# Electronic Supplementary Material (ESI) for Polymer Chemistry.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_a

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            'Pd-alkyne cat'
_chemical_melting_point          ?
_chemical_formula_moiety         C20H35ClP2Pd
_chemical_formula_sum            'C20 H35 Cl P2 Pd'
_chemical_formula_weight         479.27

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'
P P 0.1023 0.0942 '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'
Pd Pd -0.9988 1.0072 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           orthorhombic
_symmetry_space_group_name_H-M   Pna2(1)

loop_
_symmetry_equiv_pos_as_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'

_cell_length_a                   23.6604(11)
_cell_length_b                   9.3856(4)
_cell_length_c                   10.4813(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2327.55(18)
_cell_formula_units_Z            4
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    3650
_cell_measurement_theta_min      3.3820
_cell_measurement_theta_max      28.0400

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.12
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             992
_exptl_absorpt_coefficient_mu    1.050
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.86938
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      180(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         "SuperNova (Mo) X-ray Source'"
_diffrn_radiation_monochromator  mirror
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.3914
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        none
_diffrn_reflns_number            7787
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_sigmaI/netI    0.0465
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         2.91
_diffrn_reflns_theta_max         26.02
_reflns_number_total             3646
_reflns_number_gt                3228
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material  'SHELX-97 (Sheldrick, 1997)'

_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)+(0.0178P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_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   0.00(3)
_refine_ls_number_reflns         3646
_refine_ls_number_parameters     223
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0374
_refine_ls_R_factor_gt           0.0284
_refine_ls_wR_factor_ref         0.0552
_refine_ls_wR_factor_gt          0.0500
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_refine_ls_shift/su_max          0.001
_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
C1 C 0.42652(16) 0.7598(3) 0.5578(5) 0.0269(10) Uani 1 1 d . . .
C2 C 0.46803(17) 0.6868(4) 0.5412(4) 0.0290(12) Uani 1 1 d . . .
C3 C 0.51961(18) 0.6092(3) 0.5201(4) 0.0286(11) Uani 1 1 d . . .
C4 C 0.56382(17) 0.6153(4) 0.6061(4) 0.0331(13) Uani 1 1 d . . .
H4 H 0.5598 0.6700 0.6818 0.040 Uiso 1 1 calc R . .
C5 C 0.61391(17) 0.5431(4) 0.5834(7) 0.0434(11) Uani 1 1 d . . .
H5 H 0.6439 0.5491 0.6433 0.052 Uiso 1 1 calc R . .
C6 C 0.6203(2) 0.4630(5) 0.4753(6) 0.0474(13) Uani 1 1 d . . .
H6 H 0.6545 0.4122 0.4609 0.057 Uiso 1 1 calc R . .
C7 C 0.5774(2) 0.4564(5) 0.3880(5) 0.0423(12) Uani 1 1 d . . .
H7 H 0.5823 0.4028 0.3119 0.051 Uiso 1 1 calc R . .
C8 C 0.5273(2) 0.5267(4) 0.4096(5) 0.0356(11) Uani 1 1 d . . .
H8 H 0.4976 0.5195 0.3490 0.043 Uiso 1 1 calc R . .
C9 C 0.41201(17) 1.2299(3) 0.5873(6) 0.0352(11) Uani 1 1 d . . .
H9A H 0.3721 1.2617 0.5903 0.042 Uiso 1 1 calc R . .
H9B H 0.4351 1.3012 0.6334 0.042 Uiso 1 1 calc R . .
C10 C 0.4311(2) 1.2231(5) 0.4500(5) 0.0496(14) Uani 1 1 d . . .
H10A H 0.4709 1.1943 0.4466 0.074 Uiso 1 1 calc R . .
H10B H 0.4268 1.3172 0.4105 0.074 Uiso 1 1 calc R . .
H10C H 0.4081 1.1536 0.4036 0.074 Uiso 1 1 calc R . .
C11 C 0.49329(17) 1.0200(4) 0.6754(5) 0.0372(11) Uani 1 1 d . . .
H11A H 0.4989 0.9373 0.7326 0.045 Uiso 1 1 calc R . .
H11B H 0.5060 0.9912 0.5892 0.045 Uiso 1 1 calc R . .
C12 C 0.5314(2) 1.1413(5) 0.7215(6) 0.0604(16) Uani 1 1 d . . .
H12A H 0.5272 1.2234 0.6645 0.091 Uiso 1 1 calc R . .
H12B H 0.5708 1.1095 0.7212 0.091 Uiso 1 1 calc R . .
H12C H 0.5205 1.1686 0.8083 0.091 Uiso 1 1 calc R . .
C13 C 0.3966(2) 1.0972(4) 0.8307(5) 0.0364(11) Uani 1 1 d . . .
H13A H 0.4252 1.1599 0.8705 0.044 Uiso 1 1 calc R . .
H13B H 0.3604 1.1501 0.8286 0.044 Uiso 1 1 calc R . .
C14 C 0.3893(2) 0.9656(5) 0.9129(5) 0.0536(14) Uani 1 1 d . . .
H14A H 0.3594 0.9053 0.8769 0.080 Uiso 1 1 calc R . .
H14B H 0.3788 0.9942 0.9997 0.080 Uiso 1 1 calc R . .
H14C H 0.4248 0.9122 0.9154 0.080 Uiso 1 1 calc R . .
C15 C 0.26606(17) 0.7675(4) 0.3486(4) 0.0286(10) Uani 1 1 d . . .
H15A H 0.2415 0.6884 0.3196 0.034 Uiso 1 1 calc R . .
H15B H 0.2414 0.8497 0.3691 0.034 Uiso 1 1 calc R . .
C16 C 0.30601(19) 0.8090(4) 0.2404(5) 0.0378(11) Uani 1 1 d . . .
H16A H 0.3281 0.8927 0.2658 0.057 Uiso 1 1 calc R . .
H16B H 0.2840 0.8316 0.1639 0.057 Uiso 1 1 calc R . .
H16C H 0.3316 0.7295 0.2221 0.057 Uiso 1 1 calc R . .
C17 C 0.24756(18) 0.6740(4) 0.6056(4) 0.0356(14) Uani 1 1 d . . .
H17A H 0.2232 0.7591 0.6154 0.043 Uiso 1 1 calc R . .
H17B H 0.2238 0.5955 0.5723 0.043 Uiso 1 1 calc R . .
C18 C 0.2709(2) 0.6318(4) 0.7358(5) 0.0450(13) Uani 1 1 d . . .
H18A H 0.2950 0.5475 0.7266 0.068 Uiso 1 1 calc R . .
H18B H 0.2395 0.6100 0.7936 0.068 Uiso 1 1 calc R . .
H18C H 0.2931 0.7106 0.7708 0.068 Uiso 1 1 calc R . .
C19 C 0.33500(18) 0.5414(4) 0.4516(5) 0.0327(11) Uani 1 1 d . . .
H19A H 0.3640 0.5574 0.3851 0.039 Uiso 1 1 calc R . .
H19B H 0.3546 0.5049 0.5283 0.039 Uiso 1 1 calc R . .
C20 C 0.2947(2) 0.4267(4) 0.4044(5) 0.0401(12) Uani 1 1 d . . .
H20A H 0.2660 0.4080 0.4698 0.060 Uiso 1 1 calc R . .
H20B H 0.3158 0.3391 0.3869 0.060 Uiso 1 1 calc R . .
H20C H 0.2761 0.4592 0.3260 0.060 Uiso 1 1 calc R . .
Cl1 Cl 0.28380(4) 1.04122(9) 0.58562(16) 0.0326(2) Uani 1 1 d . . .
P1 P 0.41812(4) 1.05820(10) 0.66800(11) 0.0258(2) Uani 1 1 d . . .
P2 P 0.30315(4) 0.71300(10) 0.49145(12) 0.0246(2) Uani 1 1 d . . .
Pd1 Pd 0.361697(10) 0.88619(2) 0.57433(5) 0.02164(8) 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
C1 0.032(2) 0.0249(17) 0.024(3) 0.004(2) 0.000(2) -0.0018(15)
C2 0.031(2) 0.0265(19) 0.030(4) 0.0013(16) 0.003(2) 0.0001(17)
C3 0.029(2) 0.0196(18) 0.038(3) 0.0024(17) 0.006(2) 0.0000(17)
C4 0.029(2) 0.040(2) 0.030(4) -0.0026(19) -0.003(2) 0.0043(17)
C5 0.032(2) 0.050(2) 0.048(3) 0.005(3) -0.004(4) 0.0065(18)
C6 0.040(3) 0.050(3) 0.053(4) -0.001(3) 0.012(3) 0.021(2)
C7 0.050(3) 0.041(3) 0.036(3) -0.007(2) 0.006(3) 0.012(2)
C8 0.039(3) 0.027(2) 0.041(3) -0.006(2) -0.005(2) 0.0006(19)
C9 0.038(2) 0.0228(17) 0.045(4) 0.001(3) -0.007(3) -0.0035(15)
C10 0.059(4) 0.046(3) 0.043(4) 0.011(2) 0.006(3) 0.002(2)
C11 0.027(2) 0.041(2) 0.043(3) -0.010(2) -0.004(2) 0.0001(18)
C12 0.030(3) 0.074(3) 0.076(5) -0.034(3) -0.007(3) -0.008(2)
C13 0.034(3) 0.044(3) 0.031(3) -0.013(2) -0.004(2) -0.001(2)
C14 0.056(4) 0.076(3) 0.028(3) 0.006(3) 0.004(3) -0.006(3)
C15 0.027(2) 0.031(2) 0.029(3) 0.0007(18) -0.008(2) -0.0005(18)
C16 0.045(3) 0.041(3) 0.028(3) 0.004(2) 0.000(2) 0.003(2)
C17 0.042(3) 0.0271(18) 0.038(4) 0.0001(19) 0.003(2) -0.0050(17)
C18 0.067(4) 0.039(3) 0.029(3) 0.007(2) 0.004(3) -0.014(2)
C19 0.036(3) 0.023(2) 0.039(3) -0.0003(19) -0.006(2) 0.0057(18)
C20 0.052(3) 0.022(2) 0.046(3) -0.004(2) -0.005(3) -0.003(2)
Cl1 0.0279(5) 0.0296(4) 0.0402(7) -0.0036(6) -0.0015(7) 0.0074(3)
P1 0.0255(6) 0.0273(5) 0.0247(7) -0.0024(5) -0.0008(5) -0.0001(4)
P2 0.0267(6) 0.0213(5) 0.0258(6) 0.0012(5) -0.0027(5) 0.0004(4)
Pd1 0.02199(14) 0.02055(12) 0.02237(15) 0.00036(19) -0.0013(2) 0.00188(10)

_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
C1 C2 1.210(5) . ?
C1 Pd1 1.947(4) . ?
C2 C3 1.439(5) . ?
C3 C4 1.382(6) . ?
C3 C8 1.405(6) . ?
C4 C5 1.386(5) . ?
C5 C6 1.368(8) . ?
C6 C7 1.367(7) . ?
C7 C8 1.375(6) . ?
C9 C10 1.511(8) . ?
C9 P1 1.825(4) . ?
C11 C12 1.530(6) . ?
C11 P1 1.816(4) . ?
C13 C14 1.516(6) . ?
C13 P1 1.817(5) . ?
C15 C16 1.527(6) . ?
C15 P2 1.809(4) . ?
C17 C18 1.524(7) . ?
C17 P2 1.815(4) . ?
C19 C20 1.522(5) . ?
C19 P2 1.826(4) . ?
Cl1 Pd1 2.3512(8) . ?
P1 Pd1 2.3136(10) . ?
P2 Pd1 2.3055(10) . ?

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
C2 C1 Pd1 175.8(4) . . ?
C1 C2 C3 176.0(4) . . ?
C4 C3 C8 117.5(4) . . ?
C4 C3 C2 121.4(4) . . ?
C8 C3 C2 121.1(4) . . ?
C3 C4 C5 121.0(5) . . ?
C6 C5 C4 120.4(5) . . ?
C5 C6 C7 119.8(4) . . ?
C6 C7 C8 120.5(4) . . ?
C7 C8 C3 120.8(4) . . ?
C10 C9 P1 112.4(3) . . ?
C12 C11 P1 116.3(3) . . ?
C14 C13 P1 113.7(3) . . ?
C16 C15 P2 112.7(3) . . ?
C18 C17 P2 112.4(3) . . ?
C20 C19 P2 116.1(3) . . ?
C11 P1 C13 105.9(2) . . ?
C11 P1 C9 105.8(2) . . ?
C13 P1 C9 103.6(2) . . ?
C11 P1 Pd1 116.46(14) . . ?
C13 P1 Pd1 112.14(15) . . ?
C9 P1 Pd1 111.94(17) . . ?
C15 P2 C17 104.5(2) . . ?
C15 P2 C19 105.1(2) . . ?
C17 P2 C19 105.77(19) . . ?
C15 P2 Pd1 113.82(13) . . ?
C17 P2 Pd1 109.21(14) . . ?
C19 P2 Pd1 117.38(14) . . ?
C1 Pd1 P2 90.58(12) . . ?
C1 Pd1 P1 90.48(12) . . ?
P2 Pd1 P1 176.92(5) . . ?
C1 Pd1 Cl1 177.71(17) . . ?
P2 Pd1 Cl1 89.10(4) . . ?
P1 Pd1 Cl1 89.95(4) . . ?

_diffrn_measured_fraction_theta_max 0.984
_diffrn_reflns_theta_full        26.02
_diffrn_measured_fraction_theta_full 0.984
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.402
_refine_diff_density_rms         0.070
_database_code_depnum_ccdc_archive 'CCDC 1013997'
