Acta Cryst. (2009). E65, o448 [ doi:10.1107/S1600536809003699 ]
The title compound, C10H12N3O+·Cl-, is a derivative of o-phthaldehyde and methylthiourea. The molecules form dimers through intra- and intermolecular N-H
O hydrogen bonds. The dimers are further linked into chains through one C-HCl and two N-HCl hydrogen bonds.
O-phthaldehyde (200 mmol), methylthiourea (200 mmol) and a few drops of 2M HCl were mixed and ground in mortar and pestle. The product obtained was washed sequentially with hexane, ether, ethanol and water. The precipitate was dried and recrystallized from a mixture of methanol:acetone (9:1), by slow evaporation at room temperature.
Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).
![[Figure 1]](./ez2156fig1thm.gif)
| Fig. 1. The title compound (I) with displacement ellipsoids drawn at 50% probability level. Intramolecular H-bonds are indicated by broken lines. |
![[Figure 2]](./ez2156fig2thm.gif)
| Fig. 2. The packing of I (PLATON: Spek, 2003) showing the dimers and H-bonds to the chlorine anion. H-bonds are indicated by broken lines. |
| C10H12N3O+·Cl− | Z = 2 |
| Mr = 225.68 | F(000) = 236 |
| Triclinic, P1 | Dx = 1.454 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.1171 (5) Å | Cell parameters from 2369 reflections |
| b = 7.7900 (6) Å | θ = 3.1–27.5° |
| c = 10.3033 (8) Å | µ = 0.35 mm−1 |
| α = 89.484 (3)° | T = 296 K |
| β = 69.997 (2)° | Needle, light yellow |
| γ = 74.613 (4)° | 0.30 × 0.10 × 0.06 mm |
| V = 515.43 (7) Å3 |
| Bruker Kappa APEXII CCD diffractometer | 2369 independent reflections |
| Radiation source: fine-focus sealed tube | 2210 reflections with I > 2σ(I) |
| graphite | Rint = 0.020 |
| Detector resolution: 7.50 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
| ω scans | h = −9→9 |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −10→10 |
| Tmin = 0.982, Tmax = 0.989 | l = −13→13 |
| 8853 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)] = 0.032 | Hydrogen site location: mixed |
| wR(F2) = 0.101 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.00 | w = 1/[σ2(Fo2) + (0.0646P)2 + 0.2853P] where P = (Fo2 + 2Fc2)/3 |
| 2369 reflections | (Δ/σ)max < 0.001 |
| 146 parameters | Δρmax = 0.69 e Å−3 |
| 0 restraints | Δρmin = −0.21 e Å−3 |
| C10H12N3O+·Cl− | γ = 74.613 (4)° |
| Mr = 225.68 | V = 515.43 (7) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 7.1171 (5) Å | Mo Kα radiation |
| b = 7.7900 (6) Å | µ = 0.35 mm−1 |
| c = 10.3033 (8) Å | T = 296 K |
| α = 89.484 (3)° | 0.30 × 0.10 × 0.06 mm |
| β = 69.997 (2)° |
| Bruker Kappa APEXII CCD diffractometer | 2369 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2210 reflections with I > 2σ(I) |
| Tmin = 0.982, Tmax = 0.989 | Rint = 0.020 |
| 8853 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.032 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.101 | Δρmax = 0.69 e Å−3 |
| S = 1.00 | Δρmin = −0.21 e Å−3 |
| 2369 reflections | Absolute structure: ? |
| 146 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles |
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 | ||
| O1 | 0.29475 (16) | 0.09740 (13) | 0.60677 (11) | 0.0195 (3) | |
| N1 | 0.46180 (18) | 0.25619 (17) | 0.37719 (12) | 0.0161 (3) | |
| N2 | 0.19866 (18) | 0.40058 (16) | 0.58681 (12) | 0.0155 (3) | |
| N3 | 0.05849 (19) | 0.28726 (17) | 0.79177 (13) | 0.0177 (3) | |
| C1 | 0.5740 (2) | 0.29979 (19) | 0.23859 (15) | 0.0175 (4) | |
| C2 | 0.4836 (2) | 0.49861 (19) | 0.24873 (15) | 0.0165 (4) | |
| C3 | 0.5278 (2) | 0.6215 (2) | 0.15233 (15) | 0.0201 (4) | |
| C4 | 0.4209 (2) | 0.8007 (2) | 0.19298 (17) | 0.0222 (4) | |
| C5 | 0.2750 (2) | 0.8576 (2) | 0.32626 (17) | 0.0214 (4) | |
| C6 | 0.2298 (2) | 0.73562 (19) | 0.42329 (15) | 0.0183 (4) | |
| C7 | 0.3359 (2) | 0.55629 (19) | 0.38103 (14) | 0.0149 (4) | |
| C8 | 0.3263 (2) | 0.39698 (18) | 0.45638 (14) | 0.0147 (3) | |
| C9 | 0.1900 (2) | 0.24711 (19) | 0.66151 (14) | 0.0155 (3) | |
| C10 | 0.0312 (3) | 0.1475 (2) | 0.88541 (15) | 0.0218 (4) | |
| Cl1 | 0.11104 (5) | 0.28646 (4) | 0.19897 (3) | 0.0186 (1) | |
| H1A | 0.54729 | 0.23997 | 0.16735 | 0.0210* | |
| H1B | 0.72287 | 0.26795 | 0.21941 | 0.0210* | |
| H1N | 0.487 (3) | 0.156 (3) | 0.401 (2) | 0.0194* | |
| H2N | 0.113 (3) | 0.507 (3) | 0.631 (2) | 0.0186* | |
| H3 | 0.62547 | 0.58510 | 0.06360 | 0.0242* | |
| H3N | −0.007 (3) | 0.397 (3) | 0.819 (2) | 0.0212* | |
| H4 | 0.44729 | 0.88501 | 0.12976 | 0.0266* | |
| H5 | 0.20729 | 0.97864 | 0.35036 | 0.0256* | |
| H6 | 0.13317 | 0.77212 | 0.51234 | 0.0220* | |
| H10A | 0.01212 | 0.04982 | 0.83996 | 0.0327* | |
| H10B | −0.08889 | 0.19448 | 0.96722 | 0.0327* | |
| H10C | 0.15238 | 0.10608 | 0.91081 | 0.0327* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0212 (5) | 0.0138 (5) | 0.0177 (5) | −0.0003 (4) | −0.0033 (4) | 0.0024 (4) |
| N1 | 0.0167 (5) | 0.0144 (6) | 0.0145 (6) | −0.0019 (4) | −0.0039 (4) | 0.0029 (4) |
| N2 | 0.0166 (5) | 0.0126 (6) | 0.0143 (6) | −0.0020 (4) | −0.0032 (4) | 0.0016 (4) |
| N3 | 0.0208 (6) | 0.0145 (6) | 0.0145 (6) | −0.0031 (5) | −0.0036 (5) | 0.0021 (4) |
| C1 | 0.0162 (6) | 0.0182 (7) | 0.0149 (6) | −0.0030 (5) | −0.0029 (5) | 0.0021 (5) |
| C2 | 0.0146 (6) | 0.0192 (7) | 0.0165 (7) | −0.0058 (5) | −0.0057 (5) | 0.0024 (5) |
| C3 | 0.0193 (7) | 0.0251 (8) | 0.0169 (7) | −0.0097 (6) | −0.0049 (5) | 0.0049 (6) |
| C4 | 0.0251 (7) | 0.0221 (8) | 0.0249 (7) | −0.0130 (6) | −0.0111 (6) | 0.0101 (6) |
| C5 | 0.0245 (7) | 0.0158 (7) | 0.0264 (8) | −0.0074 (6) | −0.0109 (6) | 0.0047 (6) |
| C6 | 0.0181 (6) | 0.0176 (7) | 0.0200 (7) | −0.0053 (5) | −0.0074 (5) | 0.0016 (5) |
| C7 | 0.0142 (6) | 0.0160 (6) | 0.0164 (7) | −0.0055 (5) | −0.0067 (5) | 0.0037 (5) |
| C8 | 0.0140 (6) | 0.0156 (6) | 0.0158 (6) | −0.0040 (5) | −0.0071 (5) | 0.0018 (5) |
| C9 | 0.0160 (6) | 0.0156 (6) | 0.0155 (6) | −0.0048 (5) | −0.0062 (5) | 0.0033 (5) |
| C10 | 0.0280 (7) | 0.0197 (7) | 0.0156 (7) | −0.0068 (6) | −0.0050 (6) | 0.0060 (5) |
| Cl1 | 0.0195 (2) | 0.0144 (2) | 0.0192 (2) | −0.0041 (1) | −0.0040 (1) | 0.0002 (1) |
| O1—C9 | 1.2234 (17) | C4—C5 | 1.397 (2) |
| N1—C1 | 1.4654 (19) | C5—C6 | 1.390 (2) |
| N1—C8 | 1.3096 (19) | C6—C7 | 1.392 (2) |
| N2—C8 | 1.3356 (18) | C7—C8 | 1.463 (2) |
| N2—C9 | 1.4197 (19) | C1—H1A | 0.9700 |
| N3—C9 | 1.3296 (19) | C1—H1B | 0.9700 |
| N3—C10 | 1.456 (2) | C3—H3 | 0.9300 |
| N1—H1N | 0.81 (2) | C4—H4 | 0.9300 |
| N2—H2N | 0.90 (2) | C5—H5 | 0.9300 |
| N3—H3N | 0.86 (2) | C6—H6 | 0.9300 |
| C1—C2 | 1.501 (2) | C10—H10A | 0.9600 |
| C2—C3 | 1.390 (2) | C10—H10B | 0.9600 |
| C2—C7 | 1.395 (2) | C10—H10C | 0.9600 |
| C3—C4 | 1.390 (2) | ||
| Cl1···C1 | 3.4838 (16) | C8···C7vii | 3.457 (2) |
| Cl1···C2 | 3.6463 (16) | C9···C3vii | 3.539 (2) |
| Cl1···C5i | 3.6252 (16) | C9···C6ii | 3.358 (2) |
| Cl1···N2ii | 3.0969 (13) | C9···C4vii | 3.513 (2) |
| Cl1···N3ii | 3.2082 (13) | C9···C5ii | 3.575 (2) |
| Cl1···H5i | 2.9100 | C10···C4ii | 3.500 (3) |
| Cl1···H1A | 2.9300 | C10···C5ii | 3.579 (3) |
| Cl1···H1Biii | 2.7400 | C10···C10ix | 3.283 (2) |
| Cl1···H2Nii | 2.23 (2) | C1···H10Bx | 2.9400 |
| Cl1···H3iv | 3.0500 | C5···H10Aii | 3.0400 |
| Cl1···H3Nii | 2.40 (2) | C6···H2N | 2.82 (2) |
| Cl1···H6ii | 2.9900 | C9···H1N | 2.75 (2) |
| Cl1···H10Av | 3.0400 | C10···H10Bix | 3.0600 |
| O1···O1vi | 2.9982 (16) | C10···H10Cix | 3.0700 |
| O1···N1vi | 2.8760 (17) | H1A···Cl1 | 2.9300 |
| O1···N1 | 2.7097 (16) | H1B···Cl1xi | 2.7400 |
| O1···H1Nvi | 2.15 (2) | H1B···H10Bx | 2.4700 |
| O1···H10A | 2.6500 | H1N···O1vi | 2.15 (2) |
| O1···H1N | 2.22 (2) | H1N···C9 | 2.75 (2) |
| N1···O1 | 2.7097 (16) | H1N···O1 | 2.22 (2) |
| N1···O1vi | 2.8760 (17) | H2N···H6 | 2.4000 |
| N2···Cl1ii | 3.0969 (13) | H2N···H3N | 2.11 (3) |
| N3···C5ii | 3.436 (2) | H2N···C6 | 2.82 (2) |
| N3···C3vii | 3.433 (2) | H2N···Cl1ii | 2.23 (2) |
| N3···Cl1ii | 3.2082 (13) | H3···Cl1iv | 3.0500 |
| N2···H6 | 2.9400 | H3N···H2N | 2.11 (3) |
| C1···Cl1 | 3.4838 (16) | H3N···Cl1ii | 2.40 (2) |
| C2···Cl1 | 3.6463 (16) | H5···Cl1viii | 2.9100 |
| C3···N3vii | 3.433 (2) | H6···H2N | 2.4000 |
| C3···C9vii | 3.539 (2) | H6···N2 | 2.9400 |
| C4···C9vii | 3.513 (2) | H6···Cl1ii | 2.9900 |
| C4···C10ii | 3.500 (3) | H10A···O1 | 2.6500 |
| C5···N3ii | 3.436 (2) | H10A···Cl1v | 3.0400 |
| C5···C9ii | 3.575 (2) | H10A···C5ii | 3.0400 |
| C5···C10ii | 3.579 (3) | H10B···C10ix | 3.0600 |
| C5···Cl1viii | 3.6252 (16) | H10B···H1Bxii | 2.4700 |
| C6···C9ii | 3.358 (2) | H10B···C1xii | 2.9400 |
| C7···C8vii | 3.457 (2) | H10C···C10ix | 3.0700 |
| C1—N1—C8 | 112.52 (12) | N2—C9—N3 | 112.47 (12) |
| C8—N2—C9 | 124.09 (12) | O1—C9—N2 | 121.32 (12) |
| C9—N3—C10 | 120.48 (13) | O1—C9—N3 | 126.20 (13) |
| C8—N1—H1N | 125.2 (14) | N1—C1—H1A | 111.00 |
| C1—N1—H1N | 122.2 (14) | N1—C1—H1B | 111.00 |
| C8—N2—H2N | 118.4 (13) | C2—C1—H1A | 111.00 |
| C9—N2—H2N | 117.5 (13) | C2—C1—H1B | 111.00 |
| C10—N3—H3N | 121.3 (13) | H1A—C1—H1B | 109.00 |
| C9—N3—H3N | 118.2 (13) | C2—C3—H3 | 121.00 |
| N1—C1—C2 | 101.98 (12) | C4—C3—H3 | 121.00 |
| C1—C2—C3 | 130.68 (13) | C3—C4—H4 | 119.00 |
| C3—C2—C7 | 120.12 (13) | C5—C4—H4 | 119.00 |
| C1—C2—C7 | 109.19 (12) | C4—C5—H5 | 120.00 |
| C2—C3—C4 | 117.74 (14) | C6—C5—H5 | 120.00 |
| C3—C4—C5 | 121.78 (14) | C5—C6—H6 | 122.00 |
| C4—C5—C6 | 120.86 (14) | C7—C6—H6 | 122.00 |
| C5—C6—C7 | 116.91 (13) | N3—C10—H10A | 109.00 |
| C2—C7—C8 | 106.74 (12) | N3—C10—H10B | 109.00 |
| C2—C7—C6 | 122.59 (13) | N3—C10—H10C | 109.00 |
| C6—C7—C8 | 130.66 (13) | H10A—C10—H10B | 109.00 |
| N1—C8—C7 | 109.54 (12) | H10A—C10—H10C | 109.00 |
| N1—C8—N2 | 126.82 (13) | H10B—C10—H10C | 109.00 |
| N2—C8—C7 | 123.63 (12) | ||
| C8—N1—C1—C2 | 1.26 (17) | C1—C2—C7—C6 | 177.86 (14) |
| C1—N1—C8—C7 | −1.95 (18) | C1—C2—C7—C8 | −1.00 (17) |
| C1—N1—C8—N2 | 178.99 (15) | C3—C2—C7—C6 | −1.0 (2) |
| C9—N2—C8—N1 | −0.2 (3) | C3—C2—C7—C8 | −179.83 (14) |
| C8—N2—C9—N3 | 176.55 (15) | C2—C3—C4—C5 | 0.6 (2) |
| C9—N2—C8—C7 | −179.15 (14) | C3—C4—C5—C6 | −0.6 (2) |
| C8—N2—C9—O1 | −3.7 (2) | C4—C5—C6—C7 | −0.1 (2) |
| C10—N3—C9—O1 | 1.4 (3) | C5—C6—C7—C8 | 179.48 (16) |
| C10—N3—C9—N2 | −178.92 (15) | C5—C6—C7—C2 | 0.9 (2) |
| N1—C1—C2—C3 | 178.61 (16) | C2—C7—C8—N1 | 1.83 (18) |
| N1—C1—C2—C7 | −0.06 (17) | C6—C7—C8—N1 | −176.90 (16) |
| C1—C2—C3—C4 | −178.36 (16) | C6—C7—C8—N2 | 2.2 (3) |
| C7—C2—C3—C4 | 0.2 (2) | C2—C7—C8—N2 | −179.07 (15) |
| Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z+1; (iii) x−1, y, z; (iv) −x+1, −y+1, −z; (v) −x, −y, −z+1; (vi) −x+1, −y, −z+1; (vii) −x+1, −y+1, −z+1; (viii) x, y+1, z; (ix) −x, −y, −z+2; (x) x+1, y, z−1; (xi) x+1, y, z; (xii) x−1, y, z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O1 | 0.81 (2) | 2.22 (2) | 2.7097 (16) | 119.9 (18) |
| N1—H1N···O1vi | 0.81 (2) | 2.15 (2) | 2.8760 (17) | 150 (2) |
| N2—H2N···Cl1ii | 0.90 (2) | 2.23 (2) | 3.0969 (13) | 160.5 (18) |
| N3—H3N···Cl1ii | 0.86 (2) | 2.40 (2) | 3.2082 (13) | 157.0 (17) |
| C1—H1B···Cl1xi | 0.9700 | 2.7400 | 3.6755 (16) | 162.00 |
| Symmetry codes: (vi) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (xi) x+1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1N···O1 | 0.81 (2) | 2.22 (2) | 2.7097 (16) | 119.9 (18) |
| N1—H1N···O1i | 0.81 (2) | 2.15 (2) | 2.8760 (17) | 150 (2) |
| N2—H2N···Cl1ii | 0.90 (2) | 2.23 (2) | 3.0969 (13) | 160.5 (18) |
| N3—H3N···Cl1ii | 0.86 (2) | 2.40 (2) | 3.2082 (13) | 157.0 (17) |
| C1—H1B···Cl1iii | 0.9700 | 2.7400 | 3.6755 (16) | 162.00 |
| Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) x+1, y, z. |
The authors acknowledge the Higher Education Commission, Islamabad, and the University of the Punjab, Lahore, Pakistan, for funding the research.
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Iminium salts are a class of organic compounds acting as reactive intermediates. These are being extensively synthesized and further reacted in an efficient and convenient manner for the preparation of multidrug-resistance reversal agents and pesticides and for metal complexation to form new photosensitizers (Page et al., 2008; Skalkos et al., 1994; Tariq et al., 2008). The present paper relates to the continuation of our studies regarding the formation of derivatives of O-phthaldehyde with different ureas (Maliha et al., 2008; Maliha, Tariq, Tahir, Hussain & Ali, 2009; Maliha, Tariq, Tahir, Hussain & Siddiqui, 2009).
The molecule of the title compound (I; Fig 1), is almost planar. It has three N—H bonds in the asymmetric unit. The N—H of the pyrrole ring forms an intramolecular as well as an intermolecular N–H···O H-bond. The title compound forms a dimer (Fig 2) with a central four membered O···H···O···H unit. The other two N–H groups in the methyl urea moiety are involved in intermolecular H-bonding with the Cl-. The Cl- also forms H-bonds with the methylene group of the pyrrole ring. Consequently, the chlorine anion makes three H-bonds. Similar Cl- bonding behavior has been reported by Arfan et al. (2008). No strong π interactions are observed.