Reduction of 2,2,2-trichloro-1-arylethanones by RMgX: mechanistic investigation and the synthesis of substituted alpha,alpha-dichloroketones
Ali H. Essa; Reinner I. Lerrick; Floriana Tuna; Ross W. Harrington; William Clegg; Michael J. Hall; Chem.Commun. 49 (2013) 2756–; doi:10.1039/c3cc39147g

data_7109029
_publ_section_title
;
 Reduction of 2,2,2-trichloro-1-arylethanones by RMgX: mechanistic
 investigation and the synthesis of substituted
 alpha,alpha-dichloroketones
;
_journal_name_full               Chem.Commun.
_journal_page_first              2756
_journal_paper_doi               10.1039/c3cc39147g
_journal_volume                  49
_journal_year                    2013
_chemical_formula_moiety         'C14 H10 Cl2 N2 O4'
_chemical_formula_sum            'C14 H10 Cl2 N2 O4'
_chemical_formula_weight         341.14
_space_group_IT_number           61
_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-97
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   12.4615(6)
_cell_length_b                   13.4977(5)
_cell_length_c                   17.2015(7)
_cell_measurement_reflns_used    5529
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      28.50
_cell_measurement_theta_min      3.01
_cell_volume                     2893.3(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
;
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL and local programs'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 10.3968
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.873
_diffrn_measurement_device_type
'Oxford Diffraction Gemini A Ultra diffractometer'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  none
_diffrn_radiation_source         'sealed tube with Enhance optics'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_sigmaI/netI    0.0296
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            13352
_diffrn_reflns_theta_full        25.00
_diffrn_reflns_theta_max         28.56
_diffrn_reflns_theta_min         3.02
_exptl_absorpt_coefficient_mu    0.468
_exptl_absorpt_correction_T_max  0.955
_exptl_absorpt_correction_T_min  0.872
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.34.49 (release 20-01-2011 CrysAlis171 .NET)
(compiled Jan 20 2011,15:58:25)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.566
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1392
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.10
_refine_diff_density_max         0.342
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.051
_refine_ls_extinction_coef       0.0011(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         3223
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0323
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0258P)^2^+1.7441P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0693
_refine_ls_wR_factor_ref         0.0753
_reflns_number_gt                2709
_reflns_number_total             3223
_reflns_threshold_expression     I>2\s(I)
_cod_data_source_file            c3cc39147g.txt
_cod_data_source_block           mjh77_3h
_cod_database_code               7109029
_computing_special_details
;
TITL mjh77 in Pbca
CELL 0.71073 12.4615 13.4977 17.2015 90.000 90.000 90.000
ZERR 8.00 0.0006 0.0005 0.0007 0.000 0.000 0.000
LATT 1
SYMM 0.5-X, -Y, 0.5+Z
SYMM -X, 0.5+Y, 0.5-Z
SYMM 0.5+X, 0.5-Y, -Z
SFAC C H N O CL
UNIT 112 80 16 32 16
TEMP -123
L.S. 8
BOND $H
CONF
REM colourless block
SIZE 0.30 0.30 0.10
FMAP 2
PLAN 5
ACTA 50
WGHT 0.025800 1.744100
EXTI 0.001142
FVAR 0.12643
CL1 5 0.965303 0.683760 0.499291 11.00000 0.01961 0.02815 =
0.02812 0.00313 0.00662 -0.00370
CL2 5 0.868973 0.774420 0.633110 11.00000 0.02786 0.02288 =
0.03227 -0.00833 0.00047 -0.00497
N1 3 0.803058 0.457788 0.713172 11.00000 0.02646 0.01899 =
0.02050 0.00101 -0.00411 -0.00204
N3 3 0.630744 0.326189 0.352864 11.00000 0.03116 0.02432 =
0.02450 -0.00121 -0.00082 -0.00497
O1 4 0.972914 0.534492 0.615180 11.00000 0.01799 0.03488 =
0.02709 0.00309 -0.00173 0.00621
O2 4 0.694944 0.736492 0.531441 11.00000 0.02462 0.02093 =
0.03157 -0.00075 -0.00304 0.00598
O3 4 0.539655 0.323159 0.327331 11.00000 0.03572 0.03731 =
0.05173 -0.01142 -0.01542 -0.00452
O4 4 0.695916 0.259298 0.345250 11.00000 0.04365 0.02625 =
0.04454 -0.01270 -0.00319 0.00412
C1 1 0.884061 0.379732 0.710178 11.00000 0.03617 0.02107 =
0.04196 0.00461 -0.00638 0.00325
AFIX 137
H1A 2 0.861832 0.324462 0.743428 11.00000 -1.50000
H1B 2 0.952873 0.405915 0.728580 11.00000 -1.50000
H1C 2 0.891849 0.356427 0.656517 11.00000 -1.50000
AFIX 0
C2 1 0.711086 0.450937 0.753858 11.00000 0.03523 0.02561 =
0.01900 0.00189 0.00037 -0.01090
AFIX 43
H2A 2 0.692100 0.397211 0.786777 11.00000 -1.20000
AFIX 0
C3 1 0.648857 0.533075 0.740713 11.00000 0.02663 0.03102 =
0.02238 -0.00168 0.00539 -0.00572
AFIX 43
H3A 2 0.580528 0.546496 0.762824 11.00000 -1.20000
AFIX 0
C4 1 0.704549 0.592746 0.689079 11.00000 0.02197 0.02315 =
0.02182 0.00028 0.00211 0.00000
AFIX 43
H4A 2 0.680916 0.654633 0.669111 11.00000 -1.20000
AFIX 0
C5 1 0.801059 0.546186 0.671615 11.00000 0.02303 0.01790 =
0.01834 -0.00041 -0.00229 -0.00159
C6 1 0.886850 0.576111 0.621463 11.00000 0.01944 0.01974 =
0.01703 -0.00358 -0.00455 -0.00136
C7 1 0.864113 0.669899 0.570491 11.00000 0.01682 0.01809 =
0.02187 -0.00172 0.00337 -0.00126
C8 1 0.755249 0.667580 0.526408 11.00000 0.01686 0.01731 =
0.01853 0.00292 0.00168 -0.00071
C9 1 0.728508 0.577247 0.479499 11.00000 0.01635 0.01791 =
0.01796 0.00198 0.00018 -0.00046
C10 1 0.624049 0.571976 0.450055 11.00000 0.02048 0.02167 =
0.02973 -0.00120 -0.00086 0.00368
AFIX 43
H10A 2 0.575534 0.625143 0.458678 11.00000 -1.20000
AFIX 0
C11 1 0.591110 0.490032 0.408581 11.00000 0.01821 0.02825 =
0.02772 -0.00106 -0.00423 -0.00177
AFIX 43
H11A 2 0.520193 0.485681 0.388605 11.00000 -1.20000
AFIX 0
C12 1 0.664103 0.414374 0.396861 11.00000 0.02473 0.01970 =
0.01690 0.00041 0.00059 -0.00328
C13 1 0.767698 0.418068 0.424062 11.00000 0.02188 0.01966 =
0.01985 0.00163 0.00094 0.00369
AFIX 43
H13A 2 0.816207 0.365207 0.414334 11.00000 -1.20000
AFIX 0
C14 1 0.799756 0.500127 0.465778 11.00000 0.01699 0.02215 =
0.01949 0.00180 -0.00003 0.00174
AFIX 43
H14A 2 0.870984 0.503914 0.485236 11.00000 -1.20000
HKLF 4
REM mjh77 in Pbca
REM R1 = 0.0323 for 2709 Fo > 4sig(Fo) and 0.0426 for all 3223 data
REM 201 parameters refined using 0 restraints
END
;