Crystal structure of 2-(1H-imidazol-3-ium-4-yl)ethanaminium dichloride, a re-determination.

The crystal structure of the title mol-ecular salt, C5H11N3 (+)·2Cl(-), was redetermined. In comparison with the previous study [Bonnet et al. (1975 ▸). Bull. Soc. Fr. Mineral. Crist. 98, 208-213.], the positions of some H atoms were corrected, allowing a more accurate description of the hydrogen-bonding scheme. In addition, the absolute structure was also determined. The maximum differences in terms of bond lengths and angles between the two determinations are 0.022 Å and 1.43°, respectively. The organic cation display a anti conformation of the protonated amine function and the imidazolium ring. The dihedral angle between the imidazolium plane and the plane through the C-C-N side chain is 29.58 (3)°. In the crystal, the organic cations and Cl(-) anions are stacked alternatively into layers parallel to (100). N-H⋯Cl hydrogen bonds between all H atoms of the ammonium group and both N-H groups of the imidazolium ring and the Cl(-) acceptor anions lead to the linkage of organic and inorganic layers into a three-dimensional network.

Related literature

Histamine [n class="Chemical">2-(1H-imidazol-4-yl)ethanamine] is a biogenic amine present in essentially all mammalian tissues and involved in several defense mechanisms of the body. It plays a role in various physiological processes, such as control of gastric acid secretion, neurotransmission, regulation of the microcirculation, and modulation of inflammatory (Cooper et al., 1990 ▸; Barnes, 2001 ▸) and immunological reactions (Schwartz et al., 1991 ▸; Bachert et al., 1998 ▸; Emanuel et al., 1999 ▸). The contribution of histamine in these physiological and pathological processes and the use in pharmacology make it an inter­esting substance in biochemistry (Leurs et al., 1995 ▸; Galoppin & Ponvert, 1997 ▸; O’Mahony et al., 2011 ▸; Jadidi-Niaragh & Mirshafiey, 2010 ▸; Gustiananda et al., 2012 ▸). The structure of the title compound has been determined previously by Bonnet et al. (1975 ▸) who reported lattice parameters of a =7.596 (6), b = 12.706 (8), c = 4.457 (4) Å, β = 91.64 (5)° at room temperature. For the structure of the histamine copper(II) chloride complex and its catalytic activity study, see: Belfilali et al. (2015a ▸), and for the structure of monopronated histamine with Cl− as counter-anion, see: Belfilali et al. (2015b ▸).

Experimental

Crystal data

C5H11N3 +·n class="Chemical">2Cl−

M = 184.07

Monoclinic,

a = 4.4358 (2) Å

b = 12.6281 (4) Å

c = 7.5588 (3) Å

β = 91.910 (1)°

V = 423.18 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.70 mm−1

T = 150 K

0.43 × 0.32 × 0.09 mm

Data collection

Bruker APEXII CCD, diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▸) T min = 0.825, T max = 0.939

3729 measured reflections

1855 independent reflections

1815 reflections with I > 2σ(I)

R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.058

S = 1.08

1855 reflections

106 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.17 e Å−3

Absolute structure: Flack (1983 ▸), 841 Friedel pairs

Absolute structure parameter: 0.06 (5)

Data collection: APEX2 (Bruker, 2006 ▸); cell refinement: SAINT (Bruker, 2006 ▸); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015018848/wm5220sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018848/wm5220Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018848/wm5220Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015018848/wm5220fig1.tif

Tautomeric forms of histamine.

Click here for additional data file.

. DOI: 10.1107/S2056989015018848/wm5220fig2.tif

The mol­ecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S2056989015018848/wm5220fig3.tif

Part of the crystal structure with hydrogen bonds shown as dashed lines.

CCDC reference: 1051848

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

C5H11N3+·2Cl−	F(000) = 192
Mr = 184.07	Dx = 1.445 Mg m−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2786 reflections
a = 4.4358 (2) Å	θ = 2.7–27.5°
b = 12.6281 (4) Å	µ = 0.70 mm−1
c = 7.5588 (3) Å	T = 150 K
β = 91.910 (1)°	Prism, colourless
V = 423.18 (3) Å3	0.43 × 0.32 × 0.09 mm
Z = 2

Bruker APEXII CCD, diffractometer	1815 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
CCD rotation images, thin slices scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −5→5
Tmin = 0.825, Tmax = 0.939	k = −16→13
3729 measured reflections	l = −9→9
1855 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.058	w = 1/[σ2(Fo2) + (0.0327P)2] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
1855 reflections	Δρmax = 0.22 e Å−3
106 parameters	Δρmin = −0.17 e Å−3
1 restraint	Absolute structure: Flack (1983), 841 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.06 (5)

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.

	x	y	z	Uiso*/Ueq
N1	0.9759 (4)	0.18301 (13)	0.4308 (2)	0.0201 (3)
H1A	1.115 (6)	0.232 (2)	0.472 (3)	0.05*
H1B	0.787 (6)	0.217 (2)	0.441 (3)	0.05*
H1C	1.015 (6)	0.179 (2)	0.316 (4)	0.05*
C2	0.9990 (5)	0.07908 (15)	0.5236 (2)	0.0209 (4)
H2A	1.2044	0.0497	0.5125	0.025*
H2B	0.853	0.0285	0.469	0.025*
C3	0.9317 (4)	0.09457 (15)	0.7190 (2)	0.0214 (4)
H3A	1.053	0.1545	0.7669	0.026*
H3B	0.716	0.1127	0.7299	0.026*
C4	1.0019 (4)	−0.00243 (13)	0.8252 (2)	0.0160 (3)
C5	1.1983 (4)	−0.08313 (15)	0.8024 (2)	0.0189 (3)
H5	1.3185	−0.0945	0.7025	0.023*
N6	1.1904 (3)	−0.14577 (12)	0.95191 (19)	0.0206 (3)
H6	1.284 (6)	−0.206 (2)	0.964 (3)	0.05*
C7	0.9952 (4)	−0.10582 (15)	1.0615 (2)	0.0211 (4)
H7	0.9475	−0.1342	1.1736	0.025*
N8	0.8764 (3)	−0.01892 (12)	0.98803 (17)	0.0168 (3)
H8	0.745 (6)	0.021 (2)	1.031 (4)	0.05*
Cl1	0.47163 (8)	0.32961 (3)	0.59693 (5)	0.02068 (11)
Cl2	0.43148 (9)	0.15270 (3)	0.11930 (5)	0.01937 (11)

	U11	U22	U33	U12	U13	U23
N1	0.0192 (7)	0.0233 (9)	0.0178 (7)	−0.0004 (6)	0.0021 (6)	0.0025 (6)
C2	0.0264 (9)	0.0187 (9)	0.0175 (9)	−0.0022 (7)	0.0010 (7)	−0.0001 (7)
C3	0.0267 (9)	0.0202 (9)	0.0174 (8)	0.0047 (8)	0.0036 (7)	0.0012 (7)
C4	0.0168 (7)	0.0158 (8)	0.0155 (7)	−0.0017 (7)	0.0002 (6)	−0.0027 (6)
C5	0.0208 (8)	0.0177 (8)	0.0183 (8)	0.0006 (7)	0.0026 (6)	−0.0036 (7)
N6	0.0214 (7)	0.0173 (8)	0.0233 (7)	0.0014 (6)	0.0018 (6)	0.0014 (6)
C7	0.0225 (9)	0.0215 (9)	0.0195 (7)	−0.0013 (7)	0.0008 (7)	0.0033 (7)
N8	0.0167 (7)	0.0168 (7)	0.0173 (7)	−0.0009 (6)	0.0032 (5)	−0.0017 (5)
Cl1	0.01948 (19)	0.0235 (2)	0.01936 (17)	−0.00067 (18)	0.00474 (13)	−0.00219 (16)
Cl2	0.01775 (18)	0.0187 (2)	0.02194 (18)	−0.00186 (17)	0.00442 (13)	−0.00354 (15)

N1—C2	1.490 (2)	C4—C5	1.355 (3)
N1—H1A	0.92 (3)	C4—N8	1.383 (2)
N1—H1B	0.95 (3)	C5—N6	1.381 (2)
N1—H1C	0.89 (3)	C5—H5	0.95
C2—C3	1.530 (2)	N6—C7	1.319 (2)
C2—H2A	0.99	N6—H6	0.88 (3)
C2—H2B	0.99	C7—N8	1.331 (2)
C3—C4	1.492 (2)	C7—H7	0.95
C3—H3A	0.99	N8—H8	0.84 (3)
C3—H3B	0.99
C2—N1—H1A	113.7 (15)	H3A—C3—H3B	107.9
C2—N1—H1B	113.9 (15)	C5—C4—N8	106.22 (14)
H1A—N1—H1B	105 (2)	C5—C4—C3	132.25 (16)
C2—N1—H1C	112.9 (18)	N8—C4—C3	121.30 (14)
H1A—N1—H1C	103 (2)	C4—C5—N6	107.03 (15)
H1B—N1—H1C	108 (2)	C4—C5—H5	126.5
N1—C2—C3	109.22 (15)	N6—C5—H5	126.5
N1—C2—H2A	109.8	C7—N6—C5	109.26 (15)
C3—C2—H2A	109.8	C7—N6—H6	126.0 (18)
N1—C2—H2B	109.8	C5—N6—H6	124.3 (17)
C3—C2—H2B	109.8	N6—C7—N8	108.21 (15)
H2A—C2—H2B	108.3	N6—C7—H7	125.9
C4—C3—C2	111.78 (14)	N8—C7—H7	125.9
C4—C3—H3A	109.3	C7—N8—C4	109.27 (14)
C2—C3—H3A	109.3	C7—N8—H8	126.6 (18)
C4—C3—H3B	109.3	C4—N8—H8	124.2 (18)
C2—C3—H3B	109.3
N1—C2—C3—C4	−170.28 (15)	C4—C5—N6—C7	0.6 (2)
C2—C3—C4—C5	26.5 (3)	C5—N6—C7—N8	−0.2 (2)
C2—C3—C4—N8	−159.79 (15)	N6—C7—N8—C4	−0.27 (19)
N8—C4—C5—N6	−0.70 (17)	C5—C4—N8—C7	0.61 (17)
C3—C4—C5—N6	173.73 (18)	C3—C4—N8—C7	−174.57 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.92 (3)	2.19 (3)	3.1071 (17)	171 (2)
N1—H1B···Cl1	0.95 (3)	2.34 (3)	3.1930 (17)	150 (2)
N1—H1C···Cl2i	0.89 (3)	2.44 (3)	3.1768 (16)	141 (2)
N6—H6···Cl2ii	0.88 (3)	2.28 (3)	3.1046 (16)	157 (2)
N8—H8···Cl2iii	0.84 (3)	2.28 (3)	3.1157 (15)	169 (3)

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N1H1ACl1i	0.92(3)	2.19(3)	3.1071(17)	171(2)
N1H1BCl1	0.95(3)	2.34(3)	3.1930(17)	150(2)
N1H1CCl2i	0.89(3)	2.44(3)	3.1768(16)	141(2)
N6H6Cl2ii	0.88(3)	2.28(3)	3.1046(16)	157(2)
N8H8Cl2iii	0.84(3)	2.28(3)	3.1157(15)	169(3)

Symmetry codes: (i) ; (ii) ; (iii) .