# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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 
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data_harf_P21n
_database_code_depnum_ccdc_archive 'CCDC 1524544'
_audit_update_record             
;
2016-12-26 deposited with the CCDC.	2019-04-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        2-tert-ButylethynylpyrimidineCarbaldehyde
_chemical_name_common            
2-(3,3-dimethylbut-1-yn-1-yl)pyrimidine-5-carbaldehyde
_chemical_melting_point          ?
_chemical_formula_moiety         'C11 H12 N2 O'
_chemical_formula_sum            'C11 H12 N2 O'
_chemical_formula_weight         188.23

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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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.
;

loop_
_space_group_symop_operation_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                   5.6977(6)
_cell_length_b                   5.6969(6)
_cell_length_c                   32.062(3)
_cell_angle_alpha                90
_cell_angle_beta                 91.5574(10)
_cell_angle_gamma                90
_cell_volume                     1040.33(19)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    399
_cell_measurement_theta_min      3.9678
_cell_measurement_theta_max      27.8761

_exptl_crystal_description       plate
_exptl_crystal_colour            'clear white'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.202
_exptl_crystal_F_000             400
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.764
_exptl_crystal_size_mid          0.530
_exptl_crystal_size_min          0.236
_exptl_absorpt_coefficient_mu    0.079
_shelx_estimated_absorpt_T_min   0.942
_shelx_estimated_absorpt_T_max   0.982
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   'SADABS V2014/5 (Bruker AXS Inc.)'
_exptl_absorpt_correction_T_min  0.65
_exptl_absorpt_correction_T_max  0.98
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus rotating anode'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            11376
_diffrn_reflns_av_unetI/netI     0.0331
_diffrn_reflns_av_R_equivalents  0.0557
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_theta_min         2.542
_diffrn_reflns_theta_max         28.778
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.943
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.943
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.943
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             2554
_reflns_number_gt                2459
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'APEX2 v2014.11-0 (Bruker AXS)'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_structure_solution    'SHELXS-2014 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    
'Shelxle (J. Appl. Cryst., 44, (2011) 1281-1284.)'
_computing_publication_material  
'Shelxle (J. Appl. Cryst., 44, (2011) 1281-1284.)'
_refine_special_details          
"Refined with disorder., The automatic indexing and determination of space group suggested C2/m space group (a = 11.367(13)  b = 11.3648(13)  c = 31.982(3), beta = 91.5608(13) ). However, there are no reasonable structure solution in C2/m space group and the reflection position was slightly deviated from expected position when  C2/m were assumed.  Structure could be solved by direct method (SHELXS) in P-1 space group(a = 8.0354(8), b =8.0372(8), c = 31.979(3) alpha = 88.8860(10), beta = 88.9040(10), gamma =89.9900(10)). However the refinement is unstable and the residual density peaks and R1 factor is unusually high (14.59% ) considering from the quality of diffraction images and integration results (Rint = 4.2%). The structure refinement was improved by considering a pseud-merohedral twin. The twin low was estimated by TwinRotMat in PLATON and was assumed as  (0 -1 0 -1 0 0 0 0 -1). Due to the almost same length of a and b and nearly 90% of gamma, the unit cell is almost overlapped by this transformation. Refinement with this twin matrix improved the refinement  and final R1 value is improved to 5.87%.  However, the ADP of the carbon at 2-position of pyridine ring is unusually distorted and large collation matrix elements was observed between the same atoms in different independent molecules. Furthermore residual packs still observed around flipping position of pyrimidine ring  Finally  reasonable model was obtained by assuming disorder of flipping of pyrimidine ring and direction of Aldehyde oxygen. Assuming the disorder, the unit cell becomes  P21/n (a = 5.698, b =5.697, c = 32.06,  beta = 91.56°) and the  Z' = 1,  no unusual ADP was observed  and Final R1 Factor reduced to 5.07%."
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0626P)²+0.3982P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   diffmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.178(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2554
_refine_ls_number_parameters     186
_refine_ls_number_restraints     162
_refine_ls_R_factor_all          0.0517
_refine_ls_R_factor_gt           0.0506
_refine_ls_wR_factor_ref         0.1342
_refine_ls_wR_factor_gt          0.1333
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_restrained_S_all      1.034
_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_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
C6 C 0.2785(2) 0.7014(2) 0.37539(3) 0.0289(3) Uani 1 1 d . U . . .
C7 C 0.3900(2) 0.5850(2) 0.35192(3) 0.0247(3) Uani 1 1 d . U . . .
C8 C 0.52229(18) 0.44617(19) 0.32146(3) 0.0207(3) Uani 1 1 d . U . . .
C9 C 0.69455(19) 0.2812(2) 0.34479(3) 0.0238(3) Uani 1 1 d . U . . .
H9A H 0.7818 0.1892 0.3246 0.036 Uiso 1 1 calc R U . . .
H9B H 0.6069 0.1751 0.3627 0.036 Uiso 1 1 calc R U . . .
H9C H 0.8047 0.3744 0.3620 0.036 Uiso 1 1 calc R U . . .
C10 C 0.3471(2) 0.3005(2) 0.29486(4) 0.0317(3) Uani 1 1 d . U . . .
H10A H 0.4320 0.2124 0.2738 0.048 Uiso 1 1 calc R U . . .
H10B H 0.2332 0.4055 0.2810 0.048 Uiso 1 1 calc R U . . .
H10C H 0.2644 0.1907 0.3128 0.048 Uiso 1 1 calc R U . . .
C11 C 0.6587(2) 0.6155(2) 0.29368(4) 0.0324(3) Uani 1 1 d . U . . .
H11A H 0.7422 0.5256 0.2727 0.049 Uiso 1 1 calc R U . . .
H11B H 0.7720 0.7045 0.3109 0.049 Uiso 1 1 calc R U . . .
H11C H 0.5487 0.7242 0.2798 0.049 Uiso 1 1 calc R U . . .
C1A_1 C -0.261(3) 1.276(3) 0.4769(6) 0.0204(9) Uani 0.504(3) 1 d . U P A 1
H1A_1 H -0.2326 1.4396 0.4746 0.024 Uiso 0.504(3) 1 calc R U P A 1
C2A_1 C -0.129(6) 1.112(7) 0.4504(13) 0.0172(9) Uani 0.504(3) 1 d . U P A 1
C3A_1 C 0.0677(6) 1.1943(6) 0.43000(10) 0.0219(6) Uani 0.504(3) 1 d . U P A 1
H3A_1 H 0.1114 1.3543 0.4333 0.026 Uiso 0.504(3) 1 calc R U P A 1
N2A_1 N -0.0608(5) 0.7338(5) 0.42099(10) 0.0241(6) Uani 0.504(3) 1 d . U P A 1
N1A_1 N 0.1976(5) 1.0557(5) 0.40590(9) 0.0229(5) Uani 0.504(3) 1 d . U P A 1
O1A_1 O -0.4079(3) 1.2055(3) 0.50202(5) 0.0292(5) Uani 0.504(3) 1 d . U P A 1
C4A_1 C -0.1841(6) 0.8768(6) 0.44510(11) 0.0229(6) Uani 0.504(3) 1 d . U P A 1
H4A_1 H -0.3149 0.8146 0.4592 0.027 Uiso 0.504(3) 1 calc R U P A 1
C5A_1 C 0.125(2) 0.830(2) 0.4025(6) 0.0175(10) Uani 0.504(3) 1 d . U P A 1
C1B_1 C -0.281(3) 1.259(3) 0.4770(6) 0.0204(9) Uani 0.496(3) 1 d . U P A 2
H1B_1 H -0.4452 1.2319 0.4745 0.024 Uiso 0.496(3) 1 calc R U P A 2
C2B_1 C -0.118(6) 1.120(7) 0.4509(13) 0.0172(9) Uani 0.496(3) 1 d . U P A 2
C3B_1 C 0.1159(6) 1.1758(6) 0.44506(11) 0.0220(6) Uani 0.496(3) 1 d . U P A 2
H3B_1 H 0.1797 1.3104 0.4587 0.026 Uiso 0.496(3) 1 calc R U P A 2
N2B_1 N -0.0707(5) 0.7880(5) 0.40577(9) 0.0226(6) Uani 0.496(3) 1 d . U P A 2
N1B_1 N 0.2549(5) 1.0478(5) 0.42105(10) 0.0241(6) Uani 0.496(3) 1 d . U P A 2
O1B_1 O -0.2048(3) 1.4081(3) 0.50194(5) 0.0286(5) Uani 0.496(3) 1 d . U P A 2
C4B_1 C -0.2053(6) 0.9209(6) 0.42997(11) 0.0225(6) Uani 0.496(3) 1 d . U P A 2
H4B_1 H -0.3652 0.8789 0.4331 0.027 Uiso 0.496(3) 1 calc R U P A 2
C5B_1 C 0.153(3) 0.862(2) 0.4021(6) 0.0175(10) Uani 0.496(3) 1 d . U P A 2


_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
C6 C7 1.1981(16) . ?
C6 C5A_1 1.449(15) . ?
C6 C5B_1 1.455(15) . ?
C7 C8 1.4791(14) . ?
C8 C11 1.5378(15) . ?
C8 C9 1.5381(14) . ?
C8 C10 1.5384(15) . ?
C1A_1 O1A_1 1.245(17) . ?
C1A_1 C2A_1 1.48(4) . ?
C2A_1 C4A_1 1.39(4) . ?
C2A_1 C3A_1 1.39(4) . ?
C3A_1 N1A_1 1.341(4) . ?
N2A_1 C4A_1 1.336(4) . ?
N2A_1 C5A_1 1.341(12) . ?
N1A_1 C5A_1 1.357(11) . ?
C1B_1 O1B_1 1.237(18) . ?
C1B_1 C2B_1 1.49(4) . ?
C2B_1 C3B_1 1.39(4) . ?
C2B_1 C4B_1 1.40(4) . ?
C3B_1 N1B_1 1.336(4) . ?
N2B_1 C4B_1 1.340(4) . ?
N2B_1 C5B_1 1.349(12) . ?
N1B_1 C5B_1 1.345(12) . ?

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
C7 C6 C5A_1 174.7(5) . . ?
C7 C6 C5B_1 174.6(5) . . ?
C6 C7 C8 177.58(11) . . ?
C7 C8 C11 108.77(9) . . ?
C7 C8 C9 109.59(8) . . ?
C11 C8 C9 109.82(9) . . ?
C7 C8 C10 108.65(9) . . ?
C11 C8 C10 110.36(9) . . ?
C9 C8 C10 109.63(9) . . ?
O1A_1 C1A_1 C2A_1 122(2) . . ?
C4A_1 C2A_1 C3A_1 117(3) . . ?
C4A_1 C2A_1 C1A_1 124(3) . . ?
C3A_1 C2A_1 C1A_1 119(3) . . ?
N1A_1 C3A_1 C2A_1 122.5(16) . . ?
C4A_1 N2A_1 C5A_1 116.1(7) . . ?
C3A_1 N1A_1 C5A_1 115.6(7) . . ?
N2A_1 C4A_1 C2A_1 122.7(16) . . ?
N2A_1 C5A_1 N1A_1 126.5(12) . . ?
N2A_1 C5A_1 C6 123.8(9) . . ?
N1A_1 C5A_1 C6 109.7(8) . . ?
O1B_1 C1B_1 C2B_1 120.9(19) . . ?
C3B_1 C2B_1 C4B_1 117(3) . . ?
C3B_1 C2B_1 C1B_1 125(3) . . ?
C4B_1 C2B_1 C1B_1 119(2) . . ?
N1B_1 C3B_1 C2B_1 122.6(16) . . ?
C4B_1 N2B_1 C5B_1 115.5(7) . . ?
C3B_1 N1B_1 C5B_1 115.7(7) . . ?
N2B_1 C4B_1 C2B_1 122.2(16) . . ?
N1B_1 C5B_1 N2B_1 127.2(12) . . ?
N1B_1 C5B_1 C6 123.1(9) . . ?
N2B_1 C5B_1 C6 109.6(8) . . ?

_refine_diff_density_max         0.518
_refine_diff_density_min         -0.212
_refine_diff_density_rms         0.057


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Acetone'
