Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806012621/lh2031sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536806012621/lh2031Isup2.hkl |
CCDC reference: 608442
Key indicators
- Single-crystal X-ray study
- T = 303 K
- Mean (C-C) = 0.015 Å
- R factor = 0.069
- wR factor = 0.217
- Data-to-parameter ratio = 17.6
checkCIF/PLATON results
No syntax errors found
Alert level A RINTA01_ALERT_3_A The value of Rint is greater than 0.20 Rint given 0.252 PLAT020_ALERT_3_A The value of Rint is greater than 0.10 ......... 0.25
Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 34 Perc.
Alert level C RADNW01_ALERT_1_C The radiation wavelength lies outside the expected range for the supplied radiation type. Expected range 0.71065-0.71075 Wavelength given = 0.71093 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.80 mm PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT331_ALERT_2_C Small Average Phenyl C-C Dist. C8 -C16 1.37 Ang. PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 15
2 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CAD-4 Diffractometer Control Software (Enraf–Nonius, 1993); cell refinement: CAD-4 Diffractometer Control Software; data reduction: CAD-4 Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON2002 (Spek, 2003) and ORTEP-3 (Farrugia, 1997, 2005); software used to prepare material for publication: SHELXL97.
C15H19BrO3 | F(000) = 672 |
Mr = 327.21 | Dx = 1.431 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71093 Å |
a = 9.955 (2) Å | Cell parameters from 25 reflections |
b = 9.875 (3) Å | θ = 2.7–13.6° |
c = 15.896 (2) Å | µ = 2.71 mm−1 |
β = 103.62 (1)° | T = 303 K |
V = 1518.7 (6) Å3 | Plate, colourless |
Z = 4 | 0.80 × 0.32 × 0.05 mm |
Enraf–Nonius CAD-4 diffractometer | 1024 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.252 |
Graphite monochromator | θmax = 26.0°, θmin = 2.5° |
ω/2θ scans | h = −12→2 |
Absorption correction: ψ scan (North et al., 1968) | k = −12→0 |
Tmin = 0.221, Tmax = 0.877 | l = −19→19 |
3621 measured reflections | 3 standard reflections every 120 min |
2977 independent reflections | intensity decay: 10.0% |
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)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.217 | H-atom parameters constrained |
S = 0.96 | w = 1/[σ2(Fo2) + (0.0855P)2 + 2.55P] where P = (Fo2 + 2Fc2)/3 |
2977 reflections | (Δ/σ)max = 0.004 |
169 parameters | Δρmax = 0.83 e Å−3 |
6 restraints | Δρmin = −0.57 e Å−3 |
Experimental. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz, δ, p.pm.): 1.46 (s, 3H), 1.53 (s, 3H), 1.89 (s, 3H), 2.44 (dt, Jd = 13.1 Hz, Jt = 3.8 Hz, 1H), 2.70 (q, J = 13.1 Hz, 1H), 2.89 (dd, J = 3.8 and 13.1 Hz, 1H), 4.04 (dd, J = 3.8 and 13.1 Hz, 1H), 7.26–7.36 (m, 3H), 7.61 (mc, 2 H); 13C NMR (CDCl3, 63 MHz, δ, p.p.m.): 20.7, 24.6, 31.4, 32.0, 53.7, 56.7, 74.2, 78.5, 125.1, 127.6, 128.0, 145.5, 176.6. |
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 | 0.38978 (10) | 0.14319 (13) | 0.33663 (7) | 0.0822 (5) | |
O1 | 0.0929 (5) | −0.1055 (6) | 0.4028 (4) | 0.0577 (17) | |
O3 | 0.4929 (7) | −0.3429 (7) | 0.4850 (5) | 0.095 (2) | |
O2 | 0.3307 (7) | −0.4851 (8) | 0.4237 (5) | 0.105 | |
H2 | 0.3889 | −0.5390 | 0.4492 | 0.158* | |
C8 | 0.0492 (8) | 0.1009 (11) | 0.3311 (6) | 0.059 (3) | |
C6 | 0.1613 (8) | 0.0203 (10) | 0.3927 (5) | 0.054 (2) | |
C2 | 0.1678 (8) | −0.2259 (10) | 0.4405 (6) | 0.058 (3) | |
C4 | 0.3706 (8) | −0.1259 (11) | 0.3934 (6) | 0.067 (3) | |
H4A | 0.4407 | −0.1452 | 0.3618 | 0.080* | |
H4B | 0.4164 | −0.0972 | 0.4514 | 0.080* | |
C12 | 0.0457 (10) | 0.2421 (13) | 0.3306 (7) | 0.078 (3) | |
H12 | 0.1143 | 0.2903 | 0.3687 | 0.093* | |
C11 | 0.3787 (9) | −0.3606 (11) | 0.4385 (6) | 0.071 (3) | |
C7 | 0.2106 (9) | 0.0939 (10) | 0.4799 (6) | 0.066 (3) | |
H7A | 0.2899 | 0.0481 | 0.5142 | 0.099* | |
H7B | 0.1377 | 0.0938 | 0.5102 | 0.099* | |
H7C | 0.2348 | 0.1855 | 0.4698 | 0.099* | |
C3 | 0.2867 (9) | −0.2491 (11) | 0.3974 (6) | 0.068 (3) | |
H3 | 0.2461 | −0.2766 | 0.3376 | 0.082* | |
C9 | 0.0553 (9) | −0.3306 (11) | 0.4200 (7) | 0.084 (3) | |
H9A | −0.0160 | −0.3079 | 0.4491 | 0.126* | |
H9B | 0.0929 | −0.4178 | 0.4393 | 0.126* | |
H9C | 0.0171 | −0.3330 | 0.3587 | 0.126* | |
C16 | −0.0516 (10) | 0.0380 (13) | 0.2717 (6) | 0.086 (3) | |
H16 | −0.0510 | −0.0561 | 0.2689 | 0.103* | |
C5 | 0.2761 (7) | −0.0152 (10) | 0.3483 (5) | 0.061 (3) | |
H5 | 0.2326 | −0.0473 | 0.2899 | 0.073* | |
C10 | 0.2195 (9) | −0.2174 (12) | 0.5400 (6) | 0.080 (3) | |
H10A | 0.3057 | −0.1694 | 0.5543 | 0.120* | |
H10B | 0.2324 | −0.3072 | 0.5637 | 0.120* | |
H10C | 0.1524 | −0.1704 | 0.5637 | 0.120* | |
C14 | −0.1573 (11) | 0.2484 (16) | 0.2184 (8) | 0.092 (4) | |
H14 | −0.2266 | 0.2982 | 0.1820 | 0.110* | |
C13 | −0.0568 (11) | 0.3102 (12) | 0.2752 (7) | 0.078 (3) | |
H13 | −0.0566 | 0.4043 | 0.2771 | 0.094* | |
C15 | −0.1566 (11) | 0.1088 (15) | 0.2145 (8) | 0.098 (4) | |
H15 | −0.2245 | 0.0627 | 0.1746 | 0.118* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0662 (6) | 0.1083 (10) | 0.0694 (7) | −0.0119 (7) | 0.0106 (4) | 0.0101 (8) |
O1 | 0.052 (3) | 0.058 (5) | 0.065 (4) | 0.002 (3) | 0.015 (3) | 0.002 (3) |
O3 | 0.076 (4) | 0.064 (6) | 0.122 (6) | 0.017 (4) | −0.026 (4) | −0.012 (4) |
O2 | 0.078 | 0.067 | 0.145 | 0.011 | −0.025 | −0.023 |
C8 | 0.039 (5) | 0.074 (9) | 0.067 (6) | −0.006 (5) | 0.017 (4) | 0.006 (6) |
C6 | 0.067 (6) | 0.056 (7) | 0.037 (5) | −0.002 (5) | 0.010 (4) | −0.009 (5) |
C2 | 0.044 (5) | 0.062 (7) | 0.068 (6) | 0.019 (5) | 0.011 (4) | 0.003 (6) |
C4 | 0.057 (5) | 0.090 (9) | 0.055 (6) | 0.015 (6) | 0.017 (4) | −0.016 (6) |
C12 | 0.077 (7) | 0.081 (10) | 0.073 (7) | 0.005 (7) | 0.012 (6) | −0.006 (7) |
C11 | 0.054 (5) | 0.068 (8) | 0.085 (7) | 0.019 (6) | 0.007 (5) | −0.019 (7) |
C7 | 0.081 (6) | 0.059 (7) | 0.055 (6) | 0.001 (5) | 0.013 (4) | −0.004 (5) |
C3 | 0.067 (6) | 0.074 (9) | 0.056 (6) | 0.011 (6) | 0.000 (4) | −0.006 (6) |
C9 | 0.067 (6) | 0.070 (9) | 0.107 (8) | 0.000 (6) | 0.006 (5) | 0.008 (7) |
C16 | 0.079 (7) | 0.088 (9) | 0.081 (7) | 0.014 (7) | −0.001 (6) | 0.024 (7) |
C5 | 0.035 (4) | 0.092 (9) | 0.055 (5) | 0.002 (5) | 0.011 (4) | −0.006 (5) |
C10 | 0.078 (6) | 0.095 (9) | 0.072 (7) | 0.005 (6) | 0.027 (5) | 0.012 (7) |
C14 | 0.065 (7) | 0.108 (12) | 0.101 (9) | 0.007 (7) | 0.015 (6) | 0.038 (9) |
C13 | 0.079 (7) | 0.062 (9) | 0.097 (8) | 0.015 (6) | 0.029 (7) | 0.023 (7) |
C15 | 0.082 (8) | 0.096 (12) | 0.100 (9) | −0.003 (7) | −0.011 (6) | 0.010 (8) |
Br1—C5 | 1.965 (9) | C11—C3 | 1.481 (13) |
O1—C6 | 1.444 (10) | C7—H7A | 0.9600 |
O1—C2 | 1.455 (10) | C7—H7B | 0.9600 |
O3—C11 | 1.214 (10) | C7—H7C | 0.9600 |
O2—C11 | 1.320 (11) | C3—H3 | 0.9800 |
O2—H2 | 0.8200 | C9—H9A | 0.9600 |
C8—C16 | 1.355 (13) | C9—H9B | 0.9600 |
C8—C12 | 1.395 (14) | C9—H9C | 0.9600 |
C8—C6 | 1.525 (12) | C16—C15 | 1.401 (14) |
C6—C5 | 1.518 (10) | C16—H16 | 0.9300 |
C6—C7 | 1.539 (11) | C5—H5 | 0.9800 |
C2—C9 | 1.502 (13) | C10—H10A | 0.9600 |
C2—C3 | 1.518 (11) | C10—H10B | 0.9600 |
C2—C10 | 1.546 (12) | C10—H10C | 0.9600 |
C4—C3 | 1.486 (13) | C14—C13 | 1.327 (15) |
C4—C5 | 1.508 (12) | C14—C15 | 1.380 (16) |
C4—H4A | 0.9700 | C14—H14 | 0.9300 |
C4—H4B | 0.9700 | C13—H13 | 0.9300 |
C12—C13 | 1.358 (14) | C15—H15 | 0.9300 |
C12—H12 | 0.9300 | ||
C6—O1—C2 | 122.6 (6) | C11—C3—C2 | 112.4 (8) |
C11—O2—H2 | 109.5 | C4—C3—C2 | 113.7 (8) |
C16—C8—C12 | 116.2 (9) | C11—C3—H3 | 107.0 |
C16—C8—C6 | 121.2 (10) | C4—C3—H3 | 107.0 |
C12—C8—C6 | 122.6 (9) | C2—C3—H3 | 107.0 |
O1—C6—C5 | 106.2 (7) | C2—C9—H9A | 109.5 |
O1—C6—C8 | 103.2 (6) | C2—C9—H9B | 109.5 |
C5—C6—C8 | 109.8 (7) | H9A—C9—H9B | 109.5 |
O1—C6—C7 | 111.4 (7) | C2—C9—H9C | 109.5 |
C5—C6—C7 | 114.4 (7) | H9A—C9—H9C | 109.5 |
C8—C6—C7 | 111.2 (8) | H9B—C9—H9C | 109.5 |
O1—C2—C9 | 100.9 (6) | C8—C16—C15 | 122.7 (12) |
O1—C2—C3 | 108.4 (7) | C8—C16—H16 | 118.7 |
C9—C2—C3 | 114.8 (9) | C15—C16—H16 | 118.7 |
O1—C2—C10 | 113.1 (8) | C4—C5—C6 | 113.6 (7) |
C9—C2—C10 | 108.1 (8) | C4—C5—Br1 | 108.2 (5) |
C3—C2—C10 | 111.2 (7) | C6—C5—Br1 | 111.9 (7) |
C3—C4—C5 | 108.7 (7) | C4—C5—H5 | 107.6 |
C3—C4—H4A | 110.0 | C6—C5—H5 | 107.6 |
C5—C4—H4A | 110.0 | Br1—C5—H5 | 107.6 |
C3—C4—H4B | 110.0 | C2—C10—H10A | 109.5 |
C5—C4—H4B | 110.0 | C2—C10—H10B | 109.5 |
H4A—C4—H4B | 108.3 | H10A—C10—H10B | 109.5 |
C13—C12—C8 | 120.8 (10) | C2—C10—H10C | 109.5 |
C13—C12—H12 | 119.6 | H10A—C10—H10C | 109.5 |
C8—C12—H12 | 119.6 | H10B—C10—H10C | 109.5 |
O3—C11—O2 | 119.3 (9) | C13—C14—C15 | 118.6 (11) |
O3—C11—C3 | 123.7 (10) | C13—C14—H14 | 120.7 |
O2—C11—C3 | 117.0 (8) | C15—C14—H14 | 120.7 |
C6—C7—H7A | 109.5 | C14—C13—C12 | 123.0 (12) |
C6—C7—H7B | 109.5 | C14—C13—H13 | 118.5 |
H7A—C7—H7B | 109.5 | C12—C13—H13 | 118.5 |
C6—C7—H7C | 109.5 | C14—C15—C16 | 118.7 (11) |
H7A—C7—H7C | 109.5 | C14—C15—H15 | 120.6 |
H7B—C7—H7C | 109.5 | C16—C15—H15 | 120.6 |
C11—C3—C4 | 109.4 (8) | ||
C2—O1—C6—C5 | 50.3 (9) | O1—C2—C3—C11 | 173.5 (8) |
C2—O1—C6—C8 | 165.8 (7) | C9—C2—C3—C11 | −74.6 (11) |
C2—O1—C6—C7 | −74.8 (9) | C10—C2—C3—C11 | 48.6 (12) |
C16—C8—C6—O1 | −29.3 (10) | O1—C2—C3—C4 | 48.5 (10) |
C12—C8—C6—O1 | 152.3 (8) | C9—C2—C3—C4 | 160.5 (8) |
C16—C8—C6—C5 | 83.6 (10) | C10—C2—C3—C4 | −76.4 (10) |
C12—C8—C6—C5 | −94.8 (10) | C12—C8—C16—C15 | −1.9 (15) |
C16—C8—C6—C7 | −148.8 (8) | C6—C8—C16—C15 | 179.6 (9) |
C12—C8—C6—C7 | 32.8 (11) | C3—C4—C5—C6 | 58.7 (10) |
C6—O1—C2—C9 | −169.5 (7) | C3—C4—C5—Br1 | −176.3 (6) |
C6—O1—C2—C3 | −48.5 (10) | O1—C6—C5—C4 | −53.0 (9) |
C6—O1—C2—C10 | 75.3 (9) | C8—C6—C5—C4 | −163.9 (8) |
C16—C8—C12—C13 | 2.2 (14) | C7—C6—C5—C4 | 70.3 (10) |
C6—C8—C12—C13 | −179.3 (8) | O1—C6—C5—Br1 | −175.9 (5) |
O3—C11—C3—C4 | 21.4 (14) | C8—C6—C5—Br1 | 73.2 (8) |
O2—C11—C3—C4 | −159.7 (8) | C7—C6—C5—Br1 | −52.6 (9) |
O3—C11—C3—C2 | −105.9 (11) | C15—C14—C13—C12 | −1.0 (17) |
O2—C11—C3—C2 | 73.0 (12) | C8—C12—C13—C14 | −0.8 (16) |
C5—C4—C3—C11 | 177.8 (7) | C13—C14—C15—C16 | 1.3 (18) |
C5—C4—C3—C2 | −55.7 (10) | C8—C16—C15—C14 | 0.2 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O3i | 0.82 | 1.81 | 2.622 (10) | 174 |
Symmetry code: (i) −x+1, −y−1, −z+1. |