Allyl­ammonium hydrogen oxalate hemihydrate

Dziuk, B.; Zarychta, B.; Ejsmont, K.

doi:10.1107/S1600536814015190

organic compounds

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Volume 70| Part 8| August 2014| Page o852

doi:10.1107/S1600536814015190

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Allylammonium hydrogen oxalate hemihydrate

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

^aFaculty of Chemistry, University of Opole, Oleska 48, 45-052 Opole, Poland
^*Correspondence e-mail: eismont@uni.opole.pl

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 18 June 2014; accepted 27 June 2014; online 5 July 2014)

In the title hydrated molecular salt, C₃H₈N⁺·C₂HO₄⁻·0.5H₂O, the water O atom lies on a crystallographic twofold axis. The C=C—C—N torsion angle in the cation is 2.8 (3)° and the dihedral angle between the CO₂ and CO₂H planes in the anion is 1.0 (4)°. In the crystal, the hydrogen oxalate ions are linked by O—H⋯O hydrogen bonds, generating [010] chains. The allylammonium cations bond to the chains through N—H⋯O and N—H⋯(O,O) hydrogen bonds. The water molecule accepts two N—H⋯O hydrogen bonds and makes two O—H⋯O hydrogen bonds. Together, the hydrogen bonds generate (100) sheets.

Keywords: crystal structure.

CCDC reference: 1010915

Related literature

For the crystal structures of oxalic acid salts with aliphatic amines, see: Ejsmont (2006 ), (2007 ); Ejsmont & Zaleski (2006a ,b ); Vaidhyanathan et al. (2001 , 2002 ); MacDonald et al. (2001 ) For information on the Cambridge Database, see: Allen (2002 ).

Experimental

Crystal data

C₃H₈N⁺·C₂HO₄⁻·0.5H₂O
M_r = 156.14
Monoclinic, C 2/c
a = 21.578 (3) Å
b = 5.6521 (4) Å
c = 13.8629 (17) Å
β = 118.415 (17)°
V = 1487.0 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 100 K
0.33 × 0.18 × 0.14 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
4525 measured reflections
1376 independent reflections
958 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.098
S = 0.90
1376 reflections
136 parameters
All H-atom parameters refined
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O9	0.98 (3)	1.86 (3)	2.825 (2)	169 (2)
N1—H1A⋯O11	0.98 (3)	1.82 (3)	2.769 (2)	161 (2)
N1—H1C⋯O8ⁱ	0.91 (3)	2.19 (3)	3.014 (2)	151 (2)
N1—H1C⋯O10ⁱ	0.91 (3)	2.16 (3)	2.853 (2)	132 (2)
O7—H7⋯O10ⁱⁱ	0.94 (3)	1.62 (3)	2.5563 (19)	179 (4)
O11—H11⋯O9ⁱⁱⁱ	0.88 (3)	1.86 (3)	2.739 (2)	176 (3)
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) x, y+1, z; (iii) $[-x+1, y+1, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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.

Supporting information

CCDC reference: 1010915

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814015190/hb7243sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814015190/hb7243Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814015190/hb7243Isup3.cml

checkCIF report

Comment top

Oxalic acid, together with its anions, is one of the best building blocks for the construction of supramolecular structures based on hydrogen bonds. The adducts of oxalic acid and aliphatic amines have been examined by single-crystal X-ray diffraction and other techniques. Three types of characteristic structural motifs are present: (i) linear chains of dicarboxylic acids formed by strong hydrogen bonds; (ii) dimers of dicarboxylic acid molecules; (iii) isolated oxalate monoanions or dianion units (MacDonald et al., 2001; Vaidhyanathan et al., 2001, 2002); Ejsmont, 2006, 2007; Ejsmont & Zaleski 2006a, 2006b).

The crystal structure of the title salt, (I), consists of allyloammonium cations, hydrogen oxalate anions and water molecules (Fig. 1). A search of the Cambridge Structural Database (CSD; CONQUEST Version 1.16; Allen, 2002) afforded that the geometrical parameters of the allyloammonium cation (Table 1) compare well with those found in other crystal structures which include this cation (Allen, 2002). The oxalate monoanions are nearly planar and are connected to each other by strong O—H···O hydrogen bonds along the b axis. The allyloammonium cations form N—H···O H atoms bonds to the anions and water molecules (Fig. 2 and Table 2).

Related literature top

For the crystal structures of oxalic acid salts with aliphatic amines, see: Ejsmont (2006), (2007); Ejsmont & Zaleski (2006a,b); Vaidhyanathan et al. (2001, 2002); MacDonald et al. (2001) For information on the Cambridge Database, see: Allen (2002).

Experimental top

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

Computing details top

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

Figures top

	Fig. 1. The molecular structure of (I), showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Hydrogen bonds are shown as dotted lines.
	Fig. 2. The packing diagram of (I), viewed along the b axis, showing the intermolecular hydrogen-bonding scheme (dashed lines).

Allylammonium hydrogen oxalate hemihydrate top

Crystal data top

C₃H₈N⁺·C₂HO₄⁻·0.5H₂O	F(000) = 664
M_r = 156.14	D_x = 1.395 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4525 reflections
a = 21.578 (3) Å	θ = 3.3–25.5°
b = 5.6521 (4) Å	µ = 0.12 mm⁻¹
c = 13.8629 (17) Å	T = 100 K
β = 118.415 (17)°	Prism, colourless
V = 1487.0 (3) Å³	0.33 × 0.18 × 0.14 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur diffractometer	958 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.045
Graphite monochromator	θ_max = 25.5°, θ_min = 3.3°
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm^-1	h = −26→26
ω–scan	k = −6→5
4525 measured reflections	l = −16→16
1376 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	All H-atom parameters refined
S = 0.90	w = 1/[σ²(F_o²) + (0.0628P)²] where P = (F_o² + 2F_c²)/3
1376 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₃H₈N⁺·C₂HO₄⁻·0.5H₂O	V = 1487.0 (3) Å³
M_r = 156.14	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.578 (3) Å	µ = 0.12 mm⁻¹
b = 5.6521 (4) Å	T = 100 K
c = 13.8629 (17) Å	0.33 × 0.18 × 0.14 mm
β = 118.415 (17)°

Data collection top

Oxford Diffraction Xcalibur diffractometer	958 reflections with I > 2σ(I)
4525 measured reflections	R_int = 0.045
1376 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.098	All H-atom parameters refined
S = 0.90	Δρ_max = 0.26 e Å⁻³
1376 reflections	Δρ_min = −0.27 e Å⁻³
136 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N1	0.40092 (10)	0.2394 (3)	0.23240 (15)	0.0196 (4)
H1A	0.4411 (13)	0.348 (4)	0.2556 (19)	0.033 (6)*
H1B	0.4018 (14)	0.132 (5)	0.177 (2)	0.050 (8)*
H1C	0.4052 (14)	0.154 (5)	0.291 (2)	0.046 (8)*
C2	0.33560 (12)	0.3802 (4)	0.18227 (19)	0.0231 (5)
H2A	0.3367 (11)	0.466 (4)	0.1271 (18)	0.021 (5)*
H2B	0.3376 (12)	0.486 (4)	0.233 (2)	0.032 (6)*
C3	0.27053 (13)	0.2364 (4)	0.13940 (19)	0.0284 (5)
H3	0.2311 (12)	0.325 (4)	0.1035 (18)	0.026 (6)*
C4	0.26561 (15)	0.0080 (5)	0.1452 (2)	0.0327 (6)
H4A	0.2203 (14)	−0.075 (4)	0.111 (2)	0.042 (7)*
H4B	0.3053 (13)	−0.085 (4)	0.1769 (19)	0.028 (6)*
C5	0.41682 (10)	0.1591 (3)	−0.03835 (16)	0.0167 (5)
C6	0.41572 (10)	−0.0892 (3)	0.00740 (16)	0.0177 (5)
O7	0.41788 (8)	0.3311 (2)	0.02573 (11)	0.0211 (4)
H7	0.4173 (16)	0.482 (6)	−0.002 (3)	0.077 (10)*
O8	0.41599 (8)	0.1838 (2)	−0.12581 (11)	0.0228 (4)
O9	0.41549 (8)	−0.1043 (2)	0.09658 (11)	0.0231 (4)
O10	0.41539 (8)	−0.2570 (2)	−0.05214 (11)	0.0221 (4)
O11	0.5000	0.5720 (4)	0.2500	0.0199 (5)
H11	0.5269 (14)	0.672 (5)	0.302 (2)	0.055 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0289 (11)	0.0222 (10)	0.0119 (8)	−0.0017 (8)	0.0133 (8)	0.0000 (8)
C2	0.0356 (13)	0.0234 (12)	0.0166 (11)	0.0039 (10)	0.0175 (10)	0.0007 (10)
C3	0.0273 (14)	0.0331 (14)	0.0255 (12)	0.0051 (11)	0.0132 (11)	0.0020 (10)
C4	0.0290 (14)	0.0362 (15)	0.0294 (13)	−0.0024 (12)	0.0110 (11)	0.0021 (12)
C5	0.0189 (11)	0.0201 (10)	0.0113 (10)	−0.0001 (8)	0.0073 (8)	−0.0027 (8)
C6	0.0202 (11)	0.0194 (10)	0.0136 (10)	0.0009 (8)	0.0082 (9)	−0.0002 (8)
O7	0.0383 (9)	0.0158 (7)	0.0148 (7)	−0.0003 (7)	0.0172 (7)	0.0003 (6)
O8	0.0394 (9)	0.0224 (8)	0.0128 (7)	−0.0011 (6)	0.0173 (7)	0.0005 (6)
O9	0.0416 (9)	0.0222 (8)	0.0145 (8)	0.0049 (6)	0.0206 (7)	0.0037 (6)
O10	0.0395 (9)	0.0172 (7)	0.0148 (7)	−0.0003 (6)	0.0170 (7)	−0.0014 (6)
O11	0.0283 (12)	0.0207 (11)	0.0119 (10)	0.000	0.0107 (9)	0.000

Geometric parameters (Å, º) top

N1—C2	1.473 (3)	C4—H4A	0.98 (3)
N1—H1A	0.98 (3)	C4—H4B	0.92 (2)
N1—H1B	0.98 (3)	C5—O8	1.212 (2)
N1—H1C	0.91 (3)	C5—O7	1.309 (2)
C2—C3	1.480 (3)	C5—C6	1.545 (3)
C2—H2A	0.92 (2)	C6—O9	1.242 (2)
C2—H2B	0.91 (2)	C6—O10	1.255 (2)
C3—C4	1.301 (3)	O7—H7	0.94 (3)
C3—H3	0.91 (2)	O11—H11	0.88 (3)

C2—N1—H1A	108.3 (13)	C4—C3—H3	120.1 (14)
C2—N1—H1B	109.5 (15)	C2—C3—H3	112.3 (14)
H1A—N1—H1B	108 (2)	C3—C4—H4A	122.4 (14)
C2—N1—H1C	112.2 (17)	C3—C4—H4B	120.8 (14)
H1A—N1—H1C	110 (2)	H4A—C4—H4B	116.6 (19)
H1B—N1—H1C	109 (2)	O8—C5—O7	125.49 (18)
N1—C2—C3	113.87 (18)	O8—C5—C6	121.27 (17)
N1—C2—H2A	106.4 (13)	O7—C5—C6	113.24 (15)
C3—C2—H2A	110.6 (13)	O9—C6—O10	126.98 (18)
N1—C2—H2B	108.0 (14)	O9—C6—C5	118.63 (16)
C3—C2—H2B	111.1 (15)	O10—C6—C5	114.39 (16)
H2A—C2—H2B	106.5 (19)	C5—O7—H7	113.9 (19)
C4—C3—C2	127.6 (2)

N1—C2—C3—C4	2.8 (3)	O8—C5—C6—O10	1.4 (3)
O8—C5—C6—O9	−178.8 (2)	O7—C5—C6—O10	−179.34 (17)
O7—C5—C6—O9	0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O9	0.98 (3)	1.86 (3)	2.825 (2)	169 (2)
N1—H1A···O11	0.98 (3)	1.82 (3)	2.769 (2)	161 (2)
N1—H1C···O8ⁱ	0.91 (3)	2.19 (3)	3.014 (2)	151 (2)
N1—H1C···O10ⁱ	0.91 (3)	2.16 (3)	2.853 (2)	132 (2)
O7—H7···O10ⁱⁱ	0.94 (3)	1.62 (3)	2.5563 (19)	179 (4)
O11—H11···O9ⁱⁱⁱ	0.88 (3)	1.86 (3)	2.739 (2)	176 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O9	0.98 (3)	1.86 (3)	2.825 (2)	169 (2)
N1—H1A···O11	0.98 (3)	1.82 (3)	2.769 (2)	161 (2)
N1—H1C···O8ⁱ	0.91 (3)	2.19 (3)	3.014 (2)	151 (2)
N1—H1C···O10ⁱ	0.91 (3)	2.16 (3)	2.853 (2)	132 (2)
O7—H7···O10ⁱⁱ	0.94 (3)	1.62 (3)	2.5563 (19)	179 (4)
O11—H11···O9ⁱⁱⁱ	0.88 (3)	1.86 (3)	2.739 (2)	176 (3)

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

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 8| August 2014| Page o852

doi:10.1107/S1600536814015190

Open

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