Crystal structure of allyl­ammonium hydrogen succinate at 100 K

Błażej Dziuk; Bartosz Zarychta; Krzysztof Ejsmont

doi:10.1107/S1600536814015633

. 2014 Aug 1;70(Pt 9):o917–o918. doi: 10.1107/S1600536814015633

Crystal structure of allylammonium hydrogen succinate at 100 K

Błażej Dziuk ^a, Bartosz Zarychta ^a, Krzysztof Ejsmont ^a,^*

PMCID: PMC4186065 PMID: 25309251

Abstract

The asymmetric unit of the title compound, C₂H₈N⁺·C₄H₅O₄ ⁻, consists of two allylammonium cations and two hydrogen succinate anions (Z′ = 2). One of the cations has a near-perfect syn-periplanar (cis) conformation with an N—C—C—C torsion angle of 0.4 (3)°, while the other is characterized by a gauche conformation and a torsion angle of 102.5 (3)°. Regarding the anions, three out of four carboxilic groups are twisted with respect to the central C–CH₂–CH₂–C group [dihedral angles = 24.4 (2), 31.2 (2) and 40.4 (2)°], the remaining one being instead almost coplanar, with a dihedral angle of 4.0 (2)°. In the crystal, there are two very short, near linear O—H⋯O hydrogen bonds between anions, with the H atoms shifted notably from the donor O towards the O⋯O midpoint. These O—H⋯O hydrogen bonds form helical chains along the [011] which are further linked to each other through N—H⋯O hydrogen bonds (involving all the available NH groups), forming layers lying parallel to (100).

Keywords: crystal structure, allylammonium, succinate, hydrogen bonds

Related literature

For other crystal structures of succinate salts with amines, see: Bhardwaj et al. (2013 ▶); Bruni et al. (2013 ▶); Khorasani & Fernandes (2012 ▶). For the characteristic structural motifs in ammonium dicarboxylate salts, see: Kashino et al. (1998 ▶); Barnes & Weakley (2000 ▶); MacDonald et al. (2001 ▶); Vaidhyanathan et al. (2001 ▶, 2002 ▶); Saraswathi & Vijayan (2002 ▶); Ejsmont (2007 ▶). Salts of succinic acid and amines have strong N—H⋯O and O—H⋯O hydrogen bonds and are thus used as building blocks for the construction of supramolecular structures, see: Khorasani et al. (2012 ▶); Lemmerer (2011 ▶). For hydrogen bonding, see: Steiner (2002 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). graphic file with name e-70-0o917-scheme1.jpg

Experimental

Crystal data

C₃H₈N⁺·C₄H₅O₄ ⁻
M _r = 175.19
Triclinic,
a = 8.5649 (3) Å
b = 9.4364 (3) Å
c = 10.8051 (4) Å
α = 88.838 (3)°
β = 87.482 (3)°
γ = 82.843 (3)°
V = 865.55 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
5454 measured reflections
3013 independent reflections
2373 reflections with I > 2σI)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.093
S = 1.10
3013 reflections
249 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814015633/bg2532sup1.cif

e-70-0o917-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015633/bg2532Isup2.hkl

e-70-0o917-Isup2.hkl^{(147.8KB, hkl)}

Click here for additional data file.^{(3.6KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814015633/bg2532Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S1600536814015633/bg2532fig1.tif

The molecular structure of (I), showing 50% displacement ellipsoids. Hydrogen bonds are shown as dotted lines.

Click here for additional data file.^{(1MB, tif)}

b . DOI: 10.1107/S1600536814015633/bg2532fig2.tif

Packing diagram of (I) viewed along the b axis, showing (sideways) the (100) 2D structure defined by the hydrogen-bonding network (dotted lines).

CCDC reference: 1012134

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
N11—H11A⋯O48	0.94 (2)	1.89 (2)	2.8275 (19)	174.4 (17)
N11—H11B⋯O32ⁱ	0.95 (2)	1.88 (2)	2.8107 (19)	166.9 (18)
N11—H11C⋯O41ⁱⁱ	0.90 (2)	1.95 (2)	2.844 (2)	172 (2)
N21—H21A⋯O32	0.95 (3)	2.28 (3)	2.972 (2)	128.5 (19)
N21—H21A⋯O47	0.95 (3)	2.21 (3)	2.994 (2)	138.7 (19)
N21—H21B⋯O42ⁱⁱⁱ	0.93 (2)	1.86 (2)	2.786 (2)	169.2 (17)
N21—H21C⋯O38^iv	0.92 (2)	1.86 (2)	2.7809 (19)	177 (2)
O37—H37⋯O41^v	1.18 (3)	1.28 (3)	2.4510 (15)	180 (3)
O47—H47⋯O31	1.08 (3)	1.39 (3)	2.4707 (15)	176 (3)

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

supplementary crystallographic information

S1. Comment

Crystal engineering is extremely fast growing area of experimental chemistry leading to new materials with controlled and understood nature. Hydrogen bonding plays an important role in organizing molecules, assembling them to create supramolecules and controlling their dimensions in one-, two- or three-dimensions (Khorasani et al., 2012). The adducts of succinic acid and amines have strong N—H···O and O—H···O hydrogen bonds, thus they can be used to align molecules in chosen directions, as building blocks for the construction of supramolecular structures. (Khorasani et al., 2012; Lemmerer, 2011).

There are three characteristic structural motifs in ammonium dicarboxylate salts: (i) linear chains of dicarboxylic acids formed by strong hydrogen bonds; (ii) dimers of dicarboxylic acid molecules; (iii) isolated oxalate monoanions or dianion units (for example: Kashino et al., 1998; Barnes & Weakley 2000; MacDonald et al., 2001; Vaidhyanathan et al., 2001, 2002; Saraswathi & Vijayan 2002; and Ejsmont, 2007).

The independent part of the unit cell of the title salt, (I), consists with two allyloammonium cations and two hydrogen succinate anions (Fig. 1). A geometry of amonium cations is normal (CSD; CONQUEST Version 1.16; Allen, 2002) and comparable with those found in other crystal structures which include this cation (Allen, 2002). The N11 cation has perfect syn-periplanar (cis) conformation with N11–C12–C13–C14 torsion angle of 0.4 (3)°, while N21 cataion is characterized by gauche conformation (the torsion angle N21–C22–C23—C24 amounts 102.5 (3)°). Three out of four carboxalic groups are twisted with respect to the central C–CH₂–CH₂–C group; the remaining one being rather co-planar.

In the crystal structure of (I), there are two linear or nearly linear O–H···O hydrogen bonds between the hydrogen succinate, which can be identified as a very strong interactions (Steiner, 2002). The O···O distances in these interactions are close to that observed for O–H···O hydrogen bonds formed between the monoanionic oxalate units in the structures of diethylammonium hydrogen oxalate (Ejsmont, 2007). These O–H···O hydrogen bonds forming helical chains along <011> direction. The allylammonium cations are linked to polianionic chains through the N–H···O hydrogen bonds (Table 2, Fig. 2).

S2. Experimental

Crystals of (I) were grown at room temperature by slow evaporation of an aqueous solution containing allylamine and succinatic acid in a 1:1 stoichiometric ratio.