4,4′-Tri­methyl­enedipyridinium dinitrate

Lee, T.W.; Lau, J.P.K.; Szeto, L.

doi:10.1107/S1600536803009589

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4,4′-Trimethylenedipyridinium dinitrate

T. W. Lee, J. P. K. Lau and L. Szeto

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.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803009589/ob6242sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803009589/ob6242Isup2.hkl Contains datablock I

CCDC reference: 214822

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (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


 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. π–π 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 NO₃⁻ions (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.

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

	Fig. 1. An ORTEPII (Johnson, 1976) drawing of the title compound, (I), with 50% probability ellipsoids, showing the crystallographic labeling scheme.
	Fig. 2. The packing diagram of (I), showing π–π interactions and the hydrogen-bonding interactions (as dashed lines) between the nitrate ions and the pyridine rings.

(I) top

Crystal data top

C₁₃H₁₆N₂²⁺·2NO₃⁻	F(000) = 680.00
M_r = 324.29	D_x = 1.420 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.894 (6) Å	θ = 13.5–16.6°
b = 21.037 (4) Å	µ = 0.11 mm⁻¹
c = 9.879 (6) Å	T = 298 K
β = 112.39 (4)°	Block, yellow
V = 1516.9 (16) Å³	0.28 × 0.19 × 0.15 mm
Z = 4

Data collection top

AFC-7R diffractometer	R_int = 0.019
Radiation source: X-ray tube	θ_max = 25.0°, θ_min = 2.2°
Graphite monochromator	h = 0→9
ω/2–θ scans	k = 0→25
2966 measured reflections	l = −11→10
2761 independent reflections	3 standard reflections every 250 reflections
1718 reflections with I > 1.5σ(I)	intensity decay: 3.0%

Refinement top

Refinement on F	H-atom parameters not refined
Least-squares matrix: full	Weighting scheme based on measured s.u.'s w = 1/[(σ)²(F_o) + 0.00025(F_o)²]
R[F² > 2σ(F²)] = 0.044	(Δ/σ)_max = 0.001
wR(F²) = 0.048	Δρ_max = 0.17 e Å⁻³
S = 1.46	Δρ_min = −0.17 e Å⁻³
1718 reflections	Extinction correction: Zachariasen_type_2_Gaussian_isotropic (Zachariasen, 1967)
209 parameters	Extinction coefficient: 16.860 (4)
0 restraints

Crystal data top

C₁₃H₁₆N₂²⁺·2NO₃⁻	V = 1516.9 (16) Å³
M_r = 324.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.894 (6) Å	µ = 0.11 mm⁻¹
b = 21.037 (4) Å	T = 298 K
c = 9.879 (6) Å	0.28 × 0.19 × 0.15 mm
β = 112.39 (4)°

Data collection top

AFC-7R diffractometer	R_int = 0.019
2966 measured reflections	3 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)] = 0.044	0 restraints
wR(F²) = 0.048	H-atom parameters not refined
S = 1.46	Δρ_max = 0.17 e Å⁻³
1718 reflections	Δρ_min = −0.17 e Å⁻³
209 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.0584 (3)	0.2367 (1)	0.2522 (2)	0.0820 (8)
O2	0.1876 (3)	0.32731 (10)	0.3132 (2)	0.0650 (7)
O3	−0.0203 (4)	0.3139 (1)	0.0994 (2)	0.0972 (9)
O4	0.3617 (3)	0.44510 (9)	0.6683 (2)	0.0624 (6)
O5	0.3474 (3)	0.42756 (9)	0.8784 (2)	0.0640 (6)
O6	0.2798 (3)	0.51917 (9)	0.7807 (2)	0.0713 (7)
N1	0.3728 (3)	0.2384 (1)	0.0646 (2)	0.0482 (7)
N2	0.7550 (3)	0.5016 (1)	0.9219 (2)	0.0488 (7)
N3	0.0738 (3)	0.2920 (1)	0.2194 (2)	0.0535 (7)
N4	0.3295 (3)	0.4642 (1)	0.7737 (2)	0.0427 (6)
C1	0.4697 (4)	0.2083 (1)	0.1885 (3)	0.0515 (9)
C2	0.6089 (4)	0.2395 (1)	0.2959 (3)	0.0465 (8)
C3	0.6504 (3)	0.3020 (1)	0.2756 (3)	0.0386 (7)
C4	0.5421 (4)	0.3313 (1)	0.1455 (3)	0.0438 (7)
C5	0.4043 (4)	0.2989 (1)	0.0415 (3)	0.0470 (8)
C6	0.8050 (3)	0.3370 (1)	0.3886 (3)	0.0460 (8)
C7	0.7436 (3)	0.3743 (1)	0.4947 (3)	0.0459 (8)
C8	0.9007 (4)	0.4145 (1)	0.5961 (3)	0.0471 (8)
C9	0.8523 (3)	0.4465 (1)	0.7120 (2)	0.0401 (7)
C10	0.8631 (4)	0.4130 (1)	0.8365 (3)	0.0473 (8)
C11	0.8126 (4)	0.4417 (1)	0.9397 (3)	0.0487 (8)
C12	0.7459 (4)	0.5359 (1)	0.8056 (3)	0.0523 (8)
C13	0.7927 (4)	0.5088 (1)	0.6991 (3)	0.0495 (8)
H1	0.4425	0.1654	0.2023	0.0618
H1n	0.2860	0.2179	−0.0035	0.0578
H2	0.6773	0.2182	0.3849	0.0557
H2n	0.7223	0.5191	0.9881	0.0586
H4	0.5643	0.3744	0.1289	0.0526
H5	0.3309	0.3193	−0.0473	0.0564
H6a	0.8958	0.3072	0.4428	0.0552
H6b	0.8558	0.3659	0.3404	0.0552
H7a	0.6442	0.4012	0.4407	0.0551
H7b	0.7055	0.3453	0.5514	0.0551
H8a	1.0041	0.3880	0.6418	0.0565
H8b	0.9300	0.4461	0.5398	0.0565
H10	0.9053	0.3703	0.8497	0.0568
H11	0.8187	0.4187	1.0243	0.0585
H12	0.7070	0.5789	0.7970	0.0627
H13	0.7843	0.5330	0.6155	0.0594

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.098 (2)	0.056 (1)	0.073 (2)	−0.006 (1)	0.011 (1)	0.009 (1)
O2	0.064 (1)	0.060 (1)	0.059 (1)	−0.004 (1)	0.011 (1)	0.009 (1)
O3	0.119 (2)	0.100 (2)	0.045 (1)	0.025 (2)	0.000 (1)	0.021 (1)
O4	0.079 (1)	0.068 (1)	0.047 (1)	0.005 (1)	0.032 (1)	−0.0054 (10)
O5	0.091 (2)	0.055 (1)	0.046 (1)	0.007 (1)	0.028 (1)	0.0161 (10)
O6	0.109 (2)	0.039 (1)	0.076 (1)	0.013 (1)	0.047 (1)	0.0026 (10)
N1	0.049 (1)	0.049 (1)	0.043 (1)	−0.009 (1)	0.013 (1)	−0.011 (1)
N2	0.051 (1)	0.056 (2)	0.041 (1)	−0.005 (1)	0.019 (1)	−0.010 (1)
N3	0.058 (2)	0.059 (2)	0.044 (1)	0.013 (1)	0.019 (1)	0.007 (1)
N4	0.043 (1)	0.043 (1)	0.038 (1)	−0.004 (1)	0.0120 (10)	0.000 (1)
C1	0.064 (2)	0.038 (1)	0.055 (2)	−0.003 (1)	0.025 (2)	0.000 (1)
C2	0.057 (2)	0.043 (2)	0.040 (1)	0.003 (1)	0.018 (1)	0.006 (1)
C3	0.042 (1)	0.042 (1)	0.035 (1)	0.002 (1)	0.018 (1)	−0.007 (1)
C4	0.054 (2)	0.037 (1)	0.040 (1)	−0.002 (1)	0.017 (1)	0.000 (1)
C5	0.055 (2)	0.048 (2)	0.036 (1)	−0.001 (1)	0.014 (1)	0.000 (1)
C6	0.045 (2)	0.053 (2)	0.040 (1)	0.000 (1)	0.015 (1)	−0.008 (1)
C7	0.043 (2)	0.057 (2)	0.037 (1)	−0.006 (1)	0.015 (1)	−0.010 (1)
C8	0.050 (2)	0.052 (2)	0.041 (1)	−0.008 (1)	0.019 (1)	−0.009 (1)
C9	0.038 (1)	0.045 (1)	0.034 (1)	−0.008 (1)	0.010 (1)	−0.007 (1)
C10	0.054 (2)	0.043 (1)	0.043 (1)	−0.002 (1)	0.016 (1)	−0.002 (1)
C11	0.054 (2)	0.053 (2)	0.036 (1)	−0.009 (1)	0.014 (1)	0.003 (1)
C12	0.061 (2)	0.044 (2)	0.052 (2)	0.002 (1)	0.022 (1)	0.000 (1)
C13	0.060 (2)	0.051 (2)	0.039 (1)	0.000 (1)	0.020 (1)	0.004 (1)

Geometric parameters (Å, º) top

O1—N3	1.226 (3)	C4—H4	0.950
O2—N3	1.258 (3)	C5—H5	0.950
O3—N3	1.223 (3)	C6—C7	1.527 (3)
O4—N4	1.229 (2)	C6—H6a	0.950
O5—N4	1.254 (2)	C6—H6b	0.950
O6—N4	1.232 (3)	C7—C8	1.520 (3)
N1—C1	1.330 (3)	C7—H7a	0.950
N1—C5	1.333 (3)	C7—H7b	0.950
N1—H1n	0.870	C8—C9	1.498 (3)
N2—C11	1.329 (3)	C8—H8a	0.950
N2—C12	1.334 (3)	C8—H8b	0.950
N2—H2n	0.870	C9—C10	1.392 (3)
C1—C2	1.370 (4)	C9—C13	1.382 (3)
C1—H1	0.950	C10—C11	1.369 (3)
C2—C3	1.388 (3)	C10—H10	0.950
C2—H2	0.950	C11—H11	0.950
C3—C4	1.388 (3)	C12—C13	1.365 (4)
C3—C6	1.497 (3)	C12—H12	0.950
C4—C5	1.361 (4)	C13—H13	0.950

C1—N1—C5	122.2 (2)	C7—C6—H6a	108.7
C1—N1—H1n	118.9	C7—C6—H6b	108.7
C5—N1—H1n	118.9	H6a—C6—H6b	109.5
C11—N2—C12	122.0 (2)	C6—C7—C8	110.2 (2)
C11—N2—H2n	119.0	C6—C7—H7a	109.3
C12—N2—H2n	119.0	C6—C7—H7b	109.3
O1—N3—O2	118.7 (2)	C8—C7—H7a	109.3
O1—N3—O3	121.8 (3)	C8—C7—H7b	109.3
O2—N3—O3	119.5 (3)	H7a—C7—H7b	109.5
O4—N4—O5	120.2 (2)	C7—C8—C9	111.9 (2)
O4—N4—O6	121.8 (2)	C7—C8—H8a	108.9
O5—N4—O6	118.0 (2)	C7—C8—H8b	108.9
N1—C1—C2	119.7 (2)	C9—C8—H8a	108.9
N1—C1—H1	120.1	C9—C8—H8b	108.9
C2—C1—H1	120.1	H8a—C8—H8b	109.5
C1—C2—C3	120.4 (2)	C8—C9—C10	120.0 (2)
C1—C2—H2	119.8	C8—C9—C13	122.2 (2)
C3—C2—H2	119.8	C10—C9—C13	117.8 (2)
C2—C3—C4	117.3 (2)	C9—C10—C11	119.9 (2)
C2—C3—C6	121.9 (2)	C9—C10—H10	120.1
C4—C3—C6	120.8 (2)	C11—C10—H10	120.1
C3—C4—C5	120.7 (2)	N2—C11—C10	120.1 (2)
C3—C4—H4	119.6	N2—C11—H11	119.9
C5—C4—H4	119.7	C10—C11—H11	119.9
N1—C5—C4	119.7 (2)	N2—C12—C13	119.8 (2)
N1—C5—H5	120.1	N2—C12—H12	120.1
C4—C5—H5	120.1	C13—C12—H12	120.1
C3—C6—C7	112.5 (2)	C9—C13—C12	120.4 (2)
C3—C6—H6a	108.7	C9—C13—H13	119.8
C3—C6—H6b	108.7	C12—C13—H13	119.8

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.87	2.58	3.182 (4)	127
N1—H1N···O2ⁱ	0.87	1.93	2.730 (3)	153
N2—H2N···O5ⁱⁱ	0.87	1.96	2.825 (4)	170
N2—H2N···O6ⁱⁱ	0.87	2.43	3.084 (4)	133
C1—H1···O4ⁱ	0.95	2.40	3.324 (4)	164
C4—H4···O6ⁱⁱⁱ	0.95	2.55	3.409 (4)	151
C5—H5···O5^iv	0.95	2.41	3.094 (4)	129
C5—H5···O1ⁱ	0.95	2.59	3.200 (4)	123
C10—H10···O3^v	0.95	2.59	3.181 (4)	120
C11—H11···O3^v	0.95	2.51	3.142 (4)	124
C12—H12···O2ⁱⁱⁱ	0.95	2.54	3.225 (4)	129

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆N₂²⁺·2NO₃⁻
M_r	324.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	7.894 (6), 21.037 (4), 9.879 (6)
β (°)	112.39 (4)
V (Å³)	1516.9 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.28 × 0.19 × 0.15

Data collection
Diffractometer	AFC-7R diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 1.5σ(I)] reflections	2966, 2761, 1718
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.048, 1.46
No. of reflections	1718
No. of parameters	209
H-atom treatment	H-atom parameters not refined
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ⁱ	0.87	2.58	3.182 (4)	127
N1—H1N···O2ⁱ	0.87	1.93	2.730 (3)	153
N2—H2N···O5ⁱⁱ	0.87	1.96	2.825 (4)	170
N2—H2N···O6ⁱⁱ	0.87	2.43	3.084 (4)	133
C1—H1···O4ⁱ	0.95	2.40	3.324 (4)	164
C4—H4···O6ⁱⁱⁱ	0.95	2.55	3.409 (4)	151
C5—H5···O5^iv	0.95	2.41	3.094 (4)	129
C5—H5···O1ⁱ	0.95	2.59	3.200 (4)	123
C10—H10···O3^v	0.95	2.59	3.181 (4)	120
C11—H11···O3^v	0.95	2.51	3.142 (4)	124
C12—H12···O2ⁱⁱⁱ	0.95	2.54	3.225 (4)	129

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

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