# Electronic Supplementary Material (ESI) for Chemical Communications
# This journal is © The Royal Society of Chemistry 2011


data_global

_journal_coden_Cambridge         182
_journal_volume                  ?
_journal_page_first              ?
_journal_year                    ?

_publ_contact_author_name        'Dr T Donohoe'
_publ_contact_author_email       timothy.donohoe@chem.ox.ac.uk

_publ_section_title              
;
Synthesis of 2,4,6-Trisubstituted Pyridines via an
Olefin Cross-Metathesis/Heck-Cyclisation-Elimination Sequence

;
loop_
_publ_author_name
T.Donohoe
J.Bower
D.Baker
J.Basutto
L.Chan
P.Gallagher

# Attachment '- CrystallographicData.cif'

#==============================================================================

#==============================================================================
data_4f
_database_code_depnum_ccdc_archive 'CCDC 834833'
#TrackingRef '- CrystallographicData.cif'

#==============================================================================
_audit_creation_date             11-06-27
_audit_creation_method           CRYSTALS_ver_14.11

_oxford_structure_analysis_title 006tjd11
_chemical_name_systematic        .
_chemical_melting_point          '87-89 \% C'

_cell_length_a                   8.0582(2)
_cell_length_b                   9.9181(3)
_cell_length_c                   9.9557(3)
_cell_angle_alpha                62.2103(15)
_cell_angle_beta                 85.9715(14)
_cell_angle_gamma                87.9363(12)
_cell_volume                     702.17(4)

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_H-M   'P -1 '
_symmetry_space_group_name_Hall  '-P 1 '
loop_
_symmetry_equiv_pos_as_xyz
x,y,z
-x,-y,-z

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512
0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998
0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4'
N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826
-11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4'

_cell_formula_units_Z            2

# Given Formula = C17 N4
# Dc = 1.23 Fooo = 284.00 Mu = 0.78 M = 260.21
# Found Formula = C19 H14 N2
# Dc = 1.28 FOOO = 284.00 Mu = 0.76 M = 270.33

_chemical_formula_sum            'C19 H14 N2'
_chemical_formula_moiety         'C19 H14 N2'
_chemical_compound_source        synthetic
_chemical_formula_weight         270.33

_cell_measurement_reflns_used    2954
_cell_measurement_theta_min      5
_cell_measurement_theta_max      27
_cell_measurement_temperature    150

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_min          0.040
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_max          0.250

_exptl_crystal_density_diffrn    1.279
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
# Non-dispersive F(000):
_exptl_crystal_F_000             284
_exptl_absorpt_coefficient_mu    0.076

# Sheldrick geometric approximatio 0.99 1.00
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_absorpt_correction_T_min  0.95
_exptl_absorpt_correction_T_max  1.00
# For a Kappa CCD, set Tmin to 1.0 and
# Tmax to the ratio of max:min frame scales in scale_all.log
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_device       Area
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_measurement_method       \w

# If a reference occurs more than once, delete the author
# and date from subsequent references.
_computing_data_collection       'COLLECT (Nonius, 2001).'
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_structure_solution    'Superflip (Palatinus & Chapuis, 2007)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'

_diffrn_standards_interval_time  .
_diffrn_standards_interval_count .
_diffrn_standards_number         0
_diffrn_standards_decay_%        .

_diffrn_ambient_temperature      150
_diffrn_reflns_number            11611
_reflns_number_total             3194
_diffrn_reflns_av_R_equivalents  0.019
# Number of reflections without Friedels Law is 5541
# Number of reflections with Friedels Law is 3194
# Theoretical number of reflections is about 3241

_diffrn_reflns_theta_min         5.150
_diffrn_reflns_theta_max         27.545
_diffrn_measured_fraction_theta_max 0.988

_diffrn_reflns_theta_full        26.719
_diffrn_measured_fraction_theta_full 0.990

_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       12
_reflns_limit_h_min              -10
_reflns_limit_h_max              10
_reflns_limit_k_min              -10
_reflns_limit_k_max              12
_reflns_limit_l_min              0
_reflns_limit_l_max              12

_oxford_diffrn_Wilson_B_factor   2.15
_oxford_diffrn_Wilson_scale      0.46

_atom_sites_solution_primary     direct #heavy,direct,difmap,geom
# _atom_sites_solution_secondary difmap
_atom_sites_solution_hydrogens   geom

_refine_diff_density_min         -0.22
_refine_diff_density_max         0.29

# The current dictionary definitions do not cover the
# situation where the reflections used for refinement were
# selected by a user-defined sigma threshold

# The values actually used during refinement
_oxford_reflns_threshold_expression_ref I>-3.0\s(I)
_refine_ls_number_reflns         3194
_refine_ls_number_restraints     0
_refine_ls_number_parameters     190
_oxford_refine_ls_R_factor_ref   0.0539
_refine_ls_wR_factor_ref         0.1224
_refine_ls_goodness_of_fit_ref   0.9440
_refine_ls_shift/su_max          0.0003023
_refine_ls_shift/su_mean         0.0000375

# The values computed from all data
_oxford_reflns_number_all        3194
_refine_ls_R_factor_all          0.0539
_refine_ls_wR_factor_all         0.1224

# The values computed with a 2 sigma cutoff - a la SHELX
_reflns_threshold_expression     I>2.0\s(I)
_reflns_number_gt                2659
_refine_ls_R_factor_gt           0.0431
_refine_ls_wR_factor_gt          0.1084

# choose from: rm (reference molecule of known chirality),
# ad (anomolous dispersion - Flack), rmad (rm and ad),
# syn (from synthesis), unk (unknown) or . (not applicable).
_chemical_absolute_configuration .

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_hydrogen_treatment    none # none, undef, noref, refall,
# refxyz, refU, constr or mixed
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
;
Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982)
[weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)]
where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax
Method = Robust Weighting (Prince, 1982)
W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^
A~i~ are:
32.8 50.2 25.4 6.93
;
# Insert your own references if required - in alphabetical order
_publ_section_references         
;
Betteridge, P.W., Carruthers, J.R., Cooper, R.I.,
Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487.

Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
edited by C. W. Carter Jr & R. M. Sweet, pp. 307--326.
New York: Academic Press.

Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790.

Prince, E.
Mathematical Techniques in Crystallography
and Materials Science
Springer-Verlag, New York, 1982.

Watkin D.J. (1994).
Acta Cryst, A50, 411-437.

Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical
Crystallography Laboratory, Oxford, UK.
;

# Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3

# Replace last . with number of unfound hydrogen atomsattached to an atom.

# ..._refinement_flags_...
# . no refinement constraints S special position constraint on site
# G rigid group refinement of site R riding atom
# D distance or angle restraint on site T thermal displacement constraints
# U Uiso or Uij restraint (rigid bond) P partial occupancy constraint

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_occupancy
_atom_site_adp_type
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
_atom_site_attached_hydrogens
N1 N 1.16420(13) 0.32468(12) 0.49906(11) 0.0259 1.0000 Uani . . . . . .
C2 C 1.07467(15) 0.19553(14) 0.56561(14) 0.0262 1.0000 Uani . . . . . .
C3 C 0.93130(16) 0.17766(14) 0.50525(14) 0.0274 1.0000 Uani . . . . . .
C4 C 0.87867(15) 0.29590(14) 0.36964(14) 0.0257 1.0000 Uani . . . . . .
C5 C 0.97270(15) 0.42915(14) 0.30023(14) 0.0263 1.0000 Uani . . . . . .
C6 C 1.11339(15) 0.43986(13) 0.36854(13) 0.0243 1.0000 Uani . . . . . .
C7 C 1.21833(15) 0.57958(14) 0.30007(13) 0.0253 1.0000 Uani . . . . . .
C8 C 1.38238(16) 0.57046(15) 0.34038(14) 0.0294 1.0000 Uani . . . . . .
C9 C 1.48190(17) 0.69979(16) 0.28101(15) 0.0335 1.0000 Uani . . . . . .
C10 C 1.41749(18) 0.84044(15) 0.18101(14) 0.0336 1.0000 Uani . . . . . .
C11 C 1.25553(18) 0.85043(14) 0.13805(14) 0.0318 1.0000 Uani . . . . . .
C12 C 1.15666(16) 0.72105(14) 0.19616(14) 0.0281 1.0000 Uani . . . . . .
C13 C 0.72747(15) 0.28122(13) 0.30037(14) 0.0252 1.0000 Uani . . . . . .
C14 C 0.58540(16) 0.20855(15) 0.39149(14) 0.0290 1.0000 Uani . . . . . .
C15 C 0.44374(16) 0.19637(15) 0.32664(15) 0.0297 1.0000 Uani . . . . . .
C16 C 0.44302(15) 0.25617(14) 0.16914(15) 0.0277 1.0000 Uani . . . . . .
C17 C 0.58487(16) 0.32661(14) 0.07675(14) 0.0285 1.0000 Uani . . . . . .
C18 C 0.72594(15) 0.33873(14) 0.14286(14) 0.0277 1.0000 Uani . . . . . .
C19 C 0.29424(17) 0.24823(15) 0.10084(16) 0.0335 1.0000 Uani . . . . . .
N20 N 0.17500(17) 0.24367(16) 0.04588(16) 0.0461 1.0000 Uani . . . . . .
C21 C 1.13939(17) 0.06978(15) 0.70888(15) 0.0333 1.0000 Uani . . . . . .
H31 H 0.8702 0.0836 0.5567 0.0330 1.0000 Uiso R . . . . .
H51 H 0.9377 0.5136 0.2061 0.0315 1.0000 Uiso R . . . . .
H81 H 1.4263 0.4741 0.4081 0.0345 1.0000 Uiso R . . . . .
H91 H 1.5944 0.6919 0.3099 0.0399 1.0000 Uiso R . . . . .
H101 H 1.4841 0.9308 0.1401 0.0406 1.0000 Uiso R . . . . .
H111 H 1.2114 0.9464 0.0683 0.0385 1.0000 Uiso R . . . . .
H121 H 1.0457 0.7310 0.1653 0.0332 1.0000 Uiso R . . . . .
H141 H 0.5862 0.1682 0.4986 0.0354 1.0000 Uiso R . . . . .
H151 H 0.3464 0.1488 0.3912 0.0369 1.0000 Uiso R . . . . .
H171 H 0.5862 0.3657 -0.0308 0.0341 1.0000 Uiso R . . . . .
H181 H 0.8233 0.3852 0.0789 0.0353 1.0000 Uiso R . . . . .
H212 H 1.0627 -0.0156 0.7581 0.0502 1.0000 Uiso R . . . . .
H211 H 1.1558 0.1078 0.7819 0.0498 1.0000 Uiso R . . . . .
H213 H 1.2466 0.0315 0.6883 0.0509 1.0000 Uiso R . . . . .
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
N1 0.0268(5) 0.0249(5) 0.0244(5) -0.0102(4) -0.0016(4) -0.0005(4)
C2 0.0272(6) 0.0242(6) 0.0257(6) -0.0106(5) -0.0001(4) 0.0004(4)
C3 0.0298(6) 0.0241(6) 0.0269(6) -0.0108(5) 0.0001(5) -0.0031(4)
C4 0.0268(6) 0.0268(6) 0.0255(6) -0.0137(5) -0.0011(4) -0.0021(4)
C5 0.0299(6) 0.0238(6) 0.0241(6) -0.0099(5) -0.0040(4) -0.0004(4)
C6 0.0266(6) 0.0231(5) 0.0226(5) -0.0101(4) -0.0014(4) -0.0012(4)
C7 0.0296(6) 0.0250(6) 0.0217(5) -0.0108(5) -0.0020(4) -0.0034(5)
C8 0.0324(6) 0.0283(6) 0.0242(6) -0.0084(5) -0.0073(5) -0.0035(5)
C9 0.0343(7) 0.0358(7) 0.0271(6) -0.0107(5) -0.0065(5) -0.0097(5)
C10 0.0437(7) 0.0299(6) 0.0247(6) -0.0098(5) -0.0012(5) -0.0126(5)
C11 0.0420(7) 0.0236(6) 0.0264(6) -0.0083(5) -0.0041(5) -0.0020(5)
C12 0.0316(6) 0.0258(6) 0.0254(6) -0.0103(5) -0.0037(5) -0.0003(5)
C13 0.0276(6) 0.0227(5) 0.0269(6) -0.0126(5) -0.0025(4) -0.0013(4)
C14 0.0309(6) 0.0298(6) 0.0262(6) -0.0130(5) 0.0013(5) -0.0033(5)
C15 0.0270(6) 0.0290(6) 0.0322(6) -0.0138(5) 0.0026(5) -0.0037(5)
C16 0.0270(6) 0.0248(6) 0.0337(6) -0.0154(5) -0.0041(5) -0.0012(4)
C17 0.0310(6) 0.0291(6) 0.0266(6) -0.0138(5) -0.0022(5) -0.0032(5)
C18 0.0280(6) 0.0289(6) 0.0269(6) -0.0134(5) 0.0002(5) -0.0048(5)
C19 0.0318(7) 0.0294(6) 0.0374(7) -0.0134(5) -0.0052(5) -0.0021(5)
N20 0.0380(7) 0.0408(7) 0.0528(8) -0.0143(6) -0.0134(6) -0.0066(5)
C21 0.0335(7) 0.0271(6) 0.0306(6) -0.0060(5) -0.0037(5) 0.0005(5)

_refine_ls_extinction_method     None
_oxford_refine_ls_scale          1.582(11)
loop_
_geom_bond_atom_site_label_1
_geom_bond_site_symmetry_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
N1 . C2 . 1.3447(15) yes
N1 . C6 . 1.3483(15) yes
C2 . C3 . 1.3925(17) yes
C2 . C21 . 1.5035(17) yes
C3 . C4 . 1.3951(17) yes
C3 . H31 . 0.963 no
C4 . C5 . 1.3947(17) yes
C4 . C13 . 1.4852(16) yes
C5 . C6 . 1.3941(16) yes
C5 . H51 . 0.974 no
C6 . C7 . 1.4908(16) yes
C7 . C8 . 1.3960(17) yes
C7 . C12 . 1.3981(17) yes
C8 . C9 . 1.3923(17) yes
C8 . H81 . 0.950 no
C9 . C10 . 1.390(2) yes
C9 . H91 . 0.959 no
C10 . C11 . 1.388(2) yes
C10 . H101 . 0.960 no
C11 . C12 . 1.3902(17) yes
C11 . H111 . 0.953 no
C12 . H121 . 0.953 no
C13 . C14 . 1.3989(17) yes
C13 . C18 . 1.3974(17) yes
C14 . C15 . 1.3859(18) yes
C14 . H141 . 0.949 no
C15 . C16 . 1.3944(18) yes
C15 . H151 . 0.962 no
C16 . C17 . 1.3969(17) yes
C16 . C19 . 1.4412(18) yes
C17 . C18 . 1.3888(17) yes
C17 . H171 . 0.953 no
C18 . H181 . 0.957 no
C19 . N20 . 1.1510(19) yes
C21 . H212 . 0.973 no
C21 . H211 . 0.979 no
C21 . H213 . 0.978 no
loop_
_geom_angle_atom_site_label_1
_geom_angle_site_symmetry_1
_geom_angle_atom_site_label_2
_geom_angle_site_symmetry_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
C2 . N1 . C6 . 118.46(11) yes
N1 . C2 . C3 . 122.32(11) yes
N1 . C2 . C21 . 116.10(11) yes
C3 . C2 . C21 . 121.57(11) yes
C2 . C3 . C4 . 119.54(11) yes
C2 . C3 . H31 . 119.8 no
C4 . C3 . H31 . 120.6 no
C3 . C4 . C5 . 117.96(11) yes
C3 . C4 . C13 . 121.37(11) yes
C5 . C4 . C13 . 120.67(11) yes
C4 . C5 . C6 . 119.32(11) yes
C4 . C5 . H51 . 119.4 no
C6 . C5 . H51 . 121.2 no
C5 . C6 . N1 . 122.38(11) yes
C5 . C6 . C7 . 121.76(11) yes
N1 . C6 . C7 . 115.86(10) yes
C6 . C7 . C8 . 119.69(11) yes
C6 . C7 . C12 . 121.70(11) yes
C8 . C7 . C12 . 118.61(11) yes
C7 . C8 . C9 . 120.90(12) yes
C7 . C8 . H81 . 119.1 no
C9 . C8 . H81 . 120.0 no
C8 . C9 . C10 . 119.86(12) yes
C8 . C9 . H91 . 120.0 no
C10 . C9 . H91 . 120.1 no
C9 . C10 . C11 . 119.74(12) yes
C9 . C10 . H101 . 120.8 no
C11 . C10 . H101 . 119.4 no
C10 . C11 . C12 . 120.40(12) yes
C10 . C11 . H111 . 120.0 no
C12 . C11 . H111 . 119.6 no
C7 . C12 . C11 . 120.46(12) yes
C7 . C12 . H121 . 120.8 no
C11 . C12 . H121 . 118.8 no
C4 . C13 . C14 . 120.67(11) yes
C4 . C13 . C18 . 120.28(11) yes
C14 . C13 . C18 . 119.05(11) yes
C13 . C14 . C15 . 120.63(12) yes
C13 . C14 . H141 . 119.4 no
C15 . C14 . H141 . 119.9 no
C14 . C15 . C16 . 119.74(11) yes
C14 . C15 . H151 . 119.2 no
C16 . C15 . H151 . 121.0 no
C15 . C16 . C17 . 120.33(12) yes
C15 . C16 . C19 . 119.93(12) yes
C17 . C16 . C19 . 119.72(12) yes
C16 . C17 . C18 . 119.45(12) yes
C16 . C17 . H171 . 120.8 no
C18 . C17 . H171 . 119.7 no
C13 . C18 . C17 . 120.77(11) yes
C13 . C18 . H181 . 120.3 no
C17 . C18 . H181 . 118.9 no
C16 . C19 . N20 . 179.18(15) yes
C2 . C21 . H212 . 112.2 no
C2 . C21 . H211 . 110.0 no
H212 . C21 . H211 . 107.4 no
C2 . C21 . H213 . 111.2 no
H212 . C21 . H213 . 108.2 no
H211 . C21 . H213 . 107.6 no

_iucr_refine_instruction_details_constraints 
;
#
# Punched on 27/06/11 at 18:14:16
#
#LIST 12
BLOCK SCALE X'S, U'S
RIDE C ( 3,X'S) H ( 31,X'S)
RIDE C ( 5,X'S) H ( 51,X'S)
RIDE C ( 8,X'S) H ( 81,X'S)
RIDE C ( 9,X'S) H ( 91,X'S)
RIDE C ( 10,X'S) H ( 101,X'S)
RIDE C ( 11,X'S) H ( 111,X'S)
RIDE C ( 12,X'S) H ( 121,X'S)
RIDE C ( 14,X'S) H ( 141,X'S)
RIDE C ( 15,X'S) H ( 151,X'S)
RIDE C ( 17,X'S) H ( 171,X'S)
RIDE C ( 18,X'S) H ( 181,X'S)
RIDE C ( 21,X'S) H ( 212,X'S) H ( 211,X'S) H ( 213,X'S)
END
;

_iucr_refine_instruction_details_restraints 
;
#
# Punched on 27/06/11 at 18:14:16
#
#LIST 16
NO
REM HREST START (DO NOT REMOVE THIS LINE)
REM HREST END (DO NOT REMOVE THIS LINE)
END
;