Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807026463/lw2016sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807026463/lw2016Isup2.hkl |
CCDC reference: 654922
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (Wave) = 0.000 Å
- R factor = 0.041
- wR factor = 0.098
- Data-to-parameter ratio = 14.0
checkCIF/PLATON results
No syntax errors found
Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.222 0.706 Tmin and Tmax expected: 0.198 0.703 RR = 1.118 Please check that your absorption correction is appropriate.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Compound (I) was synthesized as essayed in (Nodiff et al., 1971). A mixture of 2-Methyl benzaldehyde (6.6 mmol), (4-bromophenyl) acetic acid (6.6 mmol), potassium carbonate (15.4 mmol) and acetic anhydride (15.4 mmol) was slowly heated to 358 K and continued at that temperature for 24 h. To this hot solution, 10.0 ml distilled water and 5.0 ml 10% HCl were added sequentially. The solution was stirred for a further 2 h and after that filtered. Impurities were removed from the precipitated product by washing with water. Recrystallization was carried out in chloroform. (yield; 80%, m.p. 163–168 C.
The molecules form hydrogen-bonded dimers across inversion centres. The O1—O2 distance is 2.617 (4) Å.
Cinnamic Acid derived antibacterial drugs have increased the importance of these acids, especially halogenated Cinnamic acids. These acids have been revealed to enhance the efficiency of prototype medicinals (Nodiff et al., 1971). The derivatives of these acids have been used as precursors in the shikimic acid metabolic pathways of higher plants (Forgo et al., 2005). In an extension of such studies, in order to observe the effect of different substituents for improvement of the efficacy of these drugs, we have synthesized derivitives of these compounds and report the structure of compound (I). In the molecular structure of Compound (I), the central C8—C9 bond length of acrylate moiety proves a clear double bond character, and bonds C1—C8 and C9—C11 single bond character, which confirms localized bonding. In all the bond lengths and bond angles, a comparable behavior is observed as found in (Allen et al., 1987), 3-(6-nitro-1, 3-benzodioxol-5-yl)-2-phenylacrylic acid, (II) (Hussain et al., 2006). In the crystal structure of (I), Centro symmetric dimers are formed via O—H···O hydrogen bonds linking carboxylic acid groups. This arrangement is like that observed in the crystal structure of (II). In compound (I), these dimers are further connected by small links which form a slab like structure of the compound.
For related literature, see: Allen et al. (1987); Forgo et al. (2005); Hussain et al. (2006); Nodiff et al. (1971).
Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. A thermal ellipsoid perspective drawing of the molecule, 50% probability. | |
Fig. 2. Thermal ellipsoid perspective drawing showing the hydrogen-bonded dimer. |
C16H13BrO2 | F(000) = 640 |
Mr = 317.17 | Dx = 1.505 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.0641 (12) Å | Cell parameters from 4981 reflections |
b = 15.208 (3) Å | θ = 3.0–25.7° |
c = 15.187 (3) Å | µ = 2.93 mm−1 |
β = 91.98 (3)° | T = 298 K |
V = 1399.7 (5) Å3 | Plate, colourless |
Z = 4 | 0.72 × 0.48 × 0.12 mm |
Rigaku Mercury CCD diffractometer | 2454 independent reflections |
Radiation source: sealed tube | 2133 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.055 |
Detector resolution: 14.6199 pixels mm-1 | θmax = 25.0°, θmin = 3.0° |
dtprofit.ref scans | h = −7→7 |
Absorption correction: multi-scan (REQAB; Rigaku/MSC, 1999) | k = −18→14 |
Tmin = 0.222, Tmax = 0.706 | l = −18→18 |
10277 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0375P)2 + 1.3644P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max < 0.001 |
2454 reflections | Δρmax = 0.43 e Å−3 |
175 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Bruker, 2000), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0086 (17) |
C16H13BrO2 | V = 1399.7 (5) Å3 |
Mr = 317.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.0641 (12) Å | µ = 2.93 mm−1 |
b = 15.208 (3) Å | T = 298 K |
c = 15.187 (3) Å | 0.72 × 0.48 × 0.12 mm |
β = 91.98 (3)° |
Rigaku Mercury CCD diffractometer | 2454 independent reflections |
Absorption correction: multi-scan (REQAB; Rigaku/MSC, 1999) | 2133 reflections with I > 2σ(I) |
Tmin = 0.222, Tmax = 0.706 | Rint = 0.055 |
10277 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.43 e Å−3 |
2454 reflections | Δρmin = −0.40 e Å−3 |
175 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 | ||
Br1 | 0.34229 (6) | 0.49805 (2) | 0.61545 (2) | 0.04791 (18) | |
O1 | 0.0639 (4) | 0.89770 (16) | 0.50704 (15) | 0.0498 (6) | |
O2 | 0.2513 (4) | 1.00144 (14) | 0.43676 (16) | 0.0423 (5) | |
H2 | 0.1630 | 1.0340 | 0.4617 | 0.051* | |
C1 | 0.6456 (5) | 0.8217 (2) | 0.30564 (17) | 0.0333 (6) | |
C2 | 0.8343 (5) | 0.8622 (2) | 0.27221 (19) | 0.0384 (7) | |
C3 | 0.9804 (5) | 0.8094 (3) | 0.2261 (2) | 0.0449 (8) | |
H3 | 1.1139 | 0.8351 | 0.2056 | 0.054* | |
C4 | 0.9393 (6) | 0.7225 (3) | 0.2094 (2) | 0.0495 (9) | |
H4 | 1.0415 | 0.6885 | 0.1766 | 0.059* | |
C5 | 0.7502 (6) | 0.6839 (2) | 0.2397 (2) | 0.0467 (8) | |
H5 | 0.7189 | 0.6232 | 0.2271 | 0.056* | |
C6 | 0.6057 (5) | 0.7333 (2) | 0.2884 (2) | 0.0408 (7) | |
H6 | 0.4762 | 0.7059 | 0.3106 | 0.049* | |
C7 | 0.8753 (6) | 0.9589 (3) | 0.2828 (2) | 0.0510 (9) | |
H7A | 1.0260 | 0.9718 | 0.2701 | 0.076* | |
H7B | 0.8473 | 0.9761 | 0.3422 | 0.076* | |
H7C | 0.7790 | 0.9909 | 0.2428 | 0.076* | |
C8 | 0.4923 (5) | 0.8763 (2) | 0.35516 (18) | 0.0343 (7) | |
H8 | 0.4826 | 0.9369 | 0.3376 | 0.041* | |
C9 | 0.3640 (4) | 0.8527 (2) | 0.42163 (18) | 0.0325 (6) | |
C10 | 0.2132 (5) | 0.9190 (2) | 0.45829 (19) | 0.0371 (7) | |
C11 | 0.3587 (5) | 0.7651 (2) | 0.46472 (17) | 0.0321 (6) | |
C12' | 0.5391 (5) | 0.7379 (2) | 0.51683 (18) | 0.0352 (7) | |
H12' | 0.6678 | 0.7746 | 0.5218 | 0.042* | |
C12 | 0.1737 (5) | 0.7111 (2) | 0.45780 (19) | 0.0371 (7) | |
H12 | 0.0482 | 0.7294 | 0.4221 | 0.045* | |
C13' | 0.5357 (5) | 0.6588 (2) | 0.56153 (19) | 0.0397 (7) | |
H13' | 0.6609 | 0.6404 | 0.5973 | 0.048* | |
C13 | 0.1680 (5) | 0.6314 (2) | 0.5017 (2) | 0.0398 (7) | |
H13 | 0.0408 | 0.5940 | 0.4961 | 0.048* | |
C14 | 0.3499 (5) | 0.6066 (2) | 0.55412 (18) | 0.0362 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0670 (3) | 0.0365 (2) | 0.0413 (2) | 0.00595 (16) | 0.01678 (16) | 0.00548 (14) |
O1 | 0.0596 (15) | 0.0398 (14) | 0.0518 (14) | 0.0139 (11) | 0.0273 (11) | 0.0084 (11) |
O2 | 0.0446 (12) | 0.0343 (12) | 0.0493 (13) | 0.0058 (10) | 0.0193 (10) | −0.0007 (10) |
C1 | 0.0336 (15) | 0.0408 (17) | 0.0258 (13) | 0.0039 (13) | 0.0046 (11) | 0.0038 (12) |
C2 | 0.0329 (15) | 0.052 (2) | 0.0303 (15) | 0.0013 (14) | 0.0023 (11) | 0.0037 (14) |
C3 | 0.0361 (16) | 0.065 (2) | 0.0344 (16) | 0.0060 (15) | 0.0106 (13) | 0.0085 (16) |
C4 | 0.051 (2) | 0.065 (3) | 0.0337 (16) | 0.0210 (18) | 0.0112 (14) | 0.0043 (16) |
C5 | 0.066 (2) | 0.0388 (19) | 0.0359 (16) | 0.0105 (16) | 0.0116 (15) | 0.0028 (14) |
C6 | 0.0455 (17) | 0.0439 (19) | 0.0338 (15) | 0.0043 (14) | 0.0124 (13) | 0.0040 (14) |
C7 | 0.0441 (19) | 0.060 (2) | 0.0496 (19) | −0.0080 (17) | 0.0098 (15) | −0.0006 (18) |
C8 | 0.0363 (15) | 0.0363 (17) | 0.0306 (14) | 0.0026 (13) | 0.0047 (11) | 0.0010 (13) |
C9 | 0.0313 (14) | 0.0366 (16) | 0.0297 (14) | 0.0011 (12) | 0.0040 (11) | −0.0023 (12) |
C10 | 0.0375 (15) | 0.0411 (19) | 0.0332 (15) | 0.0067 (13) | 0.0086 (12) | 0.0008 (13) |
C11 | 0.0339 (14) | 0.0372 (17) | 0.0256 (13) | 0.0035 (12) | 0.0084 (11) | −0.0021 (12) |
C12' | 0.0350 (15) | 0.0399 (18) | 0.0309 (14) | −0.0007 (13) | 0.0047 (11) | −0.0021 (13) |
C12 | 0.0302 (15) | 0.0437 (19) | 0.0377 (16) | 0.0036 (13) | 0.0040 (12) | 0.0004 (14) |
C13' | 0.0461 (18) | 0.0446 (19) | 0.0281 (14) | 0.0048 (14) | −0.0016 (12) | −0.0018 (13) |
C13 | 0.0335 (15) | 0.0417 (18) | 0.0448 (17) | −0.0037 (13) | 0.0103 (12) | −0.0014 (15) |
C14 | 0.0458 (17) | 0.0364 (17) | 0.0272 (14) | 0.0047 (13) | 0.0126 (12) | 0.0002 (12) |
Br1—C14 | 1.896 (3) | C7—H7B | 0.9599 |
O1—C10 | 1.233 (4) | C7—H7C | 0.9599 |
O2—C10 | 1.318 (4) | C8—C9 | 1.344 (4) |
O2—H2 | 0.8299 | C8—H8 | 0.9600 |
C1—C6 | 1.390 (5) | C9—C10 | 1.483 (4) |
C1—C2 | 1.410 (4) | C9—C11 | 1.485 (4) |
C1—C8 | 1.472 (4) | C11—C12' | 1.391 (4) |
C2—C3 | 1.401 (5) | C11—C12 | 1.391 (4) |
C2—C7 | 1.499 (5) | C12'—C13' | 1.381 (5) |
C3—C4 | 1.367 (5) | C12'—H12' | 0.9600 |
C3—H3 | 0.9600 | C12—C13 | 1.384 (5) |
C4—C5 | 1.382 (5) | C12—H12 | 0.9600 |
C4—H4 | 0.9600 | C13'—C14 | 1.380 (4) |
C5—C6 | 1.387 (5) | C13'—H13' | 0.9600 |
C5—H5 | 0.9600 | C13—C14 | 1.391 (4) |
C6—H6 | 0.9600 | C13—H13 | 0.9600 |
C7—H7A | 0.9599 | ||
C10—O2—H2 | 109.5 | C9—C8—H8 | 115.7 |
C6—C1—C2 | 119.6 (3) | C1—C8—H8 | 115.7 |
C6—C1—C8 | 122.2 (3) | C8—C9—C10 | 118.7 (3) |
C2—C1—C8 | 118.2 (3) | C8—C9—C11 | 126.4 (3) |
C3—C2—C1 | 117.7 (3) | C10—C9—C11 | 114.9 (2) |
C3—C2—C7 | 120.7 (3) | O1—C10—O2 | 122.5 (3) |
C1—C2—C7 | 121.6 (3) | O1—C10—C9 | 121.4 (3) |
C4—C3—C2 | 122.2 (3) | O2—C10—C9 | 116.0 (3) |
C4—C3—H3 | 118.9 | C12'—C11—C12 | 119.0 (3) |
C2—C3—H3 | 118.9 | C12'—C11—C9 | 119.3 (3) |
C3—C4—C5 | 119.8 (3) | C12—C11—C9 | 121.7 (3) |
C3—C4—H4 | 120.1 | C13'—C12'—C11 | 120.9 (3) |
C5—C4—H4 | 120.1 | C13'—C12'—H12' | 119.6 |
C4—C5—C6 | 119.6 (3) | C11—C12'—H12' | 119.6 |
C4—C5—H5 | 120.2 | C13—C12—C11 | 120.9 (3) |
C6—C5—H5 | 120.2 | C13—C12—H12 | 119.5 |
C5—C6—C1 | 121.0 (3) | C11—C12—H12 | 119.5 |
C5—C6—H6 | 119.5 | C14—C13'—C12' | 119.2 (3) |
C1—C6—H6 | 119.5 | C14—C13'—H13' | 120.4 |
C2—C7—H7A | 109.5 | C12'—C13'—H13' | 120.4 |
C2—C7—H7B | 109.5 | C12—C13—C14 | 118.8 (3) |
H7A—C7—H7B | 109.5 | C12—C13—H13 | 120.6 |
C2—C7—H7C | 109.5 | C14—C13—H13 | 120.6 |
H7A—C7—H7C | 109.5 | C13'—C14—C13 | 121.3 (3) |
H7B—C7—H7C | 109.5 | C13'—C14—Br1 | 119.7 (2) |
C9—C8—C1 | 128.7 (3) | C13—C14—Br1 | 119.0 (2) |
C6—C1—C2—C3 | −3.1 (4) | C8—C9—C10—O2 | −14.9 (4) |
C8—C1—C2—C3 | 179.2 (3) | C11—C9—C10—O2 | 164.3 (3) |
C6—C1—C2—C7 | 175.1 (3) | C8—C9—C11—C12' | 69.4 (4) |
C8—C1—C2—C7 | −2.6 (4) | C10—C9—C11—C12' | −109.6 (3) |
C1—C2—C3—C4 | 3.4 (4) | C8—C9—C11—C12 | −113.7 (3) |
C7—C2—C3—C4 | −174.8 (3) | C10—C9—C11—C12 | 67.3 (4) |
C2—C3—C4—C5 | −1.2 (5) | C12—C11—C12'—C13' | −0.3 (4) |
C3—C4—C5—C6 | −1.3 (5) | C9—C11—C12'—C13' | 176.7 (3) |
C4—C5—C6—C1 | 1.5 (5) | C12'—C11—C12—C13 | −0.1 (4) |
C2—C1—C6—C5 | 0.8 (4) | C9—C11—C12—C13 | −177.0 (3) |
C8—C1—C6—C5 | 178.3 (3) | C11—C12'—C13'—C14 | −0.1 (4) |
C6—C1—C8—C9 | 33.4 (5) | C11—C12—C13—C14 | 0.9 (4) |
C2—C1—C8—C9 | −149.0 (3) | C12'—C13'—C14—C13 | 0.9 (4) |
C1—C8—C9—C10 | −176.8 (3) | C12'—C13'—C14—Br1 | −179.8 (2) |
C1—C8—C9—C11 | 4.2 (5) | C12—C13—C14—C13' | −1.3 (4) |
C8—C9—C10—O1 | 166.2 (3) | C12—C13—C14—Br1 | 179.4 (2) |
C11—C9—C10—O1 | −14.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.83 | 1.80 | 2.617 (3) | 167 |
Symmetry code: (i) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H13BrO2 |
Mr | 317.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 6.0641 (12), 15.208 (3), 15.187 (3) |
β (°) | 91.98 (3) |
V (Å3) | 1399.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.93 |
Crystal size (mm) | 0.72 × 0.48 × 0.12 |
Data collection | |
Diffractometer | Rigaku Mercury CCD |
Absorption correction | Multi-scan (REQAB; Rigaku/MSC, 1999) |
Tmin, Tmax | 0.222, 0.706 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10277, 2454, 2133 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.098, 1.11 |
No. of reflections | 2454 |
No. of parameters | 175 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.40 |
Computer programs: CrystalClear (Rigaku/MSC, 2001), CrystalClear, SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.83 | 1.801 | 2.617 (3) | 167 |
Symmetry code: (i) −x, −y+2, −z+1. |
Cinnamic Acid derived antibacterial drugs have increased the importance of these acids, especially halogenated Cinnamic acids. These acids have been revealed to enhance the efficiency of prototype medicinals (Nodiff et al., 1971). The derivatives of these acids have been used as precursors in the shikimic acid metabolic pathways of higher plants (Forgo et al., 2005). In an extension of such studies, in order to observe the effect of different substituents for improvement of the efficacy of these drugs, we have synthesized derivitives of these compounds and report the structure of compound (I). In the molecular structure of Compound (I), the central C8—C9 bond length of acrylate moiety proves a clear double bond character, and bonds C1—C8 and C9—C11 single bond character, which confirms localized bonding. In all the bond lengths and bond angles, a comparable behavior is observed as found in (Allen et al., 1987), 3-(6-nitro-1, 3-benzodioxol-5-yl)-2-phenylacrylic acid, (II) (Hussain et al., 2006). In the crystal structure of (I), Centro symmetric dimers are formed via O—H···O hydrogen bonds linking carboxylic acid groups. This arrangement is like that observed in the crystal structure of (II). In compound (I), these dimers are further connected by small links which form a slab like structure of the compound.