Supramolecular aggregation in 4,4′-bipyridin-1,1′-ium dichloride, 4,4′-bipyridin-1,1′-ium dinitrate and 4,4′-bipyridin-1-ium bromide

4,4′-Bipyridin-1,1′-ium dichloride [C₁₀H₁₀Cl₂N₂ (I)] and 4,4′-bipyridin-1,1′-ium dinitrate [C₁₀H₁₀N₄O₆ (II)] have been prepared and the crystal structures determined at 90.0 (2) K. Molecules of (I) are linked by two chlorine-bridged, three-centered N—H...Cl hydrogen bonds into chains along the b axis. The chains are coupled by weak C—H...Cl interactions into a molecular ladder along the c direction. In (II) each nitrate is coordinated to four bipyridinium ions through the interplay of the N—H...O and C—H...O contacts, resulting in a three-dimensional zigzag sheet on the ab plane. The sheets stack along the c axis. In 4,4′-bipyridin-1-ium bromide monohydrate [C₁₀H₉N₂⁺·Br⁻·H₂O (III)] the bipyridinium ions are linked by three-center N—H...N′ hydrogen bonds in a head-to-tail fashion to form chains along the b axis. The chains are linked by C—H...Br and C—H...OH₂ into a three-dimensional framework.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in Siemens SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELX97-2 (Sheldrick, 1997) and local procedures.

Figures

(dichloride)

Crystal data

C10H10Cl2N2	F(000) = 472
Mr = 229.10	Dx = 1.530 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 12.663 (1) Å	Cell parameters from 1163 reflections
b = 12.098 (1) Å	θ = 1.0–27.5°
c = 7.033 (1) Å	µ = 0.61 mm^−1
β = 112.600 (1)°	T = 90 K
V = 994.70 (18) Å^3	Irregular shard, colourless
Z = 4	0.50 × 0.25 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer	1135 independent reflections
Radiation source: fine-focus sealed tube	959 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 18 pixels mm^-1	θmax = 27.4°, θmin = 2.4°
ω scans at fixed χ = 55°	h = −16→16
Absorption correction: multi-scan SCALEPACK (Otwinowski & Minor, 1997)	k = −15→15
Tmin = 0.750, Tmax = 0.925	l = −9→9
2173 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.065	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0239P)^2 + 1.1028P] where P = (Fo^2 + 2Fc^2)/3
1135 reflections	(Δ/σ)max < 0.001
66 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

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.

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl	0.34857 (3)	0.13826 (3)	0.22822 (5)	0.01348 (12)
N1	0.5000	0.35053 (14)	0.2500	0.0129 (4)
H1	0.5000	0.2778	0.2500	0.015*
N2	0.5000	0.92602 (14)	0.2500	0.0124 (4)
H2	0.5000	0.9988	0.2500	0.015*
C1	0.39952 (13)	0.40378 (13)	0.1891 (2)	0.0147 (3)
H1A	0.3301	0.3631	0.1469	0.018*
C2	0.39733 (13)	0.51780 (12)	0.1879 (2)	0.0136 (3)
H2A	0.3264	0.5560	0.1452	0.016*
C3	0.5000	0.57700 (17)	0.2500	0.0112 (4)
C4	0.5000	0.70026 (17)	0.2500	0.0109 (4)
C5	0.58993 (13)	0.75872 (12)	0.2293 (2)	0.0132 (3)
H5	0.6524	0.7205	0.2164	0.016*
C6	0.58712 (13)	0.87245 (12)	0.2277 (2)	0.0140 (3)
H6	0.6471	0.9131	0.2107	0.017*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl	0.01123 (19)	0.01032 (19)	0.0191 (2)	0.00051 (14)	0.00612 (14)	0.00090 (14)
N1	0.0175 (9)	0.0073 (9)	0.0132 (9)	0.000	0.0053 (7)	0.000
N2	0.0177 (9)	0.0058 (9)	0.0136 (9)	0.000	0.0058 (7)	0.000
C1	0.0146 (8)	0.0135 (8)	0.0153 (7)	−0.0028 (6)	0.0051 (6)	−0.0005 (6)
C2	0.0122 (7)	0.0137 (8)	0.0152 (7)	0.0013 (6)	0.0055 (6)	0.0015 (6)
C3	0.0143 (10)	0.0102 (11)	0.0100 (9)	0.000	0.0057 (8)	0.000
C4	0.0121 (10)	0.0101 (10)	0.0097 (9)	0.000	0.0032 (8)	0.000
C5	0.0119 (8)	0.0126 (8)	0.0157 (7)	0.0005 (6)	0.0059 (6)	−0.0007 (6)
C6	0.0146 (8)	0.0132 (8)	0.0152 (7)	−0.0025 (6)	0.0069 (6)	−0.0009 (6)

Geometric parameters (Å, º)

N1—C1	1.3412 (18)	C2—H2A	0.9500
N1—C1^i	1.3412 (18)	C3—C2^i	1.3991 (18)
N1—H1	0.8800	C3—C4	1.491 (3)
N2—C6	1.3397 (17)	C4—C5	1.3949 (18)
N2—C6^i	1.3398 (17)	C4—C5^i	1.3950 (18)
N2—H2	0.8800	C5—C6	1.376 (2)
C1—C2	1.380 (2)	C5—H5	0.9500
C1—H1A	0.9500	C6—H6	0.9500
C2—C3	1.3991 (18)
C1—N1—C1^i	122.58 (19)	C2^i—C3—C2	118.42 (19)
C1—N1—H1	118.7	C2^i—C3—C4	120.79 (10)
C1^i—N1—H1	118.7	C2—C3—C4	120.79 (10)
C6—N2—C6^i	122.14 (18)	C5—C4—C5^i	119.07 (19)
C6—N2—H2	118.9	C5—C4—C3	120.47 (10)
C6^i—N2—H2	118.9	C5^i—C4—C3	120.46 (10)
N1—C1—C2	119.77 (15)	C6—C5—C4	119.22 (15)
N1—C1—H1A	120.1	C6—C5—H5	120.4
C2—C1—H1A	120.1	C4—C5—H5	120.4
C1—C2—C3	119.72 (15)	N2—C6—C5	120.17 (14)
C1—C2—H2A	120.1	N2—C6—H6	119.9
C3—C2—H2A	120.1	C5—C6—H6	119.9
C1^i—N1—C1—C2	−0.06 (10)	C2^i—C3—C4—C5^i	−153.99 (10)
N1—C1—C2—C3	0.1 (2)	C2—C3—C4—C5^i	26.01 (10)
C1—C2—C3—C2^i	−0.06 (10)	C5^i—C4—C5—C6	−0.66 (10)
C1—C2—C3—C4	179.94 (10)	C3—C4—C5—C6	179.34 (10)
C2^i—C3—C4—C5	26.01 (10)	C6^i—N2—C6—C5	−0.68 (10)
C2—C3—C4—C5	−153.99 (10)	C4—C5—C6—N2	1.3 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl	0.88	2.52	3.173	132.17
N1—H1···Cl	0.88	2.52	3.173	132.17
N2—H2···Cl	0.88	2.51	3.173	132.15
N2—H2···Cl	0.88	2.51	3.173	132.15

(dinitrate)

Crystal data

C10H10N4O6	Dx = 1.625 Mg m^−3
Mr = 282.22	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 3415 reflections
a = 27.4380 (16) Å	θ = 1.0–27.5°
b = 23.4310 (12) Å	µ = 0.14 mm^−1
c = 3.5877 (2) Å	T = 90 K
V = 2306.5 (2) Å^3	Block, colourless
Z = 8	0.35 × 0.22 × 0.22 mm
F(000) = 1168

Data collection

Nonius KappaCCD diffractometer	969 independent reflections
Radiation source: fine-focus sealed tube	910 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 18 pixels mm^-1	θmax = 25.0°, θmin = 2.3°
ω scans at fixed χ = 55°	h = −32→32
Absorption correction: SCALEPACK Otwinowski & Minor, 1997)	k = −24→27
Tmin = 0.954, Tmax = 0.971	l = −3→4
2901 measured reflections

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.027	w = 1/[σ^2(Fo^2) + (0.0334P)^2 + 1.7936P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.068	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.17 e Å^−3
969 reflections	Δρmin = −0.17 e Å^−3
92 parameters	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
1 restraint	Extinction coefficient: 0.0021 (4)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier map	Absolute structure parameter: −1.1 (15)

Special details

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.

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.

The absolute structure is NOT determined by the quoted Flack parameter

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.24593 (6)	0.21849 (7)	0.3622 (5)	0.0131 (4)
C2	0.28269 (6)	0.18137 (7)	0.4737 (5)	0.0147 (4)
H2	0.3138	0.1957	0.5426	0.018*
C3	0.27359 (6)	0.12345 (8)	0.4835 (5)	0.0157 (4)
H3	0.2982	0.0977	0.5632	0.019*
N4	0.22977 (5)	0.10379 (6)	0.3797 (5)	0.0169 (4)
H4	0.2244	0.0668	0.3879	0.020*
C5	0.19384 (6)	0.13830 (8)	0.2640 (5)	0.0167 (4)
H5	0.1635	0.1226	0.1879	0.020*
C6	0.20076 (6)	0.19635 (8)	0.2552 (6)	0.0152 (4)
H6	0.1752	0.2210	0.1777	0.018*
N1A	0.16244 (5)	−0.01299 (6)	0.5158 (4)	0.0152 (4)
O1A	0.20540 (4)	−0.00721 (5)	0.3875 (4)	0.0202 (4)
O2A	0.14410 (4)	−0.06162 (5)	0.5236 (4)	0.0206 (3)
O3A	0.13986 (5)	0.02977 (5)	0.6319 (4)	0.0220 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0136 (9)	0.0162 (9)	0.0096 (9)	0.0001 (7)	0.0036 (8)	−0.0005 (7)
C2	0.0131 (9)	0.0179 (9)	0.0131 (10)	0.0002 (7)	−0.0004 (7)	−0.0005 (8)
C3	0.0151 (9)	0.0173 (9)	0.0148 (10)	0.0034 (8)	0.0031 (8)	0.0011 (8)
N4	0.0202 (8)	0.0119 (7)	0.0187 (8)	−0.0007 (6)	0.0029 (7)	0.0004 (6)
C5	0.0145 (9)	0.0201 (10)	0.0155 (11)	−0.0022 (8)	0.0013 (8)	−0.0007 (9)
C6	0.0151 (9)	0.0164 (9)	0.0141 (10)	0.0011 (7)	0.0019 (8)	−0.0004 (8)
N1A	0.0135 (8)	0.0178 (8)	0.0143 (9)	0.0004 (7)	−0.0020 (7)	0.0000 (7)
O1A	0.0128 (6)	0.0182 (7)	0.0295 (8)	−0.0015 (5)	0.0066 (6)	−0.0022 (6)
O2A	0.0186 (6)	0.0153 (6)	0.0279 (8)	−0.0055 (6)	0.0025 (6)	−0.0005 (6)
O3A	0.0194 (6)	0.0176 (7)	0.0289 (9)	0.0062 (6)	0.0037 (6)	−0.0030 (6)

Geometric parameters (Å, º)

C1—C2	1.391 (2)	N4—H4	0.8800
C1—C6	1.397 (2)	C5—C6	1.374 (2)
C1—C1^i	1.493 (3)	C5—H5	0.9500
C2—C3	1.380 (3)	C6—H6	0.9500
C2—H2	0.9500	N1A—O2A	1.2459 (18)
C3—N4	1.340 (2)	N1A—O3A	1.2494 (19)
C3—H3	0.9500	N1A—O1A	1.2727 (19)
N4—C5	1.341 (2)
C2—C1—C6	119.34 (16)	C5—N4—H4	118.7
C2—C1—C1^i	120.67 (17)	N4—C5—C6	120.18 (15)
C6—C1—C1^i	119.99 (18)	N4—C5—H5	119.9
C3—C2—C1	119.42 (15)	C6—C5—H5	119.9
C3—C2—H2	120.3	C5—C6—C1	118.94 (16)
C1—C2—H2	120.3	C5—C6—H6	120.5
N4—C3—C2	119.55 (16)	C1—C6—H6	120.5
N4—C3—H3	120.2	O2A—N1A—O3A	121.71 (15)
C2—C3—H3	120.2	O2A—N1A—O1A	118.64 (14)
C3—N4—C5	122.56 (15)	O3A—N1A—O1A	119.65 (14)
C3—N4—H4	118.7
C6—C1—C2—C3	−1.2 (3)	C3—N4—C5—C6	−1.3 (3)
C1—C2—C3—N4	1.1 (3)	N4—C5—C6—C1	1.1 (3)
C2—C3—N4—C5	0.2 (3)	C2—C1—C6—C5	0.1 (3)

Symmetry code: (i) −x+1/2, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···OlA	0.88	1.81	2.686	173
Yes—N4···H4	N1A	0.88	2.567	3
N4—H4···O3A	0.88	2.63	3.148	119.02