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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o35.
Published online 2007 December 6. doi:  10.1107/S1600536807062617
PMCID: PMC2914995

4,4′-Bis(acetyl­amino)-1,1′-ethyl­enedipyridinium bis­(tetra­fluorido­borate)

Abstract

In the organic cation of the title compound, C16H20N4O2 2+·2BF4 , the pyridinium rings are nearly parallel, with a dihedral angle of 12.54 (12)°. The crystal packing is stabilized by N—H(...)F, C—H(...)F and C—H(...)O hydrogen bonds.

Related literature

For the 1,2-bis­(amino­pyridinium)ethane dication, see: Xu et al. (2007 [triangle]); Fan et al. (2007 [triangle]).

For related literature, see: Allen et al. (1987 [triangle]); Li (2007 [triangle]); Loeb & Wisner (1998 [triangle]).

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Object name is e-64-00o35-scheme1.jpg

Experimental

Crystal data

  • C16H20N4O2 2+·2BF4
  • M r = 473.98
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-00o35-efi1.jpg
  • a = 11.368 (2) Å
  • b = 19.422 (4) Å
  • c = 9.0959 (18) Å
  • β = 101.12 (3)°
  • V = 1970.6 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.16 mm−1
  • T = 113 (2) K
  • 0.32 × 0.20 × 0.18 mm

Data collection

  • Rigaku Saturn diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 [triangle]) T min = 0.952, T max = 0.973
  • 21399 measured reflections
  • 3846 independent reflections
  • 3138 reflections with I > 2σ(I)
  • R int = 0.054

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.144
  • S = 1.15
  • 3846 reflections
  • 299 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.33 e Å−3
  • Δρmin = −0.30 e Å−3

Data collection: CrystalClear (Rigaku/MSC, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Bruker, 1997 [triangle]); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2005 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807062617/bt2653sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062617/bt2653Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

As part of our continuous studies of derivatives of 1,2-bis(pyridinium)ethane dications (Xu et al., 2007; Fan et al., 2007), which can thread through the 24-membered crown ether (Loeb & Wisner, 1998), we herein report the crystal structure of the title compound (Fig. 1).

The organic dication has two pyridinium rings with a dihedral angle of 12.54 (12) Å. The C3—N2 and C12—N4 bond lengths of 1.382 (3) and 1.379 (3) Å, respectively, are between typical C=N (1.34–1.38 Å) and C—N bond lengths (1.47–1.50 Å; Allen et al., 1987), suggesting significant double-bond character. The N1+···N3+ distance is 3.765 (3) Å, similar to those reported for the related analogues (Xu et al., 2007; Fan et al., 2007; Loeb & Wisner, 1998).

The crystal structure is stabilized by a series of inter-molecular N—H···F, C—H···F and C—H···O hydrogen bonds (Table 1).

Experimental

The title compound was prepared using the method of Li (2007). Colourless single crystals were grown by vapor diffusion of (iPr)2O into its acetonitrile solution.

Refinement

The N-bound H atoms were refined freely while the other H atoms were positioned geometrically (C—H = 0.95, 0.98 and 0.99 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I) with the atom-numbering scheme and 50% probability displacement ellipsoids.

Crystal data

C16H20N4O22+·2BF4F000 = 968
Mr = 473.98Dx = 1.598 Mg m3
Monoclinic, P21/cMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4669 reflections
a = 11.368 (2) Åθ = 2.5–25.0º
b = 19.422 (4) ŵ = 0.16 mm1
c = 9.0959 (18) ÅT = 113 (2) K
β = 101.12 (3)ºPrism, colorless
V = 1970.6 (7) Å30.32 × 0.20 × 0.18 mm
Z = 4

Data collection

Rigaku Saturn diffractometer3846 independent reflections
Radiation source: Rotating anode3138 reflections with I > 2σ(I)
Monochromator: confocalRint = 0.054
Detector resolution: 7.31 pixels mm-1θmax = 26.0º
T = 113(2) Kθmin = 1.8º
ω scansh = −14→13
Absorption correction: multi-scan(CrystalClear; Rigaku/MSC, 2005)k = −23→23
Tmin = 0.952, Tmax = 0.973l = −11→11
21399 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.144  w = 1/[σ2(Fo2) + (0.0635P)2 + 1.1885P] where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
3846 reflectionsΔρmax = 0.33 e Å3
299 parametersΔρmin = −0.30 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
N10.32100 (17)0.51691 (10)0.6784 (2)0.0170 (4)
N20.56501 (18)0.63875 (11)0.9608 (2)0.0198 (5)
N30.15074 (17)0.44990 (10)0.3099 (2)0.0185 (4)
N4−0.11675 (18)0.34400 (11)0.0245 (2)0.0193 (5)
O10.72991 (16)0.57022 (9)1.0292 (2)0.0329 (5)
O2−0.23344 (15)0.42922 (9)−0.09946 (19)0.0256 (4)
C10.2934 (2)0.58226 (12)0.7114 (3)0.0189 (5)
H10.21720.60070.66850.023*
C20.3735 (2)0.62158 (12)0.8049 (3)0.0191 (5)
H20.35250.66720.82750.023*
C30.4868 (2)0.59555 (12)0.8686 (2)0.0165 (5)
C40.5144 (2)0.52784 (12)0.8323 (2)0.0182 (5)
H40.59020.50820.87280.022*
C50.4291 (2)0.49065 (12)0.7369 (2)0.0176 (5)
H50.44730.44490.71170.021*
C60.6832 (2)0.62699 (13)1.0264 (3)0.0214 (5)
C70.7466 (2)0.69017 (13)1.0942 (3)0.0261 (6)
H7A0.83070.67911.13500.039*
H7B0.70820.70701.17490.039*
H7C0.74260.72591.01720.039*
C80.2312 (2)0.47529 (12)0.5753 (2)0.0181 (5)
H8A0.14930.48930.58480.022*
H8B0.24150.42590.60190.022*
C90.2478 (2)0.48615 (13)0.4140 (3)0.0215 (5)
H9A0.24530.53600.39040.026*
H9B0.32670.46800.40200.026*
C100.0551 (2)0.48478 (13)0.2363 (3)0.0192 (5)
H100.05090.53310.25120.023*
C11−0.0370 (2)0.45266 (12)0.1399 (3)0.0182 (5)
H11−0.10390.47830.08930.022*
C12−0.0302 (2)0.38156 (12)0.1180 (2)0.0179 (5)
C130.0700 (2)0.34627 (13)0.1969 (3)0.0206 (5)
H130.07670.29800.18430.025*
C140.1577 (2)0.38076 (13)0.2913 (3)0.0217 (5)
H140.22470.35620.34490.026*
C15−0.2133 (2)0.36836 (13)−0.0805 (3)0.0203 (5)
C16−0.2881 (2)0.31331 (14)−0.1681 (3)0.0276 (6)
H16A−0.37160.3287−0.19380.041*
H16B−0.28340.2713−0.10770.041*
H16C−0.25810.3039−0.26020.041*
B10.0229 (2)0.65645 (12)0.4308 (3)0.0138 (5)
B20.5204 (3)0.83160 (14)0.9965 (3)0.0203 (6)
F10.02861 (13)0.59066 (7)0.49479 (16)0.0253 (4)
F2−0.09234 (14)0.68388 (8)0.43197 (18)0.0347 (4)
F30.03702 (16)0.65177 (9)0.28453 (19)0.0407 (5)
F40.10691 (17)0.69772 (9)0.5142 (2)0.0533 (6)
F50.44339 (13)0.88840 (7)0.97263 (16)0.0284 (4)
F60.60218 (15)0.83575 (8)0.90042 (18)0.0344 (4)
F70.45540 (13)0.77098 (7)0.96911 (17)0.0289 (4)
F80.58269 (13)0.83141 (8)1.14353 (17)0.0337 (4)
H4A−0.110 (2)0.3030 (16)0.024 (3)0.025 (8)*
H2A0.541 (2)0.6827 (15)0.963 (3)0.026 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0198 (10)0.0167 (10)0.0145 (9)−0.0025 (8)0.0037 (8)0.0001 (8)
N20.0203 (11)0.0165 (11)0.0206 (10)−0.0009 (9)−0.0008 (8)−0.0030 (8)
N30.0212 (10)0.0190 (10)0.0152 (9)−0.0043 (9)0.0031 (8)−0.0012 (8)
N40.0209 (11)0.0158 (11)0.0191 (10)−0.0011 (9)−0.0017 (8)−0.0017 (8)
O10.0231 (10)0.0234 (10)0.0467 (12)0.0029 (8)−0.0072 (9)−0.0055 (9)
O20.0256 (10)0.0233 (10)0.0242 (9)0.0037 (8)−0.0043 (7)0.0023 (7)
C10.0191 (12)0.0186 (12)0.0191 (11)0.0012 (10)0.0041 (9)0.0013 (9)
C20.0226 (13)0.0157 (12)0.0192 (12)0.0017 (10)0.0050 (10)−0.0010 (9)
C30.0164 (12)0.0194 (12)0.0135 (11)−0.0040 (10)0.0020 (9)−0.0001 (9)
C40.0188 (12)0.0192 (12)0.0160 (11)0.0006 (10)0.0017 (9)0.0019 (9)
C50.0199 (12)0.0159 (11)0.0173 (11)0.0013 (10)0.0043 (9)0.0009 (9)
C60.0217 (13)0.0215 (13)0.0194 (12)−0.0034 (11)0.0000 (10)0.0002 (10)
C70.0209 (13)0.0249 (14)0.0287 (14)−0.0047 (11)−0.0047 (11)−0.0040 (11)
C80.0162 (12)0.0192 (12)0.0168 (11)−0.0049 (10)−0.0015 (9)−0.0003 (9)
C90.0226 (13)0.0237 (13)0.0171 (12)−0.0070 (10)0.0010 (10)−0.0028 (10)
C100.0231 (13)0.0192 (12)0.0159 (11)0.0005 (10)0.0051 (10)0.0012 (9)
C110.0193 (12)0.0187 (12)0.0166 (11)−0.0007 (10)0.0033 (9)0.0005 (9)
C120.0181 (12)0.0209 (12)0.0152 (11)−0.0029 (10)0.0043 (9)−0.0006 (9)
C130.0202 (13)0.0193 (12)0.0212 (12)0.0020 (10)0.0014 (10)−0.0024 (9)
C140.0209 (13)0.0225 (13)0.0206 (12)0.0030 (10)0.0014 (10)−0.0006 (10)
C150.0189 (12)0.0254 (14)0.0166 (11)−0.0012 (10)0.0033 (10)0.0008 (10)
C160.0266 (14)0.0269 (14)0.0249 (13)−0.0052 (11)−0.0062 (11)0.0008 (11)
B10.0190 (13)0.0070 (12)0.0138 (12)0.0019 (10)−0.0013 (10)0.0015 (9)
B20.0228 (14)0.0180 (14)0.0208 (13)−0.0001 (11)0.0058 (11)0.0009 (11)
F10.0282 (8)0.0186 (7)0.0283 (8)0.0002 (6)0.0031 (6)0.0028 (6)
F20.0340 (9)0.0373 (9)0.0337 (9)0.0130 (7)0.0087 (7)0.0055 (7)
F30.0468 (10)0.0440 (10)0.0365 (9)0.0125 (8)0.0209 (8)0.0144 (8)
F40.0494 (11)0.0233 (9)0.0726 (14)−0.0099 (8)−0.0250 (10)0.0009 (8)
F50.0339 (9)0.0204 (8)0.0316 (8)0.0070 (6)0.0081 (7)−0.0004 (6)
F60.0409 (10)0.0280 (9)0.0403 (9)0.0029 (7)0.0231 (8)0.0036 (7)
F70.0277 (8)0.0187 (8)0.0374 (9)−0.0036 (6)−0.0004 (7)0.0015 (6)
F80.0268 (8)0.0462 (10)0.0257 (8)0.0029 (7)−0.0010 (6)−0.0096 (7)

Geometric parameters (Å, °)

N1—C51.342 (3)C8—C91.529 (3)
N1—C11.355 (3)C8—H8A0.9900
N1—C81.485 (3)C8—H8B0.9900
N2—C61.380 (3)C9—H9A0.9900
N2—C31.382 (3)C9—H9B0.9900
N2—H2A0.90 (3)C10—C111.378 (3)
N3—C101.345 (3)C10—H100.9500
N3—C141.358 (3)C11—C121.400 (3)
N3—C91.485 (3)C11—H110.9500
N4—C121.379 (3)C12—C131.403 (3)
N4—C151.391 (3)C13—C141.360 (3)
N4—H4A0.80 (3)C13—H130.9500
O1—C61.222 (3)C14—H140.9500
O2—C151.210 (3)C15—C161.496 (3)
C1—C21.355 (3)C16—H16A0.9800
C1—H10.9500C16—H16B0.9800
C2—C31.401 (3)C16—H16C0.9800
C2—H20.9500B1—F41.361 (3)
C3—C41.406 (3)B1—F31.373 (3)
C4—C51.375 (3)B1—F11.401 (3)
C4—H40.9500B1—F21.416 (3)
C5—H50.9500B2—F71.387 (3)
C6—C71.495 (3)B2—F81.387 (3)
C7—H7A0.9800B2—F61.396 (3)
C7—H7B0.9800B2—F51.399 (3)
C7—H7C0.9800
C5—N1—C1120.1 (2)N3—C9—C8109.43 (19)
C5—N1—C8120.6 (2)N3—C9—H9A109.8
C1—N1—C8119.3 (2)C8—C9—H9A109.8
C6—N2—C3128.4 (2)N3—C9—H9B109.8
C6—N2—H2A114.9 (18)C8—C9—H9B109.8
C3—N2—H2A115.4 (18)H9A—C9—H9B108.2
C10—N3—C14119.8 (2)N3—C10—C11122.1 (2)
C10—N3—C9120.6 (2)N3—C10—H10119.0
C14—N3—C9119.6 (2)C11—C10—H10119.0
C12—N4—C15128.2 (2)C10—C11—C12118.7 (2)
C12—N4—H4A118 (2)C10—C11—H11120.6
C15—N4—H4A114 (2)C12—C11—H11120.6
N1—C1—C2120.7 (2)N4—C12—C11123.9 (2)
N1—C1—H1119.6N4—C12—C13118.0 (2)
C2—C1—H1119.6C11—C12—C13118.1 (2)
C1—C2—C3120.6 (2)C14—C13—C12120.4 (2)
C1—C2—H2119.7C14—C13—H13119.8
C3—C2—H2119.7C12—C13—H13119.8
N2—C3—C2117.7 (2)N3—C14—C13120.8 (2)
N2—C3—C4124.3 (2)N3—C14—H14119.6
C2—C3—C4118.0 (2)C13—C14—H14119.6
C5—C4—C3118.5 (2)O2—C15—N4122.2 (2)
C5—C4—H4120.7O2—C15—C16123.3 (2)
C3—C4—H4120.7N4—C15—C16114.5 (2)
N1—C5—C4122.1 (2)C15—C16—H16A109.5
N1—C5—H5119.0C15—C16—H16B109.5
C4—C5—H5119.0H16A—C16—H16B109.5
O1—C6—N2122.8 (2)C15—C16—H16C109.5
O1—C6—C7124.0 (2)H16A—C16—H16C109.5
N2—C6—C7113.2 (2)H16B—C16—H16C109.5
C6—C7—H7A109.5F4—B1—F3112.2 (2)
C6—C7—H7B109.5F4—B1—F1109.50 (19)
H7A—C7—H7B109.5F3—B1—F1109.73 (19)
C6—C7—H7C109.5F4—B1—F2109.0 (2)
H7A—C7—H7C109.5F3—B1—F2108.29 (19)
H7B—C7—H7C109.5F1—B1—F2108.0 (2)
N1—C8—C9109.54 (19)F7—B2—F8109.0 (2)
N1—C8—H8A109.8F7—B2—F6109.4 (2)
C9—C8—H8A109.8F8—B2—F6109.0 (2)
N1—C8—H8B109.8F7—B2—F5110.2 (2)
C9—C8—H8B109.8F8—B2—F5109.9 (2)
H8A—C8—H8B108.2F6—B2—F5109.2 (2)
C5—N1—C1—C2−0.9 (3)C14—N3—C9—C8−78.7 (3)
C8—N1—C1—C2−179.9 (2)N1—C8—C9—N3−174.58 (18)
N1—C1—C2—C30.5 (4)C14—N3—C10—C11−0.7 (3)
C6—N2—C3—C2−174.5 (2)C9—N3—C10—C11−179.4 (2)
C6—N2—C3—C44.2 (4)N3—C10—C11—C12−0.2 (3)
C1—C2—C3—N2178.8 (2)C15—N4—C12—C1111.1 (4)
C1—C2—C3—C40.0 (3)C15—N4—C12—C13−169.5 (2)
N2—C3—C4—C5−178.8 (2)C10—C11—C12—N4−179.9 (2)
C2—C3—C4—C5−0.1 (3)C10—C11—C12—C130.6 (3)
C1—N1—C5—C40.7 (3)N4—C12—C13—C14−179.6 (2)
C8—N1—C5—C4179.8 (2)C11—C12—C13—C14−0.2 (4)
C3—C4—C5—N1−0.2 (3)C10—N3—C14—C131.2 (3)
C3—N2—C6—O1−11.9 (4)C9—N3—C14—C13179.9 (2)
C3—N2—C6—C7168.7 (2)C12—C13—C14—N3−0.7 (4)
C5—N1—C8—C9−89.3 (3)C12—N4—C15—O2−1.4 (4)
C1—N1—C8—C989.7 (3)C12—N4—C15—C16177.8 (2)
C10—N3—C9—C8100.0 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2A···F70.90 (3)1.98 (3)2.862 (3)168 (3)
N4—H4A···F4i0.80 (3)2.08 (3)2.868 (3)170 (3)
C1—H1···F10.952.413.269 (3)150
C1—H1···F40.952.533.358 (3)145
C4—H4···O2ii0.952.503.404 (3)159
C5—H5···F6iii0.952.373.251 (3)153
C10—H10···F30.952.333.285 (3)179
C11—H11···O1iv0.952.583.496 (3)162
C13—H13···F2i0.952.483.391 (3)162
C14—H14···F8iii0.952.223.050 (3)145

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x+1, y, z+1; (iii) −x+1, y−1/2, −z+3/2; (iv) x−1, y, z−1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2653).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (1997). SHELXTL Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fan, X.-P., Li, J.-S., Zhang, Y.-Y. & Zhou, X.-L. (2007). Acta Cryst. E63, o1717–o1718.
  • Li, J. S. (2007). PhD dissertation. Tianjin University, People’s Republic of China.
  • Loeb, S. J. & Wisner, J. A. (1998). Angew. Chem. Int. Ed.37, 2838–2840.
  • Rigaku/MSC (2005). CrystalClear and CrystalStructure Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Xu, Y.-J., Li, J.-S., Qin, L. & Wang, W. (2007). Acta Cryst. E63, o1825–o1826.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography