organic compounds
2-[(2-Azaniumylethyl)carbamoyl]phenolate–phenol (1/1)
aLaboratoire de Chimie Inorganiue et d'Environment, Université def Tlemcen, BP 119, Tlemcen 13 000, Algeria, bUnité de Recherche de Cimie de l'Environnement et Moléculaire Structurale, CHEMS, Université Mentouri-Constantine, 25000 , Algeria, cLaboratoire d'Electrochimie, d'Ingénierie Moléculaire et de Catalyse Redox (LEIMCR), Faculté des Sciences de l'Ingénieur, Université Farhat Abbas, Sétif 19000, Algeria, and dCentre de Difractométrie X, UMR 6226 CNRS Unité Sciences Chimiques de Rennes, Université de Rennes I, 263 Avenue du Général Leclerc, 35042 Rennes, France
*Correspondence e-mail: bouacida_sofiane@yahoo.fr
In the title 1:1 adduct, C9H12N2O2·C6H6O, the dihedral angle between the benzene ring and the salicylic amide group is 6.68 (6)°. The conformation of the amide group is supported by two intramolecular N—H⋯O hydrogen bonds, which close S(6) and S(7) rings. In the crystal, the components are linked by O—H⋯O and N—H⋯O hydrogen bonds, generating (100) sheets.
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2011); cell SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536813005849/hb7050sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536813005849/hb7050Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536813005849/hb7050Isup3.cml
0.06 g (1 mmol) ethylenediamine was dissolved in 20 ml of methanol. To this methanolic solution 0.214 g (1 mmol) of phenyl salicylate were added in one portion. This mixture was stirred for one hour at room temperature, and then 0.172 g (1 mmol) of 2-hydroxynaphtaldehyde were also added and heated to 60 °C for 4 h. The solid obtained was recovered by filtration after reducing of its volume on vaccum with rotating evaporator to obtain colourless prisms.
The H atoms were localized on Fourier maps but introduced in calculated positions and treated as riding on their parent atom (C,O and N) with C—H = 0.97 Å (ethylene)or 0.93 Å (aromatic), O—H = 0.82 Å and N—H = 0.86 Å or 0.89 Å (ammonium); with Uiso(H) = 1.2Ueq(ammonium and hydroxy) and Uiso(H) = 1.5Ueq.
Data collection: APEX2 (Bruker, 2011); cell
SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); program(s) used to solve structure: SIR2002 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C9H12N2O2·C6H6O | F(000) = 584 |
Mr = 274.31 | Dx = 1.298 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 4306 reflections |
a = 12.6494 (4) Å | θ = 2.9–27.4° |
b = 13.2145 (6) Å | µ = 0.09 mm−1 |
c = 8.5445 (4) Å | T = 150 K |
β = 100.637 (2)° | Prism, colorless |
V = 1403.72 (10) Å3 | 0.58 × 0.52 × 0.38 mm |
Z = 4 |
Bruker APEXII CCD diffractometer | 2649 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
CCD rotation images, thin slices scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | h = −16→16 |
Tmin = 0.860, Tmax = 0.966 | k = −12→17 |
12244 measured reflections | l = −11→11 |
3208 independent 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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0448P)2 + 0.4498P] where P = (Fo2 + 2Fc2)/3 |
3208 reflections | (Δ/σ)max < 0.001 |
181 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C9H12N2O2·C6H6O | V = 1403.72 (10) Å3 |
Mr = 274.31 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.6494 (4) Å | µ = 0.09 mm−1 |
b = 13.2145 (6) Å | T = 150 K |
c = 8.5445 (4) Å | 0.58 × 0.52 × 0.38 mm |
β = 100.637 (2)° |
Bruker APEXII CCD diffractometer | 3208 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2011) | 2649 reflections with I > 2σ(I) |
Tmin = 0.860, Tmax = 0.966 | Rint = 0.035 |
12244 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.27 e Å−3 |
3208 reflections | Δρmin = −0.21 e Å−3 |
181 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. |
x | y | z | Uiso*/Ueq | ||
O2 | 0.59307 (7) | 0.65808 (6) | 0.29145 (10) | 0.0207 (2) | |
O3 | 0.56158 (7) | 0.34524 (7) | 0.37386 (11) | 0.0260 (2) | |
N1 | 0.47865 (8) | 0.48940 (8) | 0.27880 (12) | 0.0195 (2) | |
H1N | 0.4845 | 0.5532 | 0.2627 | 0.023* | |
N2 | 0.43633 (8) | 0.32203 (8) | 0.03416 (11) | 0.0186 (2) | |
H2A | 0.5036 | 0.3421 | 0.0701 | 0.022* | |
H2B | 0.4287 | 0.306 | −0.0684 | 0.022* | |
H2C | 0.4219 | 0.2681 | 0.0891 | 0.022* | |
C7 | 0.67497 (10) | 0.60303 (9) | 0.36441 (13) | 0.0192 (3) | |
C8 | 0.77747 (11) | 0.64776 (10) | 0.40959 (17) | 0.0290 (3) | |
H8 | 0.7869 | 0.7148 | 0.3819 | 0.035* | |
C9 | 0.86393 (11) | 0.59533 (11) | 0.49331 (19) | 0.0338 (3) | |
H9 | 0.9302 | 0.6274 | 0.5215 | 0.041* | |
C10 | 0.85282 (11) | 0.49477 (11) | 0.53593 (17) | 0.0302 (3) | |
H10 | 0.9106 | 0.4599 | 0.595 | 0.036* | |
C11 | 0.75500 (10) | 0.44784 (10) | 0.48917 (14) | 0.0227 (3) | |
H11 | 0.7478 | 0.3803 | 0.5162 | 0.027* | |
C12 | 0.66564 (10) | 0.49853 (9) | 0.40198 (13) | 0.0183 (3) | |
C13 | 0.56553 (10) | 0.43867 (9) | 0.35241 (13) | 0.0186 (3) | |
C14 | 0.37497 (10) | 0.44126 (9) | 0.22499 (14) | 0.0201 (3) | |
H14A | 0.3182 | 0.4889 | 0.2346 | 0.024* | |
H14B | 0.3681 | 0.3839 | 0.2933 | 0.024* | |
C15 | 0.36081 (10) | 0.40533 (9) | 0.05392 (14) | 0.0202 (3) | |
H15A | 0.2875 | 0.382 | 0.0195 | 0.024* | |
H15B | 0.3726 | 0.4617 | −0.0135 | 0.024* | |
O1 | 0.65559 (7) | 0.32899 (7) | −0.02109 (12) | 0.0300 (2) | |
H1 | 0.6334 | 0.2758 | −0.0644 | 0.045* | |
C1 | 0.76300 (10) | 0.33979 (9) | −0.02608 (15) | 0.0212 (3) | |
C2 | 0.82529 (11) | 0.39958 (10) | 0.08869 (16) | 0.0272 (3) | |
H2 | 0.7942 | 0.4332 | 0.1645 | 0.033* | |
C3 | 0.93442 (12) | 0.40858 (11) | 0.08896 (19) | 0.0368 (4) | |
H3 | 0.9769 | 0.4482 | 0.1659 | 0.044* | |
C4 | 0.98085 (12) | 0.35932 (12) | −0.0238 (2) | 0.0418 (4) | |
H4 | 1.0544 | 0.3648 | −0.0217 | 0.05* | |
C5 | 0.91760 (12) | 0.30184 (11) | −0.1397 (2) | 0.0374 (4) | |
H5 | 0.9485 | 0.2695 | −0.2168 | 0.045* | |
C6 | 0.80857 (11) | 0.29210 (10) | −0.14187 (16) | 0.0265 (3) | |
H6 | 0.766 | 0.2538 | −0.2206 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0266 (5) | 0.0161 (4) | 0.0188 (4) | 0.0027 (3) | 0.0023 (3) | 0.0004 (3) |
O3 | 0.0273 (5) | 0.0163 (4) | 0.0321 (5) | 0.0016 (4) | −0.0003 (4) | 0.0016 (4) |
N1 | 0.0217 (5) | 0.0143 (5) | 0.0213 (5) | 0.0006 (4) | 0.0008 (4) | −0.0005 (4) |
N2 | 0.0217 (5) | 0.0175 (5) | 0.0163 (5) | −0.0020 (4) | 0.0026 (4) | −0.0013 (4) |
C7 | 0.0242 (6) | 0.0188 (6) | 0.0148 (5) | 0.0032 (5) | 0.0042 (4) | −0.0022 (4) |
C8 | 0.0284 (7) | 0.0205 (7) | 0.0378 (8) | −0.0028 (5) | 0.0052 (6) | −0.0014 (5) |
C9 | 0.0219 (7) | 0.0310 (8) | 0.0462 (9) | −0.0034 (6) | −0.0001 (6) | −0.0067 (6) |
C10 | 0.0250 (7) | 0.0284 (7) | 0.0332 (7) | 0.0060 (6) | −0.0050 (5) | −0.0052 (6) |
C11 | 0.0274 (7) | 0.0189 (6) | 0.0203 (6) | 0.0038 (5) | 0.0009 (5) | −0.0030 (5) |
C12 | 0.0222 (6) | 0.0177 (6) | 0.0150 (5) | 0.0014 (5) | 0.0030 (4) | −0.0028 (4) |
C13 | 0.0240 (6) | 0.0168 (6) | 0.0147 (5) | 0.0023 (5) | 0.0029 (4) | −0.0021 (4) |
C14 | 0.0201 (6) | 0.0192 (6) | 0.0209 (6) | 0.0014 (5) | 0.0033 (5) | −0.0013 (5) |
C15 | 0.0211 (6) | 0.0177 (6) | 0.0203 (6) | 0.0018 (5) | 0.0004 (4) | 0.0015 (5) |
O1 | 0.0244 (5) | 0.0233 (5) | 0.0436 (6) | −0.0046 (4) | 0.0096 (4) | −0.0114 (4) |
C1 | 0.0237 (6) | 0.0157 (6) | 0.0240 (6) | −0.0004 (5) | 0.0033 (5) | 0.0034 (5) |
C2 | 0.0358 (8) | 0.0214 (6) | 0.0235 (6) | −0.0041 (6) | 0.0030 (5) | 0.0011 (5) |
C3 | 0.0340 (8) | 0.0288 (8) | 0.0420 (8) | −0.0099 (6) | −0.0076 (6) | 0.0050 (6) |
C4 | 0.0240 (7) | 0.0311 (8) | 0.0709 (11) | −0.0010 (6) | 0.0101 (7) | 0.0105 (8) |
C5 | 0.0388 (8) | 0.0247 (7) | 0.0543 (10) | 0.0025 (6) | 0.0232 (7) | 0.0029 (7) |
C6 | 0.0338 (7) | 0.0192 (6) | 0.0272 (7) | −0.0009 (5) | 0.0074 (5) | −0.0004 (5) |
O2—C7 | 1.3239 (15) | C12—C13 | 1.4868 (17) |
O3—C13 | 1.2505 (15) | C14—C15 | 1.5158 (16) |
N1—C13 | 1.3408 (16) | C14—H14A | 0.97 |
N1—C14 | 1.4537 (15) | C14—H14B | 0.97 |
N1—H1N | 0.86 | C15—H15A | 0.97 |
N2—C15 | 1.4874 (16) | C15—H15B | 0.97 |
N2—H2A | 0.8899 | O1—C1 | 1.3747 (15) |
N2—H2B | 0.8897 | O1—H1 | 0.8195 |
N2—H2C | 0.8904 | C1—C6 | 1.3852 (18) |
C7—C8 | 1.4123 (18) | C1—C2 | 1.3862 (18) |
C7—C12 | 1.4276 (17) | C2—C3 | 1.385 (2) |
C8—C9 | 1.378 (2) | C2—H2 | 0.93 |
C8—H8 | 0.93 | C3—C4 | 1.381 (2) |
C9—C10 | 1.392 (2) | C3—H3 | 0.93 |
C9—H9 | 0.93 | C4—C5 | 1.380 (2) |
C10—C11 | 1.3758 (19) | C4—H4 | 0.93 |
C10—H10 | 0.93 | C5—C6 | 1.382 (2) |
C11—C12 | 1.4037 (17) | C5—H5 | 0.93 |
C11—H11 | 0.93 | C6—H6 | 0.93 |
C13—N1—C14 | 122.89 (10) | N1—C14—H14A | 109.1 |
C13—N1—H1N | 118.6 | C15—C14—H14A | 109.1 |
C14—N1—H1N | 118.5 | N1—C14—H14B | 109.1 |
C15—N2—H2A | 109.5 | C15—C14—H14B | 109.1 |
C15—N2—H2B | 109.4 | H14A—C14—H14B | 107.9 |
H2A—N2—H2B | 109.5 | N2—C15—C14 | 112.16 (10) |
C15—N2—H2C | 109.5 | N2—C15—H15A | 109.2 |
H2A—N2—H2C | 109.5 | C14—C15—H15A | 109.2 |
H2B—N2—H2C | 109.4 | N2—C15—H15B | 109.2 |
O2—C7—C8 | 119.86 (11) | C14—C15—H15B | 109.2 |
O2—C7—C12 | 123.18 (11) | H15A—C15—H15B | 107.9 |
C8—C7—C12 | 116.95 (11) | C1—O1—H1 | 109.5 |
C9—C8—C7 | 122.14 (13) | O1—C1—C6 | 121.26 (12) |
C9—C8—H8 | 118.9 | O1—C1—C2 | 118.24 (12) |
C7—C8—H8 | 118.9 | C6—C1—C2 | 120.50 (12) |
C8—C9—C10 | 120.46 (13) | C3—C2—C1 | 119.09 (13) |
C8—C9—H9 | 119.8 | C3—C2—H2 | 120.5 |
C10—C9—H9 | 119.8 | C1—C2—H2 | 120.5 |
C11—C10—C9 | 118.90 (13) | C4—C3—C2 | 120.70 (14) |
C11—C10—H10 | 120.5 | C4—C3—H3 | 119.6 |
C9—C10—H10 | 120.5 | C2—C3—H3 | 119.6 |
C10—C11—C12 | 122.14 (12) | C5—C4—C3 | 119.69 (14) |
C10—C11—H11 | 118.9 | C5—C4—H4 | 120.2 |
C12—C11—H11 | 118.9 | C3—C4—H4 | 120.2 |
C11—C12—C7 | 119.27 (11) | C4—C5—C6 | 120.38 (14) |
C11—C12—C13 | 117.22 (11) | C4—C5—H5 | 119.8 |
C7—C12—C13 | 123.50 (11) | C6—C5—H5 | 119.8 |
O3—C13—N1 | 120.72 (11) | C5—C6—C1 | 119.60 (13) |
O3—C13—C12 | 122.58 (11) | C5—C6—H6 | 120.2 |
N1—C13—C12 | 116.68 (11) | C1—C6—H6 | 120.2 |
N1—C14—C15 | 112.41 (10) | ||
O2—C7—C8—C9 | 176.44 (12) | C7—C12—C13—O3 | 173.39 (11) |
C12—C7—C8—C9 | −3.24 (19) | C11—C12—C13—N1 | 175.56 (10) |
C7—C8—C9—C10 | 0.3 (2) | C7—C12—C13—N1 | −4.97 (16) |
C8—C9—C10—C11 | 1.8 (2) | C13—N1—C14—C15 | −92.17 (13) |
C9—C10—C11—C12 | −1.0 (2) | N1—C14—C15—N2 | 66.25 (13) |
C10—C11—C12—C7 | −2.00 (18) | O1—C1—C2—C3 | 177.79 (12) |
C10—C11—C12—C13 | 177.50 (11) | C6—C1—C2—C3 | −1.91 (19) |
O2—C7—C12—C11 | −175.68 (11) | C1—C2—C3—C4 | 0.4 (2) |
C8—C7—C12—C11 | 3.98 (16) | C2—C3—C4—C5 | 1.1 (2) |
O2—C7—C12—C13 | 4.86 (17) | C3—C4—C5—C6 | −1.0 (2) |
C8—C7—C12—C13 | −175.47 (11) | C4—C5—C6—C1 | −0.5 (2) |
C14—N1—C13—O3 | 2.23 (17) | O1—C1—C6—C5 | −177.71 (12) |
C14—N1—C13—C12 | −179.37 (10) | C2—C1—C6—C5 | 1.98 (19) |
C11—C12—C13—O3 | −6.08 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 1.87 | 2.6696 (13) | 166 |
N1—H1N···O2 | 0.86 | 1.93 | 2.6490 (13) | 140 |
N2—H2A···O1 | 0.89 | 2.21 | 2.8995 (14) | 134 |
N2—H2A···O3 | 0.89 | 2.56 | 3.0547 (13) | 116 |
N2—H2B···O2ii | 0.89 | 1.93 | 2.7506 (13) | 152 |
N2—H2C···O2iii | 0.89 | 1.81 | 2.6939 (13) | 174 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H12N2O2·C6H6O |
Mr | 274.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 12.6494 (4), 13.2145 (6), 8.5445 (4) |
β (°) | 100.637 (2) |
V (Å3) | 1403.72 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.58 × 0.52 × 0.38 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2011) |
Tmin, Tmax | 0.860, 0.966 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12244, 3208, 2649 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.102, 1.03 |
No. of reflections | 3208 |
No. of parameters | 181 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 |
Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O3i | 0.82 | 1.87 | 2.6696 (13) | 166 |
N1—H1N···O2 | 0.86 | 1.93 | 2.6490 (13) | 140 |
N2—H2A···O1 | 0.89 | 2.21 | 2.8995 (14) | 134 |
N2—H2A···O3 | 0.89 | 2.56 | 3.0547 (13) | 116 |
N2—H2B···O2ii | 0.89 | 1.93 | 2.7506 (13) | 152 |
N2—H2C···O2iii | 0.89 | 1.81 | 2.6939 (13) | 174 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y+1, −z; (iii) −x+1, y−1/2, −z+1/2. |
Acknowledgements
Thanks are due to MESRS and ATRST (Ministére de l'Enseignement Supérieur et de la Recherche Scientifique et la direction générale de la recherche - Algeria) for financial support.
References
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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.
Salicylic amide with its diverse amidic forms namely ethylelenediamine or other amines were found to be as good chelating agents currently applied in coordination chemistry (Koch, 2001; Hancock et al., 1989).
The molecule structure of (I), is illustrated in Fig. 1. In the title structure the phenol molecule is cocrystalized with ethylenediamine Salicylic amide The crystal packing can be described by layers parallel to (100) planes (Fig. 2). It features intermolecular O—H···O and N—H···O hydrogen bonds (Fig. 2, Table 1). These interactions link the molecules within the layers and also link the layers together.