#------------------------------------------------------------------------------
#$Date: 2020-05-22 06:38:31 +0300 (Fri, 22 May 2020) $
#$Revision: 252271 $
#$URL: file:///home/coder/svn-repositories/cod/cif/7/15/75/7157512.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_7157512
loop_
_publ_author_name
'Wang, Dungai'
'Liang, Xiao'
'Xiong, Mingteng'
'Zhu, Heping'
'Zhou, Yifeng'
'Pan, Yuanjiang'
_publ_section_title
;
 Synthesis of unsymmetrical disulfides via PPh3-mediated reductive
 coupling of thiophenols with sulfonyl chlorides
;
_journal_name_full               'Organic & Biomolecular Chemistry'
_journal_paper_doi               10.1039/D0OB00804D
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C14 H11 N S2'
_chemical_formula_sum            'C14 H11 N S2'
_chemical_formula_weight         257.36
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-03 deposited with the CCDC.	2020-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   27.604(2)
_cell_length_b                   7.7285(6)
_cell_length_c                   5.8633(5)
_cell_measurement_reflns_used    8130
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      26.37
_cell_measurement_theta_min      2.74
_cell_volume                     1250.86(17)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0340
_diffrn_reflns_av_unetI/netI     0.0278
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            13139
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.415
_diffrn_reflns_theta_min         2.737
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.400
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6568
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1095 before and 0.0555 after correction.
The Ratio of minimum to maximum transmission is 0.8811.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       plate
_exptl_crystal_F_000             536
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.216
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1009 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     155
_refine_ls_number_reflns         2562
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0358P)^2^+0.3965P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0754
_refine_ls_wR_factor_ref         0.0773
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                2405
_reflns_number_total             2562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ob00804d2.cif
_cod_data_source_block           190621_wdg_0ma
_cod_original_cell_volume        1250.85(17)
_cod_database_code               7157512
_shelx_shelxl_version_number     2016/6
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.914
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C4(H4), C5(H5), C9(H9), C10(H10), C12(H12), C13(H13)
2.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_file
;
TITL 190621_wdg_0ma_a.res in Pna2(1)
    190621_wdg_0ma.res
    created by SHELXL-2016/6 at 14:32:47 on 21-Jun-2019
REM Old TITL 190621_wdg_0ma in Pnma
REM SHELXT solution in Pna2(1)
REM R1 0.064, Rweak 0.005, Alpha 0.007, Orientation a'=-a, b'=c, c'=b
REM Flack x = -0.013 ( 0.033 ) from Parsons' quotients
REM Formula found by SHELXT: C14 N S2
CELL 0.71073 27.6037 7.7285 5.8633 90 90 90
ZERR 4 0.0021 0.0006 0.0005 0 0 0
LATT -1
SYMM -X,-Y,0.5+Z
SYMM 0.5+X,0.5-Y,+Z
SYMM 0.5-X,0.5+Y,0.5+Z
SFAC C H N S
UNIT 56 44 4 8

L.S. 4 0 0
PLAN  20
SIZE 0.05 0.18 0.23
TEMP -103.15
htab
BOND $H
list 4
fmap 2 53
acta
REM <olex2.extras>
REM <HklSrc "%.\\190621_wdg_0ma.hkl">
REM </olex2.extras>

WGHT    0.035800    0.396500
FVAR       0.68016
S1    4    0.225260    0.675283    0.155499    11.00000    0.02929    0.02862 =
         0.02754    0.00520   -0.00111   -0.00134
S2    4    0.273181    0.474917    0.138861    11.00000    0.02938    0.03078 =
         0.02718   -0.00790    0.00172   -0.00125
N1    3    0.475143    0.640535    0.864524    11.00000    0.03448    0.06404 =
         0.06511   -0.00842   -0.00951    0.00501
C1    1    0.182360    0.522074    0.540100    11.00000    0.02589    0.02606 =
         0.02936    0.00020   -0.00411    0.00279
AFIX  43
H1    2    0.213843    0.493749    0.593861    11.00000   -1.20000
AFIX   0
C2    1    0.141915    0.481407    0.669893    11.00000    0.03628    0.02741 =
         0.02369    0.00217    0.00049    0.00171
AFIX  43
H2    2    0.146193    0.423211    0.811180    11.00000   -1.20000
AFIX   0
C3    1    0.095175    0.523474    0.598976    11.00000    0.03028    0.02670 =
         0.03344   -0.00605    0.00267   -0.00128
C4    1    0.090368    0.606838    0.389560    11.00000    0.02632    0.03557 =
         0.03348   -0.00345   -0.00493    0.00250
AFIX  43
H4    2    0.058987    0.638276    0.337523    11.00000   -1.20000
AFIX   0
C5    1    0.130254    0.644960    0.255457    11.00000    0.03129    0.02939 =
         0.02719    0.00137   -0.00643    0.00200
AFIX  43
H5    2    0.125940    0.698971    0.111335    11.00000   -1.20000
AFIX   0
C6    1    0.176648    0.604325    0.331346    11.00000    0.02688    0.02288 =
         0.02445   -0.00299   -0.00052   -0.00070
C7    1    0.051695    0.481103    0.743533    11.00000    0.03321    0.04762 =
         0.04264   -0.00276    0.00700   -0.00216
AFIX 137
H7A   2    0.033979    0.384265    0.675068    11.00000   -1.50000
H7B   2    0.030440    0.582447    0.752396    11.00000   -1.50000
H7C   2    0.062360    0.449014    0.897241    11.00000   -1.50000
AFIX   0
C8    1    0.321602    0.530989    0.324876    11.00000    0.02575    0.02134 =
         0.02700    0.00121    0.00278   -0.00062
C9    1    0.367435    0.473849    0.256026    11.00000    0.03289    0.02710 =
         0.02823   -0.00218    0.00644    0.00093
AFIX  43
H9    2    0.371176    0.414794    0.115021    11.00000   -1.20000
AFIX   0
C10   1    0.407152    0.503420    0.393217    11.00000    0.02517    0.03153 =
         0.03746    0.00148    0.00570    0.00425
AFIX  43
H10   2    0.438286    0.464390    0.347162    11.00000   -1.20000
AFIX   0
C11   1    0.401533    0.590856    0.600013    11.00000    0.02831    0.02575 =
         0.03385    0.00520    0.00004   -0.00142
C12   1    0.355926    0.649354    0.667525    11.00000    0.03086    0.02615 =
         0.02679   -0.00231    0.00020   -0.00104
AFIX  43
H12   2    0.352231    0.709919    0.807440    11.00000   -1.20000
AFIX   0
C13   1    0.315956    0.618774    0.529581    11.00000    0.02505    0.02652 =
         0.02686   -0.00205    0.00412    0.00130
AFIX  43
H13   2    0.284804    0.657873    0.575251    11.00000   -1.20000
AFIX   0
C14   1    0.442830    0.619672    0.746352    11.00000    0.02917    0.03625 =
         0.04699    0.00042    0.00109    0.00318
HKLF 4




REM  190621_wdg_0ma_a.res in Pna2(1)
REM R1 =  0.0293 for    2405 Fo > 4sig(Fo)  and  0.0319 for all    2562 data
REM    155 parameters refined using      1 restraints

END

WGHT      0.0358      0.3966

REM Instructions for potential hydrogen bonds
EQIV $1 -x+1/2, y-1/2, z+1/2
HTAB C1 S1_$1
EQIV $2 -x+1/2, y+1/2, z+1/2
HTAB C13 S2_$2

REM Highest difference peak  0.216,  deepest hole -0.317,  1-sigma level  0.042
Q1    1   0.2379  0.4874  0.1299  11.00000  0.05    0.22
Q2    1   0.2326  0.3960  0.2381  11.00000  0.05    0.21
Q3    1   0.2672  0.7491  0.1475  11.00000  0.05    0.21
Q4    1   0.2322  0.3783  0.0454  11.00000  0.05    0.21
Q5    1   0.2625  0.6890  0.1561  11.00000  0.05    0.21
Q6    1   0.1962  0.6572  0.1605  11.00000  0.05    0.20
Q7    1   0.3019  0.4751  0.1434  11.00000  0.05    0.18
Q8    1   0.2834  0.4694  0.2931  11.00000  0.05    0.18
Q9    1   0.3810  0.5984  0.6426  11.00000  0.05    0.16
Q10   1   0.2312  0.6947  0.5585  11.00000  0.05    0.16
Q11   1   0.2169  0.6765 -0.0002  11.00000  0.05    0.16
Q12   1   0.1614  0.6387  0.3108  11.00000  0.05    0.16
Q13   1   0.2345  0.6774  0.7531  11.00000  0.05    0.16
Q14   1   0.1790  0.5348  0.3998  11.00000  0.05    0.15
Q15   1   0.0197  0.4732  0.6953  11.00000  0.05    0.15
Q16   1   0.2025  0.6408  0.2878  11.00000  0.05    0.15
Q17   1   0.2053  0.7191  0.5615  11.00000  0.05    0.15
Q18   1   0.3399  0.4803  0.2860  11.00000  0.05    0.15
Q19   1   0.1193  0.4826  0.6289  11.00000  0.05    0.14
Q20   1   0.3206  0.5264  0.4483  11.00000  0.05    0.14
;
_shelx_res_checksum              98492
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'x+1/2, -y+1/2, z'
'-x+1/2, y+1/2, z+1/2'
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_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
S1 S 0.22526(2) 0.67528(8) 0.15550(12) 0.02848(17) Uani 1 1 d . . . . .
S2 S 0.27318(2) 0.47492(8) 0.13886(13) 0.02911(18) Uani 1 1 d . . . . .
N1 N 0.47514(10) 0.6405(4) 0.8645(6) 0.0545(8) Uani 1 1 d . . . . .
C1 C 0.18236(10) 0.5221(4) 0.5401(5) 0.0271(6) Uani 1 1 d . . . . .
H1 H 0.213843 0.493749 0.593861 0.033 Uiso 1 1 calc R . . . .
C2 C 0.14191(10) 0.4814(3) 0.6699(5) 0.0291(6) Uani 1 1 d . . . . .
H2 H 0.146193 0.423211 0.811180 0.035 Uiso 1 1 calc R . . . .
C3 C 0.09517(10) 0.5235(3) 0.5990(5) 0.0301(6) Uani 1 1 d . . . . .
C4 C 0.09037(10) 0.6068(4) 0.3896(6) 0.0318(6) Uani 1 1 d . . . . .
H4 H 0.058987 0.638276 0.337523 0.038 Uiso 1 1 calc R . . . .
C5 C 0.13025(10) 0.6450(4) 0.2555(5) 0.0293(6) Uani 1 1 d . . . . .
H5 H 0.125940 0.698971 0.111335 0.035 Uiso 1 1 calc R . . . .
C6 C 0.17665(9) 0.6043(3) 0.3313(5) 0.0247(6) Uani 1 1 d . . . . .
C7 C 0.05169(11) 0.4811(4) 0.7435(6) 0.0412(7) Uani 1 1 d . . . . .
H7A H 0.033979 0.384265 0.675068 0.062 Uiso 1 1 calc GR . . . .
H7B H 0.030440 0.582447 0.752396 0.062 Uiso 1 1 calc GR . . . .
H7C H 0.062360 0.449014 0.897241 0.062 Uiso 1 1 calc GR . . . .
C8 C 0.32160(9) 0.5310(3) 0.3249(5) 0.0247(6) Uani 1 1 d . . . . .
C9 C 0.36743(10) 0.4738(3) 0.2560(5) 0.0294(6) Uani 1 1 d . . . . .
H9 H 0.371176 0.414794 0.115021 0.035 Uiso 1 1 calc R . . . .
C10 C 0.40715(10) 0.5034(4) 0.3932(6) 0.0314(6) Uani 1 1 d . . . . .
H10 H 0.438286 0.464390 0.347162 0.038 Uiso 1 1 calc R . . . .
C11 C 0.40153(9) 0.5909(3) 0.6000(5) 0.0293(6) Uani 1 1 d . . . . .
C12 C 0.35593(9) 0.6494(3) 0.6675(6) 0.0279(6) Uani 1 1 d . . . . .
H12 H 0.352231 0.709919 0.807440 0.034 Uiso 1 1 calc R . . . .
C13 C 0.31596(9) 0.6188(4) 0.5296(5) 0.0261(6) Uani 1 1 d . . . . .
H13 H 0.284804 0.657873 0.575251 0.031 Uiso 1 1 calc R . . . .
C14 C 0.44283(10) 0.6197(4) 0.7464(6) 0.0375(7) Uani 1 1 d . . . . .
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
S1 0.0293(3) 0.0286(3) 0.0275(3) 0.0052(4) -0.0011(3) -0.0013(2)
S2 0.0294(3) 0.0308(3) 0.0272(3) -0.0079(4) 0.0017(3) -0.0012(2)
N1 0.0345(14) 0.0640(19) 0.065(2) -0.0084(19) -0.0095(16) 0.0050(14)
C1 0.0259(13) 0.0261(13) 0.0294(14) 0.0002(11) -0.0041(11) 0.0028(10)
C2 0.0363(13) 0.0274(12) 0.0237(15) 0.0022(13) 0.0005(12) 0.0017(10)
C3 0.0303(13) 0.0267(12) 0.0334(16) -0.0060(12) 0.0027(12) -0.0013(10)
C4 0.0263(13) 0.0356(15) 0.0335(15) -0.0035(13) -0.0049(13) 0.0025(12)
C5 0.0313(14) 0.0294(14) 0.0272(14) 0.0014(12) -0.0064(11) 0.0020(11)
C6 0.0269(12) 0.0229(12) 0.0244(14) -0.0030(11) -0.0005(10) -0.0007(10)
C7 0.0332(16) 0.0476(18) 0.0426(18) -0.0028(15) 0.0070(14) -0.0022(13)
C8 0.0257(12) 0.0213(12) 0.0270(15) 0.0012(10) 0.0028(11) -0.0006(10)
C9 0.0329(14) 0.0271(13) 0.0282(15) -0.0022(12) 0.0064(12) 0.0009(11)
C10 0.0252(12) 0.0315(14) 0.0375(16) 0.0015(13) 0.0057(12) 0.0042(11)
C11 0.0283(12) 0.0257(12) 0.0338(16) 0.0052(12) 0.0000(12) -0.0014(9)
C12 0.0309(12) 0.0261(12) 0.0268(14) -0.0023(13) 0.0002(13) -0.0010(9)
C13 0.0251(12) 0.0265(13) 0.0269(13) -0.0020(11) 0.0041(11) 0.0013(10)
C14 0.0292(14) 0.0363(15) 0.0470(18) 0.0004(14) 0.0011(13) 0.0032(12)
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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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
C6 S1 S2 106.44(9) . . ?
C8 S2 S1 105.85(9) . . ?
C2 C1 H1 120.1 . . ?
C2 C1 C6 119.7(2) . . ?
C6 C1 H1 120.1 . . ?
C1 C2 H2 119.1 . . ?
C1 C2 C3 121.9(3) . . ?
C3 C2 H2 119.1 . . ?
C2 C3 C7 121.3(3) . . ?
C4 C3 C2 117.3(3) . . ?
C4 C3 C7 121.4(3) . . ?
C3 C4 H4 119.2 . . ?
C5 C4 C3 121.5(3) . . ?
C5 C4 H4 119.2 . . ?
C4 C5 H5 119.9 . . ?
C4 C5 C6 120.1(3) . . ?
C6 C5 H5 119.9 . . ?
C1 C6 S1 124.5(2) . . ?
C1 C6 C5 119.3(3) . . ?
C5 C6 S1 116.1(2) . . ?
C3 C7 H7A 109.5 . . ?
C3 C7 H7B 109.5 . . ?
C3 C7 H7C 109.5 . . ?
H7A C7 H7B 109.5 . . ?
H7A C7 H7C 109.5 . . ?
H7B C7 H7C 109.5 . . ?
C9 C8 S2 115.2(2) . . ?
C13 C8 S2 124.4(2) . . ?
C13 C8 C9 120.4(3) . . ?
C8 C9 H9 120.1 . . ?
C10 C9 C8 119.9(3) . . ?
C10 C9 H9 120.1 . . ?
C9 C10 H10 120.1 . . ?
C9 C10 C11 119.9(3) . . ?
C11 C10 H10 120.1 . . ?
C10 C11 C14 120.2(3) . . ?
C12 C11 C10 120.2(3) . . ?
C12 C11 C14 119.6(3) . . ?
C11 C12 H12 120.1 . . ?
C13 C12 C11 119.8(3) . . ?
C13 C12 H12 120.1 . . ?
C8 C13 C12 119.9(2) . . ?
C8 C13 H13 120.1 . . ?
C12 C13 H13 120.1 . . ?
N1 C14 C11 178.9(4) . . ?
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
S1 S2 2.0389(9) . ?
S1 C6 1.779(3) . ?
S2 C8 1.779(3) . ?
N1 C14 1.141(4) . ?
C1 H1 0.9500 . ?
C1 C2 1.387(4) . ?
C1 C6 1.388(4) . ?
C2 H2 0.9500 . ?
C2 C3 1.394(4) . ?
C3 C4 1.393(4) . ?
C3 C7 1.505(4) . ?
C4 H4 0.9500 . ?
C4 C5 1.385(4) . ?
C5 H5 0.9500 . ?
C5 C6 1.392(4) . ?
C7 H7A 0.9800 . ?
C7 H7B 0.9800 . ?
C7 H7C 0.9800 . ?
C8 C9 1.400(4) . ?
C8 C13 1.388(4) . ?
C9 H9 0.9500 . ?
C9 C10 1.379(4) . ?
C10 H10 0.9500 . ?
C10 C11 1.397(4) . ?
C11 C12 1.395(4) . ?
C11 C14 1.444(4) . ?
C12 H12 0.9500 . ?
C12 C13 1.388(4) . ?
C13 H13 0.9500 . ?