2,2′-Bipyridin-1-ium hemioxalate oxalic acid monohydrate

Dziuk, B.; Jezuita, A.

doi:10.1107/S2414314618012191

organic compounds

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Volume 3| Part 8| August 2018| x181219

https://doi.org/10.1107/S2414314618012191

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2,2′-Bipyridin-1-ium hemioxalate oxalic acid monohydrate

Błażej Dziuk ^a ^* and Anna Jezuita ^a

^aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
^*Correspondence e-mail: bdziuk@uni.opole.pl

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 24 August 2018; accepted 28 August 2018; online 31 August 2018)

The asymmetric unit of the title compound, C₁₀H₉N₂⁺·0.5C₂O₄²⁻·C₂H₂O₄·H₂O, consists of a 2,2′-bipyridinium cation, half an oxalate dianion, one oxalic acid and one water molecule. One N atom in 2,2′-bipyridine is unprotonated, while the second is protonated and forms an N—H⋯O hydrogen bond. In the crystal, the anions are connected with surrounding acid molecules and water molecules by strong near-linear O—H⋯O hydrogen bonds. The water molecules are located between the anions and oxalic acids; their O atoms participate as donors and acceptors, respectively, in O—H⋯O hydrogen bonds, which form sheets arranged parallel to the ac plane.

Keywords: crystal structure; 2,2′-bipyridinium; hydrogen bonds.

CCDC reference: 1864309

Structure description

Hydrogen bonds are one of the most important intermolecular interactions in structural chemistry (Desiraju, 2013 ). The strong interactions between cations and anions have been studied extensively for use in supramolecular chemistry and crystal engineering. Carboxylic acids, especially in hydrates, form strong interactions that may strongly influence the different forms of structures, usually forming supramolecular synthons (Dziuk et al., 2014a ,b , 2017 ; Braga et al., 2013 ; Ejsmont & Zaleski, 2006 ). 2,2′-Bipyridine derivatives are classical bidentate chelating heterocyclic ligands (Steel, 1996 ) employed in transition metal catalysis and inorganic syntheses (e.g. aluminium-initiated polymerization; Blau, 1888 ; Mardare & Matyjaszewski, 1994 ) because of their robust redox stability and ease of functionalization (Kaes et al., 2000 ). Many complexes with 2,2′-bipyridine have distinctive optical properties and are used in studies of electron and energy transfer, catalysis and supramolecular chemistry (Balzani et al., 2006 ). Their use as building blocks for the construction of efficient molecular and macromolecular non-linear optical chromophores is an area of great interest (Coe et al., 2005 ). 2,2′-Bipyridine has been used for more than a century as common chelating ligand in analytical, organometallic and coordination chemistry (Steel, 1996).

The crystal structure of the title hydrated salt, (I), consists of a 2,2′-bipyridinium cation, half an oxalate anion, one oxalic acid and one water molecule (Fig. 1). The oxalate anion is planar with an inversion center at the mid-point of the C—C bond. One nitrogen atom in the 2,2′-bipyridinium cation is unprotonated while second one is protonated and forms a strong N—H⋯O hydrogen bond. In the crystal, two different types of strong hydrogen bonds are observed: N—H⋯O and O—H⋯O (Table 1, Fig. 2). The anions are connected with the cations and surrounding acid molecules and water molecules by strong near-linear O—H⋯O hydrogen bonds. The water molecules are located between the anions and oxalic acid molecules; their O atoms participate as donors and acceptors, respectively, in O—H⋯O hydrogen bonds, which form sheets arranged parallel to the ac plane.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O2ⁱ	0.84	1.99	2.8192 (12)	170
N1—H1⋯O1	0.86	1.99	2.7586 (13)	148
O4—H4⋯O1	0.94	1.64	2.5795 (11)	176
O4—H4⋯O2	0.94	2.62	3.2259 (12)	122
O6—H6⋯O7	0.92	1.63	2.5467 (11)	169
O7—H7B⋯O2ⁱⁱ	0.93	1.75	2.6802 (12)	174
C8—H8⋯O3	0.93	2.52	3.3132 (18)	144
C10—H10⋯O7ⁱⁱⁱ	0.93	2.43	3.2562 (17)	148
C13—H13⋯O6^iv	0.93	2.59	3.3876 (16)	144
Symmetry codes: (i) -x+2, -y, -z+1; (ii) x, y, z-1; (iii) x-1, y+1, z+1; (iv) x, y, z+1.

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Figure 2
The packing viewed along the b axis, showing the hydrogen-bonding scheme (dashed lines).

Synthesis and crystallization

Crystals were grown at room temperature by slow evaporation of an aqueous solution containing 2,2′-bipyridine and oxalic acid in a 1:1 stoichiometric ratio.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₀H₉N₂⁺·0.5C₂O₄²⁻·C₂H₂O₄·H₂O
M_r	309.25
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	7.2618 (4), 8.9419 (6), 11.0001 (7)
α, β, γ (°)	85.545 (5), 86.177 (5), 75.248 (5)
V (Å³)	687.84 (8)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.4 × 0.35 × 0.3

Data collection
Diffractometer	Oxford Diffraction Xcalibur
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4712, 2648, 2054
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.04
No. of reflections	2648
No. of parameters	200
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16
Computer programs: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD. Oxford Diffraction Ltd, Abingdon, England.]$ ), SHELXS2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1864309

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618012191/bt4073sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012191/bt4073Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618012191/bt4073Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

2,2'-Bipyridin-1-ium hemioxalate oxalic acid monohydrate top

Crystal data top

C₁₀H₉N₂⁺·0.5C₂O₄²⁻·C₂H₂O₄·H₂O	Z = 2
M_r = 309.25	F(000) = 322
Triclinic, P1	D_x = 1.493 Mg m⁻³
a = 7.2618 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.9419 (6) Å	Cell parameters from 4712 reflections
c = 11.0001 (7) Å	θ = 3.1–26.0°
α = 85.545 (5)°	µ = 0.12 mm⁻¹
β = 86.177 (5)°	T = 293 K
γ = 75.248 (5)°	Plate, pink
V = 687.84 (8) Å³	0.4 × 0.35 × 0.3 mm

Data collection top

Oxford Diffraction Xcalibur diffractometer	2054 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	θ_max = 26.0°, θ_min = 3.1°
ω–scan	h = −8→8
4712 measured reflections	k = −9→11
2648 independent reflections	l = −13→13

Refinement top

Refinement on F²	Hydrogen site location: difference Fourier map
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.051P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.089	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.16 e Å⁻³
2648 reflections	Δρ_min = −0.15 e Å⁻³
200 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.138 (7)

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. All H atoms were located in a difference map and set to this position. During refinement they were treated as riding on their parent N, O and C atoms, with and U_iso (H) = 1.2U_eq(C, N, O).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.49365 (11)	0.08583 (10)	0.85141 (7)	0.0386 (2)
N1	0.27452 (14)	0.38740 (12)	0.84585 (10)	0.0408 (3)
H1	0.3370	0.2997	0.8775	0.049*
C1	0.56889 (16)	0.02093 (13)	0.94780 (10)	0.0294 (3)
O2	0.74212 (11)	−0.01433 (10)	0.96493 (8)	0.0465 (3)
N2	0.38268 (15)	0.33461 (12)	1.07479 (10)	0.0406 (3)
C2	0.68092 (17)	0.05604 (14)	0.56545 (11)	0.0349 (3)
O3	0.55452 (14)	0.17018 (12)	0.54737 (8)	0.0594 (3)
C3	0.80116 (17)	−0.03224 (15)	0.46116 (10)	0.0339 (3)
O4	0.73101 (12)	−0.00942 (11)	0.67194 (7)	0.0470 (3)
H4	0.6457	0.0297	0.7370	0.056*
C4	0.21997 (17)	0.50713 (14)	0.91815 (12)	0.0389 (3)
C5	0.11417 (19)	0.64602 (15)	0.86672 (15)	0.0510 (4)
H5	0.0713	0.7310	0.9141	0.061*
O5	0.91375 (13)	−0.15528 (11)	0.47742 (8)	0.0506 (3)
C6	0.0722 (2)	0.65872 (18)	0.74540 (17)	0.0589 (4)
H6A	0.0006	0.7522	0.7113	0.071*
O6	0.76264 (12)	0.04452 (10)	0.35664 (7)	0.0453 (3)
H6	0.8398	−0.0028	0.2934	0.054*
C7	0.1354 (2)	0.53431 (19)	0.67463 (15)	0.0591 (4)
H7	0.1098	0.5430	0.5923	0.071*
O7	0.94612 (12)	−0.06711 (10)	0.16511 (7)	0.0440 (3)
H7A	1.0359	−0.0334	0.1317	0.053*
H7B	0.8673	−0.0478	0.0991	0.053*
C8	0.2373 (2)	0.39662 (18)	0.72765 (14)	0.0524 (4)
H8	0.2802	0.3104	0.6817	0.063*
C9	0.27939 (17)	0.47844 (14)	1.04566 (12)	0.0377 (3)
C10	0.2316 (2)	0.59226 (17)	1.12833 (15)	0.0546 (4)
H10	0.1623	0.6917	1.1047	0.066*
C11	0.2885 (2)	0.5560 (2)	1.24680 (16)	0.0633 (4)
H11	0.2570	0.6305	1.3043	0.076*
C12	0.3922 (2)	0.40849 (19)	1.27819 (14)	0.0563 (4)
H12	0.4313	0.3805	1.3574	0.068*
C13	0.43656 (19)	0.30303 (16)	1.18919 (13)	0.0481 (4)
H13	0.5086	0.2037	1.2104	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0423 (5)	0.0424 (5)	0.0235 (4)	0.0008 (4)	0.0009 (4)	0.0047 (4)
N1	0.0347 (6)	0.0340 (6)	0.0480 (7)	0.0002 (5)	−0.0044 (5)	0.0057 (5)
C1	0.0346 (7)	0.0280 (6)	0.0231 (6)	−0.0036 (5)	0.0005 (5)	−0.0022 (5)
O2	0.0339 (5)	0.0719 (7)	0.0328 (5)	−0.0137 (5)	−0.0012 (4)	0.0040 (4)
N2	0.0397 (6)	0.0320 (6)	0.0479 (7)	−0.0060 (5)	−0.0037 (5)	0.0025 (5)
C2	0.0320 (6)	0.0421 (7)	0.0286 (6)	−0.0071 (6)	−0.0025 (5)	0.0027 (5)
O3	0.0621 (6)	0.0590 (7)	0.0374 (6)	0.0187 (5)	0.0016 (5)	0.0013 (5)
C3	0.0303 (6)	0.0421 (8)	0.0287 (6)	−0.0083 (6)	−0.0030 (5)	0.0007 (5)
O4	0.0449 (5)	0.0603 (6)	0.0252 (5)	0.0035 (4)	0.0024 (4)	0.0038 (4)
C4	0.0279 (6)	0.0304 (7)	0.0561 (9)	−0.0064 (5)	0.0018 (6)	0.0043 (6)
C5	0.0404 (7)	0.0320 (8)	0.0755 (11)	−0.0041 (6)	−0.0029 (7)	0.0109 (7)
O5	0.0542 (6)	0.0474 (6)	0.0384 (5)	0.0080 (5)	−0.0009 (4)	−0.0006 (4)
C6	0.0400 (8)	0.0480 (10)	0.0833 (12)	−0.0080 (7)	−0.0128 (8)	0.0285 (8)
O6	0.0493 (5)	0.0512 (6)	0.0265 (5)	0.0015 (4)	0.0015 (4)	0.0022 (4)
C7	0.0470 (9)	0.0685 (11)	0.0592 (10)	−0.0142 (8)	−0.0145 (7)	0.0217 (8)
O7	0.0389 (5)	0.0597 (6)	0.0311 (5)	−0.0090 (4)	0.0007 (4)	−0.0025 (4)
C8	0.0464 (8)	0.0574 (9)	0.0501 (9)	−0.0077 (7)	−0.0067 (7)	0.0024 (7)
C9	0.0296 (6)	0.0324 (7)	0.0507 (8)	−0.0092 (5)	0.0029 (5)	0.0001 (6)
C10	0.0519 (9)	0.0371 (8)	0.0727 (11)	−0.0077 (7)	0.0052 (8)	−0.0087 (7)
C11	0.0676 (10)	0.0655 (11)	0.0637 (11)	−0.0268 (9)	0.0104 (8)	−0.0241 (8)
C12	0.0579 (9)	0.0687 (11)	0.0495 (9)	−0.0289 (8)	−0.0027 (7)	−0.0048 (8)
C13	0.0468 (8)	0.0463 (8)	0.0518 (9)	−0.0137 (7)	−0.0076 (7)	0.0051 (7)

Geometric parameters (Å, º) top

O1—C1	1.2569 (13)	C5—H5	0.9300
N1—C8	1.3375 (17)	C6—C7	1.371 (2)
N1—C4	1.3453 (17)	C6—H6A	0.9300
N1—H1	0.8600	O6—H6	0.9224
C1—O2	1.2401 (13)	C7—C8	1.3733 (19)
C1—C1ⁱ	1.559 (2)	C7—H7	0.9300
N2—C13	1.3306 (16)	O7—H7A	0.8379
N2—C9	1.3402 (15)	O7—H7B	0.9327
C2—O3	1.1997 (14)	C8—H8	0.9300
C2—O4	1.2996 (13)	C9—C10	1.380 (2)
C2—C3	1.5355 (18)	C10—C11	1.383 (2)
C3—O5	1.2007 (14)	C10—H10	0.9300
C3—O6	1.3014 (13)	C11—C12	1.373 (2)
O4—H4	0.9417	C11—H11	0.9300
C4—C5	1.3841 (17)	C12—C13	1.378 (2)
C4—C9	1.4791 (19)	C12—H12	0.9300
C5—C6	1.378 (2)	C13—H13	0.9300

C8—N1—C4	123.91 (11)	C3—O6—H6	112.1
C8—N1—H1	118.0	C6—C7—C8	118.73 (15)
C4—N1—H1	118.0	C6—C7—H7	120.6
O2—C1—O1	125.34 (10)	C8—C7—H7	120.6
O2—C1—C1ⁱ	118.21 (12)	H7A—O7—H7B	98.0
O1—C1—C1ⁱ	116.44 (12)	N1—C8—C7	119.56 (14)
C13—N2—C9	117.25 (12)	N1—C8—H8	120.2
O3—C2—O4	125.59 (12)	C7—C8—H8	120.2
O3—C2—C3	122.43 (11)	N2—C9—C10	122.62 (13)
O4—C2—C3	111.97 (10)	N2—C9—C4	115.25 (12)
O5—C3—O6	126.36 (12)	C10—C9—C4	122.13 (12)
O5—C3—C2	122.97 (11)	C9—C10—C11	118.92 (14)
O6—C3—C2	110.67 (11)	C9—C10—H10	120.5
C2—O4—H4	114.2	C11—C10—H10	120.5
N1—C4—C5	117.27 (13)	C12—C11—C10	118.99 (14)
N1—C4—C9	116.89 (11)	C12—C11—H11	120.5
C5—C4—C9	125.84 (13)	C10—C11—H11	120.5
C6—C5—C4	120.14 (15)	C11—C12—C13	118.18 (15)
C6—C5—H5	119.9	C11—C12—H12	120.9
C4—C5—H5	119.9	C13—C12—H12	120.9
C7—C6—C5	120.36 (13)	N2—C13—C12	124.03 (13)
C7—C6—H6A	119.8	N2—C13—H13	118.0
C5—C6—H6A	119.8	C12—C13—H13	118.0

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O2ⁱⁱ	0.84	1.99	2.8192 (12)	170
N1—H1···O1	0.86	1.99	2.7586 (13)	148
O4—H4···O1	0.94	1.64	2.5795 (11)	176
O4—H4···O2	0.94	2.62	3.2259 (12)	122
O6—H6···O7	0.92	1.63	2.5467 (11)	169
O7—H7B···O2ⁱⁱⁱ	0.93	1.75	2.6802 (12)	174
C8—H8···O3	0.93	2.52	3.3132 (18)	144
C10—H10···O7^iv	0.93	2.43	3.2562 (17)	148
C13—H13···O6^v	0.93	2.59	3.3876 (16)	144

Symmetry codes: (ii) −x+2, −y, −z+1; (iii) x, y, z−1; (iv) x−1, y+1, z+1; (v) x, y, z+1.

References

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

2,2′-Bipyridin-1-ium hemioxalate oxalic acid monohydrate

Structure description

Synthesis and crystallization

Refinement

Structural data

References

organic compounds