organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2414-3146

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

Edited by S. Parkin, University of Kentucky, USA (Received 29 April 2016; accepted 14 June 2016; online 24 June 2016)

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[link]). The presence of the twofold axis perpendicular to the c-glide plane in space group 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 ππ inter­actions between benzene rings on adjacent mol­ecules.

[Figure 1]
Figure 1
The mol­ecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms. Only one of the solvent water mol­ecules is shown. Symmetry-equivalent atoms are generated by inversion ([{1\over 2}] − x, [{3\over 2}] − y, 1 − z).
3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

The title compound, C24H16N2O4·2H2O, (Fig. 1[link]), 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. Zwitterions 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[Aulakh, D., Varghese, J. R. & Wriedt, M. (2015). Inorg. Chem. 54, 1756-1764.]).

The Z-Lig mol­ecule is positioned on a center of inversion (Fig. 1[link]). The presence of the twofold axis perpendicular to the c-glide plane in space group 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[link] and Fig. 2[link]). 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[link]]. 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.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C12—H12⋯O3i 0.95 2.35 3.0641 (15) 132
C11—H11⋯O2i 0.95 2.47 3.3980 (16) 165
C4—H4⋯O3ii 0.95 2.57 3.4735 (16) 159
O1—H1B⋯O2iii 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⋯O3iv 0.95 2.26 3.0834 (16) 145
C9—H9⋯O1iv 0.95 2.66 3.2673 (17) 122
Symmetry codes: (i) [-x+1, y-1, -z+{\script{3\over 2}}]; (ii) x, y-1, z; (iii) [-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]; (iv) -x+1, -y+3, -z+1.
[Figure 2]
Figure 2
Mol­ecule of Z-Lig showing hydrogen bonding to nearby solvent water and neighboring mol­ecules. Distances are given in Å. Symmetry codes: (i) 1 − x, 1 + y, [{3\over 2}] − z; (ii) x, 1 + y, z; (iii) [{3\over 2}] − x, −[{1\over 2}] + y, [{3\over 2}] − z; (iv) 1 − x, 3 − y, 1 − z; (v) 1 − x, −1 + y, [{3\over 2}] − z; (vi) x, −1 + y, z. Distance cutoff = 2.7 Å.

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[link]. 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[link] 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[link] illustrates an important ππ stacking inter­action between Z-Lig mol­ecules related via (1 − x, y, [{3\over 2}] − z), in which the centroid–centroid distance is 3.514 (2) Å.

[Figure 3]
Figure 3
Packing diagram showing hydrogen bonding between Z-Lig mol­ecules and water along with other inter­molecular inter­actions. See text for details.
[Figure 4]
Figure 4
Illustration of the ππ inter­action between adjacent Z-Lig mol­ecules in the structure.

Similar structures to Z-Lig have been published by Gutov et al. (2009[Gutov, A. V., Rusanov, E. B., Ryabitsky, A. B., Tsymbal, I. F. & Chernega, A. N. (2009). Zh. Obshch. Khim. 79, 1553-1561.]) 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[Liu, J.-J., Guan, Y.-F, Lin, M.-J., Huang, C.-C. & Dai, W.-X. (2015). Cryst. Growth Des. 15, 5040-5046.]). For a related structure with similar C—H⋯O inter­molecular inter­actions, see Fun et al. (2010[Fun, H.-K., Goh, J. H., Nithinchandra & Kalluraya, B. (2010). Acta Cryst. E66, o3252.]).

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 refinement details are summarized in Table 2[link].

Table 2
Experimental details

Crystal data
Chemical formula C24H16N2O4·2H2O
Mr 432.43
Crystal system, space group Monoclinic, C2/c
Temperature (K) 100
a, b, c (Å) 19.1437 (6), 7.6420 (3), 13.2619 (4)
β (°) 97.369 (1)
V3) 1924.14 (11)
Z 4
Radiation type Cu Kα
μ (mm−1) 0.90
Crystal size (mm) 0.20 × 0.15 × 0.10
 
Data collection
Diffractometer CMOS area detector
Absorption correction Multi-scan (SADABS; Krause et al., 2015[Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3-10.])
Tmin, Tmax 0.86, 0.91
No. of measured, independent and observed [I > 2σ(I)] reflections 9869, 1933, 1782
Rint 0.038
(sin θ/λ)max−1) 0.625
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.139, 1.12
No. of reflections 1933
No. of parameters 153
No. of restraints 2
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 0.26, −0.38
Computer programs: SAINT and SHELXS (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) in APEX2 (Bruker, 2014[Bruker (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), Mercury (Macrae et al., 2008[Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466-470.]) and Materials Studio (Accelrys, 2013[Accelrys (2013). Materials Studio. Accelrys Software Inc., San Diego, CA, USA.]).

Structural data


Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: 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).

4,4'-([4,4'-Bipyridine]-1,1'-diium-1,1'-diyl)dibenzoate dihydrate top
Crystal data top
C24H16N2O4·2H2OF(000) = 904
Mr = 432.43Dx = 1.493 Mg m3
Monoclinic, C2/cCu Kα radiation, λ = 1.54178 Å
a = 19.1437 (6) ÅCell parameters from 200 reflections
b = 7.6420 (3) Åθ = 4.7–74.4°
c = 13.2619 (4) ŵ = 0.90 mm1
β = 97.369 (1)°T = 100 K
V = 1924.14 (11) Å3Block, orange
Z = 40.20 × 0.15 × 0.10 mm
Data collection top
CMOS area detector
diffractometer
1782 reflections with I > 2σ(I)
Radiation source: microfocusRint = 0.038
ω and φ scansθmax = 74.4°, θmin = 4.7°
Absorption correction: multi-scan
(SADABS; Krause et al., 2015)
h = 2323
Tmin = 0.86, Tmax = 0.91k = 99
9869 measured reflectionsl = 1614
1933 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: mixed
wR(F2) = 0.139H 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 parametersΔρmax = 0.26 e Å3
2 restraintsΔρmin = 0.38 e Å3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.78102 (5)1.70456 (15)0.67740 (8)0.0281 (3)
H1A0.7441 (9)1.649 (3)0.6973 (15)0.040 (5)*
H1B0.7896 (11)1.788 (2)0.7251 (14)0.042 (6)*
O20.66644 (5)1.49477 (13)0.70827 (8)0.0257 (3)
O30.58676 (5)1.70850 (12)0.67687 (7)0.0196 (3)
N10.38723 (5)1.04952 (14)0.56125 (8)0.0137 (3)
C10.60486 (7)1.55138 (17)0.67957 (9)0.0168 (3)
C20.54808 (7)1.41649 (17)0.64604 (9)0.0149 (3)
C30.56309 (6)1.23826 (18)0.64965 (10)0.0163 (3)
H30.60971.20000.67210.020*
C40.51070 (7)1.11543 (17)0.62088 (10)0.0161 (3)
H40.52090.99370.62330.019*
C50.44304 (6)1.17558 (17)0.58849 (9)0.0140 (3)
C60.42649 (7)1.35231 (17)0.58328 (9)0.0161 (3)
H60.37991.39030.56040.019*
C70.47989 (7)1.47252 (17)0.61249 (9)0.0162 (3)
H70.46971.59420.60950.019*
C80.34121 (7)1.07409 (17)0.47631 (9)0.0164 (3)
H80.34651.17190.43370.020*
C90.28684 (7)0.95821 (17)0.45133 (9)0.0167 (3)
H90.25460.97650.39160.020*
C100.27881 (6)0.81375 (16)0.51321 (9)0.0136 (3)
C110.32705 (6)0.79378 (17)0.60111 (10)0.0162 (3)
H110.32300.69710.64500.019*
C120.38017 (7)0.91350 (17)0.62417 (9)0.0163 (3)
H120.41210.90060.68470.020*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0223 (6)0.0283 (6)0.0353 (6)0.0051 (4)0.0098 (5)0.0033 (4)
O20.0163 (5)0.0204 (6)0.0395 (6)0.0046 (4)0.0005 (4)0.0017 (4)
O30.0243 (5)0.0157 (5)0.0185 (5)0.0052 (4)0.0019 (4)0.0006 (3)
N10.0114 (5)0.0150 (6)0.0149 (5)0.0022 (4)0.0027 (4)0.0008 (4)
C10.0170 (6)0.0193 (7)0.0146 (6)0.0040 (5)0.0045 (5)0.0007 (5)
C20.0168 (6)0.0170 (7)0.0116 (6)0.0040 (5)0.0052 (5)0.0015 (4)
C30.0130 (6)0.0194 (7)0.0168 (6)0.0013 (5)0.0031 (5)0.0017 (5)
C40.0161 (7)0.0154 (6)0.0171 (6)0.0016 (5)0.0028 (5)0.0015 (5)
C50.0132 (6)0.0174 (7)0.0118 (6)0.0045 (5)0.0026 (4)0.0008 (4)
C60.0147 (6)0.0176 (7)0.0161 (6)0.0006 (5)0.0027 (5)0.0001 (5)
C70.0192 (7)0.0158 (7)0.0142 (6)0.0016 (5)0.0047 (5)0.0001 (5)
C80.0165 (6)0.0166 (6)0.0159 (6)0.0026 (5)0.0016 (5)0.0027 (5)
C90.0153 (6)0.0189 (7)0.0152 (6)0.0023 (5)0.0012 (5)0.0030 (5)
C100.0110 (6)0.0154 (7)0.0151 (6)0.0000 (5)0.0034 (5)0.0007 (5)
C110.0163 (6)0.0152 (6)0.0169 (6)0.0019 (5)0.0010 (5)0.0029 (5)
C120.0151 (6)0.0175 (7)0.0156 (6)0.0013 (5)0.0002 (5)0.0016 (5)
Geometric parameters (Å, º) top
O1—H1A0.892 (16)C5—C61.3869 (19)
O1—H1B0.898 (16)C6—C71.3919 (18)
O2—C11.2674 (16)C6—H60.9500
O3—C11.2490 (17)C7—H70.9500
N1—C121.3506 (17)C8—C91.3743 (18)
N1—C81.3513 (16)C8—H80.9500
N1—C51.4495 (15)C9—C101.3957 (18)
C1—C21.5226 (17)C9—H90.9500
C2—C31.3916 (19)C10—C111.3996 (17)
C2—C71.3916 (18)C10—C10i1.480 (2)
C3—C41.3908 (17)C11—C121.3730 (17)
C3—H30.9500C11—H110.9500
C4—C51.3895 (18)C12—H120.9500
C4—H40.9500
H1A—O1—H1B101.9 (19)C5—C6—H6120.9
C12—N1—C8121.05 (11)C7—C6—H6120.9
C12—N1—C5119.11 (10)C2—C7—C6120.75 (12)
C8—N1—C5119.76 (11)C2—C7—H7119.6
O3—C1—O2125.50 (12)C6—C7—H7119.6
O3—C1—C2117.22 (11)N1—C8—C9120.27 (12)
O2—C1—C2117.28 (12)N1—C8—H8119.9
C3—C2—C7119.56 (12)C9—C8—H8119.9
C3—C2—C1121.07 (11)C8—C9—C10120.33 (11)
C7—C2—C1119.37 (11)C8—C9—H9119.8
C4—C3—C2120.84 (12)C10—C9—H9119.8
C4—C3—H3119.6C9—C10—C11117.73 (11)
C2—C3—H3119.6C9—C10—C10i121.10 (14)
C5—C4—C3118.19 (12)C11—C10—C10i121.17 (14)
C5—C4—H4120.9C12—C11—C10120.24 (11)
C3—C4—H4120.9C12—C11—H11119.9
C6—C5—C4122.38 (12)C10—C11—H11119.9
C6—C5—N1118.58 (11)N1—C12—C11120.35 (11)
C4—C5—N1119.03 (11)N1—C12—H12119.8
C5—C6—C7118.29 (12)C11—C12—H12119.8
Symmetry code: (i) x+1/2, y+3/2, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O3ii0.952.353.0641 (15)132
C11—H11···O2ii0.952.473.3980 (16)165
C4—H4···O3iii0.952.573.4735 (16)159
O1—H1B···O2iv0.90 (2)1.95 (2)2.7997 (15)158 (2)
O1—H1A···O20.89 (2)1.92 (2)2.7893 (15)165 (2)
C8—H8···O3v0.952.263.0834 (16)145
C9—H9···O1v0.952.663.2673 (17)122
Symmetry codes: (ii) x+1, y1, z+3/2; (iii) x, y1, 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.

References

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