Crystal structure of 4,4′-[(1,3,5,7-tetra­oxo-1,3,3a,4,4a,5,7,7a,8,8a-deca­hydro-4,8-etheno­pyrrolo­[3,4-f]iso­indole-2,6-di­yl)bis­(methyl­ene)]bis­(pyridin-1-ium) dinitrate

Zhimin Liu

doi:10.1107/S2056989015022227

. 2015 Nov 25;71(Pt 12):o986–o987. doi: 10.1107/S2056989015022227

Crystal structure of 4,4′-[(1,3,5,7-tetraoxo-1,3,3a,4,4a,5,7,7a,8,8a-decahydro-4,8-ethenopyrrolo[3,4-f]isoindole-2,6-diyl)bis(methylene)]bis(pyridin-1-ium) dinitrate

Zhimin Liu ^a,^*

PMCID: PMC4719937 PMID: 26870565

Abstract

In the title salt, C₂₄H₂₂N₄O₄ ²⁺·2NO₃ ⁻, the cation is U-shaped with the two isoindole dione rings inclined to one another by 60.41 (13)°, while the two outer pyridine rings are inclined to one another by 2.77 (12)°. The dihedral angles between the pyridine ring and the adjacent isoindole dione ring are 71.82 (12) and 86.44 (13)°. In the crystal, each nitrate anion is linked to a protonated pyridine ring by N—H⋯O hydrogen bonds. These units are linked by a series of C—H⋯O hydrogen bonds, forming a three-dimensional structure.

Keywords: crystal structure, salt, isoindole, pyrrolo, pyridinium, nitrate(V) salt, N—H⋯O hydrogen bonds

Related literature

For the crystal structures of compounds with similar ligands, see: Yu et al. (2012 ▸); Li et al. (2011 ▸, 2012a ▸,b ▸). For the synthetic method used to prepare 2,6-bis(pyridin-4-ylmethyl)-3a,4,4a,7a,8,8a-hexahydro-4,8-ethenopyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone, see: Liu et al. (2007 ▸).

Experimental

Crystal data

C₂₄H₂₂N₄O₄ ²⁺·2NO₃ ⁻
M _r = 554.48
Monoclinic,
a = 13.0706 (6) Å
b = 14.3587 (5) Å
c = 12.9893 (5) Å
β = 104.861 (4)°
V = 2356.25 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 153 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker MWPC diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T _min = 0.963, T _max = 0.976
13323 measured reflections
4555 independent reflections
2623 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.146
S = 1.00
4555 reflections
361 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: FRAMBO (Bruker, 2004 ▸); cell refinement: FRAMBO and SAINT (Bruker, 2004 ▸); data reduction: SAINT (Bruker, 2004 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015022227/su5240sup1.cif

e-71-0o986-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022227/su5240Isup2.hkl

e-71-0o986-Isup2.hkl^{(223.2KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015022227/su5240Isup3.cml

Click here for additional data file.^{(1.8MB, tif)}

. DOI: 10.1107/S2056989015022227/su5240fig1.tif

The molecular structure of the title salt, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(1.7MB, tif)}

c . DOI: 10.1107/S2056989015022227/su5240fig2.tif

Crystal packing of the title salt, viewed along the c axis. hydrogen bonds are shown as dashed lines (see Table 1).

CCDC reference: 1434635

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O6ⁱ	0.86	2.40	3.096 (3)	138
N1—H1A⋯O7ⁱ	0.86	1.90	2.728 (3)	161
N4—H4A⋯O9ⁱⁱ	0.86	1.93	2.771 (3)	164
C6—H6B⋯O3ⁱⁱⁱ	0.97	2.57	3.386 (3)	142
C8—H8A⋯O8	0.98	2.30	3.155 (3)	145
C11—H11A⋯O5^iv	0.98	2.48	3.386 (3)	153
C13—H13A⋯O5^v	0.93	2.30	3.121 (3)	147
C14—H14A⋯O2^iv	0.98	2.54	3.403 (3)	147
C19—H19A⋯O6^vi	0.97	2.55	3.246 (3)	129
C21—H21A⋯O6^vi	0.93	2.56	3.362 (3)	145
C22—H22A⋯O2^vii	0.93	2.43	3.257 (3)	149
C23—H23A⋯O7^v	0.93	2.56	3.345 (3)	143

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

S1. Comment

In recent years, complexes with terminal pyridyl-substituted ligands have been used to construct various metal-organic frameworks (MOFs). MOFs have aroused considerable interests not only owing to their novel topological structures and for their potential applications (Li et al., 2011, 2012a,b; Yu et al., 2012). The title salt was synthesized from the reaction of

2,6-bis(pyridin-4-ylmethyl)-3a,4,4a,7a,8,8a-hexahydro-4,8-ethenopyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone and nitric acid in chloroform.

In the title salt, Fig. 1, the cation has two terminal protonated pyridine N atoms, N1 and N4. The backbone of the cation has essentially a cis-U conformation. The two isoindole dione rings (N2/C7—C10 and N3/C15—C18) are inclined to one another by 60.41 (13) °, while the two outer pyridine rings (N1/C1—C5 and N4/C20—C24) are inclined to one another by 2.77 (12) °. The dihedral angles between the pyridine ring and the adjacent isoindole dione ring are 86.44 (13) ° for rings N1/C1—C5 and N2/C7—C10, and 71.82 (12)° for rings N4/C20—C24 and N3/C15—C18. The bond angles C3—C6—N2 and C20—C19—N3 are 114.1 (2) and 113.52 (19) °, respectively, larger than normal (109 °)

In the crystal, each anion is linked to a protonated pyridine ring by N—H···O hydrogen bonds (Table 1). These units are linked by a series of C—H···O hydrogen bonds forming a three-dimensional structure (Table 1 and Fig. 2).

S2. Synthesis and crystallization

The compound 2,6-bis(pyridin-4-ylmethyl)-3a,4,4a,7a,8,8a-hexahydro-4,8-ethenopyrrolo[3,4-f]isoindole-1,3,5,7(2H,6H)-tetraone (L) was prepared according to a reported procedure (Liu et al., 2007). L (1 mmol, 0.43g) was added to CHCl₃ (5 ml) under vigorous stirring. The clear solution was combined with nitric(V) acid (0.1 M, 1 ml) and stirred for 20 min. The resulting solution was left to crystallize at ambient temperature. After two weeks, large block-shaped yellow single crystals of the title salt suitable for X-ray diffraction analysis were obtained [yield: 73%; based on the 4-(aminomethyl)-pyridine].

S3. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were placed in calculated positions and refined in a riding-model approximation: N—H = 0.86 Å and C—H = 0.93-0.98 Å with U_iso(H) = 1.2U_eq(N,C).