4-Bromobenzoyl 4-bromobenzoate monohydrate

Schmitt, B.; Gerber, T.; Hosten, E.; Betz, R.

doi:10.1107/S1600536811022264

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1662

doi:10.1107/S1600536811022264

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4-Bromobenzoyl 4-bromobenzoate monohydrate

Bonell Schmitt,^a Thomas Gerber,^a Eric Hosten ^a and Richard Betz ^a ^*

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 25 May 2011; accepted 8 June 2011; online 18 June 2011)

In the title compound, C₁₄H₈Br₂O₃·H₂O, the organic and water molecules both have crystallographically imposed C_s symmetry. The dihedral angle between the aromatic rings is 45.76 (11)°. In the crystal structure, intermolecular C—H⋯O and O—H⋯O hydrogen bonds link the molecules into chains parallel to the a axis. No π–π stacking interactions are observed in the crystal structure.

Related literature

For the crystal structure of anhydrous para-bromobenzoic acid anhydride, see: McCammon & Trotter (1964 ); Duesler et al. (1981 ). For the use of chelate ligands in coordination chemistry, see: Gade (1998 ). For details of graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₄H₈Br₂O₃·H₂O
M_r = 402.04
Orthorhombic, P n m a
a = 12.6118 (3) Å
b = 28.2378 (7) Å
c = 3.8898 (1) Å
V = 1385.27 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.86 mm⁻¹
T = 200 K
0.35 × 0.12 × 0.05 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.825, T_max = 1.000
11620 measured reflections
1728 independent reflections
1519 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.093
S = 1.30
1728 reflections
98 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O90—H901⋯O2ⁱ	0.84 (1)	2.24 (2)	3.043 (6)	161 (5)
C3—H3⋯O2ⁱⁱ	0.95	2.58	3.211 (5)	124
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+1]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811022264/rz2605sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022264/rz2605Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022264/rz2605Isup3.cdx

Supporting information file. DOI: 10.1107/S1600536811022264/rz2605Isup4.cml

checkCIF report

Comment top

Chelate ligands have found widespread use in coordination chemistry due to the enhanced thermodynamic stability of resultant coordination compounds in relation to coordination compounds exclusively applying comparable monodentate ligands (Gade 1998). Combining different sets of donor atoms in one chelate ligand molecule, a probe for testing and accomodating metal centers of different Lewis acidities is at hand. In our efforts to synthesize a chelate ligand featuring a set of oxygen, sulfur and nitrogen as possible donor atoms, a crystalline reaction product was obtained whose crystal structure analysis revealed the unintentional synthesis of the hydrated anhydride of para-bromobenzoic acid. The crystal structure of the anhydrous anhydride is apparent in the literature (McCammon & Trotter, 1964; Duesler et al., 1981).

The asymmetric unit comprises half of the organic molecule and half of the molecule of crystal water. The least-squares planes defined by the atoms of both aromatic moieties intersect at an angle of 45.76 (11)° (Fig. 1). In the crystal structure, intermolecular C—H···O and O—-H···O hydrogen bonds can be observed (Table 1). The carbonylic O atoms of the anhydride serve as twofold acceptors for the hydrogen bonds originating from the water molecule as well as the H atom of an adjacent molecule bonded to the C atom in ortho position to the carboxylic acid functionality. A description of the C—H···O hydrogen bonds in terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995) necessitates a R²₂(14) descriptor on the unitary level. In total, the moieties of the crystal structure are connected to chains parallel to the crystallographic a axis (Fig. 2). No π–π stacking interaction is observed. The packing of the compound in the crystal structure is shown in Fig. 3.

Related literature top

For the crystal structure of anhydrous para-bromobenzoic acid anhydride, see: McCammon & Trotter (1964); Duesler et al. (1981). For the use of chelate ligands in coordination chemistry, see: Gade (1998). For details of graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

The compound was prepared upon reacting 4-bromobenzyl chloride (2.5 mmol) with potassium thiocyanate (2.5 mmol) and dipyridin-2-ylamine (2.5 mmol) in refluxing acetone (15 ml) for two hours. Crystals suitable for the X-ray diffraction study were obtained upon free evaporation of the reaction mixture.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with anisotropic displacement ellipsoids drawn at 50% probability level. Symmetry code: (i) x, -y + 1/2, z.
	Fig. 2. Intermolecular contacts, viewed along [001]. Displacement ellipsoids are drawn at 50% probability level.
	Fig. 3. Molecular packing of the title compound, viewed along [001]. Displacement ellipsoids drawn at 50% probability level.

4-Bromobenzoyl 4-bromobenzoate monohydrate top

Crystal data top

C₁₄H₈Br₂O₃·H₂O	F(000) = 784
M_r = 402.04	D_x = 1.928 Mg m⁻³
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 4619 reflections
a = 12.6118 (3) Å	θ = 2.9–28.1°
b = 28.2378 (7) Å	µ = 5.86 mm⁻¹
c = 3.8898 (1) Å	T = 200 K
V = 1385.27 (6) Å³	Needle, yellow
Z = 4	0.35 × 0.12 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1728 independent reflections
Radiation source: fine-focus sealed tube	1519 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −16→16
T_min = 0.825, T_max = 1.000	k = −26→37
11620 measured reflections	l = −3→5

Refinement top

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.30	w = 1/[σ²(F_o²) + (0.0068P)² + 7.342P] where P = (F_o² + 2F_c²)/3
1728 reflections	(Δ/σ)_max < 0.001
98 parameters	Δρ_max = 0.69 e Å⁻³
2 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

C₁₄H₈Br₂O₃·H₂O	V = 1385.27 (6) Å³
M_r = 402.04	Z = 4
Orthorhombic, Pnma	Mo Kα radiation
a = 12.6118 (3) Å	µ = 5.86 mm⁻¹
b = 28.2378 (7) Å	T = 200 K
c = 3.8898 (1) Å	0.35 × 0.12 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1728 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1519 reflections with I > 2σ(I)
T_min = 0.825, T_max = 1.000	R_int = 0.024
11620 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	2 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.30	Δρ_max = 0.69 e Å⁻³
1728 reflections	Δρ_min = −0.62 e Å⁻³
98 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	−0.14551 (4)	0.030824 (15)	−0.21724 (12)	0.03488 (15)
O1	0.0688 (4)	0.2500	0.0995 (14)	0.0340 (11)
O2	0.2098 (2)	0.20237 (11)	0.2371 (14)	0.0530 (12)
C1	0.1190 (3)	0.20645 (15)	0.1450 (12)	0.0244 (9)
C2	0.0521 (3)	0.16413 (13)	0.0633 (11)	0.0208 (8)
C3	−0.0548 (3)	0.16199 (14)	0.1493 (11)	0.0224 (8)
H3	−0.0880	0.1880	0.2604	0.027*
C4	−0.1125 (3)	0.12164 (14)	0.0718 (11)	0.0228 (8)
H4	−0.1854	0.1197	0.1316	0.027*
C5	−0.0637 (3)	0.08430 (14)	−0.0924 (11)	0.0225 (8)
C6	0.0432 (3)	0.08532 (14)	−0.1753 (12)	0.0257 (9)
H6	0.0761	0.0592	−0.2863	0.031*
C7	0.1007 (3)	0.12551 (14)	−0.0919 (12)	0.0240 (9)
H7	0.1744	0.1267	−0.1414	0.029*
O90	0.3607 (4)	0.2500	0.7343 (14)	0.0354 (10)
H901	0.329 (4)	0.2690 (15)	0.864 (12)	0.053*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0490 (3)	0.0237 (2)	0.0319 (2)	−0.0150 (2)	−0.0019 (2)	−0.0033 (2)
O1	0.031 (2)	0.027 (2)	0.044 (3)	0.000	−0.003 (2)	0.000
O2	0.0195 (14)	0.0242 (15)	0.115 (4)	0.0002 (13)	−0.028 (2)	0.006 (2)
C1	0.0119 (17)	0.0224 (19)	0.039 (2)	−0.0004 (14)	−0.0018 (16)	0.0024 (18)
C2	0.0185 (18)	0.0157 (18)	0.028 (2)	0.0000 (15)	−0.0027 (16)	0.0032 (16)
C3	0.0190 (18)	0.0183 (18)	0.030 (2)	0.0043 (15)	−0.0010 (17)	−0.0004 (16)
C4	0.0207 (18)	0.0215 (19)	0.026 (2)	−0.0021 (15)	0.0018 (17)	0.0019 (17)
C5	0.032 (2)	0.0164 (18)	0.020 (2)	−0.0068 (16)	−0.0036 (17)	0.0024 (16)
C6	0.032 (2)	0.0169 (18)	0.028 (2)	0.0044 (16)	0.0029 (18)	−0.0031 (17)
C7	0.0181 (18)	0.0231 (19)	0.031 (2)	0.0034 (15)	0.0022 (17)	0.0018 (18)
O90	0.029 (2)	0.044 (3)	0.033 (3)	0.000	0.006 (2)	0.000

Geometric parameters (Å, º) top

Br1—C5	1.893 (4)	C3—H3	0.9500
O1—C1ⁱ	1.395 (4)	C4—C5	1.378 (6)
O1—C1	1.395 (4)	C4—H4	0.9500
O2—C1	1.205 (5)	C5—C6	1.387 (6)
C1—C2	1.497 (5)	C6—C7	1.385 (6)
C2—C7	1.389 (6)	C6—H6	0.9500
C2—C3	1.390 (5)	C7—H7	0.9500
C3—C4	1.385 (5)	O90—H901	0.840 (14)

C1ⁱ—O1—C1	123.7 (5)	C5—C4—H4	120.1
O2—C1—O1	123.6 (4)	C3—C4—H4	120.1
O2—C1—C2	121.5 (4)	C4—C5—C6	121.8 (4)
O1—C1—C2	114.9 (3)	C4—C5—Br1	119.1 (3)
C7—C2—C3	119.9 (4)	C6—C5—Br1	119.2 (3)
C7—C2—C1	118.0 (4)	C7—C6—C5	118.1 (4)
C3—C2—C1	122.0 (4)	C7—C6—H6	120.9
C4—C3—C2	119.5 (4)	C5—C6—H6	120.9
C4—C3—H3	120.2	C6—C7—C2	120.9 (4)
C2—C3—H3	120.2	C6—C7—H7	119.5
C5—C4—C3	119.7 (4)	C2—C7—H7	119.5

C1ⁱ—O1—C1—O2	2.1 (10)	C2—C3—C4—C5	−0.6 (6)
C1ⁱ—O1—C1—C2	−176.7 (4)	C3—C4—C5—C6	1.8 (7)
O2—C1—C2—C7	−35.8 (7)	C3—C4—C5—Br1	−176.8 (3)
O1—C1—C2—C7	143.1 (4)	C4—C5—C6—C7	−0.7 (7)
O2—C1—C2—C3	141.8 (5)	Br1—C5—C6—C7	177.8 (3)
O1—C1—C2—C3	−39.4 (6)	C5—C6—C7—C2	−1.5 (7)
C7—C2—C3—C4	−1.5 (6)	C3—C2—C7—C6	2.6 (7)
C1—C2—C3—C4	−179.0 (4)	C1—C2—C7—C6	−179.8 (4)

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O90—H901···O2ⁱⁱ	0.84 (1)	2.24 (2)	3.043 (6)	161 (5)
C3—H3···O2ⁱⁱⁱ	0.95	2.58	3.211 (5)	124

Symmetry codes: (ii) x, −y+1/2, z+1; (iii) x−1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₈Br₂O₃·H₂O
M_r	402.04
Crystal system, space group	Orthorhombic, Pnma
Temperature (K)	200
a, b, c (Å)	12.6118 (3), 28.2378 (7), 3.8898 (1)
V (Å³)	1385.27 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.86
Crystal size (mm)	0.35 × 0.12 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.825, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11620, 1728, 1519
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.093, 1.30
No. of reflections	1728
No. of parameters	98
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.62

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O90—H901···O2ⁱ	0.840 (14)	2.24 (2)	3.043 (6)	161 (5)
C3—H3···O2ⁱⁱ	0.95	2.58	3.211 (5)	124

Symmetry codes: (i) x, −y+1/2, z+1; (ii) x−1/2, y, −z+1/2.

Acknowledgements

The authors thank Mrs Jaci Neil-Schutte for helpful discussions.

References

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