The title compound, C18H15BrO3, was obtained by bromination of phenprocoumone with N-bromosuccinimide. The X-ray structure confirms an earlier proposal concerning the regioselectivity of the reaction to introduce the Br atom at the 3-position.
Supporting information
CCDC reference: 270497
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.005 Å
- R factor = 0.041
- wR factor = 0.115
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.51 Ratio
PLAT432_ALERT_2_C Short Inter X...Y Contact Br1 .. C5 .. 3.29 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
2 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
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: COLLECT (Nonius, 1998); cell refinement: COLLECT; data reduction: CORINC (Dräger et al., 1971); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
(3RS,1SR)-3-Bromo-3-(1-phenylpropyl)chroman-2,4-dione
top
Crystal data top
C18H15BrO3 | Z = 2 |
Mr = 359.21 | F(000) = 364 |
Triclinic, P1 | Dx = 1.540 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 6.2769 (16) Å | Cell parameters from 25 reflections |
b = 8.6095 (10) Å | θ = 60–71° |
c = 14.775 (3) Å | µ = 3.70 mm−1 |
α = 91.154 (12)° | T = 295 K |
β = 90.796 (18)° | Plate, colourless |
γ = 103.908 (14)° | 0.38 × 0.28 × 0.02 mm |
V = 774.7 (3) Å3 | |
Data collection top
Enraf–Nonius CAD-4 diffractometer | 2812 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.043 |
Graphite monochromator | θmax = 73.1°, θmin = 3.0° |
θ/2ω scans | h = −7→7 |
Absorption correction: numerical (de Meulenaer & Tompa; 1965) | k = −10→10 |
Tmin = 0.353, Tmax = 0.926 | l = −18→0 |
3234 measured reflections | 3 standard reflections every 60 min |
3109 independent reflections | intensity decay: 10% |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | Only H-atom displacement parameters refined |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0656P)2 + 0.3708P] where P = (Fo2 + 2Fc2)/3 |
3109 reflections | (Δ/σ)max < 0.001 |
212 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.57 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | −0.02158 (5) | −0.00819 (4) | 0.16282 (2) | 0.05098 (14) | |
C1 | 0.1725 (5) | 0.2004 (3) | 0.20421 (18) | 0.0387 (6) | |
C2 | 0.1484 (5) | 0.3042 (3) | 0.12335 (19) | 0.0418 (6) | |
C3 | 0.2876 (5) | 0.2931 (3) | 0.04549 (19) | 0.0431 (6) | |
C4 | 0.2542 (6) | 0.3556 (4) | −0.0385 (2) | 0.0519 (8) | |
H4 | 0.1410 | 0.4069 | −0.0465 | 0.060 (11)* | |
C5 | 0.3878 (7) | 0.3416 (4) | −0.1093 (2) | 0.0616 (10) | |
H5 | 0.3641 | 0.3827 | −0.1653 | 0.075 (13)* | |
C6 | 0.5586 (7) | 0.2663 (4) | −0.0977 (2) | 0.0640 (10) | |
H6 | 0.6478 | 0.2567 | −0.1462 | 0.072 (13)* | |
C7 | 0.5967 (6) | 0.2062 (4) | −0.0157 (2) | 0.0559 (8) | |
H7 | 0.7118 | 0.1567 | −0.0077 | 0.068 (12)* | |
C8 | 0.4605 (5) | 0.2204 (4) | 0.0551 (2) | 0.0461 (7) | |
O9 | 0.5154 (4) | 0.1596 (3) | 0.13657 (15) | 0.0535 (5) | |
C10 | 0.3974 (5) | 0.1572 (4) | 0.2115 (2) | 0.0446 (6) | |
O11 | 0.0143 (4) | 0.3837 (3) | 0.12442 (16) | 0.0548 (6) | |
O12 | 0.4655 (5) | 0.1128 (3) | 0.27981 (17) | 0.0632 (7) | |
C13 | 0.0904 (5) | 0.2606 (4) | 0.29277 (19) | 0.0445 (6) | |
H13 | −0.0556 | 0.2761 | 0.2778 | 0.049 (9)* | |
C14 | 0.2300 (6) | 0.4274 (4) | 0.3190 (2) | 0.0489 (7) | |
C15 | 0.1457 (8) | 0.5604 (4) | 0.3080 (2) | 0.0620 (10) | |
H15 | 0.0051 | 0.5473 | 0.2834 | 0.069 (13)* | |
C16 | 0.2656 (11) | 0.7120 (5) | 0.3328 (3) | 0.0820 (15) | |
H16 | 0.2052 | 0.7995 | 0.3247 | 0.14 (3)* | |
C17 | 0.4685 (12) | 0.7338 (6) | 0.3684 (3) | 0.0947 (18) | |
H17 | 0.5479 | 0.8366 | 0.3845 | 0.13 (2)* | |
C18 | 0.5608 (10) | 0.6068 (8) | 0.3814 (4) | 0.0970 (17) | |
H18 | 0.7021 | 0.6229 | 0.4057 | 0.11 (2)* | |
C19 | 0.4380 (8) | 0.4510 (5) | 0.3571 (3) | 0.0710 (11) | |
H19 | 0.4977 | 0.3636 | 0.3669 | 0.060 (11)* | |
C20 | 0.0557 (7) | 0.1456 (5) | 0.3717 (2) | 0.0609 (9) | |
H20A | −0.0169 | 0.0389 | 0.3495 | 0.090 (11)* | |
H20B | 0.1972 | 0.1412 | 0.3974 | 0.090 (11)* | |
C21 | −0.0807 (8) | 0.1970 (6) | 0.4444 (2) | 0.0717 (11) | |
H21A | −0.1010 | 0.1216 | 0.4924 | 0.104 (10)* | |
H21B | −0.2210 | 0.2010 | 0.4193 | 0.104 (10)* | |
H21C | −0.0068 | 0.3011 | 0.4679 | 0.104 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0536 (2) | 0.03718 (19) | 0.0596 (2) | 0.00627 (13) | −0.00442 (14) | −0.00108 (13) |
C1 | 0.0437 (15) | 0.0335 (13) | 0.0381 (13) | 0.0082 (11) | −0.0023 (11) | 0.0006 (10) |
C2 | 0.0475 (16) | 0.0358 (14) | 0.0429 (14) | 0.0119 (12) | −0.0071 (12) | 0.0011 (11) |
C3 | 0.0524 (17) | 0.0319 (13) | 0.0409 (14) | 0.0027 (12) | −0.0002 (12) | −0.0033 (10) |
C4 | 0.066 (2) | 0.0334 (14) | 0.0523 (17) | 0.0049 (13) | −0.0098 (15) | 0.0014 (12) |
C5 | 0.089 (3) | 0.0446 (18) | 0.0399 (16) | −0.0051 (17) | −0.0029 (16) | 0.0063 (13) |
C6 | 0.081 (3) | 0.052 (2) | 0.0505 (18) | −0.0007 (18) | 0.0181 (18) | −0.0060 (15) |
C7 | 0.058 (2) | 0.0458 (17) | 0.063 (2) | 0.0104 (15) | 0.0075 (16) | −0.0043 (14) |
C8 | 0.0547 (18) | 0.0386 (15) | 0.0422 (15) | 0.0058 (12) | −0.0011 (12) | 0.0023 (11) |
O9 | 0.0526 (13) | 0.0649 (14) | 0.0504 (12) | 0.0281 (11) | 0.0026 (10) | 0.0063 (10) |
C10 | 0.0558 (18) | 0.0399 (15) | 0.0414 (14) | 0.0181 (13) | −0.0026 (12) | 0.0012 (11) |
O11 | 0.0630 (14) | 0.0574 (13) | 0.0521 (12) | 0.0306 (11) | −0.0041 (10) | 0.0031 (10) |
O12 | 0.0712 (16) | 0.0774 (17) | 0.0523 (13) | 0.0400 (14) | −0.0065 (11) | 0.0085 (12) |
C13 | 0.0546 (17) | 0.0407 (15) | 0.0402 (14) | 0.0150 (13) | 0.0066 (12) | 0.0046 (11) |
C14 | 0.066 (2) | 0.0447 (16) | 0.0370 (14) | 0.0142 (14) | 0.0115 (13) | −0.0011 (11) |
C15 | 0.100 (3) | 0.0491 (19) | 0.0425 (16) | 0.0286 (19) | 0.0092 (18) | −0.0010 (13) |
C16 | 0.142 (5) | 0.048 (2) | 0.057 (2) | 0.022 (3) | 0.019 (3) | −0.0023 (17) |
C17 | 0.144 (5) | 0.054 (3) | 0.074 (3) | −0.002 (3) | 0.028 (3) | −0.016 (2) |
C18 | 0.081 (3) | 0.108 (4) | 0.088 (3) | −0.002 (3) | 0.002 (3) | −0.037 (3) |
C19 | 0.080 (3) | 0.067 (2) | 0.066 (2) | 0.019 (2) | −0.006 (2) | −0.0182 (19) |
C20 | 0.080 (3) | 0.057 (2) | 0.0486 (18) | 0.0213 (18) | 0.0122 (17) | 0.0139 (15) |
C21 | 0.083 (3) | 0.091 (3) | 0.0456 (18) | 0.026 (2) | 0.0181 (18) | 0.0125 (18) |
Geometric parameters (Å, º) top
Br1—C1 | 1.992 (3) | C16—C17 | 1.341 (8) |
C1—C2 | 1.533 (4) | C17—C18 | 1.370 (9) |
C1—C13 | 1.538 (4) | C18—C19 | 1.414 (7) |
C1—C10 | 1.547 (4) | C20—C21 | 1.507 (5) |
C2—O11 | 1.206 (4) | C4—H4 | 0.9300 |
C2—C3 | 1.469 (4) | C5—H5 | 0.9300 |
C3—C8 | 1.384 (5) | C6—H6 | 0.9300 |
C3—C4 | 1.396 (4) | C7—H7 | 0.9300 |
C4—C5 | 1.371 (5) | C13—H13 | 0.9800 |
C5—C6 | 1.390 (6) | C15—H15 | 0.9300 |
C6—C7 | 1.369 (6) | C16—H16 | 0.9300 |
C7—C8 | 1.382 (5) | C17—H17 | 0.9300 |
C8—O9 | 1.393 (4) | C18—H18 | 0.9300 |
O9—C10 | 1.339 (4) | C19—H19 | 0.9300 |
C10—O12 | 1.195 (4) | C20—H20A | 0.9700 |
C13—C20 | 1.529 (4) | C20—H20B | 0.9700 |
C13—C14 | 1.531 (4) | C21—H21A | 0.9600 |
C14—C19 | 1.383 (6) | C21—H21B | 0.9600 |
C14—C15 | 1.383 (5) | C21—H21C | 0.9600 |
C15—C16 | 1.380 (6) | | |
| | | |
C2—C1—C13 | 112.7 (2) | C21—C20—C13 | 111.6 (3) |
C2—C1—C10 | 114.4 (2) | C3—C4—H4 | 120.00 |
C13—C1—C10 | 115.3 (2) | C5—C4—H4 | 120.00 |
C2—C1—Br1 | 100.32 (18) | C4—C5—H5 | 120.00 |
C13—C1—Br1 | 111.1 (2) | C6—C5—H5 | 120.00 |
C10—C1—Br1 | 101.28 (18) | C5—C6—H6 | 120.00 |
O11—C2—C3 | 123.6 (3) | C7—C6—H6 | 120.00 |
O11—C2—C1 | 120.1 (3) | C6—C7—H7 | 121.00 |
C3—C2—C1 | 116.3 (2) | C8—C7—H7 | 121.00 |
C8—C3—C4 | 118.1 (3) | C1—C13—H13 | 105.00 |
C8—C3—C2 | 119.5 (3) | C14—C13—H13 | 105.00 |
C4—C3—C2 | 122.4 (3) | C20—C13—H13 | 105.00 |
C5—C4—C3 | 120.2 (3) | C14—C15—H15 | 119.00 |
C4—C5—C6 | 120.2 (3) | C16—C15—H15 | 119.00 |
C7—C6—C5 | 120.6 (3) | C15—C16—H16 | 120.00 |
C6—C7—C8 | 118.6 (4) | C17—C16—H16 | 120.00 |
C7—C8—C3 | 122.1 (3) | C16—C17—H17 | 120.00 |
C7—C8—O9 | 114.5 (3) | C18—C17—H17 | 120.00 |
C3—C8—O9 | 123.3 (3) | C17—C18—H18 | 120.00 |
C10—O9—C8 | 123.0 (2) | C19—C18—H18 | 121.00 |
O12—C10—O9 | 118.2 (3) | C14—C19—H19 | 120.00 |
O12—C10—C1 | 123.1 (3) | C18—C19—H19 | 120.00 |
O9—C10—C1 | 118.6 (2) | C13—C20—H20A | 109.00 |
C20—C13—C14 | 113.0 (3) | C13—C20—H20B | 109.00 |
C20—C13—C1 | 116.7 (3) | C21—C20—H20A | 109.00 |
C14—C13—C1 | 110.2 (2) | C21—C20—H20B | 109.00 |
C19—C14—C15 | 117.7 (4) | H20A—C20—H20B | 108.00 |
C19—C14—C13 | 122.2 (3) | C20—C21—H21A | 109.00 |
C15—C14—C13 | 120.0 (3) | C20—C21—H21B | 109.00 |
C16—C15—C14 | 121.4 (5) | C20—C21—H21C | 109.00 |
C17—C16—C15 | 120.4 (5) | H21A—C21—H21B | 109.00 |
C16—C17—C18 | 121.0 (5) | H21A—C21—H21C | 109.00 |
C17—C18—C19 | 119.0 (6) | H21B—C21—H21C | 110.00 |
C14—C19—C18 | 120.5 (5) | | |
| | | |
C13—C1—C2—O11 | −23.8 (4) | C13—C1—C10—O12 | 27.9 (4) |
C10—C1—C2—O11 | −158.0 (3) | Br1—C1—C10—O12 | −92.1 (3) |
Br1—C1—C2—O11 | 94.5 (3) | C2—C1—C10—O9 | −23.4 (4) |
C13—C1—C2—C3 | 159.3 (3) | C13—C1—C10—O9 | −156.5 (3) |
C10—C1—C2—C3 | 25.0 (4) | Br1—C1—C10—O9 | 83.5 (3) |
Br1—C1—C2—C3 | −82.5 (3) | C2—C1—C13—C20 | 165.9 (3) |
O11—C2—C3—C8 | 169.6 (3) | C10—C1—C13—C20 | −60.3 (4) |
C1—C2—C3—C8 | −13.5 (4) | Br1—C1—C13—C20 | 54.2 (3) |
O11—C2—C3—C4 | −9.4 (5) | C2—C1—C13—C14 | −63.5 (3) |
C1—C2—C3—C4 | 167.4 (3) | C10—C1—C13—C14 | 70.4 (3) |
C8—C3—C4—C5 | 1.2 (4) | Br1—C1—C13—C14 | −175.2 (2) |
C2—C3—C4—C5 | −179.7 (3) | C20—C13—C14—C19 | 56.0 (4) |
C3—C4—C5—C6 | −0.5 (5) | C1—C13—C14—C19 | −76.6 (4) |
C4—C5—C6—C7 | −0.4 (5) | C20—C13—C14—C15 | −121.5 (3) |
C5—C6—C7—C8 | 0.7 (5) | C1—C13—C14—C15 | 105.9 (3) |
C6—C7—C8—C3 | 0.1 (5) | C19—C14—C15—C16 | 1.0 (5) |
C6—C7—C8—O9 | −178.4 (3) | C13—C14—C15—C16 | 178.6 (3) |
C4—C3—C8—C7 | −1.0 (5) | C14—C15—C16—C17 | 0.0 (6) |
C2—C3—C8—C7 | 179.9 (3) | C15—C16—C17—C18 | −0.3 (7) |
C4—C3—C8—O9 | 177.3 (3) | C16—C17—C18—C19 | −0.4 (8) |
C2—C3—C8—O9 | −1.8 (4) | C15—C14—C19—C18 | −1.7 (6) |
C7—C8—O9—C10 | −177.3 (3) | C13—C14—C19—C18 | −179.3 (4) |
C3—C8—O9—C10 | 4.3 (5) | C17—C18—C19—C14 | 1.5 (7) |
C8—O9—C10—O12 | −174.9 (3) | C14—C13—C20—C21 | 66.3 (4) |
C8—O9—C10—C1 | 9.2 (4) | C1—C13—C20—C21 | −164.4 (3) |
C2—C1—C10—O12 | 161.0 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O11i | 0.93 | 2.54 | 3.372 (4) | 150 |
Symmetry code: (i) −x, −y+1, −z. |