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In the title compound, C13H16N22+·2NO3, the cation is the diprotonated form of 4,4′-tri­methyl­enedi­pyridine. There are intermolecular hydrogen bonds and π–π interactions between the pyridinium moieties of the cation and nitrate anions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009589/ob6242sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009589/ob6242Isup2.hkl
Contains datablock I

CCDC reference: 214822

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.044
  • wR factor = 0.048
  • Data-to-parameter ratio = 8.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.5947 Proportion of unique data used 0.6222 Ratio reflections to parameters 8.2201
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

4,4'-Trimethylenedipyridine (bpp) is one of the most commonly employed bridging ligands in metal-organic coordination chemistry (Belcher et al., 2002; Tong et al., 2002). A salt of the monoprotonated form of bpp has been prepared and characterized (Wheatley et al., 1999), but no structure of the diprotonated form (bppH22+) has been reported. We report here the crystal structure of the nitrate salt of bppH22+, (I), which was obtained as a by-product in the course of attempts to prepare a coordination polymer by reaction of bpp and Cr(NO3)3·9H2O.

The structure determination of (I) reveals the presence of one bppH22+ and two NO3 ions. The bppH22+ ion adopts approximately an anti–anti' conformation in the trimethylene group (Fig. 1). This conformation is thermodynamically most favourable, since it minimizes intramolecular steric hindrance. The planes of the pyridine rings of the bppH22+ ion are nearly orthogonal to the plane containing the trimethylene C atoms. The dihedral angles between the planes of the trimethylene group and those of the two pyridine rings are 89.8 (3) and 83.5 (3)°. This orthogonality increases the effficiency of stacking of bppH22+ ions. ππ interaction between the nitrate ions and the pyridine rings were observed. Both the NO3 ions sit below and nearly parallel to the pyridine rings of the bppH22+ ion. Nitrate atom N3 is under the N-pyridine ring, with a dihedral angle of 5.2 (3)°. Similarly, nitrate atom N4 is under the N2-pyridine ring, making a dihedral angle of 2.2 (3)°. There are intermolecular hydrogen bonds between the pyridinium moieties of the bppH22+ ion and NO3ions (Table 1 and Fig. 2).

Experimental top

In an attempt to prepare a coordination polymer, Cr(NO3)3·9H2O (0.429 g, 1.072 mmol) and bpp (0.071 g, 0.358 mmol) were dissolved in methanol (5 ml). By slow evaporation of the solution at room temperature, crystals of the title compound, (I), of considerable size (ca 0.5 mm) formed after six weeks.

Refinement top

All H atoms were placed at geometrically calculated positions and refined as riding, with C—H = 0.95 Å and N—H = 0.87 Å, and with Uiso(H) = 1.2Ueq(carrier atom).

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1992); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.

Figures top
[Figure 1] Fig. 1. An ORTEPII (Johnson, 1976) drawing of the title compound, (I), with 50% probability ellipsoids, showing the crystallographic labeling scheme.
[Figure 2] Fig. 2. The packing diagram of (I), showing ππ interactions and the hydrogen-bonding interactions (as dashed lines) between the nitrate ions and the pyridine rings.
(I) top
Crystal data top
C13H16N22+·2NO3F(000) = 680.00
Mr = 324.29Dx = 1.420 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 7.894 (6) Åθ = 13.5–16.6°
b = 21.037 (4) ŵ = 0.11 mm1
c = 9.879 (6) ÅT = 298 K
β = 112.39 (4)°Block, yellow
V = 1516.9 (16) Å30.28 × 0.19 × 0.15 mm
Z = 4
Data collection top
AFC-7R
diffractometer
Rint = 0.019
Radiation source: X-ray tubeθmax = 25.0°, θmin = 2.2°
Graphite monochromatorh = 09
ω/2–θ scansk = 025
2966 measured reflectionsl = 1110
2761 independent reflections3 standard reflections every 250 reflections
1718 reflections with I > 1.5σ(I) intensity decay: 3.0%
Refinement top
Refinement on FH-atom parameters not refined
Least-squares matrix: fullWeighting scheme based on measured s.u.'s w = 1/[(σ)2(Fo) + 0.00025(Fo)2]
R[F2 > 2σ(F2)] = 0.044(Δ/σ)max = 0.001
wR(F2) = 0.048Δρmax = 0.17 e Å3
S = 1.46Δρmin = 0.17 e Å3
1718 reflectionsExtinction correction: Zachariasen_type_2_Gaussian_isotropic (Zachariasen, 1967)
209 parametersExtinction coefficient: 16.860 (4)
0 restraints
Crystal data top
C13H16N22+·2NO3V = 1516.9 (16) Å3
Mr = 324.29Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.894 (6) ŵ = 0.11 mm1
b = 21.037 (4) ÅT = 298 K
c = 9.879 (6) Å0.28 × 0.19 × 0.15 mm
β = 112.39 (4)°
Data collection top
AFC-7R
diffractometer
Rint = 0.019
2966 measured reflections3 standard reflections every 250 reflections
2761 independent reflections intensity decay: 3.0%
1718 reflections with I > 1.5σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.048H-atom parameters not refined
S = 1.46Δρmax = 0.17 e Å3
1718 reflectionsΔρmin = 0.17 e Å3
209 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.0584 (3)0.2367 (1)0.2522 (2)0.0820 (8)
O20.1876 (3)0.32731 (10)0.3132 (2)0.0650 (7)
O30.0203 (4)0.3139 (1)0.0994 (2)0.0972 (9)
O40.3617 (3)0.44510 (9)0.6683 (2)0.0624 (6)
O50.3474 (3)0.42756 (9)0.8784 (2)0.0640 (6)
O60.2798 (3)0.51917 (9)0.7807 (2)0.0713 (7)
N10.3728 (3)0.2384 (1)0.0646 (2)0.0482 (7)
N20.7550 (3)0.5016 (1)0.9219 (2)0.0488 (7)
N30.0738 (3)0.2920 (1)0.2194 (2)0.0535 (7)
N40.3295 (3)0.4642 (1)0.7737 (2)0.0427 (6)
C10.4697 (4)0.2083 (1)0.1885 (3)0.0515 (9)
C20.6089 (4)0.2395 (1)0.2959 (3)0.0465 (8)
C30.6504 (3)0.3020 (1)0.2756 (3)0.0386 (7)
C40.5421 (4)0.3313 (1)0.1455 (3)0.0438 (7)
C50.4043 (4)0.2989 (1)0.0415 (3)0.0470 (8)
C60.8050 (3)0.3370 (1)0.3886 (3)0.0460 (8)
C70.7436 (3)0.3743 (1)0.4947 (3)0.0459 (8)
C80.9007 (4)0.4145 (1)0.5961 (3)0.0471 (8)
C90.8523 (3)0.4465 (1)0.7120 (2)0.0401 (7)
C100.8631 (4)0.4130 (1)0.8365 (3)0.0473 (8)
C110.8126 (4)0.4417 (1)0.9397 (3)0.0487 (8)
C120.7459 (4)0.5359 (1)0.8056 (3)0.0523 (8)
C130.7927 (4)0.5088 (1)0.6991 (3)0.0495 (8)
H10.44250.16540.20230.0618
H1n0.28600.21790.00350.0578
H20.67730.21820.38490.0557
H2n0.72230.51910.98810.0586
H40.56430.37440.12890.0526
H50.33090.31930.04730.0564
H6a0.89580.30720.44280.0552
H6b0.85580.36590.34040.0552
H7a0.64420.40120.44070.0551
H7b0.70550.34530.55140.0551
H8a1.00410.38800.64180.0565
H8b0.93000.44610.53980.0565
H100.90530.37030.84970.0568
H110.81870.41871.02430.0585
H120.70700.57890.79700.0627
H130.78430.53300.61550.0594
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.098 (2)0.056 (1)0.073 (2)0.006 (1)0.011 (1)0.009 (1)
O20.064 (1)0.060 (1)0.059 (1)0.004 (1)0.011 (1)0.009 (1)
O30.119 (2)0.100 (2)0.045 (1)0.025 (2)0.000 (1)0.021 (1)
O40.079 (1)0.068 (1)0.047 (1)0.005 (1)0.032 (1)0.0054 (10)
O50.091 (2)0.055 (1)0.046 (1)0.007 (1)0.028 (1)0.0161 (10)
O60.109 (2)0.039 (1)0.076 (1)0.013 (1)0.047 (1)0.0026 (10)
N10.049 (1)0.049 (1)0.043 (1)0.009 (1)0.013 (1)0.011 (1)
N20.051 (1)0.056 (2)0.041 (1)0.005 (1)0.019 (1)0.010 (1)
N30.058 (2)0.059 (2)0.044 (1)0.013 (1)0.019 (1)0.007 (1)
N40.043 (1)0.043 (1)0.038 (1)0.004 (1)0.0120 (10)0.000 (1)
C10.064 (2)0.038 (1)0.055 (2)0.003 (1)0.025 (2)0.000 (1)
C20.057 (2)0.043 (2)0.040 (1)0.003 (1)0.018 (1)0.006 (1)
C30.042 (1)0.042 (1)0.035 (1)0.002 (1)0.018 (1)0.007 (1)
C40.054 (2)0.037 (1)0.040 (1)0.002 (1)0.017 (1)0.000 (1)
C50.055 (2)0.048 (2)0.036 (1)0.001 (1)0.014 (1)0.000 (1)
C60.045 (2)0.053 (2)0.040 (1)0.000 (1)0.015 (1)0.008 (1)
C70.043 (2)0.057 (2)0.037 (1)0.006 (1)0.015 (1)0.010 (1)
C80.050 (2)0.052 (2)0.041 (1)0.008 (1)0.019 (1)0.009 (1)
C90.038 (1)0.045 (1)0.034 (1)0.008 (1)0.010 (1)0.007 (1)
C100.054 (2)0.043 (1)0.043 (1)0.002 (1)0.016 (1)0.002 (1)
C110.054 (2)0.053 (2)0.036 (1)0.009 (1)0.014 (1)0.003 (1)
C120.061 (2)0.044 (2)0.052 (2)0.002 (1)0.022 (1)0.000 (1)
C130.060 (2)0.051 (2)0.039 (1)0.000 (1)0.020 (1)0.004 (1)
Geometric parameters (Å, º) top
O1—N31.226 (3)C4—H40.950
O2—N31.258 (3)C5—H50.950
O3—N31.223 (3)C6—C71.527 (3)
O4—N41.229 (2)C6—H6a0.950
O5—N41.254 (2)C6—H6b0.950
O6—N41.232 (3)C7—C81.520 (3)
N1—C11.330 (3)C7—H7a0.950
N1—C51.333 (3)C7—H7b0.950
N1—H1n0.870C8—C91.498 (3)
N2—C111.329 (3)C8—H8a0.950
N2—C121.334 (3)C8—H8b0.950
N2—H2n0.870C9—C101.392 (3)
C1—C21.370 (4)C9—C131.382 (3)
C1—H10.950C10—C111.369 (3)
C2—C31.388 (3)C10—H100.950
C2—H20.950C11—H110.950
C3—C41.388 (3)C12—C131.365 (4)
C3—C61.497 (3)C12—H120.950
C4—C51.361 (4)C13—H130.950
C1—N1—C5122.2 (2)C7—C6—H6a108.7
C1—N1—H1n118.9C7—C6—H6b108.7
C5—N1—H1n118.9H6a—C6—H6b109.5
C11—N2—C12122.0 (2)C6—C7—C8110.2 (2)
C11—N2—H2n119.0C6—C7—H7a109.3
C12—N2—H2n119.0C6—C7—H7b109.3
O1—N3—O2118.7 (2)C8—C7—H7a109.3
O1—N3—O3121.8 (3)C8—C7—H7b109.3
O2—N3—O3119.5 (3)H7a—C7—H7b109.5
O4—N4—O5120.2 (2)C7—C8—C9111.9 (2)
O4—N4—O6121.8 (2)C7—C8—H8a108.9
O5—N4—O6118.0 (2)C7—C8—H8b108.9
N1—C1—C2119.7 (2)C9—C8—H8a108.9
N1—C1—H1120.1C9—C8—H8b108.9
C2—C1—H1120.1H8a—C8—H8b109.5
C1—C2—C3120.4 (2)C8—C9—C10120.0 (2)
C1—C2—H2119.8C8—C9—C13122.2 (2)
C3—C2—H2119.8C10—C9—C13117.8 (2)
C2—C3—C4117.3 (2)C9—C10—C11119.9 (2)
C2—C3—C6121.9 (2)C9—C10—H10120.1
C4—C3—C6120.8 (2)C11—C10—H10120.1
C3—C4—C5120.7 (2)N2—C11—C10120.1 (2)
C3—C4—H4119.6N2—C11—H11119.9
C5—C4—H4119.7C10—C11—H11119.9
N1—C5—C4119.7 (2)N2—C12—C13119.8 (2)
N1—C5—H5120.1N2—C12—H12120.1
C4—C5—H5120.1C13—C12—H12120.1
C3—C6—C7112.5 (2)C9—C13—C12120.4 (2)
C3—C6—H6a108.7C9—C13—H13119.8
C3—C6—H6b108.7C12—C13—H13119.8
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.872.583.182 (4)127
N1—H1N···O2i0.871.932.730 (3)153
N2—H2N···O5ii0.871.962.825 (4)170
N2—H2N···O6ii0.872.433.084 (4)133
C1—H1···O4i0.952.403.324 (4)164
C4—H4···O6iii0.952.553.409 (4)151
C5—H5···O5iv0.952.413.094 (4)129
C5—H5···O1i0.952.593.200 (4)123
C10—H10···O3v0.952.593.181 (4)120
C11—H11···O3v0.952.513.142 (4)124
C12—H12···O2iii0.952.543.225 (4)129
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y+1, z+2; (iii) x+1, y+1, z+1; (iv) x, y, z1; (v) x+1, y, z+1.

Experimental details

Crystal data
Chemical formulaC13H16N22+·2NO3
Mr324.29
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.894 (6), 21.037 (4), 9.879 (6)
β (°) 112.39 (4)
V3)1516.9 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.28 × 0.19 × 0.15
Data collection
DiffractometerAFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 1.5σ(I)] reflections
2966, 2761, 1718
Rint0.019
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.048, 1.46
No. of reflections1718
No. of parameters209
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)0.17, 0.17

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1992), SIR92 (Altomare et al., 1994), TEXSAN.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.872.583.182 (4)127
N1—H1N···O2i0.871.932.730 (3)153
N2—H2N···O5ii0.871.962.825 (4)170
N2—H2N···O6ii0.872.433.084 (4)133
C1—H1···O4i0.952.403.324 (4)164
C4—H4···O6iii0.952.553.409 (4)151
C5—H5···O5iv0.952.413.094 (4)129
C5—H5···O1i0.952.593.200 (4)123
C10—H10···O3v0.952.593.181 (4)120
C11—H11···O3v0.952.513.142 (4)124
C12—H12···O2iii0.952.543.225 (4)129
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y+1, z+2; (iii) x+1, y+1, z+1; (iv) x, y, z1; (v) x+1, y, z+1.
 

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