The 'alpha' test file was based on an article in press for
Acta Crystallographica Section C
. This file was
used to develop proof-of-concept tools and to demonstrate the
feasibility of electronic publication based on CIFs, although in
this case the article was prepared for press in the conventional way.
This version still retains units attributes as additional tags, an
approach that is syntactically invalid in the final version of CIF.
Several of the data names in this file differ from those finally
adopted.
CIF Documents: #5 Version: Oct22-89
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@@@ Example of CIF Manuscript Submission @@@
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This is the alpha-test manuscript submitted to Acta Cryst. C by email
on August 14 1989. This manuscript provides a typical example of an
actual application of a CIF.
#---------------------------------------------------------------------------
data_alpha_test
_publ_contact_author_address
;
Dr. Richard Goddard
Max-Planck-Institut fuer Kohlenforschung
Kaiser-Wilhelm-Platz 1
D-4330 Muelheim a.d. Ruhr
F.R.G.
;
_publ_contact_letter
;
10 August 1989
Mr. Michael H. Dacombe
Technical Editor
Acta Crystallographica
IUCr Office
5 Abbey Square
Chester CH1 2HU
U. K.
Dear Mr. Dacombe,
Attached is a manuscript with the above-mentioned title
and authors, submitted for publication in Acta Crystallographica C.
Yours sincerely
Richard Goddard
;
_publ_contact_author_phone '[49]208 306 485'
_publ_contact_author_fax '[49]208 306 407'
_publ_contact_author_email '[email protected]'
_publ_requested_journal 'Acta Cryst. C'
_publ_title
;
Structure of 1-Butene(trimethylphosphine)zirconocene
;
loop_
_publ_author_name
_publ_author_address
'Goddard, Richard'
; Max-Planck-Institut fuer Kohlenforschung
Kaiser-Wilhelm-Platz 1
D-4330 Muelheim a.d. Ruhr
F.R.G.
;
'Binger, Paul'
; Max-Planck-Institut fuer Kohlenforschung
Kaiser-Wilhelm-Platz 1
D-4330 Muelheim a.d. Ruhr
F.R.G.
;
'Hall, Sydney'
; Max-Planck-Institut fuer Kohlenforschung
Kaiser-Wilhelm-Platz 1
D-4330 Muelhelm a.d. Ruhr
F.R.G.
;
'Mueller, Patrik'
; Max-Planck-Institut fuer Kohlenforschung
Kaiser-Wilhelm-Platz 1
D-4330 Muelhelm a.d. Ruhr
F.R.G.
;
_publ_abstract
;
C17H27PZr, Mr = 353.6, orthorhombic, Pca21, a = 27.946(8), b = 8.733(1),
c = 14.462(3) A, V = 3529(1) A^3, T = 293 K, Z = 8, Dx = 1.33 gcm-3,
F(000) = 1472. Lambda(Mo-Kalpha) = 0.71069 A, mu = 6.89 cm-1.
Final R = 0.046 (wR = 0.050) for 3295 unique observed reflections.
The C=C bond of the coordinated butene ligand is coplanar with the P and
Zr atoms and this plane approximately bisects the angle made by the planes
of the two cyclopentadienyl ligands. There are two molecules in the
asymmetric unit which differ only in the conformation of the butene ligand.
;
_publ_introduction
;
The title compound 1 is prepared in ca. 83% yield from zirconocene
dichloride with two equivalents of n-butyllithium and trimethylphosphine
(Buchwald, Watson & Huffman, 1987; Binger, Mueller, Benn, Rufinska, Gabor,
Krueger & Betz, 1989; Takahashi, Murakami, Kunishige, Saburi, Uchida, Kozawa,
Uchida, Swanson & Negishi, 1989). Subsequent reaction of 1 with other alkynes
and alkenes such as ethylene and styrene result in substitution of the
butane and indicate that this compound is an ideal starting material for
synthesizing other alkene- or alkyne-zirconocene complexes. The
structures of ethylene(trimethylphosphine)zirconocene and styrene-
(trimethylphosphine)zirconocene have already been reported (Binger,
Mueller, Benn, Rufinska, Gabor, Krueger & Betz, 1989) as well as that of
stilbene(trimethylphosphine)zirconocene (Takahashi, Murakami, Kunishige,
Saburi, Uchida, Kozawa, Uchida, Swanson & Negishi, 1989). Here we describe
the structure of 1-butene(trimethylphosphine)zirconocene and compare
it with the structures of the other known alkene derivatives.
;
_publ_experimental
;
Crystals of the title compound were grown as dark brown prisms from
pentane solution. The crystal chosen for data collection was
0.47x0.47x0.47 mm. The unit cell parameters were obtained by a
least-squares fit to the theta values of 77 automatically centered
reflections (16.6 < theta < 20.8 deg). 4577 intensity data
(0 < h < 36, 0 < k < 10, 0 < l < 18) were measured within the range
1.41 < theta < 27.32 deg. on an Enraf-Nonius CAD4 diffractometer with
graphite monochromated Mo-Kalpha X-radiation by a theta-2theta scan
technique in 48 steps, where the time spent measuring the background was
half that taken to measure the peak. The intensity of a reflection and
its e.s.d. were calculated from I = INT - 2(BGL + BGR) and
sigma(I) = sqrt[INT + 4(BGL + BGR)], where INT, BGL and BGR are
the peak intensity, left and right background counts, respectively.
The horizontal detector aperture and the (omega)-scan range varied as
3.0 + 1.05tan(theta)mm and 0.6 + 0.35tan(theta)deg. The intensities
of three standard reflections, remeasured every 60 minutes,
showed a variation of 7% during data collection. Data were
corrected for decay, Lorentz, polarization and absorption effects.
The absorption correction was spherical based on an interpolation
from a table of absorption coefficients (Dwiggins, 1975).
Sigma(F) was calculated from sigma(F) = sqrt[sigma(I)^2 + (Ik)^2]/2F,
where k = 0.02. Of a total of 4577 measured intensities, 4109 were unique
and 3295 satisfied the criterion I > 2.0sigma(I). Only the latter were
used in the solution and refinement of the structure.
Computer programs used in this investigation include modified versions
of the data reduction program DATAP (Coppens, Leiserowitz & Rabinovich,
1965), the TRACER program for cell reduction (Lawton & Jacobson, 1965),
the structure factor least squares program GFMLX (Hirshfeld; modified by
Coppens, Leiserowitz, Rabinovich, Brauer & Flack) which is an adaption
of ORFLS (Busing, Martin & Levy, 1962), the distance and angle programs
BONDLA (Dreissig, Doherty & Stewart, 1989) and DAESD (Davis & Harris,
1970), the least squares plane program LSQPL (Davenport, 1989), the
geometry display program XANADU (Roberts & Sheldrick, 1976) and the
ellipsoid plotting program ORTEP (Johnson, 1976).
The structure was solved by the heavy atom method using SHELX (Sheldrick,
1974). Refinement was by block matrix least-squares (one block per molecule),
where the function minimized was sum[w(deltaF)^2]; w = 1/sigma(Fo)^2 and
deltaF = |Fo| - |Fc|. The positions of the H atoms were calculated
(d(C_H) 0.95 A) and included in the refinement with fixed positions and
isotropic thermal parameters (UH = 0.08 A^2). Refinement converged at
R = 0.046 (wR = 0.050) for 342 variables and 3295 reflections, and the value
of the S = 2.8, indicating a slight underestimation of the error of an
observation of unit weight. In the final refinement cycle the maximum shift
to error ratio was 0.1. A correction for the effects of anomalous dispersion
for Zr |deltaF'=-2.965, deltaf"=0.560] and P [deltaf'=0.090, deltaf"= 0.095]
was included in the structure factor calculations. Refinement of
the enantiopol parameter (Flack, 1983) indicated the chosen polar axis
to be correct. Atomic scattering curves were taken from International Tables
for X-Ray Crystallography. In the final difference Fourier synthesis,
peaks of -0.7 eA-3 and +1.0 eA-3 were observed in the vicinity of the Zr
atom. The results of the X-ray analysis are summarized in Tables 1 and 2,
which give the final atomic coordinates and selected interatomic distances
and angles. Fig. 1 shows the molecular structure and Fig. 2 the packing of
molecules in the unit cell.
;
_publ_discussion
;
The structure analysis reveals an opened sandwich structure in which the
phosphorus atom and the C=C bond of the coordinated butene lie in a plane
approximately bisecting the angle at the metal made by the centers of the
two cylcopentadienyl ligands (Table 2e). There are two molecules in the
asymmetric unit which differ only in the conformation of the butene group
(Table 2c). The overall geometry of the molecule is essentially similar to
that observed for all known alkyne- and alkene-(trimethylphosphine)zirconocene
complexes. The Zr-P distance at 2.685(6) A (mean) lies between that found in
the ethylene- [2.695(1) A] and the styrene- [2.679(4) A] complexes (Binger,
Mueller, Benn, Rufinska, Gabor, Krueger & Betz, 1989) but is a little shorter
than in the corresponding stilbene structure [2.715(5) A] (Takahashi, Murakami,
Kunishige, Saburi, Uchida, Kozawa, Uchida, Swanson & Negishi, 1989) while
longer than in the hexyne derivative [2.658(1) A] (Buchwald, Watson & Huffman,
1987). There appears, however, to be no correlation between this distance and
the type of the acceptor ligand. The C=C bond distance of the coordinated
alkenes also provides no explanation for the difference. The average C=C
bond distance of the coordinated butene ligand in the two independent
molecules is 1.45(4) A and this is not significantly different from
that of the coordinated ethylene [1.449(6) A] nor that of the coordinated
styrene [1.46(2) A]. The C=C bond distance in the trans-stilbene complex
is, however, 1.38(2) A, and since this complex has the longest Zr-P distance
of the series this suggests an inverse relationship between the C=C and
Zr-P bond distances in these compounds. Although the trend can be observed in
the other complexes the differences are not significant. In all cases
the C-C bond of the coordinated alkyne or alkene is coplanar with
the Zr and the P atom. The preference for the single-faced pi-acceptor
ligands to adopt this conformation has been discussed by Lauher and
Hoffmann (1976).
There are no important short intermolecular contacts between non-H atoms.
Intermolecular distances less than 3.7 A are given in Table 2d.
;
_publ_references
;
Binger, P., Mueller, P., Benn, R., Rufinska, A., Gabor, B., Krueger, C. &
Betz, P. (1989). Chem. Ber. 122, 1035-1042.
Buchwald, S.L., Watson, B.T. & Huffman, J.C. (1987). J. Amer. Chem. Soc.
109, 2544-2546.
Busing, W.R., Martin, K.O. & Levy, N.A. (1962). ORFLS. Report ORNL-TM-305.
Oak Ridge National Laboratory, Tennessee, U.S.A.
Coppens, P., Leiserowitz, L. & Rabinovich, D. (1965). DATAP. Acta Cryst.,
18, 1035-1038.
Davenport, G. (1989). LSQPL: XTAL2.6 System. Ed.s S.R. Hall & J.M. Stewart,
Universities of Western Australia & Maryland.
Davis, R.E. & Harris, D.R. (1970). DAESD. Roswell Park Memorial Institute,
New York, USA.
Dreissig, W., Doherty, R. & Stewart, J.M. (1989). BONDLA: XTAL2.6 System.
Ed.s S.R. Hall & J.M. Stewart, Universities of Western Australia & Maryland.
Dwiggins, C.W., Jr. (1975). Acta Cryst. A31, 395-396.
Flack, H.D. (1983). Acta Cryst. A39, 876-881.
International Tables for X-ray Crystallography (1974). Vol. IV.
Birmingham: Kynoch Press. (Present distributor D. Reidel, Dordrecht.)
Johnson, C.K. (1976). ORTEP. Report ORNL-5138. Oak Ridge National Laboratory,
Tennessee, USA.
Lauher, J.W. & Hoffmann, R. (1976). J. Amer. Chem. Soc. 98, 1729-1742.
Lawton, S.L. & Jacobson, R.A. (1965). TRACER. United States Energy
Commission, Report IS-1141. Iowa State Univ., USA.
Roberts, P. & Sheldrick, G.M. (1976). XANADU. Program for crystallographic
calculations. Univ. of Cambridge, England.
Sheldrick, G.M. (1974). SHELX. Program for crystal structure determination.
Univ. of Cambridge, England.
Takahashi, T., Murakami, M., Kunishige, M., Saburi, M., Uchida, Y., Kozawa, K.,
Uchida, T., Swanson, D.R. & Negishi, E. (1989). Chem. Lett., 761-764.
;
_publ_figure_captions
;
Fig. 1. The molecular structure of the title compound (molecule A).
------
Fig. 2. The packing of the title compound in the unit cell, viewed
------ down -b looking towards the origin.
;
_publ_tables
;
Table 1. Atomic coordinates and equivalent isotropic thermal parameters
------- (provided in list_atom_site of CIF)
Table 2. Selected distances (Angstroms) and angles (degrees),
------- with e.s.d.'s in parentheses.
2a. Selected Bond Distances
---------------------------
Molecule A Molecule B
Zr1 P1 2.689(3) 2.681(2)
Zr1 C1 2.35 (1) 2.357(9)
Zr1 C2 2.38 (1) 2.364(8)
Zr1 C11 2.50 (1) 2.49 (1)
Zr1 C12 2.50 (1) 2.52 (2)
Zr1 C13 2.51 (1) 2.56 (2)
Zr1 C14 2.546(9) 2.57 (1)
Zr1 C15 2.53 (1) 2.51 (1)
Zr1 C21 2.52 (1) 2.503(9)
Zr1 C22 2.520(9) 2.511(8)
Zr1 C23 2.52 (1) 2.508(9)
Zr1 C24 2.54 (1) 2.570(9)
Zr1 C25 2.529(9) 2.526(9)
P1 C5 1.79 (1) 1.831(9)
P1 C6 1.82 (1) 1.84 (1)
P1 C7 1.79 (1) 1.82 (1)
C1 C2 1.47 (1) 1.42 (1)
C2 C3 1.42 (1) 1.54 (1)
C3 C4 1.54 (2) 1.53 (1)
C11 C12 1.36 (2) 1.31 (2)
C11 C15 1.41 (1) 1.37 (2)
C12 C13 1.38 (2) 1.35 (2)
C13 C14 1.41 (2) 1.40 (2)
C14 C15 1.37 (2) 1.37 (2)
C21 C22 1.39 (1) 1.39 (1)
C21 C25 1.37 (1) 1.41 (1)
C22 C23 1.37 (2) 1.40 (1)
C23 C24 1.47 (2) 1.40 (1)
C24 C25 1.36 (2) 1.39 (1)
2b. Selected Bond Angles
------------------------
D1, D2 and D3 are respectively the midpoints
of the cyclopentadienyl rings (C11-C15, C21-25)
and the C1-C2 bond.
Molecule A Molecule B
C2 Zr1 C1 36.1(3) 34.9(3)
C2 Zr1 P1 109.9(2) 108.3(2)
C1 Zr1 P1 73.8(2) 73.5(2)
P1 Zr1 D3 92.0(1) 90.9(1)
P1 Zr1 D2 103.0(1) 101.1(1)
P1 Zr1 D1 102.0(1) 103.7(1)
D3 Zr1 D2 113.1(1) 113.7(1)
D3 Zr1 D1 107.9(1) 107.8(1)
D2 Zr1 D1 130.4(1) 130.7(1)
C7 P1 C6 101.8(5) 97.5(5)
C7 P1 C5 97.6(5) 101.8(5)
C7 P1 Zr1 117.80) 117.3(4)
C6 P1 C5 99.30) 100.9(5)
C6 PI Zr1 118.60) 119.9(4)
C5 P1 Zr1 118.00) 116.1(3)
C2 C1 Zr1 73.10) 72.8(5)
C3 C2 C1 118.7(9) 117.3(8)
C3 C2 Zr1 133.5(8) 125.0(6)
C1 C2 Zr1 70.8(5) 72.3(5)
C4 C3 C2 114 (1) 111.0(7)
C15 C11 C12 106.6(9) 109 (1)
C13 C12 C11 111 (1) 108 (1)
C14 C13 C12 106 (1) 109 (1)
C15 C14 C13 107.7(9) 104 (1)
C14 C15 C11 109 (1) 109 (1)
C25 C21 C22 108.30) 106.9(8)
C23 C22 C21 109.1(9) 108.0(7)
C24 C23 C22 106 (1) 109.1(7)
C25 C24 C23 107 (1) 106.4(8)
C24 C25 C21 109.6(9) 109.4(8)
2c. Selected Torsion Angles
---------------------------
Molecule A Molecule B
P1 Zr1 C1 C2 178.6(6) -174.7(5)
P1 Zr1 C2 C3 -113.2(9) -105.9(5)
Zr1 C1 C2 C3 130 (1) 120.9(7)
C1 C2 C3 C4 81 (1) 76 (1)
2d. Selected Intermolecular Distances
-------------------------------------
C7a C11b [x,y-1,z] 3.67(1)
C7a C15b [x,y-1,z] 3.65(2)
C21a C7b [x-.5,2-y,z] 3.62(1)
C25a C22b [1-x,1-y,.5+z] 3.55(1)
2e. Least-squares Planes
------------------------
(i) Definition of planes and Maximum Deviation
Plane Atoms Molecule A Molecule B
1 C11 C12 C13 C14 C15 0.01(1) 0.01(2)
2 C21 C22 C23 C24 C25 0.01(2) 0.02(1)
3 ZR1 P1 C1 C2 0.02(1) 0.06(1)
(ii) Angles between planes
Molecule A Molecule B
1 - 2 49.4(5) 51.3(6)
1 - 3 22.5(4) 24.8(5)
2 - 3 27.0(4) 26.7(3)
;
#-------------------------- data section of block ---------------------------
_chemical_name_systematic
;
1-butene(trimethylphosphine)zirconocene
;
_chemical_formula_moiety 'C17 H27 P Zr'
_chemical_formula_structural '(C5 H5)2 ((C H3)3 P) (C4 N8) Zr'
_chemical_formula_sum 'C17 H27 P Zr'
_chemical_formula_weight 353.6
_chemical_melting_point 323
_computing_data_collection 'CAD4 (Enraf-Nonius)'
_computing_cell_refinement 'LSCELD (Davis)'
_computing_data_reduction 'DATAP (Leiserowitz et al.)'
_computing_structure_solution 'SHELX74 (Sheldrick)'
_computing_structure_refinement 'GFLMX (modified ORFLS)'
_computing_diagram_preparation 'ORTEP (Johnson)'
_cell_a 27.946(8)
_cell_b 8.733(1)
_cell_c 14.462(3)
_cell_alpha 90
_cell_beta 90
_cell_gamma 90
_cell_volume 3529(1)
_cell_formula_units_Z 8
_cell_measurement_temperature 293
_cell_measurement_reflns_used 77
_cell_measurement_theta_min 16.6
_cell_measurement_theta_max 20.8
_symmetry_crystal_system 'orthorhombic'
_symmetry_name_Hermann-Mauguin 'P c a 21'
_symmetry_name_Hall 'P 2c -2ac'
_symmetry_name_Int_Tables_number 29
_exptl_crystal_description
; Approximate parallelopiped 0.47x0.47x0.47 mm. Crystals are highly
air and moisture sensitive. Must be mounted in capillary with argon.
;
_exptl_crystal_colour 'dark brown'
_exptl_crystal_size_max 0.47
_exptl_crystal_size_mid 0.47
_exptl_crystal_size_min 0.47
_exptl_crystal_density_diffrn 1.33
_exptl_crystal_F(000) 1472
_exptl_absorpt_coefficient_mu _cm 6.89
_exptl_absorpt_correction_type 'spherical'
_exptl_absorpt_correction_T_min 0.786
_exptl_absorpt_correction_T_max 0.787
_diffrn_special_details
;
Crystal mounted in capillary in Argon gas. Data collected with a=8.733,
b=14.462, c=27.946 and subsequently transformed to published cell axes.
;
_diffrn_temperature 293
_diffrn_radiation_wavelength 0.71069
_diffrn_radiation_type 'Xray MoKalpha mean'
_diffrn_radiation_source 'standard Molybdenum anode'
_diffrn_radiation_monochromator 'graphite'
_diffrn_radiation_detector 'scintillation'
_diffrn_diffractometer_geometry 'kappa 4 circle'
_diffrn_diffractometer_model 'CAD4'
_diffrn_measurement_process 'bpb bisecting theta-2theta scan'
_diffrn_standards_number 3
_diffrn_standards_interval _hour 1
_diffrn_standards_decay_% 7.
loop_
_diffrn_standards_h
_diffrn_standards_k
_diffrn_standards_l -2 -9 -3
-2 -1 17
5 -2 6
loop_
_diffrn_attenuator_code
_diffrn_attenuator_scale '1' 16.8
_diffrn_reflns_h_min 0
_diffrn_reflns_h_max 10
_diffrn_reflns_k_min 0
_diffrn_reflns_k_max 18
_diffrn_reflns_l_min 0
_diffrn_reflns_l_max 36
_diffrn_reflns_number 4577
_diffrn_reflns_theta_min 1.41
_diffrn_reflns_theta_max 27.32
_diffrn_reflns_reduction_process
;
Only one octant of data (an asymmetric set) was measured.
The systematic absence data was measured but removed during
data reduction when the indices were transformed for the
Pca21 cell. That is, hkl(meas) -> lhk
;
loop_
_atom_type_symbol
_atom_type_number_in_cell
_atom_type_description
_atom_type_sf_dispersion_real
_atom_type_sf_dispersion_imag
_atom_type_sf_source
#
# symbol number description f' f" source
Zr 8 Zirconium -2.965 0.560 'IT.4 Tab. 2.2A 2.3.11'
p 8 Phosphorus 0.090 0.095 'IT.4 Tab. 2.2A 2.3.11'
c 136 Carbon 0.0 0.0 'IT.4 Tab. 2.2A1'
H 216 Hydrogen 0.0 0.0 'IT.4 Tab.2.2C1'
loop_
_atom_site_label
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_thermal_motion_type
_atom_site_type_symbol
_atom_site_calc_flag
_atom_site_calc_attached_atom
#
# Table 1. of publication
# -----------------------
#
#label x/a y/b z/c Ueq tmf typ calc att
Zr1a 0.41679(2) 0.62143(7) 0.59313(6) 0.040(1) aniso Zr . .
Zr1b 0.66810(2) 0.85803(6) 0.50000 0.039(1) aniso Zr . .
P1a 0.49585(9) 0.4592(3) 0.6335(2) 0.061(1) aniso P . .
P1b 0.75066(9) 0.9838(2) 0.4440(2) 0.054(1) aniso P . .
C1a 0.4767(3) 0.709(1) 0.4921(8) 0.077(6) aniso C . .
C2a 0.4329(3) 0.794(1) 0.4693(7) 0.073(7) aniso C . .
C3a 0.4351(4) 0.956(1) 0.463(1) 0.11(1) aniso C . .
C4a 0.4550(4) 1.015(1) 0.3698(8) 0.097(9) aniso C . .
C5a 0.5464(4) 0.560(1) 0.678(1) 0.11(1) aniso C . .
C6a 0.4916(4) 0.308(1) 0.7194(9) 0.107(9) aniso C . .
C7a 0.5257(4) 0.364(1) 0.5408(9) 0.092(8) aniso C . .
C11a 0.3367(3) 0.509(1) 0.5581(9) 0.078(7) aniso C . .
C12a 0.3573(4) 0.538(1) 0.4745(8) 0.080(7) aniso C . .
C13a 0.3967(4) 0.445(1) 0.4613(7) 0.080(7) aniso C . .
C14a 0.3996(4) 0.349(1) 0.5397(9) 0.084(8) aniso C . .
C15a 0.3629(4) 0.389(1) 0.5982(9) 0.079(6) aniso C . .
C21a 0.3641(3) 0.764(1) 0.7053(7) 0.068(6) aniso C . .
C22a 0.3980(5) 0.869(1) 0.6747(7) 0.082(8) aniso C . .
C23a 0.4422(4) 0.826(1) 0.7057(9) 0.090(8) aniso C . .
C24a 0.4345(5) 0.686(1) 0.7607(7) 0.088(8) aniso C . .
C25a 0.3871(4) 0.654(1) 0.7571(6) 0.069(6) aniso C . .
C1b 0.7264(3) 0.7873(9) 0.6098(6) 0.060(5) aniso C . .
C2b 0.6835(3) 0.7101(9) 0.6336(6) 0.054(5) aniso C . .
C3b 0.6851(4) 0.534(1) 0.6366(6) 0.065(6) aniso C . .
C4b 0.7103(4) 0.477(1) 0.7238(8) 0.101(9) aniso C . .
C5b 0.7969(3) 0.850(1) 0.4047(9) 0.081(7) aniso C . .
C6b 0.7508(5) 1.123(1) 0.3487(9) 0.090(7) aniso C . .
C7b 0.7834(4) 1.099(1) 0.5277(8) 0.094(8) aniso C . .
C11b 0.5922(4) 1.003(1) 0.523(1) 0.092(9) aniso C . .
C12b 0.6080(6) 0.980(1) 0.607(1) 0.11(1) aniso C . .
C13b 0.6477(7) 1.065(2) 0.619(1) 0.12(1) aniso C . .
C14b 0.6582(4) 1.144(1) 0.538(1) 0.11(1) aniso C . .
C15b 0.6224(6) 1.103(1) 0.4786(8) 0.10(1) aniso C . .
C21b 0.6117(3) 0.704(1) 0.4028(6) 0.063(6) aniso C . .
C22b 0.6438(3) 0.5999(9) 0.4396(6) 0.060(5) aniso C . .
C23b 0.6889(3) 0.631(1) 0.4021(6) 0.057(5) aniso C . .
C24b 0.6849(3) 0.750(1) 0.3381(6) 0.057(5) aniso C . .
C25b 0.6374(4) 0.796(1) 0.3400(6) 0.067(6) aniso C . .
H1a1 0.5098 0.7683 0.5104 0.080 iso H calc C1a
H1a2 0.4895 0.6299 0.4436 0.080 iso H calc C1a
H2a 0.4103 0.8114 0.4135 0.080 iso H calc C2a
H3a1 0.4621 0.9951 0.5099 0.080 iso H calc C3a
H3a2 0.3985 1.0011 0.4808 0.080 iso H calc C3a
H4a1 0.4546 1.1320 0.3650 0.080 iso H calc C4a
H4a2 0.4893 0.9699 0.3524 0.080 iso H calc C4a
H4a3 0.4257 0.9759 0.3233 0.080 iso H calc C4a
H5a1 0.5600 0.6505 0.6445 0.080 iso H calc C5a
H5a2 0.5326 0.6138 0.7398 0.080 iso H calc C5a
H5a3 0.5777 0.4934 0.6994 0.080 iso H calc C5a
H6a1 0.4791 0.3486 0.7732 0.080 iso H calc C6a
H6a2 0.5267 0.2500 0.7231 0.080 iso H calc C6a
H6a3 0.4633 0.2225 0.6964 0.080 iso H calc C6a
H7a1 0.4973 0.2913 0.5084 0.080 iso H calc C7a
H7a2 0.5371 0.4424 0.4928 0.080 iso H calc C7a
H7a3 0.5570 0.2960 0.5543 0.080 iso H calc C7a
H11a 0.3057 0.5749 0.5848 0.080 iso H calc C11a
H12a 0.3399 0.6175 0.4319 0.080 iso H calc C12a
H13a 0.4211 0.4496 0.4055 0.080 iso H calc C13a
H14a 0.4266 0.2660 0.5427 0.080 iso H calc C14a
H15a 0.3551 0.3449 0.6584 0.080 iso H calc C15a
H21a 0.3255 0.7724 0.6896 0.080 iso H calc C21a
H22a 0.3906 0.9650 0.6324 0.080 iso H calc C22a
H23a 0.4776 0.8852 0.6957 0.080 iso H calc C23a
H24a 0.4658 0.6308 0.7910 0.080 iso H calc C24a
H25a 0.3673 0.5610 0.7877 0.080 iso H calc C25a
H1b1 0.7583 0.7195 0.5879 0.080 iso H calc C1b
H1b2 0.7410 0.8745 0.6449 0.080 iso H calc C1b
H2b 0.6635 0.7115 0.6936 0.080 iso H calc C2b
H3b1 0.7057 0.4896 0.5848 0.080 iso H calc C3b
H3b2 0.6456 0.4881 0.6294 0.080 iso H calc C3b
H4b1 0.7101 0.3627 0.7277 0.080 iso H calc C4b
H4b2 0.7462 0.5239 0.7284 0.080 iso H calc C4b
H4b3 0.6860 0.5224 0.7730 0.080 iso H calc C4b
H5b1 0.8084 0.7691 0.4496 0.080 iso H calc C5b
H5b2 0.7806 0.7829 0.3527 0.080 iso H calc C5b
H5b3 0.8305 0.8995 0.3794 0.080 iso H calc C5b
H6b1 0.7324 1.0697 0.2922 0.080 iso H calc C6b
H6b2 0.7844 1.1662 0.3309 0.080 iso H calc C6b
H6b3 0.7230 1.2177 0.3589 0.080 iso H calc C6b
H7b1 0.7932 1.0289 0.5815 0.080 iso H calc C7b
H7b2 0.8168 1.1513 0.5083 0.080 iso H calc C7b
H7b3 0.7578 1.1833 0.5532 0.080 iso H calc C7b
H11b 0.5597 0.9487 0.4897 0.080 iso H calc C11b
H12b 0.5883 0.9051 0.6483 0.080 iso H calc C12b
H13b 0.6681 1.0756 0.6771 0.080 iso H calc C13b
H14b 0.6901 1.2218 0.5318 0.080 iso H calc C14b
H15b 0.6195 1.1374 0.4114 0.080 iso H calc C15b
H21b 0.5727 0.7137 0.4185 0.080 iso H calc C21b
H22b 0.6356 0.5154 0.4844 0.080 iso H calc C22b
H23b 0.7246 0.5785 0.4132 0.080 iso H calc C23b
H24b 0.7154 0.7883 0.2997 0.080 iso H calc C24b
H25b 0.6224 0.8821 0.3014 0.080 iso H calc C25b
loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_12
_atom_site_aniso_U_13
_atom_site_aniso_U_23
#label U11 U22 U33 U12 U13 U23
Zr1a 0.046(1) 0.035(1) 0.038(1) 0.001(1) 0.004(1) 0.001(1)
Zr1b 0.049(1) 0.030(1) 0.037(1) 0.001(1) -0.003(1) -0.002(1)
P1a 0.056(1) 0.059(1) 0.068(2) 0.012(1) 0.005(1) 0.013(1)
P1b 0.059(1) 0.048(1) 0.054(1) -0.011(1) -0.004(1) 0.005(1)
C1a 0.062(5) 0.080(6) 0.090(7) 0.010(5) 0.032(6) 0.036(7)
C2a 0.066(6) 0.070(6) 0.084(8) 0.007(5) 0.008(5) 0.041(5)
C3a 0.100(9) 0.073(7) 0.15(1) 0.022(7) 0.020(9) 0.040(8)
C4a 0.15(1) 0.060(6) 0.083(8) -0.002(7) 0.007(8) 0.037(6)
C5a 0.068(7) 0.103(9) 0.16(1) 0.014(7) -0.013(8) 0.022(9)
C6a 0.088(8) 0.115(9) 0.12(1) 0.030(7) 0.002(8) 0.059(8)
C7a 0.074(7) 0.090(8) 0.112(9) 0.032(6) 0.027(7) 0.004(7)
C11a 0.058(6) 0.070(6) 0.105(9) -0.008(5) 0.001(6) -0.014(7)
C12a 0.080(8) 0.086(7) 0.075(8) 0.000(6) -0.034(6) -0.006(6)
C13a 0.116(9) 0.073(7) 0.051(6) 0.001(7) 0.008(6) -0.022(5)
C14a 0.077(7) 0.048(5) 0.13(1) 0.009(5) -0.015(7) -0.033(6)
C15a 0.100(8) 0.062(5) 0.074(6) -0.037(6) -0.004(7) 0.008(6)
C21a 0.082(7) 0.072(6) 0.049(5) 0.021(6) 0.015(5) -0.010(5)
C22a 0.14(1) 0.043(5) 0.063(6) 0.011(6) 0.006(7) -0.015(5)
C23a 0.089(8) 0.099(8) 0.080(8) -0.008(7) -0.011(7) -0.041(7)
C24a 0.12(1) 0.099(8) 0.040(5) 0.039(8) -0.022(6) -0.020(6)
C25a 0.100(8) 0.066(6) 0.039(5) -0.004(6) 0.015(5) 0.000(4)
C1b 0.072(6) 0.054(5) 0.055(6) -0.013(4) -0.018(5) 0.009(4)
C2b 0.078(6) 0.039(4) 0.045(5) 0.001(4) -0.002(5) 0.002(4)
C3b 0.094(7) 0.050(5) 0.053(5) 0.002(5) -0.002(5) 0.011(4)
C4b 0.16(1) 0.062(6) 0.078(7) -0.010(7) -0.034(8) 0.023(6)
C5b 0.040(5) 0.075(6) 0.128(9) 0.003(5) 0.002(6) 0.014(7)
C6b 0.089(7) 0.084(6) 0.098(8) -0.014(7) -0.001(6) 0.049(7)
C7b 0.103(9) 0.086(7) 0.093(9) -0.041(6) -0.016(7) -0.020(6)
C11b 0.068(8) 0.062(6) 0.15(1) 0.015(5) 0.007(9) -0.029(8)
C12b 0.18(2) 0.058(7) 0.09(1) 0.028(8) 0.07(1) -0.002(7)
C13b 0.18(2) 0.078(9) 0.09(1) 0.07(1) -0.05(1) -0.053(8)
C14b 0.078(8) 0.042(5) 0.20(2) 0.006(5) -0.01(1) -0.035(8)
C15b 0.16(1) 0.064(7) 0.075(8) 0.073(8) 0.025(8) 0.018(6)
C21b 0.056(5) 0.077(6) 0.056(6) -0.007(5) -0.007(5) -0.022(5)
C22b 0.076(6) 0.043(4) 0.061(6) -0.005(4) -0.020(5) -0.026(4)
C23b 0.052(5) 0.058(5) 0.061(5) -0.003(4) 0.001(4) -0.031(5)
C24b 0.059(6) 0.070(6) 0.040(5) -0.015(5) 0.000(4) -0.016(5)
C25b 0.101(8) 0.058(5) 0.043(5) 0.001(5) -0.028(5) -0.007(4)
_refine_special_details
;
Least-squares refinement used a separate block-matrix for each
molecule. The scale and enantiomorph Flack parameter were refined
in the matrix of molecule A. The z coordinate of Zr1b was
constrained to 0.5 to fix the origin in the polar space group.
;
_refine_ls_structure_factor_coef 'F'
_refine_ls_matrix_type 'userblock'
_refine_ls_weighting_scheme 'sigma'
_refine_ls_hydrogen_treatment 'not refined'
_refine_ls_extinction_procedure 'not applied'
_refine_ls_abs_structure_Flack 0.2(1)
_refine_ls_number_reflns 3295
_refine_ls_number_parameters 342
_refine_ls_number_restraints 0
_refine_ls_number_constraints 1 # z of Zr1b fixed for polar sg
_refine_ls_R_factor_all 0.058
_refine_ls_R_factor_obs 0.046
_refine_ls_R2_factor_obs 0.050
_refine_ls_goodness_of_fit_obs 2.8
_refine_ls_shift/esd_max 0.096
_refine_ls_shift/esd_mean 0.007
_refine_difference_density_min -0.7
_refine_difference_density_max 1.1
loop_
_geom_distance_atom_label_1
_geom_distance_atom_label_2
_geom_distance
#
# This is the complete list of first-neighbour intramolecular distances
# less than 3.0 Angstroms.
#
# lab1 lab2 distance
Zr1a P1a 2.689(3)
Zr1a C1a 2.35(1)
Zr1a C2a 2.38(1)
Zr1a C11a 2.50(1)
Zr1a C12a 2.50(1)
Zr1a C13a 2.51(1)
Zr1a C14a 2.546(9)
Zr1a C15a 2.53(1)
Zr1a C21a 2.52(1)
Zr1a C22a 2.520(9)
Zr1a C23a 2.52(1)
Zr1a C24a 2.54(1)
Zr1a C25a 2.529(9)
Zr1b P1b 2.681(2)
Zr1b C1b 2.357(9)
Zr1b C2b 2.364(8)
Zr1b C11b 2.49(1)
Zr1b C12b 2.52(2)
Zr1b C13b 2.56(2)
Zr1b C14b 2.57(1)
Zr1b C15b 2.51(1)
Zr1b C21b 2.503(9)
Zr1b C22b 2.511(8)
Zr1b C23b 2.508(9)
Zr1b C24b 2.570(9)
Zr1b C25b 2.526(9)
P1a C5a 1.79(1)
P1a C6a 1.82(1)
P1a C7a 1.79(1)
P1b C5b 1.831(9)
P1b C6b 1.84(1)
P1b C7b 1.82(1)
C1a C2a 1.47(1)
C2a C3a 1.42(1)
C3a C4a 1.54(2)
C11a C12a 1.36(2)
C11a C15a 1.41(1)
C12a C13a 1.38(2)
C13a C14a 1.41(2)
C14a C15a 1.37(2)
C21a C22a 1.39(1)
C21a C25a 1.37(1)
C22a C23a 1.37(2)
C23a C24a 1.47(2)
C24a C25a 1.36(2)
C1b C2b 1.42(1)
C2b C3b 1.54(1)
C3b C4b 1.53(1)
C11b C12b 1.31(2)
C11b C15b 1.37(2)
C12b C13b 1.35(2)
C13b C14b 1.40(2)
C14b C15b 1.37(2)
C21b C22b 1.39(1)
C21b C25b 1.41(1)
C22b C23b 1.40(1)
C23b C24b 1.40(1)
C24b C25b 1.39(1)
_reflns_h_min 0
_reflns_h_max 36
_reflns_k_min 0
_reflns_k_max 10
_reflns_l_min 0
_reflns_l_max 18
_reflns_number 4109
_reflns_number_observed 3295
_reflns_observed_criterion '2.0sigma(I)'
_reflns_d_resolution_high 0.774
loop_
_refln_h
_refln_k
_refln_l
_refln_observed_status
_refln_F_meas
_refln_F_sigma
_refln_F_calc
#
# h k l stat Fm sFm Fc
#
2 0 0 . 8.6 0.1 8.0
4 0 0 . 157.9 1.7 146.9
6 0 0 < 1.6 1.2 3.4
# <<<<<<<<<<<< for the alpha test refln data is supplied as a separate file
0 3 18 . 23.1 0.9 23.3
1 3 18 . 10.4 1.7 8.8
#---------------------------------------------------------------------------
# end_end_end_end_end_end