l-Histidinium iodide

Catherine, P.; Kumar, P.P.; Gunasekaran, B.

doi:10.1107/S2414314618012555

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 9| September 2018| x181255

https://doi.org/10.1107/S2414314618012555

Open

access

L-Histidinium iodide

P. Catherine,^a P. Praveen Kumar ^b ^* and B. Gunasekaran ^c ^*

^aPG and Research Department of Physics, Pachaiyappa's College, Chennai 600 030, Tamil Nadu, India, ^bDepartment of Physics, Presidency College, Chennai 600 005, Tamil Nadu, India, and ^cDepartment of Physics & Nano Technology, SRM Institute of Science and Technology, SRM Nagar, Kattankulathur, Kancheepuram Dist, Chennai 603 203, Tamil Nadu, India
^*Correspondence e-mail: ppkpresidency@gmail.com, phdguna@gmail.com

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 27 August 2018; accepted 5 September 2018; online 25 September 2018)

In the title salt, C₆H₁₀N₃O₂⁺·I⁻, the cation is protonated at the imidazole ring and the amine group and deprotonated at the carboxylate group. The crystal packing features N—H⋯O and N—H⋯I hydrogen bonds.

Keywords: crystal structure; L-histidine; zinc metabolism; antimicrobial activity; intermolecular hydrogen bonds.

CCDC reference: 1865975

Structure description

L-Histidine derivatives plays a major role in zinc metabolism, as a zinc binding moiety in serum (Casella & Gullotti, 1983 ), and these derivatives exhibit antimicrobial activity (Garza-Ortiz et al., 2013 ). The title compound comprises a protonated L-histidine cation and an iodide anion (Fig. 1). The geometric parameters of the title cation agree well with those reported for similar structures (Gokul Raj et al., 2006 ; Johnson & Feeder, 2004 ). The crystal packing (Fig. 2) is controlled by N—H⋯O and N—H⋯I hydrogen bonds (Table 1). The title compound is isostructural with the bromide and chloride salts.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯I1	0.86	2.91	3.546 (3)	133
N2—H2A⋯O2ⁱ	0.86	1.91	2.693 (5)	151
N3—H3A⋯O1ⁱⁱ	0.89	1.94	2.819 (3)	168
N3—H3B⋯I1ⁱⁱⁱ	0.89	2.70	3.546 (2)	160
N3—H3C⋯O1^iv	0.89	1.98	2.855 (3)	167
N3—H3C⋯O2^iv	0.89	2.56	3.214 (3)	131
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (iii) x-1, y, z-1; (iv) x+1, y, z.

Figure 1
The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for the non-H atoms.

Figure 2
Packing diagram of the title compound. Hydrogen bonds are shown as dashed lines. H atoms bonded to C atoms have been omitted for clarity.

Synthesis and crystallization

L-histidine (15.0 g, 0.0966 mol) and hydriodic acid (13.2150 ml mol⁻¹) were dissolved in 50 ml of double-distilled water and stirred at 293 K for 4 h. The solution was filtered and allowed to dry at room temperature by slow evaporation. After 30 d, pale-yello block-shaped crystals were obtained in a yield of 95% (m.p. 370 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₁₀N₃O₂⁺·I⁻
M_r	283.07
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	5.7363 (2), 8.2696 (3), 10.0169 (4)
β (°)	94.314 (1)
V (Å³)	473.82 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	3.35
Crystal size (mm)	0.10 × 0.10 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )
T_min, T_max	0.731, 0.851
No. of measured, independent and observed [I > 2σ(I)] reflections	9180, 3569, 3231
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.770

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.082, 1.20
No. of reflections	3569
No. of parameters	110
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.87
Absolute structure	Flack (1983 ), with 1725 Friedel pairs
Absolute structure parameter	0.05 (3)
Computer programs: APEX2 (Bruker, 2008 ), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1865975

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012555/bt4074sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618012555/bt4074Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618012555/bt4074Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

L-Histidinium iodide top

Crystal data top

C₆H₁₀N₃O₂⁺·I⁻	F(000) = 272
M_r = 283.07	D_x = 1.984 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 3626 reflections
a = 5.7363 (2) Å	θ = 3.2–33.1°
b = 8.2696 (3) Å	µ = 3.35 mm⁻¹
c = 10.0169 (4) Å	T = 296 K
β = 94.314 (1)°	Block, pale yellow
V = 473.82 (3) Å³	0.10 × 0.10 × 0.05 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3569 independent reflections
Radiation source: fine-focus sealed tube	3231 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 0 pixels mm^-1	θ_max = 33.2°, θ_min = 3.2°
ω and φ scans	h = −8→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −12→12
T_min = 0.731, T_max = 0.851	l = −15→15
9180 measured reflections

Refinement top

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)] = 0.022	H-atom parameters constrained
wR(F²) = 0.082	w = 1/[σ²(F_o²) + (0.0422P)² + 0.0342P] where P = (F_o² + 2F_c²)/3
S = 1.20	(Δ/σ)_max = 0.003
3569 reflections	Δρ_max = 0.40 e Å⁻³
110 parameters	Δρ_min = −0.87 e Å⁻³
1 restraint	Absolute structure: Flack (1983), with 1725 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.05 (3)

Special details top

Refinement. H atoms were positioned geometrically and refined using riding model with C-H = 0.97Å and U_iso(H) = 1.2Ueq(C) for C-H₂, C-H = 0.93Å and U_iso(H) = 1.2Ueq(C) for aromatic C-H, N-H = 0.89Å and U_iso(H) = 1.5Ueq(C) for N-H3, and N-H = 0.86Å and U_iso(H) = 1.2Ueq(C) for N-H.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
I1	1.11212 (3)	0.45507 (5)	1.108570 (15)	0.03755 (7)
O1	−0.3126 (3)	0.4108 (3)	0.4822 (3)	0.0346 (5)
O2	−0.2046 (4)	0.6389 (3)	0.3852 (3)	0.0316 (4)
N1	0.6300 (6)	0.5429 (4)	0.8774 (3)	0.0322 (6)
H1A	0.7417	0.5871	0.9266	0.039*
N2	0.4093 (5)	0.3651 (3)	0.7777 (3)	0.0279 (5)
H2A	0.3535	0.2730	0.7512	0.033*
C4	0.0921 (5)	0.5337 (4)	0.6622 (3)	0.0297 (6)
H4A	0.0461	0.6462	0.6679	0.036*
H4B	−0.0251	0.4698	0.7032	0.036*
N3	0.2571 (3)	0.5839 (3)	0.4421 (2)	0.0221 (4)
H3A	0.2532	0.6863	0.4691	0.033*
H3B	0.2195	0.5790	0.3544	0.033*
H3C	0.4003	0.5442	0.4600	0.033*
C3	0.5991 (7)	0.3871 (5)	0.8599 (4)	0.0346 (7)
H3	0.6940	0.3059	0.8984	0.042*
C1	0.3171 (5)	0.5127 (4)	0.7421 (3)	0.0262 (5)
C5	0.0875 (4)	0.4873 (2)	0.5136 (2)	0.0193 (5)
H5	0.1272	0.3725	0.5068	0.023*
C6	−0.1639 (4)	0.5135 (3)	0.4518 (3)	0.0216 (4)
C2	0.4567 (6)	0.6230 (4)	0.8052 (4)	0.0338 (6)
H2	0.4381	0.7346	0.8003	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.04010 (10)	0.03940 (10)	0.03123 (9)	0.00380 (11)	−0.01003 (6)	−0.00188 (11)
O1	0.0164 (8)	0.0278 (10)	0.0587 (14)	−0.0016 (6)	−0.0025 (8)	0.0096 (9)
O2	0.0230 (9)	0.0252 (9)	0.0444 (12)	0.0030 (7)	−0.0104 (8)	0.0063 (9)
N1	0.0295 (12)	0.0385 (15)	0.0272 (13)	−0.0035 (11)	−0.0077 (10)	−0.0098 (11)
N2	0.0307 (12)	0.0248 (11)	0.0270 (11)	0.0017 (9)	−0.0059 (10)	−0.0021 (9)
C4	0.0219 (11)	0.0428 (16)	0.0239 (12)	0.0047 (11)	−0.0012 (9)	−0.0031 (11)
N3	0.0139 (8)	0.0241 (9)	0.0280 (10)	0.0007 (7)	−0.0007 (7)	−0.0019 (8)
C3	0.0324 (16)	0.0397 (17)	0.0307 (16)	0.0052 (14)	−0.0055 (12)	−0.0001 (13)
C1	0.0255 (11)	0.0304 (12)	0.0220 (11)	−0.0026 (10)	−0.0033 (9)	−0.0016 (9)
C5	0.0133 (8)	0.0181 (13)	0.0260 (10)	0.0014 (6)	−0.0025 (7)	0.0013 (7)
C6	0.0152 (9)	0.0188 (9)	0.0302 (12)	0.0019 (8)	−0.0029 (8)	−0.0012 (9)
C2	0.0323 (14)	0.0323 (15)	0.0360 (15)	−0.0033 (12)	−0.0030 (11)	−0.0036 (12)

Geometric parameters (Å, º) top

O1—C6	1.258 (3)	C4—H4B	0.9700
O2—C6	1.245 (3)	N3—C5	1.484 (3)
N1—C3	1.310 (5)	N3—H3A	0.8900
N1—C2	1.357 (5)	N3—H3B	0.8900
N1—H1A	0.8600	N3—H3C	0.8900
N2—C3	1.327 (5)	C3—H3	0.9300
N2—C1	1.367 (4)	C1—C2	1.340 (5)
N2—H2A	0.8600	C5—C6	1.542 (3)
C4—C1	1.477 (4)	C5—H5	0.9800
C4—C5	1.535 (4)	C6—O2	1.245 (3)
C4—H4A	0.9700	C2—H2	0.9300

C3—N1—C2	108.8 (3)	N1—C3—H3	125.8
C3—N1—H1A	125.6	N2—C3—H3	125.8
C2—N1—H1A	125.6	C2—C1—N2	106.2 (3)
C3—N2—C1	108.8 (3)	C2—C1—C4	129.9 (3)
C3—N2—H2A	125.6	N2—C1—C4	123.5 (3)
C1—N2—H2A	125.6	N3—C5—C4	111.7 (2)
C1—C4—C5	116.5 (2)	N3—C5—C6	110.96 (19)
C1—C4—H4A	108.2	C4—C5—C6	107.6 (2)
C5—C4—H4A	108.2	N3—C5—H5	108.9
C1—C4—H4B	108.2	C4—C5—H5	108.9
C5—C4—H4B	108.2	C6—C5—H5	108.9
H4A—C4—H4B	107.3	O2—C6—O1	126.1 (2)
C5—N3—H3A	109.5	O2—C6—O1	126.1 (2)
C5—N3—H3B	109.5	O2—C6—C5	117.7 (2)
H3A—N3—H3B	109.5	O2—C6—C5	117.7 (2)
C5—N3—H3C	109.5	O1—C6—C5	116.0 (2)
H3A—N3—H3C	109.5	C1—C2—N1	107.8 (3)
H3B—N3—H3C	109.5	C1—C2—H2	126.1
N1—C3—N2	108.3 (3)	N1—C2—H2	126.1

C2—N1—C3—N2	0.0 (5)	N3—C5—C6—O2	−21.5 (3)
C1—N2—C3—N1	0.0 (5)	C4—C5—C6—O2	100.9 (3)
C3—N2—C1—C2	0.0 (4)	N3—C5—C6—O2	−21.5 (3)
C3—N2—C1—C4	−173.7 (3)	C4—C5—C6—O2	100.9 (3)
C5—C4—C1—C2	116.5 (4)	N3—C5—C6—O1	163.6 (2)
C5—C4—C1—N2	−71.3 (4)	C4—C5—C6—O1	−74.0 (3)
C1—C4—C5—N3	−59.8 (3)	N2—C1—C2—N1	0.0 (4)
C1—C4—C5—C6	178.2 (3)	C4—C1—C2—N1	173.2 (3)
O2—O2—C6—O1	0.0 (5)	C3—N1—C2—C1	0.0 (5)
O2—O2—C6—C5	0.0 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···I1	0.86	2.91	3.546 (3)	133
N2—H2A···O2ⁱ	0.86	1.91	2.693 (5)	151
N3—H3A···O1ⁱⁱ	0.89	1.94	2.819 (3)	168
N3—H3B···I1ⁱⁱⁱ	0.89	2.70	3.546 (2)	160
N3—H3C···O1^iv	0.89	1.98	2.855 (3)	167
N3—H3C···O2^iv	0.89	2.56	3.214 (3)	131

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

Acknowledgements

The authors acknowledge the SAIF, IIT Madras, Chennai.

References

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Casella, L. & Gullotti, M. (1983). J. Inorg. Biochem. 18, 19–31. CrossRef Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Garza-Ortiz, A., Camacho-Camacho, C., Sainz-Espunes, T., Rojas-Oviedo, I., Raul Gutierrez-Lucas, R., Gutierrez Carrillo, A. & Vera Ramirez, M. A. (2013). Bioinorg. Chem. Appl. pp. 1–12. Google Scholar
Gokul Raj, S., Kumar, G. R., Mohan, R. & Jayavel, R. (2006). Acta Cryst. E62, o5–o7. CrossRef IUCr Journals Google Scholar
Johnson, M. N. & Feeder, N. (2004). Acta Cryst. E60, o1273–o1274. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.