# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_1
_database_code_depnum_ccdc_archive 'CCDC 1475274'
_audit_update_record             
;
2016-04-20 deposited with the CCDC.
2016-08-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
(S)-4-benzyl-3-(4-bromophenyl)-4-chloro-4,5-dihydro-1H-pyrazol-5-one
_chemical_name_common            ?
_chemical_melting_point          390
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H16 Br Cl N2 O'
_chemical_formula_weight         439.73
_chemical_absolute_configuration ad

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'P2(1)2(1)2(1) '


loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   8.048(3)
_cell_length_b                   9.690(3)
_cell_length_c                   25.348(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1976.7(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.31
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.478
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             888
_exptl_absorpt_coefficient_mu    2.229
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.5267
_exptl_absorpt_correction_T_max  0.5450
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            10670
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_sigmaI/netI    0.0512
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_theta_min         2.25
_diffrn_reflns_theta_max         25.00
_reflns_number_total             3461
_reflns_number_gt                3003
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'


_refine_special_details          
; 
 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 > 2sigma(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. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0314P)²+0.4400P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    'riding mode'
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.016(9)
_refine_ls_number_reflns         3461
_refine_ls_number_parameters     244
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0427
_refine_ls_R_factor_gt           0.0340
_refine_ls_wR_factor_ref         0.0859
_refine_ls_wR_factor_gt          0.0822
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_restrained_S_all      1.000
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.03369(6) 0.36235(5) 0.084353(18) 0.08323(17) Uani 1 1 d . . .
Cl2 Cl 0.82132(13) 0.20810(9) 0.21310(3) 0.0605(2) Uani 1 1 d . . .
C11 C 0.5304(4) 0.1337(3) 0.12089(11) 0.0411(6) Uani 1 1 d . . .
N2 N 0.7803(3) 0.0276(3) 0.09088(10) 0.0464(6) Uani 1 1 d . . .
C17 C 1.0532(4) -0.0638(3) 0.07099(12) 0.0487(8) Uani 1 1 d . . .
O1 O 1.0654(3) -0.0454(3) 0.18969(9) 0.0640(6) Uani 1 1 d . . .
C2 C 0.7815(4) 0.0451(3) 0.18186(11) 0.0446(7) Uani 1 1 d . . .
C14 C 0.2348(4) 0.2670(3) 0.09970(13) 0.0495(8) Uani 1 1 d . . .
C1 C 0.9491(5) -0.0124(3) 0.16274(12) 0.0476(7) Uani 1 1 d . . .
N1 N 0.9323(3) -0.0225(3) 0.10904(9) 0.0473(6) Uani 1 1 d . . .
C5 C 0.6638(4) -0.1944(3) 0.20084(11) 0.0450(7) Uani 1 1 d . . .
C13 C 0.3355(5) 0.2289(4) 0.05859(13) 0.0575(9) Uani 1 1 d . . .
H13A H 0.3047 0.2474 0.0239 0.069 Uiso 1 1 calc R . .
C22 C 1.0355(5) -0.0249(4) 0.01978(13) 0.0632(9) Uani 1 1 d . . .
H22A H 0.9448 0.0282 0.0095 0.076 Uiso 1 1 calc R . .
C4 C 0.7032(5) -0.0521(3) 0.22229(12) 0.0520(8) Uani 1 1 d . . .
H4A H 0.7784 -0.0616 0.2520 0.062 Uiso 1 1 calc R . .
H4B H 0.6013 -0.0107 0.2353 0.062 Uiso 1 1 calc R . .
C16 C 0.4245(4) 0.1726(3) 0.16143(12) 0.0471(8) Uani 1 1 d . . .
H16A H 0.4536 0.1538 0.1962 0.057 Uiso 1 1 calc R . .
C15 C 0.2757(4) 0.2394(3) 0.15071(13) 0.0512(8) Uani 1 1 d . . .
H15A H 0.2049 0.2650 0.1780 0.061 Uiso 1 1 calc R . .
C3 C 0.6924(4) 0.0678(3) 0.13002(11) 0.0413(7) Uani 1 1 d . . .
C6 C 0.5070(5) -0.2259(4) 0.18390(14) 0.0622(9) Uani 1 1 d . . .
H6A H 0.4244 -0.1588 0.1846 0.075 Uiso 1 1 calc R . .
C10 C 0.7847(5) -0.2953(4) 0.19997(15) 0.0640(10) Uani 1 1 d . . .
H10A H 0.8915 -0.2749 0.2117 0.077 Uiso 1 1 calc R . .
C18 C 1.1845(6) -0.1435(5) 0.08547(17) 0.0887(14) Uani 1 1 d . . .
H18A H 1.1963 -0.1717 0.1203 0.106 Uiso 1 1 calc R . .
C8 C 0.5897(7) -0.4564(4) 0.16513(16) 0.0793(14) Uani 1 1 d . . .
H8A H 0.5643 -0.5449 0.1534 0.095 Uiso 1 1 calc R . .
C7 C 0.4705(7) -0.3578(4) 0.16565(16) 0.0798(12) Uani 1 1 d . . .
H7A H 0.3640 -0.3783 0.1538 0.096 Uiso 1 1 calc R . .
C12 C 0.4830(4) 0.1626(3) 0.06951(12) 0.0542(8) Uani 1 1 d . . .
H12A H 0.5522 0.1367 0.0418 0.065 Uiso 1 1 calc R . .
C9 C 0.7485(7) -0.4261(4) 0.18189(19) 0.0807(13) Uani 1 1 d . . .
H9A H 0.8308 -0.4934 0.1810 0.097 Uiso 1 1 calc R . .
C20 C 1.2849(6) -0.1435(5) -0.0026(2) 0.0898(13) Uani 1 1 d . . .
H20A H 1.3635 -0.1701 -0.0275 0.108 Uiso 1 1 calc R . .
C19 C 1.3007(7) -0.1824(6) 0.0479(2) 0.1132(19) Uani 1 1 d . . .
H19A H 1.3910 -0.2363 0.0579 0.136 Uiso 1 1 calc R . .
C21 C 1.1530(6) -0.0646(5) -0.01703(16) 0.0792(12) Uani 1 1 d . . .
H21A H 1.1416 -0.0371 -0.0520 0.095 Uiso 1 1 calc R . .


_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 C14 1.904(3) . ?
Cl2 C2 1.796(3) . ?
C11 C12 1.386(4) . ?
C11 C16 1.387(4) . ?
C11 C3 1.470(4) . ?
N2 C3 1.279(4) . ?
N2 N1 1.395(4) . ?
C17 C22 1.359(4) . ?
C17 C18 1.359(5) . ?
C17 N1 1.427(4) . ?
O1 C1 1.202(4) . ?
C2 C3 1.513(4) . ?
C2 C1 1.538(5) . ?
C2 C4 1.528(4) . ?
C14 C15 1.361(5) . ?
C14 C13 1.371(5) . ?
C1 N1 1.371(4) . ?
C5 C6 1.367(5) . ?
C5 C10 1.380(5) . ?
C5 C4 1.516(4) . ?
C13 C12 1.378(5) . ?
C22 C21 1.383(6) . ?
C16 C15 1.388(5) . ?
C6 C7 1.391(5) . ?
C10 C9 1.379(6) . ?
C18 C19 1.387(6) . ?
C8 C7 1.354(7) . ?
C8 C9 1.379(7) . ?
C20 C19 1.340(7) . ?
C20 C21 1.358(7) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C12 C11 C16 118.2(3) . . ?
C12 C11 C3 118.7(3) . . ?
C16 C11 C3 123.1(3) . . ?
C3 N2 N1 109.6(2) . . ?
C22 C17 C18 119.8(4) . . ?
C22 C17 N1 119.8(3) . . ?
C18 C17 N1 120.4(3) . . ?
C3 C2 C1 101.2(2) . . ?
C3 C2 C4 118.5(3) . . ?
C1 C2 C4 110.5(2) . . ?
C3 C2 Cl2 109.8(2) . . ?
C1 C2 Cl2 107.5(2) . . ?
C4 C2 Cl2 108.7(2) . . ?
C15 C14 C13 121.8(3) . . ?
C15 C14 Br1 119.7(3) . . ?
C13 C14 Br1 118.6(2) . . ?
O1 C1 N1 128.4(3) . . ?
O1 C1 C2 126.9(3) . . ?
N1 C1 C2 104.6(3) . . ?
C1 N1 N2 112.9(3) . . ?
C1 N1 C17 128.6(3) . . ?
N2 N1 C17 118.2(2) . . ?
C6 C5 C10 119.2(3) . . ?
C6 C5 C4 120.5(3) . . ?
C10 C5 C4 120.2(3) . . ?
C14 C13 C12 118.8(3) . . ?
C17 C22 C21 119.7(4) . . ?
C5 C4 C2 114.0(2) . . ?
C11 C16 C15 120.8(3) . . ?
C14 C15 C16 119.1(3) . . ?
N2 C3 C11 120.0(3) . . ?
N2 C3 C2 111.5(3) . . ?
C11 C3 C2 128.3(3) . . ?
C5 C6 C7 120.3(4) . . ?
C5 C10 C9 120.5(4) . . ?
C19 C18 C17 119.6(4) . . ?
C7 C8 C9 120.2(4) . . ?
C8 C7 C6 120.2(4) . . ?
C11 C12 C13 121.3(3) . . ?
C8 C9 C10 119.7(4) . . ?
C19 C20 C21 119.3(4) . . ?
C20 C19 C18 121.0(5) . . ?
C20 C21 C22 120.6(4) . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.428
_refine_diff_density_min         -0.474
_refine_diff_density_rms         0.041
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_solvent_exptl_crystal_recrystallization_method 'hexane, ether'
