Ammonium 2-(3,4-di­methyl­benzo­yl)benzoate dihydrate

Ming-Hui Zhang; Yue-Lin Yuan; Jun-Feng Kou

doi:10.1107/S1600536813012087

. 2013 May 11;69(Pt 6):o860. doi: 10.1107/S1600536813012087

Ammonium 2-(3,4-dimethylbenzoyl)benzoate dihydrate

Ming-Hui Zhang ^a, Yue-Lin Yuan ^a, Jun-Feng Kou ^a,^*

PMCID: PMC3684941 PMID: 23795043

Abstract

In the anion of the title compound, NH₄ ⁺·C₁₆H₁₃O₃ ⁻·2H₂O, the benzene rings are twisted with respect to each other by 73.56 (10)°. In the crystal, extensive N—H⋯O and O—H⋯O hydrogen bonds link the cations, anions and lattice water molecules into a three dimensional supramolecular structure.

Related literature

For the synthesis of the title compound, see: Elofson et al. (1965 ▶). For related compounds, see: Boon et al. (1986 ▶); Yeung et al. (2002 ▶); Gopalakrishnan et al. (2005 ▶); Qiao et al. (2008 ▶); Gouda et al. (2010 ▶). graphic file with name e-69-0o860-scheme1.jpg

Experimental

Crystal data

NH₄ ⁺·C₁₆H₁₃O₃ ⁻·2H₂O
M _r = 307.34
Triclinic,
a = 7.5039 (15) Å
b = 7.7458 (15) Å
c = 14.439 (3) Å
α = 81.63 (3)°
β = 79.15 (3)°
γ = 78.67 (3)°
V = 803.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.20 × 0.18 × 0.15 mm

Data collection

Rigaku MM007-HF CCD (Saturn 724+) diffractometer
6289 measured reflections
2791 independent reflections
1674 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.114
S = 1.01
2791 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrystalStructure (Rigaku/MSC, 2006 ▶); cell refinement: CrystalStructure; data reduction: CrystalStructure; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(23.5KB, cif)}

Crystal structure: contains datablock(s) I, new_global_publ_block. DOI: 10.1107/S1600536813012087/xu5697sup1.cif

e-69-0o860-sup1.cif^{(23.5KB, cif)}

Click here for additional data file.^{(137KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813012087/xu5697Isup2.hkl

e-69-0o860-Isup2.hkl^{(137KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4W	0.93	1.98	2.836 (2)	152
N1—H1B⋯O3	0.93	1.90	2.820 (2)	170
N1—H1C⋯O3ⁱ	0.96	1.88	2.823 (3)	167
N1—H1D⋯O5W ⁱⁱ	0.96	2.03	2.871 (3)	144
N1—H1D⋯O4W ⁱⁱⁱ	0.96	2.45	3.067 (3)	121
O4W—H4WA⋯O2^iv	0.90	1.93	2.809 (2)	164
O4W—H4WB⋯O2ⁱⁱ	0.90	1.91	2.808 (2)	172
O5W—H5WA⋯O1^v	0.87	2.04	2.899 (2)	171
O5W—H5WB⋯O2	0.85	2.31	3.032 (2)	142

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The work was supported by the Youth Fund of Yunnan Normal University and the Scientific Research Foundation of Yunnan Provincial Department of Education (grant No. 22012Z019).

supplementary crystallographic information

Comment

Friedel-Crafts acylation provides a fundamentaland useful method for the synthesis of aromatic ketones, which are important intermediates for preparing fine chemicals in the field of pharmaceuticals, agrochemicals, and fragrances. Typically, these reactions are performed using acyl chloride (for acylation) in the presence of a little more than one equivalent of Lewis acids, such as anhydrous aluminium chloride, titanium chloride and iron chloride (Elofson et al. 1965; Boon et al. 1986; Yeung et al. 2002; Gopalakrishnan et al. 2005; Qiao et al. 2008; Gouda et al. 2010). Herein we report the synthesis and structure of the title compound with aluminium chloride.

The structure of the title compound is shown in Fig. 1, Fig. 2 and hydrogen-bond geometry is given in Table 1. The compound crystallizes in the triclinic space group p-1,and the crystallographic asymmetric unit consists of one crystallo graphically independent anion, one ammonium cation and two water molecules. As shown in Fig.2, the dihedral angle is 73.2 between benzene rings which are not coplane. An interesting part of the structure of title compound is the helical chains formed by the N—H···O and O—H···O. hydrogen-bonding interactions along c axis in this molecule (Table 1 & Fig.3). Two neighouring N atoms formed helical chain (O3—N1—O4W—O2 andO2-O4W—N1—O3) which bridge two carboxy O3 atoms formed two oppposite handed chains with the bond distances of N1···O3 2.823 (3) Å, N1···O4w 3.067 (3) Å, O4W···O2 2.808 (2) Å. Further connection of the helices via N—H···O5W hydrogen bond with the bond distance of 2.871 Å gives the three-dimensional structure.

Experimental

In a 250 ml dry three-necked round-bottom flask, aluminium chloride (34.8 g, 0.26 mol) was dissolved in dry dichloromethane (150 ml), ortho-xylene (11.2 g, 0.105 mol) was added and then phthalic anhydride portion-wise with formation of an orange liquid in ice bath for 3 h while stirring. The mixture was reacted for 10 h while elevating the temperature of the reactor up to 303 K with formation of a yellow precipitate, then cooled down to room temperature and poured over a mixture of ice (20 g) and concentrated hydrochloric acid (10 ml) with a large amount of gas generated by HCl (Elofson et al., 1965). The organic layer was separated and the aqueous layer was extracted with dichloromethane (3 × 50 ml). The combined organic layers were washed with water (20 ml), concentrated in the rotary evaporator to give the pure yell compound, dried in vaccum and yield: 20.2 g, 80%. MS(EI): m/z = 254([M—CH3]+). Crystals suitable for X-ray analysis were obtained by evaporate slowly the solution of the compound in 25% aqueous ammonia in 88% yield within a month.