# Electronic Supplementary Material (ESI) for Green Chemistry.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_I

#----------------------------------------------------------------------------#
#                   CHEMICAL INFORMATION                                     #
#----------------------------------------------------------------------------#

_database_code_depnum_ccdc_archive 'CCDC 1025549'
_audit_update_record             
;
2014-09-22 deposited with the CCDC.
2014-12-18 downloaded from the CCDC.
;

_audit_creation_date             2014-09-19T18:30:47-00:00
_audit_creation_method           'WinGX routine CIF_UPDATE'
_chemical_name_systematic        
; Ethyl 5-(4-fluorophenyl)-1H-pyrazole-3-carboxylate
;
_chemical_formula_sum            'C12 H11 F N2 O2'
_chemical_formula_moiety         'C12 H11 F N2 O2'
_chemical_formula_weight         234.23

#----------------------------------------------------------------------------#
#                   UNIT CELL INFORMATION                                    #
#----------------------------------------------------------------------------#

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 21/n'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_Int_Tables_number      14
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   14.5192(8)
_cell_length_b                   4.9710(2)
_cell_length_c                   16.4551(7)
_cell_angle_alpha                90
_cell_angle_beta                 106.074(5)
_cell_angle_gamma                90
_cell_volume                     1141.21(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    294(2)
_cell_measurement_reflns_used    2273
_cell_measurement_theta_min      4.289
_cell_measurement_theta_max      28.46

#----------------------------------------------------------------------------#
#                   CRYSTAL INFORMATION                                      #
#----------------------------------------------------------------------------#

_exptl_crystal_description       plate
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.78
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.06
_exptl_crystal_density_diffrn    1.363
_exptl_crystal_F_000             488

#----------------------------------------------------------------------------#
#                   ABSORPTION CORRECTION                                    #
#----------------------------------------------------------------------------#

_exptl_absorpt_coefficient_mu    0.105
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
; Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm using CrysAlisPro 
(Agilent Technologies, 2013).
;
_exptl_absorpt_correction_T_min  0.64703
_exptl_absorpt_correction_T_max  1
_shelx_estimated_absorpt_T_min   0.92
_shelx_estimated_absorpt_T_max   0.994

#----------------------------------------------------------------------------#
#                   DATA COLLECTION                                          #
#----------------------------------------------------------------------------#

_diffrn_source                   'fine focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo (Agilent Technologies)'
_diffrn_source_current           50
_diffrn_source_voltage           40
_diffrn_source_power             2
_diffrn_ambient_temperature      294(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 16.328
_diffrn_measurement_specimen_support 'glass fiber'
_diffrn_radiation_collimation    '0.8 mm'
_diffrn_orient_matrix_ub_11      0.044812
_diffrn_orient_matrix_ub_12      -0.0029649
_diffrn_orient_matrix_ub_13      0.0312787
_diffrn_orient_matrix_ub_21      0.0239528
_diffrn_orient_matrix_ub_22      -0.002066
_diffrn_orient_matrix_ub_23      -0.0321552
_diffrn_orient_matrix_ub_31      0.0012637
_diffrn_orient_matrix_ub_32      0.1426836
_diffrn_orient_matrix_ub_33      0.0001625
_diffrn_measurement_device       'κ-geometry diffractometer'
_diffrn_measurement_device_type  'Gemini S (Agilent Technologies)'
_diffrn_measurement_method       'ω scans'
_diffrn_reflns_av_R_equivalents  0.0242
_diffrn_reflns_av_unetI/netI     0.0257
_diffrn_reflns_number            8237
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         3.317
_diffrn_reflns_theta_max         28.811
_diffrn_reflns_theta_full        26.32
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.896
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.896
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.896
_reflns_number_total             2670
_reflns_number_gt                1927
_reflns_threshold_expression     'I > 2σ(I)'

#----------------------------------------------------------------------------#
#                   COMPUTER PROGRAMS USED                                   #
#----------------------------------------------------------------------------#

_computing_data_collection       'CrysAlisPro (Agilent Technologies, 2013)'
_computing_cell_refinement       'CrysAlisPro (Agilent Technologies, 2013)'
_computing_data_reduction        'CrysAlisPro (Agilent Technologies, 2013)'
_computing_structure_solution    'SHELXT (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2008)'
_computing_molecular_graphics    'ORTEP for Windows (Farrugia, 1997)'
_computing_publication_material  'SHELXLE (Hübschle et al., 2011)'

#----------------------------------------------------------------------------#
#                   STRUCTURE SOLUTION
#----------------------------------------------------------------------------#

_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   direct
_atom_sites_solution_hydrogens   mixed

#----------------------------------------------------------------------------#
#                   REFINEMENT INFORMATION                                   #
#----------------------------------------------------------------------------#

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0692P)²+0.1811P] where P=(Fo²+2Fc²)/3'
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_number_reflns         2670
_refine_ls_number_parameters     159
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0685
_refine_ls_R_factor_gt           0.0483
_refine_ls_wR_factor_ref         0.1422
_refine_ls_wR_factor_gt          0.1277
_refine_ls_goodness_of_fit_ref   1.04
_refine_ls_restrained_S_all      1.04
_refine_ls_shift/su_max          0
_refine_ls_shift/su_mean         0
_refine_diff_density_max         0.199
_refine_diff_density_min         -0.173
_refine_diff_density_rms         0.039

#----------------------------------------------------------------------------#
#                   ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS         #
#----------------------------------------------------------------------------#

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 0 '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 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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_calc_flag
_atom_site_disorder_assembly
_atom_site_disorder_group
F1 F 0.19878(12) 1.0302(3) 0.66851(8) 0.1135(5) Uani 1 d . .
O1 O 0.50750(10) -0.1008(3) 0.36674(8) 0.0740(4) Uani 1 d . .
O2 O 0.44929(10) 0.0658(3) 0.23628(7) 0.0743(4) Uani 1 d . .
N1 N 0.29475(10) 0.5661(3) 0.33600(7) 0.0505(3) Uani 1 d . .
H1 H 0.2522(13) 0.683(4) 0.3120(11) 0.061(5) Uiso 1 d . .
N2 N 0.33537(9) 0.4123(3) 0.28852(7) 0.0514(3) Uani 1 d . .
C1 C 0.45761(12) 0.0565(3) 0.31914(10) 0.0551(4) Uani 1 d . .
C2 C 0.50309(19) -0.1334(5) 0.20362(14) 0.0955(7) Uani 1 d . .
H2A H 0.4729 -0.3085 0.2012 0.115 Uiso 1 calc . .
H2B H 0.568 -0.1462 0.2403 0.115 Uiso 1 calc . .
C3 C 0.39823(10) 0.2601(3) 0.34503(8) 0.0486(4) Uani 1 d . .
C4 C 0.39710(11) 0.3194(3) 0.42773(9) 0.0514(4) Uani 1 d . .
H4 H 0.4342 0.2407 0.4773 0.062 Uiso 1 calc . .
C5 C 0.32961(11) 0.5186(3) 0.42041(8) 0.0471(4) Uani 1 d . .
C6 C 0.5045(2) -0.0492(7) 0.11911(16) 0.1217(10) Uani 1 d . .
H6A H 0.5341 -0.1868 0.094 0.183 Uiso 1 calc . .
H6B H 0.5404 0.1148 0.1229 0.183 Uiso 1 calc . .
H6C H 0.4401 -0.0203 0.0849 0.183 Uiso 1 calc . .
C7 C 0.29456(11) 0.6586(3) 0.48417(8) 0.0497(4) Uani 1 d . .
C8 C 0.32806(14) 0.5811(4) 0.56856(10) 0.0660(5) Uani 1 d . .
H8 H 0.373 0.4437 0.5835 0.079 Uiso 1 calc . .
C9 C 0.29559(16) 0.7051(4) 0.63028(11) 0.0765(6) Uani 1 d . .
H9 H 0.318 0.6517 0.6865 0.092 Uiso 1 calc . .
C10 C 0.23066(16) 0.9052(4) 0.60784(12) 0.0743(5) Uani 1 d . .
C11 C 0.19620(17) 0.9908(4) 0.52634(13) 0.0790(6) Uani 1 d . .
H11 H 0.152 1.1305 0.5127 0.095 Uiso 1 calc . .
C12 C 0.22849(14) 0.8650(4) 0.46426(10) 0.0649(5) Uani 1 d . .
H12 H 0.2053 0.9204 0.4083 0.078 Uiso 1 calc . .



#----------------------------------------------------------------------------#
#                   MOLECULAR GEOMETRY                                       #
#----------------------------------------------------------------------------#

_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
F1 C10 1.361(2) . ?
O1 C1 1.1983(19) . ?
O2 C1 1.3359(19) . ?
O2 C2 1.453(2) . ?
N1 N2 1.3409(18) . ?
N1 C5 1.3608(17) . ?
N1 H1 0.859(19) . ?
N2 C3 1.3416(18) . ?
C1 C3 1.467(2) . ?
C2 C6 1.458(3) . ?
C2 H2A 0.97 . ?
C2 H2B 0.97 . ?
C3 C4 1.3969(19) . ?
C4 C5 1.375(2) . ?
C4 H4 0.93 . ?
C5 C7 1.463(2) . ?
C6 H6A 0.96 . ?
C6 H6B 0.96 . ?
C6 H6C 0.96 . ?
C7 C12 1.381(2) . ?
C7 C8 1.393(2) . ?
C8 C9 1.378(2) . ?
C8 H8 0.93 . ?
C9 C10 1.350(3) . ?
C9 H9 0.93 . ?
C10 C11 1.363(3) . ?
C11 C12 1.385(2) . ?
C11 H11 0.93 . ?
C12 H12 0.93 . ?

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
C1 O2 C2 116.63(15) . . ?
N2 N1 C5 113.36(13) . . ?
N2 N1 H1 119.5(12) . . ?
C5 N1 H1 127.1(12) . . ?
N1 N2 C3 104.01(11) . . ?
O1 C1 O2 123.85(16) . . ?
O1 C1 C3 123.92(14) . . ?
O2 C1 C3 112.23(13) . . ?
O2 C2 C6 108.0(2) . . ?
O2 C2 H2A 110.1 . . ?
C6 C2 H2A 110.1 . . ?
O2 C2 H2B 110.1 . . ?
C6 C2 H2B 110.1 . . ?
H2A C2 H2B 108.4 . . ?
N2 C3 C4 111.54(13) . . ?
N2 C3 C1 121.96(13) . . ?
C4 C3 C1 126.49(13) . . ?
C5 C4 C3 105.48(12) . . ?
C5 C4 H4 127.3 . . ?
C3 C4 H4 127.3 . . ?
N1 C5 C4 105.61(13) . . ?
N1 C5 C7 122.99(14) . . ?
C4 C5 C7 131.37(13) . . ?
C2 C6 H6A 109.5 . . ?
C2 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
C2 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
C12 C7 C8 118.04(15) . . ?
C12 C7 C5 122.70(13) . . ?
C8 C7 C5 119.26(15) . . ?
C9 C8 C7 121.00(18) . . ?
C9 C8 H8 119.5 . . ?
C7 C8 H8 119.5 . . ?
C10 C9 C8 118.91(17) . . ?
C10 C9 H9 120.5 . . ?
C8 C9 H9 120.5 . . ?
C9 C10 F1 119.29(17) . . ?
C9 C10 C11 122.51(17) . . ?
F1 C10 C11 118.2(2) . . ?
C10 C11 C12 118.54(19) . . ?
C10 C11 H11 120.7 . . ?
C12 C11 H11 120.7 . . ?
C7 C12 C11 121.00(16) . . ?
C7 C12 H12 119.5 . . ?
C11 C12 H12 119.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C5 N1 N2 C3 0.29(17) . . . . ?
C2 O2 C1 O1 1.5(3) . . . . ?
C2 O2 C1 C3 -178.20(17) . . . . ?
C1 O2 C2 C6 -165.7(2) . . . . ?
N1 N2 C3 C4 -0.19(17) . . . . ?
N1 N2 C3 C1 178.80(13) . . . . ?
O1 C1 C3 N2 -172.38(16) . . . . ?
O2 C1 C3 N2 7.3(2) . . . . ?
O1 C1 C3 C4 6.4(3) . . . . ?
O2 C1 C3 C4 -173.89(15) . . . . ?
N2 C3 C4 C5 0.03(17) . . . . ?
C1 C3 C4 C5 -178.90(14) . . . . ?
N2 N1 C5 C4 -0.28(17) . . . . ?
N2 N1 C5 C7 -178.70(13) . . . . ?
C3 C4 C5 N1 0.15(16) . . . . ?
C3 C4 C5 C7 178.38(15) . . . . ?
N1 C5 C7 C12 -5.1(2) . . . . ?
C4 C5 C7 C12 176.89(17) . . . . ?
N1 C5 C7 C8 174.33(15) . . . . ?
C4 C5 C7 C8 -3.6(3) . . . . ?
C12 C7 C8 C9 0.6(3) . . . . ?
C5 C7 C8 C9 -178.91(17) . . . . ?
C7 C8 C9 C10 -0.3(3) . . . . ?
C8 C9 C10 F1 -179.48(18) . . . . ?
C8 C9 C10 C11 -0.3(3) . . . . ?
C9 C10 C11 C12 0.7(3) . . . . ?
F1 C10 C11 C12 179.85(19) . . . . ?
C8 C7 C12 C11 -0.2(3) . . . . ?
C5 C7 C12 C11 179.27(17) . . . . ?
C10 C11 C12 C7 -0.4(3) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1 N2 0.859(19) 2.119(19) 2.9301(18) 157.2(16) 2

#----------------------------------------------------------------------------#
#                       REFLECTION DATA                                      #
#----------------------------------------------------------------------------#

#===END  
#----------------------------------------------------------------------------#
#                        END OF CIF                                          #
#----------------------------------------------------------------------------#
# The following lines are used to test the character set of files sent by
# network email or other means. They are not part of the CIF data set
# abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789
# !@#$%^&*()_+{}:"~<>?|\-=[];'`,./

# END of CIF
