The title compound, C17H15BrOS, crystallizes in a non-centrosymmetric space group and shows significant nonlinear optical activity.
Supporting information
CCDC reference: 605082
Key indicators
- Single-crystal X-ray study
- T = 366 K
- Mean (C-C) = 0.003 Å
- R factor = 0.024
- wR factor = 0.054
- Data-to-parameter ratio = 22.0
checkCIF/PLATON results
No syntax errors found
Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.93
| Author Response: Data was collected out to a 2-theta value of 61.5\%. However, due
to the shape of the detector the final shell was not complete. Data
was complete to d = 0.75.
|
Alert level B
PLAT431_ALERT_2_B Short Inter HL..A Contact Br .. S .. 3.27 Ang.
Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.65 mm
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.26
Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
From the CIF: _diffrn_reflns_theta_max 30.75
From the CIF: _reflns_number_total 4028
Count of symmetry unique reflns 2512
Completeness (_total/calc) 160.35%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 1516
Fraction of Friedel pairs measured 0.604
Are heavy atom types Z>Si present yes
1 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
1 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
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL.
2-Bromo-1-(4-methylphenyl)-3-[4-(methylsulfanyl)phenyl]prop-2-en-1-one
top
Crystal data top
C17H15BrOS | F(000) = 352 |
Mr = 347.26 | Dx = 1.564 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 6302 reflections |
a = 7.9708 (9) Å | θ = 2.4–30.5° |
b = 5.5031 (6) Å | µ = 2.92 mm−1 |
c = 16.9923 (18) Å | T = 366 K |
β = 98.291 (2)° | Chunk, colorless |
V = 737.56 (14) Å3 | 0.65 × 0.30 × 0.25 mm |
Z = 2 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 4028 independent reflections |
Radiation source: fine-focus sealed tube | 3821 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
φ and ω scans | θmax = 30.8°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→11 |
Tmin = 0.230, Tmax = 0.482 | k = −7→7 |
8184 measured reflections | l = −24→24 |
Refinement top
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)] = 0.024 | H-atom parameters constrained |
wR(F2) = 0.055 | w = 1/[σ2(Fo2)] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max = 0.002 |
4028 reflections | Δρmax = 1.17 e Å−3 |
183 parameters | Δρmin = −0.52 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.029 (6) |
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 | |
Br | 0.96840 (2) | −0.00274 (4) | 0.775087 (9) | 0.01950 (5) | |
S | 0.70913 (6) | 0.13574 (8) | 1.17103 (3) | 0.01365 (9) | |
O | 0.9237 (2) | 0.3919 (3) | 0.64877 (8) | 0.0249 (3) | |
C1 | 0.5891 (3) | 0.3869 (4) | 1.20207 (11) | 0.0174 (4) | |
H1A | 0.5657 | 0.3585 | 1.2552 | 0.026* | |
H1B | 0.4843 | 0.4019 | 1.1667 | 0.026* | |
H1C | 0.6534 | 0.5340 | 1.2009 | 0.026* | |
C2 | 0.7288 (3) | 0.2139 (3) | 1.07225 (10) | 0.0128 (4) | |
C3 | 0.8147 (2) | 0.0511 (3) | 1.02957 (11) | 0.0147 (4) | |
H3A | 0.8639 | −0.0869 | 1.0547 | 0.018* | |
C4 | 0.8282 (3) | 0.0916 (3) | 0.94990 (11) | 0.0150 (4) | |
H4A | 0.8862 | −0.0191 | 0.9225 | 0.018* | |
C5 | 0.7544 (2) | 0.2997 (3) | 0.91034 (11) | 0.0129 (4) | |
C6 | 0.6733 (2) | 0.4639 (4) | 0.95536 (10) | 0.0136 (4) | |
H6A | 0.6263 | 0.6045 | 0.9310 | 0.016* | |
C7 | 0.6604 (3) | 0.4248 (3) | 1.03493 (11) | 0.0144 (4) | |
H7A | 0.6065 | 0.5383 | 1.0632 | 0.017* | |
C8 | 0.7491 (2) | 0.3614 (3) | 0.82629 (10) | 0.0133 (4) | |
H8A | 0.6812 | 0.4957 | 0.8111 | 0.016* | |
C9 | 0.8206 (3) | 0.2674 (4) | 0.76608 (11) | 0.0151 (4) | |
C10 | 0.8046 (3) | 0.3912 (4) | 0.68660 (11) | 0.0170 (4) | |
C11 | 0.6408 (2) | 0.5098 (5) | 0.65509 (9) | 0.0138 (3) | |
C12 | 0.4857 (3) | 0.4050 (3) | 0.66474 (11) | 0.0149 (4) | |
H12A | 0.4840 | 0.2640 | 0.6948 | 0.018* | |
C13 | 0.3341 (2) | 0.5077 (5) | 0.63022 (9) | 0.0164 (3) | |
H13A | 0.2321 | 0.4324 | 0.6359 | 0.020* | |
C14 | 0.3334 (3) | 0.7240 (4) | 0.58690 (11) | 0.0167 (4) | |
C15 | 0.4891 (3) | 0.8284 (4) | 0.57676 (11) | 0.0172 (4) | |
H15A | 0.4905 | 0.9712 | 0.5476 | 0.021* | |
C16 | 0.6410 (3) | 0.7230 (4) | 0.60942 (11) | 0.0158 (4) | |
H16A | 0.7432 | 0.7932 | 0.6012 | 0.019* | |
C17 | 0.1689 (3) | 0.8443 (5) | 0.55354 (12) | 0.0253 (5) | |
H17A | 0.0765 | 0.7352 | 0.5576 | 0.038* | |
H17B | 0.1707 | 0.8848 | 0.4987 | 0.038* | |
H17C | 0.1544 | 0.9897 | 0.5831 | 0.038* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br | 0.01835 (9) | 0.02282 (9) | 0.01760 (8) | 0.00999 (10) | 0.00354 (6) | −0.00004 (9) |
S | 0.0157 (2) | 0.0116 (2) | 0.01356 (19) | −0.00033 (18) | 0.00202 (16) | 0.00133 (16) |
O | 0.0159 (8) | 0.0399 (9) | 0.0206 (7) | 0.0044 (7) | 0.0080 (6) | 0.0050 (6) |
C1 | 0.0208 (11) | 0.0153 (9) | 0.0169 (9) | 0.0009 (8) | 0.0060 (8) | 0.0001 (7) |
C2 | 0.0110 (9) | 0.0152 (9) | 0.0123 (8) | −0.0024 (7) | 0.0018 (7) | 0.0004 (6) |
C3 | 0.0132 (9) | 0.0118 (10) | 0.0185 (8) | 0.0024 (6) | 0.0008 (7) | 0.0018 (6) |
C4 | 0.0134 (10) | 0.0124 (8) | 0.0197 (9) | 0.0028 (7) | 0.0047 (7) | 0.0010 (7) |
C5 | 0.0089 (9) | 0.0139 (9) | 0.0159 (8) | 0.0005 (7) | 0.0016 (7) | 0.0011 (7) |
C6 | 0.0113 (8) | 0.0120 (10) | 0.0173 (7) | 0.0018 (7) | 0.0017 (6) | 0.0013 (7) |
C7 | 0.0140 (10) | 0.0126 (9) | 0.0167 (8) | 0.0007 (7) | 0.0030 (7) | −0.0016 (6) |
C8 | 0.0115 (9) | 0.0113 (8) | 0.0169 (8) | 0.0024 (7) | 0.0016 (7) | 0.0028 (7) |
C9 | 0.0111 (9) | 0.0179 (9) | 0.0160 (8) | 0.0032 (7) | 0.0013 (7) | 0.0008 (7) |
C10 | 0.0148 (10) | 0.0203 (9) | 0.0157 (8) | −0.0007 (8) | 0.0021 (7) | −0.0007 (7) |
C11 | 0.0149 (8) | 0.0156 (8) | 0.0115 (6) | 0.0001 (9) | 0.0035 (6) | −0.0010 (9) |
C12 | 0.0164 (10) | 0.0134 (8) | 0.0153 (8) | −0.0009 (7) | 0.0043 (7) | −0.0002 (7) |
C13 | 0.0140 (8) | 0.0177 (8) | 0.0177 (7) | −0.0037 (10) | 0.0025 (6) | −0.0027 (10) |
C14 | 0.0183 (11) | 0.0194 (10) | 0.0120 (8) | 0.0035 (8) | 0.0006 (7) | −0.0017 (7) |
C15 | 0.0226 (11) | 0.0160 (9) | 0.0131 (8) | 0.0005 (8) | 0.0031 (7) | 0.0016 (7) |
C16 | 0.0166 (10) | 0.0153 (9) | 0.0161 (8) | −0.0028 (8) | 0.0039 (7) | −0.0001 (7) |
C17 | 0.0213 (12) | 0.0312 (12) | 0.0221 (10) | 0.0068 (10) | −0.0015 (8) | 0.0028 (9) |
Geometric parameters (Å, º) top
Br—C9 | 1.889 (2) | C8—C9 | 1.344 (2) |
S—C2 | 1.7613 (18) | C8—H8A | 0.9300 |
S—C1 | 1.803 (2) | C9—C10 | 1.502 (3) |
O—C10 | 1.220 (2) | C10—C11 | 1.489 (3) |
C1—H1A | 0.9600 | C11—C12 | 1.395 (3) |
C1—H1B | 0.9600 | C11—C16 | 1.407 (3) |
C1—H1C | 0.9600 | C12—C13 | 1.385 (3) |
C2—C3 | 1.393 (2) | C12—H12A | 0.9300 |
C2—C7 | 1.395 (3) | C13—C14 | 1.399 (3) |
C3—C4 | 1.391 (3) | C13—H13A | 0.9300 |
C3—H3A | 0.9300 | C14—C15 | 1.401 (3) |
C4—C5 | 1.412 (3) | C14—C17 | 1.505 (3) |
C4—H4A | 0.9300 | C15—C16 | 1.385 (3) |
C5—C6 | 1.401 (3) | C15—H15A | 0.9300 |
C5—C8 | 1.463 (2) | C16—H16A | 0.9300 |
C6—C7 | 1.388 (2) | C17—H17A | 0.9600 |
C6—H6A | 0.9300 | C17—H17B | 0.9600 |
C7—H7A | 0.9300 | C17—H17C | 0.9600 |
| | | |
C2—S—C1 | 102.45 (9) | C8—C9—Br | 124.68 (15) |
S—C1—H1A | 109.5 | C10—C9—Br | 113.62 (13) |
S—C1—H1B | 109.5 | O—C10—C11 | 121.15 (17) |
H1A—C1—H1B | 109.5 | O—C10—C9 | 120.26 (19) |
S—C1—H1C | 109.5 | C11—C10—C9 | 118.59 (17) |
H1A—C1—H1C | 109.5 | C12—C11—C16 | 118.78 (18) |
H1B—C1—H1C | 109.5 | C12—C11—C10 | 121.5 (2) |
C3—C2—C7 | 119.17 (16) | C16—C11—C10 | 119.55 (18) |
C3—C2—S | 117.20 (14) | C13—C12—C11 | 120.99 (19) |
C7—C2—S | 123.61 (14) | C13—C12—H12A | 119.5 |
C4—C3—C2 | 121.06 (17) | C11—C12—H12A | 119.5 |
C4—C3—H3A | 119.5 | C12—C13—C14 | 120.48 (19) |
C2—C3—H3A | 119.5 | C12—C13—H13A | 119.8 |
C3—C4—C5 | 120.53 (17) | C14—C13—H13A | 119.8 |
C3—C4—H4A | 119.7 | C13—C14—C15 | 118.51 (18) |
C5—C4—H4A | 119.7 | C13—C14—C17 | 120.65 (19) |
C6—C5—C4 | 117.16 (16) | C15—C14—C17 | 120.83 (19) |
C6—C5—C8 | 115.64 (16) | C16—C15—C14 | 121.20 (18) |
C4—C5—C8 | 127.18 (17) | C16—C15—H15A | 119.4 |
C7—C6—C5 | 122.46 (18) | C14—C15—H15A | 119.4 |
C7—C6—H6A | 118.8 | C15—C16—C11 | 119.99 (19) |
C5—C6—H6A | 118.8 | C15—C16—H16A | 120.0 |
C6—C7—C2 | 119.55 (17) | C11—C16—H16A | 120.0 |
C6—C7—H7A | 120.2 | C14—C17—H17A | 109.5 |
C2—C7—H7A | 120.2 | C14—C17—H17B | 109.5 |
C9—C8—C5 | 134.27 (18) | H17A—C17—H17B | 109.5 |
C9—C8—H8A | 112.9 | C14—C17—H17C | 109.5 |
C5—C8—H8A | 112.9 | H17A—C17—H17C | 109.5 |
C8—C9—C10 | 121.31 (18) | H17B—C17—H17C | 109.5 |
| | | |
C1—S—C2—C3 | −178.89 (16) | Br—C9—C10—O | −30.8 (3) |
C1—S—C2—C7 | −0.30 (19) | C8—C9—C10—C11 | −38.2 (3) |
C7—C2—C3—C4 | −2.2 (3) | Br—C9—C10—C11 | 148.63 (16) |
S—C2—C3—C4 | 176.44 (16) | O—C10—C11—C12 | 140.4 (2) |
C2—C3—C4—C5 | −0.1 (3) | C9—C10—C11—C12 | −39.0 (3) |
C3—C4—C5—C6 | 2.0 (3) | O—C10—C11—C16 | −34.8 (3) |
C3—C4—C5—C8 | −176.37 (19) | C9—C10—C11—C16 | 145.81 (18) |
C4—C5—C6—C7 | −1.7 (3) | C16—C11—C12—C13 | 0.0 (3) |
C8—C5—C6—C7 | 176.86 (18) | C10—C11—C12—C13 | −175.25 (18) |
C5—C6—C7—C2 | −0.6 (3) | C11—C12—C13—C14 | −2.1 (3) |
C3—C2—C7—C6 | 2.5 (3) | C12—C13—C14—C15 | 2.4 (3) |
S—C2—C7—C6 | −176.05 (15) | C12—C13—C14—C17 | −176.25 (18) |
C6—C5—C8—C9 | 173.5 (2) | C13—C14—C15—C16 | −0.7 (3) |
C4—C5—C8—C9 | −8.1 (4) | C17—C14—C15—C16 | 177.91 (18) |
C5—C8—C9—C10 | −173.3 (2) | C14—C15—C16—C11 | −1.3 (3) |
C5—C8—C9—Br | −0.9 (3) | C12—C11—C16—C15 | 1.7 (3) |
C8—C9—C10—O | 142.4 (2) | C10—C11—C16—C15 | 177.00 (17) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···Oi | 0.93 | 2.51 | 3.392 (2) | 159 |
C17—H17B···Oii | 0.96 | 2.51 | 3.420 (3) | 158 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, y+1/2, −z+1. |