Literature DB >> 22719671

l-Alanylglycylhistamine dihydro-chloride.

Katalin Selmeczi, Patrick Gizzi, Emmanuel Wenger, Bernard Henry.

Abstract

In the title compound {systematic name: 4-[2-({N-[(2S)-2-ammonio-propano-yl]glyc-yl}amino)-eth-yl]-1H-imidazol-3-ium dichloride}, C(10)H(19)N(5)O(2) (2+)·2Cl(-), the pseudo-tripeptide l-alanyl-glycyl-histamine is protonated at both the terminal amino group and the histidine N2 atom. The resulting positive charges are neutralized by two chloride anions. In the crystal, the organic cation adopts a twisted conformation about the CH(2)-CH(2) bond of histamine and about the C-N bond in the main chain, stabilized by a short intra-molecular C-H⋯O contact. In the crystal, N(+)-H⋯O and N(+)-H⋯Cl(-) hydrogen bonds link the mol-ecules into infinite sheets parallel to the (100) plane. The stacking of these sheets along the a axis is supported by N(amide)-H⋯Cl(-) hydrogen bonds.

Entities: Chemical Disease Gene

Year: 2012 PMID： 22719671 PMCID： PMC3379473 DOI： 10.1107/S1600536812023562

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For the complexation ability of l-Ala-Gly-HA, see: Gizzi et al. (2005 ▶). For bond lengths and angles in other oligopeptides, see: Itoh et al. (1977 ▶); Selmeczi et al. (2008 ▶). For discussion of hydrogen bonding, see: Steiner (2002 ▶). For the synthesis of pseudo-peptides, see: Henry et al. (1993 ▶). For the definition of torsion angles in peptides, see: IUPAC–IUB Commission on Biochemical Nomenclature (1970 ▶).

Experimental

Crystal data

C10H19N5O2 2+·2Cl− M = 312.20 Monoclinic, a = 7.5864 (3) Å b = 7.4083 (3) Å c = 13.7673 (6) Å β = 105.337 (2)° V = 746.20 (5) Å3 Z = 2 Mo Kα radiation μ = 0.44 mm−1 T = 100 K 0.45 × 0.25 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer 15818 measured reflections 3574 independent reflections 3459 reflections with I > 2σ(I) R int = 0.060

Refinement

R[F 2 > 2σ(F 2)] = 0.027 wR(F 2) = 0.070 S = 1.00 3574 reflections 174 parameters 1 restraint H-atom parameters constrained Δρmax = 0.21 e Å−3 Δρmin = −0.23 e Å−3 Absolute structure: Flack (1983 ▶), with 1643 Friedel-pairs Flack parameter: −0.03 (4) Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶). Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812023562/fy2052sup1.cif Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812023562/fy2052Isup2.hkl Supplementary material file. DOI: 10.1107/S1600536812023562/fy2052Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₀H₁₉N₅O₂²⁺·2Cl⁻	F(000) = 328
M_r = 312.20	D_x = 1.390 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2yb	Cell parameters from 1776 reflections
a = 7.5864 (3) Å	θ = 0.4–30.0°
b = 7.4083 (3) Å	µ = 0.44 mm⁻¹
c = 13.7673 (6) Å	T = 100 K
β = 105.337 (2)°	Prismatic, colourless
V = 746.20 (5) Å³	0.45 × 0.25 × 0.11 mm
Z = 2

Nonius KappaCCD diffractometer	3459 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.060
Horizonally mounted graphite crystal monochromator	θ_max = 28.0°, θ_min = 2.8°
Detector resolution: 9 pixels mm^-1	h = −10→10
ω scans	k = −9→9
15818 measured reflections	l = −18→18
3574 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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0395P)² + 0.2259P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
3574 reflections	Δρ_max = 0.21 e Å⁻³
174 parameters	Δρ_min = −0.23 e Å⁻³
1 restraint	Absolute structure: Flack (1983), with 1643 Friedel-pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.03 (4)

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.

	x	y	z	U_iso*/U_eq
Cl1	0.75003 (4)	0.96855 (5)	0.94053 (3)	0.01717 (9)
Cl2	0.14366 (5)	0.19501 (5)	0.69324 (3)	0.01977 (9)
O2	0.54905 (14)	0.49471 (17)	0.89693 (8)	0.0181 (2)
O1	0.73519 (18)	0.52373 (18)	0.61858 (9)	0.0267 (3)
N3	0.76898 (17)	0.74018 (19)	0.73704 (10)	0.0178 (3)
H3N	0.8002	0.7654	0.8018	0.021*
N5	0.64458 (17)	0.66369 (18)	1.08050 (10)	0.0161 (3)
H5A	0.6377	0.7686	1.0453	0.024*
H5B	0.6819	0.6876	1.1477	0.024*
H5C	0.5326	0.6103	1.0657	0.024*
N4	0.84631 (16)	0.4832 (2)	0.89235 (9)	0.0169 (3)
H4	0.9605	0.5056	0.9251	0.020*
N1	0.21053 (19)	0.5728 (2)	0.62237 (11)	0.0213 (3)
H1N	0.1619	0.4744	0.6401	0.026*
N2	0.2662 (2)	0.7937 (2)	0.53338 (11)	0.0213 (3)
H2N	0.2601	0.8665	0.4821	0.026*
C7	0.8047 (2)	0.4224 (2)	0.78845 (13)	0.0196 (3)
H7A	0.6967	0.3421	0.7760	0.023*
H7B	0.9087	0.3489	0.7801	0.023*
C2	0.3860 (2)	0.8128 (2)	0.62861 (12)	0.0192 (3)
C8	0.7130 (2)	0.5057 (2)	0.93940 (11)	0.0156 (3)
C9	0.7782 (2)	0.5401 (2)	1.05237 (11)	0.0152 (3)
H9	0.9015	0.5982	1.0689	0.018*
C4	0.5264 (2)	0.9575 (2)	0.65566 (13)	0.0222 (3)
H4A	0.5219	1.0119	0.7207	0.027*
H4B	0.4969	1.0534	0.6038	0.027*
C3	0.3491 (2)	0.6734 (2)	0.68410 (12)	0.0195 (3)
H3	0.4077	0.6494	0.7528	0.023*
C6	0.7665 (2)	0.5683 (2)	0.70817 (12)	0.0189 (3)
C10	0.7887 (2)	0.3630 (2)	1.10983 (12)	0.0198 (3)
H10A	0.8346	0.3861	1.1822	0.030*
H10B	0.8716	0.2799	1.0883	0.030*
H10C	0.6666	0.3090	1.0959	0.030*
C5	0.7215 (2)	0.8883 (2)	0.66454 (13)	0.0206 (3)
H5D	0.7305	0.8461	0.5978	0.025*
H5E	0.8095	0.9884	0.6862	0.025*
C1	0.1628 (2)	0.6491 (2)	0.53191 (13)	0.0225 (3)
H1	0.0702	0.6071	0.4757	0.027*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.01378 (15)	0.01813 (17)	0.01988 (17)	−0.00020 (13)	0.00496 (12)	−0.00123 (13)
Cl2	0.01907 (17)	0.02083 (19)	0.01823 (17)	−0.00004 (13)	0.00283 (13)	0.00210 (13)
O2	0.0129 (5)	0.0223 (6)	0.0183 (5)	−0.0021 (4)	0.0025 (4)	−0.0001 (5)
O1	0.0369 (7)	0.0261 (7)	0.0169 (5)	0.0044 (5)	0.0070 (5)	−0.0050 (5)
N3	0.0164 (6)	0.0187 (6)	0.0176 (6)	−0.0024 (5)	0.0033 (5)	−0.0018 (5)
N5	0.0142 (6)	0.0174 (7)	0.0165 (6)	0.0004 (5)	0.0036 (5)	−0.0007 (5)
N4	0.0134 (5)	0.0210 (7)	0.0165 (6)	0.0013 (5)	0.0042 (4)	−0.0017 (5)
N1	0.0191 (6)	0.0214 (7)	0.0222 (7)	−0.0018 (5)	0.0036 (5)	0.0044 (6)
N2	0.0220 (7)	0.0233 (7)	0.0178 (6)	0.0015 (5)	0.0038 (5)	0.0049 (5)
C7	0.0218 (7)	0.0188 (8)	0.0189 (7)	0.0021 (6)	0.0068 (6)	−0.0036 (6)
C2	0.0173 (7)	0.0207 (8)	0.0191 (7)	0.0030 (6)	0.0040 (6)	0.0013 (6)
C8	0.0150 (6)	0.0142 (7)	0.0174 (7)	−0.0007 (5)	0.0040 (5)	0.0004 (5)
C9	0.0122 (6)	0.0158 (7)	0.0172 (7)	0.0017 (5)	0.0032 (5)	−0.0014 (5)
C4	0.0226 (7)	0.0175 (7)	0.0262 (8)	−0.0001 (7)	0.0058 (6)	0.0016 (7)
C3	0.0176 (7)	0.0219 (8)	0.0182 (7)	0.0001 (6)	0.0034 (6)	0.0018 (6)
C6	0.0150 (7)	0.0223 (8)	0.0201 (7)	0.0007 (6)	0.0061 (6)	−0.0015 (6)
C10	0.0209 (7)	0.0173 (8)	0.0202 (7)	0.0009 (6)	0.0037 (6)	0.0007 (6)
C5	0.0210 (7)	0.0184 (8)	0.0231 (8)	−0.0017 (6)	0.0072 (6)	0.0016 (6)
C1	0.0205 (8)	0.0262 (9)	0.0189 (8)	−0.0010 (6)	0.0018 (6)	0.0019 (6)

O2—C8	1.2292 (18)	C7—C6	1.518 (2)
O1—C6	1.238 (2)	C7—H7A	0.9900
N3—C6	1.333 (2)	C7—H7B	0.9900
N3—C5	1.463 (2)	C2—C3	1.357 (2)
N3—H3N	0.8800	C2—C4	1.488 (2)
N5—C9	1.491 (2)	C8—C9	1.524 (2)
N5—H5A	0.9100	C9—C10	1.523 (2)
N5—H5B	0.9100	C9—H9	1.0000
N5—H5C	0.9100	C4—C5	1.540 (2)
N4—C8	1.3478 (19)	C4—H4A	0.9900
N4—C7	1.452 (2)	C4—H4B	0.9900
N4—H4	0.8800	C3—H3	0.9500
N1—C1	1.328 (2)	C10—H10A	0.9800
N1—C3	1.382 (2)	C10—H10B	0.9800
N1—H1N	0.8800	C10—H10C	0.9800
N2—C1	1.325 (2)	C5—H5D	0.9900
N2—C2	1.391 (2)	C5—H5E	0.9900
N2—H2N	0.8800	C1—H1	0.9500

C6—N3—C5	122.12 (14)	C8—C9—C10	110.15 (13)
C6—N3—H3N	118.9	N5—C9—H9	109.6
C5—N3—H3N	118.9	C8—C9—H9	109.6
C9—N5—H5A	109.5	C10—C9—H9	109.6
C9—N5—H5B	109.5	C2—C4—C5	112.89 (14)
H5A—N5—H5B	109.5	C2—C4—H4A	109.0
C9—N5—H5C	109.5	C5—C4—H4A	109.0
H5A—N5—H5C	109.5	C2—C4—H4B	109.0
H5B—N5—H5C	109.5	C5—C4—H4B	109.0
C8—N4—C7	121.08 (13)	H4A—C4—H4B	107.8
C8—N4—H4	119.5	C2—C3—N1	107.51 (14)
C7—N4—H4	119.5	C2—C3—H3	126.2
C1—N1—C3	108.74 (15)	N1—C3—H3	126.2
C1—N1—H1N	125.6	O1—C6—N3	122.41 (16)
C3—N1—H1N	125.6	O1—C6—C7	119.02 (15)
C1—N2—C2	109.45 (14)	N3—C6—C7	118.57 (14)
C1—N2—H2N	125.3	C9—C10—H10A	109.5
C2—N2—H2N	125.3	C9—C10—H10B	109.5
N4—C7—C6	116.51 (14)	H10A—C10—H10B	109.5
N4—C7—H7A	108.2	C9—C10—H10C	109.5
C6—C7—H7A	108.2	H10A—C10—H10C	109.5
N4—C7—H7B	108.2	H10B—C10—H10C	109.5
C6—C7—H7B	108.2	N3—C5—C4	111.23 (14)
H7A—C7—H7B	107.3	N3—C5—H5D	109.4
C3—C2—N2	105.84 (15)	C4—C5—H5D	109.4
C3—C2—C4	130.41 (15)	N3—C5—H5E	109.4
N2—C2—C4	123.71 (15)	C4—C5—H5E	109.4
O2—C8—N4	123.82 (14)	H5D—C5—H5E	108.0
O2—C8—C9	120.74 (14)	N2—C1—N1	108.46 (15)
N4—C8—C9	115.40 (13)	N2—C1—H1	125.8
N5—C9—C8	107.95 (12)	N1—C1—H1	125.8
N5—C9—C10	109.86 (13)

C8—N4—C7—C6	90.63 (19)	N2—C2—C3—N1	0.45 (19)
C1—N2—C2—C3	−0.2 (2)	C4—C2—C3—N1	−177.31 (17)
C1—N2—C2—C4	177.72 (16)	C1—N1—C3—C2	−0.5 (2)
C7—N4—C8—O2	−7.3 (2)	C5—N3—C6—O1	4.6 (2)
C7—N4—C8—C9	170.48 (14)	C5—N3—C6—C7	−175.71 (14)
O2—C8—C9—N5	−35.58 (19)	N4—C7—C6—O1	178.07 (14)
N4—C8—C9—N5	146.53 (14)	N4—C7—C6—N3	−1.6 (2)
O2—C8—C9—C10	84.37 (18)	C6—N3—C5—C4	102.05 (17)
N4—C8—C9—C10	−93.53 (16)	C2—C4—C5—N3	−56.02 (19)
C3—C2—C4—C5	72.3 (2)	C2—N2—C1—N1	−0.1 (2)
N2—C2—C4—C5	−105.10 (18)	C3—N1—C1—N2	0.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl2	0.88	2.21	3.0503 (15)	159
N2—H2N···O1ⁱ	0.88	1.82	2.6962 (19)	175
N4—H4···Cl1ⁱⁱ	0.88	2.48	3.3100 (13)	157
N5—H5A···Cl1	0.91	2.38	3.2046 (14)	151
N5—H5B···Cl2ⁱⁱⁱ	0.91	2.24	3.1130 (14)	161
N5—H5C···Cl1^iv	0.91	2.37	3.2676 (14)	170
C3—H3···O2	0.95	2.30	3.2074 (19)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl2	0.88	2.21	3.0503 (15)	159
N2—H2N⋯O1ⁱ	0.88	1.82	2.6962 (19)	175
N4—H4⋯Cl1ⁱⁱ	0.88	2.48	3.3100 (13)	157
N5—H5A⋯Cl1	0.91	2.38	3.2046 (14)	151
N5—H5B⋯Cl2ⁱⁱⁱ	0.91	2.24	3.1130 (14)	161
N5—H5C⋯Cl1^iv	0.91	2.37	3.2676 (14)	170
C3—H3⋯O2	0.95	2.30	3.2074 (19)	161

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

4 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. IUPAC-IUB Commission on Biochemical Nomenclature. Abbreviations and symbols for the description of the conformation of polypeptide chains.

Authors:
Journal: J Mol Biol Date: 1970-08-28 Impact factor: 5.469

3. A multi-approach study of the interaction of the Cu(II) and Ni(II) ions with alanylglycylhistamine, a mimicking pseudopeptide of the serum albumine N-terminal residue.

Authors: P Gizzi; B Henry; P Rubini; S Giroux; E Wenger
Journal: J Inorg Biochem Date: 2005-05 Impact factor: 4.155

4. 4-{2-[3-(2-Ammonioacetamido)propanamido]ethyl}-1H-imidazol-3-ium dichloride.

Authors: Katalin Selmeczi; Bernard Henry; Emmanuel Wenger; Slimane Dahaoui
Journal: Acta Crystallogr Sect E Struct Rep Online Date: 2008-11-29

4 in total

1 in total

1. Crystal structure of 2-(1H-imidazol-4-yl)ethanaminium chloride.

Authors: Imene Belfilali; Siham Yebdri; Samira Louhibi; Leila Boukli-Hacene; Thierry Roisnel
Journal: Acta Crystallogr E Crystallogr Commun Date: 2015-04-09

1 in total