1,1′-Methyl­enebis(4,4′-bipyridin-1-ium) dibromide

Schuster, S.A.; Nesterov, V.V.; Smucker, B.W.

doi:10.1107/S2414314622005260

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 7| Part 5| May 2022| x220526

https://doi.org/10.1107/S2414314622005260

Open

access

1,1′-Methylenebis(4,4′-bipyridin-1-ium) dibromide

Sara A. Schuster,^a Volodymyr V. Nesterov ^b and Bradley W. Smucker ^a ^*

^aAustin College, 900 N Grand, Sherman, TX 75090, USA, and ^bDepartment of Chemistry, University of North Texas, 1508 W. Mulberry, Denton, TX, 76201, USA
^*Correspondence e-mail: bsmucker@austincollege.edu

Edited by I. Brito, University of Antofagasta, Chile (Received 27 January 2022; accepted 17 May 2022; online 20 May 2022)

The asymmetric unit of the title salt, C₂₁H₁₈N₄²⁺·2Br⁻, comprises half of the molecule and a bromide ion. The chevron-shaped cations stack as columns in the [001] direction with suitable intermolecular distance for π–π interactions. These cationic columns are further stabilized by intercolumnar C—H⋯N hydrogen bonding with the bromide ions distributed between them.

Keywords: crystal structure; pyridinium; hydrogen bonding; π–π interactions.

CCDC reference: 2173318

Structure description

The N1—C1—N1(1 − x, 1 − y, z) bond angle of the chevron-shaped 1,1′-methylenebis-4,4′-bipyridinium cation in the title compound (Fig. 1) is 111.1 (4)°, which is slightly smaller than the angle of 112.3 (4)° in the corresponding PF₆⁻ salt (Blanco et al., 2007 ). The packing resulting from the smaller bromide results in the cations of the title compound stacking to form columns (Fig. 2) in the [001] direction with the bromide ions distributed between them (Fig. 3). The closest intermolecular C⋯C distance between these stacked cations is 3.493 (5) Å between C5 and C8(x, y, 1 + z), which is indicative of through space electrostatic interactions (Martinez & Iverson, 2012 ). The structure of the aforementioned PF₆⁻ salt does not form these stacked columns. Even with bromide ions, the structure of the slightly larger 1,1′-methylenebis{4-[(E)-2-(pyridin-4-yl)vinyl]pyridinium} dibromide dihydrate packs in back-to-back zigzag ribbons (Neal et al., 2022 ) instead of the columns seen in this structure. For the title compound, in the extended structure, the columns of the cation are positioned such that the H3 and H11 atoms of the bipyridinium moiety are 2.620 and 2.546 Å, respectively, from the N2(− $[{1\over 4}]$ + x, $[{5\over 4}]$ − y, $[{3\over 4}]$ + z) atom of a pyridyl group in an adjacent column (Fig. 4). The shorter N⋯H distance for H11 results from the rotation of the pyridyl ring relative to the pyridinium ring by 21.00 (14)° [dihedral angle between the planes of the pyridinium (N1/C2–C6) and pyridyl (N2/C7–C11) rings].

Figure 1
Ellipsoid (50%) representation of the title complex with the cation expanded by symmetry.

Figure 2
Ellipsoid (50%) representation of the columnar stacking of the cations with distance between C5 and C8(x, y, z + 1) shown. Bromide ions are omitted for clarity.

Figure 3
View down the crystallographic c axis showing the distribution of bromide ions (brown) between the columns of cations. Cell axes shown with ellipsoid (50%) representation.

Figure 4
Ellipsoid (50%) representation of the inter-columnar N⋯H distances between H3 and H11 atoms of the bipyridinium and the N2(− $[{1\over 4}]$ + x, $[{5\over 4}]$ − y, $[{3\over 4}]$ + z) atom on the terminal pyridyl ring. Bromide ions are omitted for clarity.

Synthesis and crystallization

The title compound was synthesized following published procedures (Blanco et al., 2007). Colorless block-shaped crystals were grown from the vapor diffusion of THF into a DMF solution of the compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₂₁H₁₈N₄²⁺·2Br⁻
M_r	486.21
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	220
a, b, c (Å)	18.0776 (2), 48.2301 (5), 4.5424 (2)
V (Å³)	3960.45 (18)
Z	8
Radiation type	Cu Kα
μ (mm⁻¹)	5.29
Crystal size (mm)	0.04 × 0.02 × 0.01

Data collection
Diffractometer	XtaLAB Synergy, Dualflex, HyPix
Absorption correction	Multi-scan CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD, (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.775, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	21913, 2127, 2118
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.053, 1.16
No. of reflections	2127
No. of parameters	123
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.26
Absolute structure	Flack x determined using 895 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.015 (7)
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD, (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ), and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2173318

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314622005260/bx4020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314622005260/bx4020Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314622005260/bx4020Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S2414314622005260/bx4020Isup4.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009) Mercury (Macrae et al., 2020); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

1,1'-Methylenebis(4,4'-bipyridin-1-ium) dibromide top

Crystal data top

C₂₁H₁₈N₄²⁺·2Br⁻	D_x = 1.631 Mg m⁻³
M_r = 486.21	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Fdd2	Cell parameters from 18629 reflections
a = 18.0776 (2) Å	θ = 3.7–78.7°
b = 48.2301 (5) Å	µ = 5.29 mm⁻¹
c = 4.5424 (2) Å	T = 220 K
V = 3960.45 (18) Å³	Block, clear light colourless
Z = 8	0.04 × 0.02 × 0.01 mm
F(000) = 1936

Data collection top

XtaLAB Synergy, Dualflex, HyPix diffractometer	2127 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2118 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.028
Detector resolution: 10.0000 pixels mm^-1	θ_max = 79.9°, θ_min = 3.7°
ω scans	h = −22→22
Absorption correction: multi-scan CrysAlisPro (Rigaku OD, 2021)	k = −60→59
T_min = 0.775, T_max = 1.000	l = −5→5
21913 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.022	w = 1/[σ²(F_o²) + (0.0076P)² + 10.8403P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.053	(Δ/σ)_max = 0.002
S = 1.16	Δρ_max = 0.26 e Å⁻³
2127 reflections	Δρ_min = −0.25 e Å⁻³
123 parameters	Absolute structure: Flack x determined using 895 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: −0.015 (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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Br1	0.65219 (2)	0.46137 (2)	0.25829 (7)	0.04764 (12)
N1	0.53731 (13)	0.52084 (5)	0.8226 (6)	0.0304 (6)
N2	0.71760 (17)	0.62446 (6)	−0.0002 (10)	0.0532 (8)
C1	0.500000	0.500000	1.0054 (12)	0.0327 (8)
H1A	0.463945	0.509067	1.130882	0.039*	0.5
H1B	0.536051	0.490934	1.130908	0.039*	0.5
C2	0.49878 (16)	0.54322 (6)	0.7299 (10)	0.0360 (7)
H2	0.449003	0.545007	0.778057	0.043*
C3	0.53289 (17)	0.56327 (6)	0.5653 (8)	0.0370 (8)
H3	0.506094	0.578632	0.502375	0.044*
C4	0.60776 (15)	0.56086 (5)	0.4907 (10)	0.0318 (6)
C5	0.64502 (17)	0.53725 (7)	0.5872 (8)	0.0383 (8)
H5	0.694617	0.534836	0.539168	0.046*
C6	0.60952 (15)	0.51762 (6)	0.7513 (10)	0.0365 (6)
H6	0.635047	0.501967	0.814337	0.044*
C7	0.64574 (17)	0.58273 (6)	0.3206 (8)	0.0353 (8)
C8	0.71058 (19)	0.57758 (7)	0.1703 (9)	0.0425 (8)
H8	0.731788	0.560015	0.174291	0.051*
C9	0.7435 (2)	0.59865 (7)	0.0146 (12)	0.0515 (9)
H9	0.786861	0.594616	−0.087262	0.062*
C10	0.6558 (2)	0.62938 (8)	0.1498 (11)	0.0561 (12)
H10	0.637202	0.647358	0.148926	0.067*
C11	0.6175 (2)	0.60960 (7)	0.3062 (11)	0.0492 (10)
H11	0.573509	0.614083	0.400858	0.059*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03445 (16)	0.0558 (2)	0.0527 (2)	0.01006 (15)	−0.00518 (18)	0.0093 (2)
N1	0.0247 (11)	0.0267 (11)	0.0400 (16)	−0.0010 (9)	−0.0013 (10)	−0.0019 (10)
N2	0.0482 (16)	0.0388 (14)	0.073 (2)	−0.0034 (12)	0.015 (2)	0.0040 (19)
C1	0.0306 (18)	0.0320 (18)	0.035 (2)	−0.0004 (15)	0.000	0.000
C2	0.0255 (13)	0.0324 (14)	0.0500 (19)	0.0050 (11)	0.0050 (16)	0.0038 (15)
C3	0.0287 (15)	0.0304 (14)	0.052 (2)	0.0047 (11)	0.0043 (14)	0.0056 (14)
C4	0.0273 (13)	0.0283 (12)	0.0396 (16)	−0.0010 (10)	0.0011 (15)	−0.0045 (16)
C5	0.0233 (14)	0.0355 (16)	0.056 (2)	0.0030 (11)	0.0061 (13)	0.0021 (14)
C6	0.0245 (12)	0.0331 (14)	0.0520 (18)	0.0053 (10)	0.0012 (16)	0.0047 (16)
C7	0.0315 (15)	0.0295 (13)	0.045 (2)	−0.0018 (11)	0.0014 (13)	−0.0021 (13)
C8	0.0353 (17)	0.0331 (16)	0.059 (2)	0.0028 (13)	0.0115 (15)	−0.0021 (14)
C9	0.0421 (18)	0.0399 (16)	0.073 (3)	−0.0003 (13)	0.021 (2)	−0.001 (2)
C10	0.050 (2)	0.0330 (17)	0.085 (3)	0.0041 (15)	0.022 (2)	0.0093 (18)
C11	0.0384 (17)	0.0357 (16)	0.073 (3)	0.0041 (13)	0.0183 (19)	0.0022 (18)

Geometric parameters (Å, º) top

N1—C1	1.468 (4)	C4—C7	1.477 (4)
N1—C2	1.352 (4)	C5—H5	0.9300
N1—C6	1.354 (4)	C5—C6	1.365 (5)
N2—C9	1.332 (4)	C6—H6	0.9300
N2—C10	1.330 (5)	C7—C8	1.379 (4)
C1—H1A	0.9700	C7—C11	1.394 (4)
C1—H1B	0.9700	C8—H8	0.9300
C2—H2	0.9300	C8—C9	1.374 (5)
C2—C3	1.369 (5)	C9—H9	0.9300
C3—H3	0.9300	C10—H10	0.9300
C3—C4	1.400 (4)	C10—C11	1.376 (5)
C4—C5	1.394 (4)	C11—H11	0.9300

C2—N1—C1	119.1 (2)	C6—C5—C4	120.7 (3)
C2—N1—C6	120.9 (3)	C6—C5—H5	119.6
C6—N1—C1	120.0 (2)	N1—C6—C5	120.3 (3)
C10—N2—C9	115.9 (3)	N1—C6—H6	119.9
N1—C1—N1ⁱ	111.1 (4)	C5—C6—H6	119.9
N1—C1—H1A	109.4	C8—C7—C4	121.7 (3)
N1ⁱ—C1—H1A	109.4	C8—C7—C11	117.1 (3)
N1—C1—H1B	109.4	C11—C7—C4	121.2 (3)
N1ⁱ—C1—H1B	109.4	C7—C8—H8	120.3
H1A—C1—H1B	108.0	C9—C8—C7	119.4 (3)
N1—C2—H2	119.9	C9—C8—H8	120.3
N1—C2—C3	120.1 (3)	N2—C9—C8	124.4 (3)
C3—C2—H2	119.9	N2—C9—H9	117.8
C2—C3—H3	119.7	C8—C9—H9	117.8
C2—C3—C4	120.6 (3)	N2—C10—H10	117.9
C4—C3—H3	119.7	N2—C10—C11	124.3 (3)
C3—C4—C7	121.1 (3)	C11—C10—H10	117.9
C5—C4—C3	117.3 (3)	C7—C11—H11	120.5
C5—C4—C7	121.6 (3)	C10—C11—C7	119.0 (3)
C4—C5—H5	119.6	C10—C11—H11	120.5

N1—C2—C3—C4	0.1 (6)	C4—C7—C8—C9	179.8 (4)
N2—C10—C11—C7	2.5 (8)	C4—C7—C11—C10	178.7 (4)
C1—N1—C2—C3	178.4 (4)	C5—C4—C7—C8	20.9 (6)
C1—N1—C6—C5	−178.5 (4)	C5—C4—C7—C11	−158.9 (4)
C2—N1—C1—N1ⁱ	87.1 (3)	C6—N1—C1—N1ⁱ	−93.5 (3)
C2—N1—C6—C5	1.0 (6)	C6—N1—C2—C3	−1.0 (6)
C2—C3—C4—C5	0.9 (6)	C7—C4—C5—C6	178.1 (4)
C2—C3—C4—C7	−178.2 (4)	C7—C8—C9—N2	0.9 (7)
C3—C4—C5—C6	−0.9 (6)	C8—C7—C11—C10	−1.1 (6)
C3—C4—C7—C8	−160.1 (4)	C9—N2—C10—C11	−2.1 (8)
C3—C4—C7—C11	20.1 (6)	C10—N2—C9—C8	0.3 (7)
C4—C5—C6—N1	0.1 (6)	C11—C7—C8—C9	−0.4 (6)

Symmetry code: (i) −x+1, −y+1, z.

Funding information

Funding for this research was provided by: National Science Foundation (grant No. 1726652 to UNT; grant No. 1712066 to Austin College); Welch Foundation (grant No. AD-0007 to Austin College).

References

Blanco, V., Chas, M., Abella, D., Peinador, C. & Quintela, J. M. (2007). J. Am. Chem. Soc. 129, 13978–13986. CrossRef PubMed CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Martinez, C. R. & Iverson, B. L. (2012). Chem. Sci. 3, 2191–2201. Web of Science CrossRef CAS Google Scholar
Neal, H. C., Nesterov, V. V. & Smucker, B. W. (2022). IUCrData, 7, x220525. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku OD, (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.