organic compounds
2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium chloride
aDepartment of Chemistry, Yazd Branch, Islamic Azad University, Yazd, Iran, bDepartment of Chemistry, Qom Branch, Islamic Azad University, Qom, Iran, and cInstitute of Physics ASCR, v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic
*Correspondence e-mail: tabatabaee45m@yahoo.com
In the 4H8N3O+·Cl−, N—H⋯Cl hydrogen bonds link the components into chains along [010]. In addition, weak C—H⋯Cl hydrogen bonds link the chains into a two-dimensional network perpendicular to (001).
of the title compound, CRelated literature
For creatinine (2-amino-1-methyl-5H-imidazol-4-one), which is used in the synthesis of some 1:1 proton-transfer compounds, see; Moghimi et al. (2004); Soleimannejad et al. (2005). For related structures, see: Tabatabaee et al. (2007); Bujak & Zaleski (2002); Tabatabaee, Abbasi et al. (2011); Tabatabaee, Tahriri et al. (2011, 2012); Tabatabaee, Adineh et al. (2012). For background information on weak C—H⋯Cl hydrogen bonds, see: Freytag & Jones (2000); Taylor & Kennard (1982).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell CrysAlis CCD data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536812027080/lh5487sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812027080/lh5487Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812027080/lh5487Isup3.cml
An aqueous solution of ZrCl4, (0.233 g, 1 mmol) in water (10 ml) was added to a stirring solution of (20 ml) pyridine-2,6-dicarboxylic acid (0.167 g, 1 mmol) and creatinine (0.113 g, 1 mmol). The reaction mixture was stirred at 298K for 4 h. The resulting solid residue was filtered and the colorless crystals of the title compound were obtained after few days at 277K from mother liquor.
H atoms bonded to C atoms were included in calculated positions with C—H = 0.96 and 0.97Å and with Uiso(H) = 1.5Ueq(C). H atoms bonded to N atom were included with N—H 0.86 amd 0.89Å and with Uiso(H) = 1.5Ueq(N).
In continuation of our research to synthesize transition metal complexes with dicarboxylic acids (especially pyridine-2,6-dicarboxilic acid) in the presence of some amino compounds (Tabatabaee, Abbasi et al., 2011; Tabatabaee, Tahriri et al., 2011; Tabatabaee, Tahriri et al., 2012; Tabatabaee, Adineh et al., 2012), the reaction of zirconium tetrachloride, with pyridine-2,6-dicarboxilic acid in the presence of creatinine was performed. The title compound (I) was fortuitously obtained as a result of this reaction. Creatinine has previously been used as a proton acceptor in the synthesis of some 1:1 proton-transfer compounds (Moghimi et al., 2004; Soleimannejad et al., 2005).
The molecular structure of (I) is shown in Fig. 1. During the reaction a proton was transferred to the ring N atom of the creatinine (2-Amino-1-methyl-5H-imidazol-4-one) molecule. In (I) the C3—N1 bond [1.3094 (18) Å] and C3—N2 bond [1.3647 (17) Å] can be compared to the C═N bond [1.3108 (18) Å] and C—N bond [1.3612 (17) Å] in the reported proton transfer compound, bis(creatininium)2,5-dicarboxybenzene-1,4-dicarboxylate (Tabatabaee et al., 2007).
In the crystal, intermolecular N—H···Cl hydrogen bonds link the components into one-dimensional chains along [010]. In addition, weak intermolecular C—H···Cl hydrogen bonds link one-dimensional-chains into a two-dimensional network perpendicular to (001) (Fig. 2). When compared with the
of 1,2,4-triazolium chloride (Bujak & Zaleski 2002), the N—H···Cl interactions are weaker in the present structure while C—H···Cl interactions are similar. For the weak intermolecular hydrogen bonds the C—H···Cl angles are in the range of those previously reported (Freytag & Jones, 2000; Taylor & Kennard, 1982).For creatinine (2-amino-1-methyl-5H-imidazol-4-one), which is used in in the synthesis of some 1:1 proton-transfer compounds, see; Moghimi et al. (2004); Soleimannejad et al. (2005). For related structures, see: Tabatabaee et al. (2007); Bujak & Zaleski (2002); Tabatabaee, Abbasi et al. (2011); Tabatabaee, Tahriri et al. (2011, 2012); Tabatabaee, Adineh et al. (2012). For background information on weak C—H···Cl hydrogen bonds, see: Freytag & Jones (2000); Taylor & Kennard (1982).
Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell
CrysAlis CCD (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).C4H8N3O+·Cl− | F(000) = 312 |
Mr = 149.58 | Dx = 1.507 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 5086 reflections |
a = 8.4617 (2) Å | θ = 4.4–66.9° |
b = 7.7073 (2) Å | µ = 4.51 mm−1 |
c = 10.2215 (3) Å | T = 120 K |
β = 98.369 (2)° | Plate, colourless |
V = 659.52 (3) Å3 | 0.57 × 0.35 × 0.15 mm |
Z = 4 |
Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer | 1167 independent reflections |
Radiation source: Enhance Ultra (Cu) X-ray Source | 1158 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.023 |
Detector resolution: 10.3784 pixels mm-1 | θmax = 67.0°, θmin = 6.4° |
Rotation method data acquisition using ω scans | h = −10→9 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −9→9 |
Tmin = 0.509, Tmax = 1.000 | l = −12→11 |
5373 measured reflections |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.1996P] where P = (Fo2 + 2Fc2)/3 |
1167 reflections | (Δ/σ)max < 0.001 |
83 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C4H8N3O+·Cl− | V = 659.52 (3) Å3 |
Mr = 149.58 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 8.4617 (2) Å | µ = 4.51 mm−1 |
b = 7.7073 (2) Å | T = 120 K |
c = 10.2215 (3) Å | 0.57 × 0.35 × 0.15 mm |
β = 98.369 (2)° |
Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer | 1167 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1158 reflections with I > 2σ(I) |
Tmin = 0.509, Tmax = 1.000 | Rint = 0.023 |
5373 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.074 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.28 e Å−3 |
1167 reflections | Δρmin = −0.18 e Å−3 |
83 parameters |
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. The H atoms were all located in a difference map, but those attached to carbon atoms and the nitrogen atom in amino group were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, N—H in the range 0.86–0.89 N—H to 0.86 O—H = 0.82 Å) and Uiso(H) (in the range 1.2 times Ueq of the parent atom). The distance between hydrogen atom H3 and N2 was left unrestrained. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.86814 (3) | 0.71590 (4) | 0.45236 (3) | 0.02046 (16) | |
O1 | 0.43618 (13) | 0.57647 (13) | 0.32081 (12) | 0.0358 (3) | |
N1 | 0.79940 (13) | 0.13245 (15) | 0.41934 (11) | 0.0238 (3) | |
H1 | 0.8035 | 0.0210 | 0.4217 | 0.029* | |
H2 | 0.8847 | 0.1923 | 0.4421 | 0.029* | |
N2 | 0.64629 (13) | 0.38708 (14) | 0.37714 (11) | 0.0217 (3) | |
H3 | 0.7227 | 0.4646 | 0.4031 | 0.026* | |
C1 | 0.48933 (16) | 0.43236 (18) | 0.33205 (13) | 0.0234 (3) | |
C2 | 0.40103 (16) | 0.26312 (17) | 0.30246 (14) | 0.0211 (3) | |
H4 | 0.3128 | 0.2525 | 0.3529 | 0.025* | |
H5 | 0.3606 | 0.2526 | 0.2090 | 0.025* | |
N3 | 0.52395 (13) | 0.13463 (14) | 0.34360 (11) | 0.0189 (3) | |
C3 | 0.66330 (16) | 0.21100 (17) | 0.38107 (13) | 0.0184 (3) | |
C4 | 0.49578 (15) | −0.04876 (17) | 0.31667 (13) | 0.0222 (3) | |
H6 | 0.4772 | −0.0674 | 0.2228 | 0.027* | |
H7 | 0.4040 | −0.0858 | 0.3545 | 0.027* | |
H8 | 0.5876 | −0.1142 | 0.3549 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0170 (2) | 0.0197 (2) | 0.0238 (2) | −0.00117 (10) | 0.00001 (14) | −0.00029 (10) |
O1 | 0.0308 (6) | 0.0202 (6) | 0.0562 (7) | 0.0037 (4) | 0.0058 (5) | 0.0023 (5) |
N1 | 0.0176 (6) | 0.0207 (6) | 0.0312 (6) | −0.0022 (4) | −0.0029 (5) | −0.0001 (5) |
N2 | 0.0203 (6) | 0.0182 (6) | 0.0262 (6) | −0.0030 (4) | 0.0019 (5) | −0.0020 (4) |
C1 | 0.0225 (7) | 0.0205 (7) | 0.0279 (7) | 0.0009 (5) | 0.0055 (5) | 0.0006 (5) |
C2 | 0.0162 (7) | 0.0191 (6) | 0.0276 (7) | 0.0028 (5) | 0.0021 (5) | 0.0011 (6) |
N3 | 0.0166 (5) | 0.0163 (6) | 0.0233 (6) | −0.0002 (4) | 0.0007 (4) | 0.0001 (4) |
C3 | 0.0203 (7) | 0.0188 (7) | 0.0163 (6) | −0.0019 (5) | 0.0032 (5) | −0.0007 (4) |
C4 | 0.0195 (7) | 0.0175 (6) | 0.0285 (7) | −0.0017 (5) | 0.0002 (5) | −0.0008 (5) |
O1—C1 | 1.1976 (18) | C2—N3 | 1.4533 (16) |
N1—C3 | 1.3094 (18) | C2—H4 | 0.9700 |
N1—H1 | 0.8600 | C2—H5 | 0.9700 |
N1—H2 | 0.8600 | N3—C3 | 1.3237 (18) |
N2—C3 | 1.3647 (17) | N3—C4 | 1.4530 (17) |
N2—C1 | 1.3856 (17) | C4—H6 | 0.9600 |
N2—H3 | 0.8921 | C4—H7 | 0.9600 |
C1—C2 | 1.5118 (19) | C4—H8 | 0.9600 |
C3—N1—H1 | 120.0 | H4—C2—H5 | 109.2 |
C3—N1—H2 | 120.0 | C3—N3—C4 | 127.01 (11) |
H1—N1—H2 | 120.0 | C3—N3—C2 | 110.53 (11) |
C3—N2—C1 | 110.62 (11) | C4—N3—C2 | 121.15 (10) |
C3—N2—H3 | 126.1 | N1—C3—N3 | 126.05 (12) |
C1—N2—H3 | 123.3 | N1—C3—N2 | 123.57 (12) |
O1—C1—N2 | 126.44 (13) | N3—C3—N2 | 110.36 (11) |
O1—C1—C2 | 127.82 (12) | N3—C4—H6 | 109.5 |
N2—C1—C2 | 105.73 (11) | N3—C4—H7 | 109.5 |
N3—C2—C1 | 102.59 (11) | H6—C4—H7 | 109.5 |
N3—C2—H4 | 111.2 | N3—C4—H8 | 109.5 |
C1—C2—H4 | 111.2 | H6—C4—H8 | 109.5 |
N3—C2—H5 | 111.2 | H7—C4—H8 | 109.5 |
C1—C2—H5 | 111.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.86 | 2.42 | 3.2714 (12) | 169 |
N1—H2···Cl1ii | 0.86 | 2.32 | 3.1506 (12) | 163 |
N2—H3···Cl1 | 0.89 | 2.31 | 3.1808 (11) | 165 |
C2—H4···Cl1iii | 0.97 | 2.69 | 3.6271 (14) | 162 |
C4—H8···Cl1i | 0.96 | 2.77 | 3.7241 (13) | 175 |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C4H8N3O+·Cl− |
Mr | 149.58 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 8.4617 (2), 7.7073 (2), 10.2215 (3) |
β (°) | 98.369 (2) |
V (Å3) | 659.52 (3) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 4.51 |
Crystal size (mm) | 0.57 × 0.35 × 0.15 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Atlas Gemini ultra |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.509, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5373, 1167, 1158 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.074, 1.08 |
No. of reflections | 1167 |
No. of parameters | 83 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.18 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl1i | 0.86 | 2.42 | 3.2714 (12) | 169 |
N1—H2···Cl1ii | 0.86 | 2.32 | 3.1506 (12) | 163 |
N2—H3···Cl1 | 0.89 | 2.31 | 3.1808 (11) | 165 |
C2—H4···Cl1iii | 0.97 | 2.69 | 3.6271 (14) | 162 |
C4—H8···Cl1i | 0.96 | 2.77 | 3.7241 (13) | 175 |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
Acknowledgements
This research was supported by the Islamic Azad University, Yazd Branch (grant No. 50678) and the Praemium Academiae project of the Academy of Sciences of the Czech Republic.
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In continuation of our research to synthesize transition metal complexes with dicarboxylic acids (especially pyridine-2,6-dicarboxilic acid) in the presence of some amino compounds (Tabatabaee, Abbasi et al., 2011; Tabatabaee, Tahriri et al., 2011; Tabatabaee, Tahriri et al., 2012; Tabatabaee, Adineh et al., 2012), the reaction of zirconium tetrachloride, with pyridine-2,6-dicarboxilic acid in the presence of creatinine was performed. The title compound (I) was fortuitously obtained as a result of this reaction. Creatinine has previously been used as a proton acceptor in the synthesis of some 1:1 proton-transfer compounds (Moghimi et al., 2004; Soleimannejad et al., 2005).
The molecular structure of (I) is shown in Fig. 1. During the reaction a proton was transferred to the ring N atom of the creatinine (2-Amino-1-methyl-5H-imidazol-4-one) molecule. In (I) the C3—N1 bond [1.3094 (18) Å] and C3—N2 bond [1.3647 (17) Å] can be compared to the C═N bond [1.3108 (18) Å] and C—N bond [1.3612 (17) Å] in the reported proton transfer compound, bis(creatininium)2,5-dicarboxybenzene-1,4-dicarboxylate (Tabatabaee et al., 2007).
In the crystal, intermolecular N—H···Cl hydrogen bonds link the components into one-dimensional chains along [010]. In addition, weak intermolecular C—H···Cl hydrogen bonds link one-dimensional-chains into a two-dimensional network perpendicular to (001) (Fig. 2). When compared with the crystal structure of 1,2,4-triazolium chloride (Bujak & Zaleski 2002), the N—H···Cl interactions are weaker in the present structure while C—H···Cl interactions are similar. For the weak intermolecular hydrogen bonds the C—H···Cl angles are in the range of those previously reported (Freytag & Jones, 2000; Taylor & Kennard, 1982).