | 119.9 |
C6—C5—N1 | 118.58 (11) | N1—C12—C11 | 120.35 (11) |
C4—C5—N1 | 119.03 (11) | N1—C12—H12 | 119.8 |
C5—C6—C7 | 118.29 (12) | C11—C12—H12 | 119.8 |
Symmetry code: (i) −x+1/2, −y+3/2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O3ii | 0.95 | 2.35 | 3.0641 (15) | 132 |
C11—H11···O2ii | 0.95 | 2.47 | 3.3980 (16) | 165 |
C4—H4···O3iii | 0.95 | 2.57 | 3.4735 (16) | 159 |
O1—H1B···O2iv | 0.90 (2) | 1.95 (2) | 2.7997 (15) | 158 (2) |
O1—H1A···O2 | 0.89 (2) | 1.92 (2) | 2.7893 (15) | 165 (2) |
C8—H8···O3v | 0.95 | 2.26 | 3.0834 (16) | 145 |
C9—H9···O1v | 0.95 | 2.66 | 3.2673 (17) | 122 |
Symmetry codes: (ii) −x+1, y−1, −z+3/2; (iii) x, y−1, z; (iv) −x+3/2, y+1/2, −z+3/2; (v) −x+1, −y+3, −z+1. |
Acknowledgements
This work was supported by the Laboratory Directed Research and Development Program at Sandia National Laboratories. Sandia is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04–94 A L85000. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02–05CH11231.
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