Acta Cryst. (2010). E66, o1945 [ doi:10.1107/S1600536810024554 ]
In the crystal structure of the title compound, C6H9N2+·ClCH2COO-, prepared by the reaction of OPDA (orthophenelynediamine) with chloroacetic acid, N-H
O hydrogen bonds generate ladder-like chains and very weak intermolecular C-HCl hydrogen-bonding interactions between the anions and cations lead to a supramolecular network. C-HO interactions also occur.
OPDA (Orthophenelynediamine)(0.108 g, 1 mmol) was dissolved in 20 ml of acetonitrile solution and which was added the solution of 25 ml of methanol containing chloroaceticacid (0.23 g, 1 mmol); this reaction mixture was stirred for 5 min and kept for crystalization at room temperature. Colorless needle-like crystals were formed after 3 days (yield: 0.145 g, 72% based on OPDA).
All H atoms were found on difference maps, with C—H=0.93 Å and included in the final cycles of refinement using a riding model, with Uiso(H)=1.2Ueq(C)
Data collection: SMART (Bruker, 2003); cell refinement: SMAIT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./ds2035fig1thm.gif)
| Fig. 1. ORTEP diagram of the compound 1 (Thermal ellipsoids are at 50% probability level). |
![[Figure 2]](./ds2035fig2thm.gif)
| Fig. 2. Interactions of C—H···cl in the compound 1 give rise to diverse supramolecular network and all the inetractions arround the cation and anion respectively with symetry codes All the symetry codes for hyderogen bonding were written in the Table 1 |
![[Figure 3]](./ds2035fig3thm.gif)
| Fig. 3. The ladder-type one-dimensional chainlike arrangement generated by N—H···O hydrogen bonding interactions. |
![[Figure 4]](./ds2035fig4thm.gif)
| Fig. 4. Hydrogen bonding situation around the cation. |
![[Figure 5]](./ds2035fig5thm.gif)
| Fig. 5. Hydrogen bonding situation around the anion. |
![[Figure 6]](./ds2035fig6thm.gif)
| Fig. 6. The formation of the title compound. |
| C6H9N2+·C2H2ClO2− | F(000) = 424 |
| Mr = 202.64 | Dx = 1.400 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5050 reflections |
| a = 11.371 (3) Å | θ = 2.3–26.1° |
| b = 4.4852 (11) Å | µ = 0.37 mm−1 |
| c = 20.115 (4) Å | T = 298 K |
| β = 110.439 (12)° | Needle, colorless |
| V = 961.3 (4) Å3 | 0.36 × 0.20 × 0.16 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 1922 independent reflections |
| Radiation source: fine-focus sealed tube | 1651 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| phi and ω scans | θmax = 26.2°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −14→14 |
| Tmin = 0.879, Tmax = 0.944 | k = −5→5 |
| 9366 measured reflections | l = −24→24 |
| 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.137 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0676P)2 + 0.3616P] where P = (Fo2 + 2Fc2)/3 |
| 1922 reflections | (Δ/σ)max = 0.001 |
| 126 parameters | Δρmax = 0.33 e Å−3 |
| 0 restraints | Δρmin = −0.29 e Å−3 |
| C6H9N2+·C2H2ClO2− | V = 961.3 (4) Å3 |
| Mr = 202.64 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 11.371 (3) Å | µ = 0.37 mm−1 |
| b = 4.4852 (11) Å | T = 298 K |
| c = 20.115 (4) Å | 0.36 × 0.20 × 0.16 mm |
| β = 110.439 (12)° |
| Bruker SMART CCD area-detector diffractometer | 1922 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2003) | 1651 reflections with I > 2σ(I) |
| Tmin = 0.879, Tmax = 0.944 | Rint = 0.025 |
| 9366 measured reflections | θmax = 26.2° |
| R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.137 | Δρmax = 0.33 e Å−3 |
| S = 1.09 | Δρmin = −0.29 e Å−3 |
| 1922 reflections | Absolute structure: ? |
| 126 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.38338 (15) | 0.3513 (3) | 0.89834 (8) | 0.0425 (4) | |
| H1A | 0.4696 | 0.3585 | 0.9056 | 0.051* | |
| H1B | 0.3687 | 0.1914 | 0.9249 | 0.051* | |
| H1C | 0.3625 | 0.5114 | 0.9189 | 0.051* | |
| N2 | 0.4570 (2) | −0.0303 (6) | 0.80725 (13) | 0.0819 (7) | |
| H2A | 0.4758 | −0.1428 | 0.7809 | 0.098* | |
| H2B | 0.5201 | 0.0394 | 0.8428 | 0.098* | |
| C1 | 0.1923 (2) | 0.4640 (5) | 0.79778 (11) | 0.0539 (5) | |
| H1 | 0.1695 | 0.5954 | 0.8269 | 0.065* | |
| C2 | 0.1128 (2) | 0.4187 (6) | 0.72902 (12) | 0.0641 (6) | |
| H2 | 0.0360 | 0.5167 | 0.7117 | 0.077* | |
| C3 | 0.1485 (3) | 0.2267 (6) | 0.68631 (12) | 0.0655 (7) | |
| H3 | 0.0950 | 0.1932 | 0.6400 | 0.079* | |
| C4 | 0.2628 (2) | 0.0833 (6) | 0.71141 (12) | 0.0630 (6) | |
| H4 | 0.2861 | −0.0422 | 0.6813 | 0.076* | |
| C5 | 0.3443 (2) | 0.1229 (5) | 0.78112 (11) | 0.0499 (5) | |
| C6 | 0.30556 (18) | 0.3157 (4) | 0.82373 (10) | 0.0422 (4) | |
| Cl1 | 0.88856 (6) | −0.20415 (18) | 1.05309 (4) | 0.0787 (3) | |
| O1 | 0.63853 (15) | 0.3221 (4) | 0.92605 (9) | 0.0630 (5) | |
| O2 | 0.65904 (16) | 0.1467 (3) | 1.03239 (8) | 0.0563 (4) | |
| C7 | 0.69161 (19) | 0.1690 (4) | 0.97966 (10) | 0.0453 (5) | |
| C8 | 0.8017 (2) | −0.0074 (7) | 0.97533 (13) | 0.0612 (6) | |
| H8A | 0.855 (3) | 0.122 (8) | 0.9661 (16) | 0.090 (10)* | |
| H8B | 0.767 (3) | −0.161 (9) | 0.938 (2) | 0.118 (13)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| N1 | 0.0520 (9) | 0.0381 (8) | 0.0424 (8) | −0.0007 (7) | 0.0229 (7) | −0.0024 (6) |
| N2 | 0.0660 (13) | 0.0873 (16) | 0.0926 (16) | 0.0075 (12) | 0.0278 (12) | −0.0425 (13) |
| C1 | 0.0615 (13) | 0.0508 (12) | 0.0534 (12) | 0.0014 (10) | 0.0250 (10) | 0.0040 (9) |
| C2 | 0.0615 (13) | 0.0702 (15) | 0.0563 (13) | 0.0000 (12) | 0.0150 (11) | 0.0151 (12) |
| C3 | 0.0715 (15) | 0.0782 (16) | 0.0434 (12) | −0.0223 (13) | 0.0160 (11) | 0.0026 (11) |
| C4 | 0.0819 (17) | 0.0650 (14) | 0.0515 (12) | −0.0217 (13) | 0.0351 (12) | −0.0159 (11) |
| C5 | 0.0571 (12) | 0.0476 (11) | 0.0528 (11) | −0.0117 (9) | 0.0290 (10) | −0.0088 (9) |
| C6 | 0.0515 (11) | 0.0379 (9) | 0.0421 (10) | −0.0073 (8) | 0.0228 (8) | 0.0004 (7) |
| Cl1 | 0.0550 (4) | 0.0965 (6) | 0.0777 (5) | 0.0095 (3) | 0.0146 (3) | 0.0200 (4) |
| O1 | 0.0545 (9) | 0.0749 (11) | 0.0602 (10) | 0.0028 (8) | 0.0207 (8) | 0.0171 (8) |
| O2 | 0.0803 (10) | 0.0421 (8) | 0.0640 (9) | −0.0001 (7) | 0.0472 (8) | −0.0018 (6) |
| C7 | 0.0480 (11) | 0.0445 (10) | 0.0471 (11) | −0.0094 (8) | 0.0214 (9) | −0.0046 (8) |
| C8 | 0.0584 (13) | 0.0771 (17) | 0.0549 (13) | 0.0100 (12) | 0.0285 (11) | 0.0064 (12) |
| N1—C6 | 1.461 (2) | C3—C4 | 1.378 (4) |
| N1—H1A | 0.9402 | C3—H3 | 0.9300 |
| N1—H1B | 0.9425 | C4—C5 | 1.396 (3) |
| N1—H1C | 0.9015 | C4—H4 | 0.9300 |
| N2—C5 | 1.385 (3) | C5—C6 | 1.393 (3) |
| N2—H2A | 0.8138 | Cl1—C8 | 1.767 (3) |
| N2—H2B | 0.8747 | O1—C7 | 1.243 (3) |
| C1—C2 | 1.378 (3) | O2—C7 | 1.244 (2) |
| C1—C6 | 1.380 (3) | C7—C8 | 1.509 (3) |
| C1—H1 | 0.9300 | C8—H8A | 0.90 (3) |
| C2—C3 | 1.374 (4) | C8—H8B | 0.99 (4) |
| C2—H2 | 0.9300 | ||
| C6—N1—H1A | 112.9 | C3—C4—C5 | 121.3 (2) |
| C6—N1—H1B | 109.6 | C3—C4—H4 | 119.4 |
| H1A—N1—H1B | 108.6 | C5—C4—H4 | 119.4 |
| C6—N1—H1C | 113.4 | N2—C5—C6 | 121.6 (2) |
| H1A—N1—H1C | 109.2 | N2—C5—C4 | 121.3 (2) |
| H1B—N1—H1C | 102.6 | C6—C5—C4 | 117.1 (2) |
| C5—N2—H2A | 118.7 | C1—C6—C5 | 121.37 (19) |
| C5—N2—H2B | 121.3 | C1—C6—N1 | 119.11 (17) |
| H2A—N2—H2B | 115.2 | C5—C6—N1 | 119.45 (18) |
| C2—C1—C6 | 120.5 (2) | O1—C7—O2 | 125.8 (2) |
| C2—C1—H1 | 119.8 | O1—C7—C8 | 113.63 (18) |
| C6—C1—H1 | 119.8 | O2—C7—C8 | 120.5 (2) |
| C3—C2—C1 | 119.1 (2) | C7—C8—Cl1 | 115.41 (16) |
| C3—C2—H2 | 120.4 | C7—C8—H8A | 107 (2) |
| C1—C2—H2 | 120.4 | Cl1—C8—H8A | 107 (2) |
| C2—C3—C4 | 120.7 (2) | C7—C8—H8B | 107 (2) |
| C2—C3—H3 | 119.7 | Cl1—C8—H8B | 106 (2) |
| C4—C3—H3 | 119.7 | H8A—C8—H8B | 114 (3) |
| C6—C1—C2—C3 | −0.8 (3) | N2—C5—C6—C1 | −178.9 (2) |
| C1—C2—C3—C4 | −0.7 (4) | C4—C5—C6—C1 | −0.9 (3) |
| C2—C3—C4—C5 | 1.5 (4) | N2—C5—C6—N1 | −1.8 (3) |
| C3—C4—C5—N2 | 177.4 (2) | C4—C5—C6—N1 | 176.18 (18) |
| C3—C4—C5—C6 | −0.7 (3) | O1—C7—C8—Cl1 | 174.88 (19) |
| C2—C1—C6—C5 | 1.6 (3) | O2—C7—C8—Cl1 | −7.3 (3) |
| C2—C1—C6—N1 | −175.42 (18) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1C···O2i | 0.90 | 1.88 | 2.777 (2) | 173 |
| N1—H1B···O2ii | 0.94 | 1.82 | 2.763 (2) | 173 |
| N2—H2B···O1 | 0.87 | 2.16 | 3.004 (3) | 163 |
| C4—H4···O1iii | 0.93 | 2.66 | 3.527 (3) | 156 |
| C3—H3···Cl1iv | 0.93 | 3.24 | 3.985 (3) | 138 |
| N2—H2A···N2iii | 0.81 | 2.77 | 3.587 (4) | 179 |
| C8—H8A···Cl1v | 0.90 (3) | 3.10 (3) | 3.878 (3) | 146 (3) |
| C8—H8B···O1vi | 0.99 (4) | 2.71 (4) | 3.491 (4) | 136 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+2; (iii) −x+1, y−1/2, −z+3/2; (iv) x−1, −y−1/2, z−1/2; (v) −x+2, −y, −z+2; (vi) x, y−1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1C···O2i | 0.90 | 1.88 | 2.777 (2) | 173 |
| N1—H1B···O2ii | 0.94 | 1.82 | 2.763 (2) | 173 |
| N2—H2B···O1 | 0.87 | 2.16 | 3.004 (3) | 163 |
| C4—H4···O1iii | 0.93 | 2.66 | 3.527 (3) | 156 |
| C3—H3···Cl1iv | 0.93 | 3.24 | 3.985 (3) | 138 |
| N2—H2A···N2iii | 0.81 | 2.77 | 3.587 (4) | 179 |
| C8—H8A···Cl1v | 0.90 (3) | 3.10 (3) | 3.878 (3) | 146 (3) |
| C8—H8B···O1vi | 0.99 (4) | 2.71 (4) | 3.491 (4) | 136 (3) |
| Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+2; (iii) −x+1, y−1/2, −z+3/2; (iv) x−1, −y−1/2, z−1/2; (v) −x+2, −y, −z+2; (vi) x, y−1, z. |
We thank the Department of Science and Technology, Government of India, for the National X-ray Diffractometer facility at the University of Hyderabad. We acknowledge the Department of Science and Technology, Government of India, for financial support (project No. SR/S1/IC-23/2007). ASR and RK are grateful to the CSIR, Government of India, and BKT thanks the UGC, Government of India, for their fellowships. We also thank Dr A. R. Bijju, School of Chemistry, University of Hyderabad, for helpful discussions.
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We have reported here the synthesis and structural characterization of a hitherto unknown organic ion pair compound 1, consisting of orthophenylenediammonium cation and chloroacetate anion, that provides a good supramolecular information. The ladder-type one-dimensional chainlike arrangement has been generated because of N—H···O hydrogen bonding interaction in the crystal of compound 1, as shown in Fig. 3.