What is Disorder?

Treating of Disorder • Sometimes, a part of the molecule or rarely the

whole molecule have in the crystal different
Dr. Vojtech Jancik orientations, they are DISORDERED
!
!
CCIQS UAEM-UNAM
! • Before spending time on trying to treat the disorder,
! we have to be sure, it is not caused by twinning or a
wrong space group selection.
14th SHELX Workshop Sept. 5-8th 2011
Göttingen

1 2

Types of disorder Substitutional Disorder

• Substitutional disorder
• Discrete (static) or Continuous (dynamic) disorder
• Symmetry induced disorder
• Two atoms sharing the same or nearly the same
position
• Often in Minerals
different cations with partial occupancies on the same position

• Mess
• Substitution of heavier element in the molecule by a
lighter homologue
!

replacement of a sulfur atom by oxygen in metal sulfides

Taken from Crystal Structure Refinement – A
Crystallographer’s Guide to SHELXL Indication: too small or too big thermal ellipsoids

3 4
Discrete (static) or Continuous
(dynamic) disorder
Discrete Disorder
• Part of or the whole molecule has two (sometimes
three) well separated positions
Continuous Disorder
• Caused mostly by free rotation of part of a
molecule, or free movement of solvent molecules
in channels
5 6
Mess
No order what so ever and usually, it is not possible
to localize any reasonable peaks and it is necessary to
use SWAT (SHELXL) or SQUEEZE (PLATON)
• In compounds with huge channels full of
amorphously frozen solvent.
• SWAT refines two parameters, the first grows with
the amount of amorphous solvent, whereas the
second determines, which data (low or high
resolution) are affected by the amorphously
distributed scatters. High value means that only
the low resolution data are affected.
7 8
Symmetry Induced Disorder
The molecule occupies a special position in the
crystal. The symmetry of this position is higher than
that of the molecule.
Clasic example:
• Toluene on an inversion center,
perpendicular to a two fold axis or a
plane.
• Occupancy of the positions depends on
the multiplicity of the symmetry element.
• The two different orientations of the disordered parts are mostly
very close to each other and thus, it is necessary to eliminate
bonds between them.
• The connectivity list can be modified using the command PART.
As default, all atoms belong to PART 0 if not specified differently.
• PART X (X is integer, can be positive or negative)
Each of these positions is should be defined by PART X (at the beginning) and
PART 0 at the end. Effect of this command is that bonds are made only between
atoms with the same part number. In XP, it is also conveniently used to eliminate
selectively one of the parts (KILL PARTX – CAREFUL! erases atoms that belong to
ALL PART X domains – in case of a multiple disorder in the model).
PART 1
C300 1 -0.064112 0.493068 1.096790 21.00000 0.13197
...
C306 1 0.102760 0.392121 1.045125 21.00000 0.12138
PART 2
C030 1 0.115824 0.229505 0.933867 31.00000 0.10545
• PART -1 (X is negative)
...
C036 1 0.220975 0.318122 0.911817 31.00000 0.12382
PART 3 Used in case of disorder on special position
C130 1 -0.003788 0.619285 1.031744 41.00000 0.11839
...
C136 1 0.129449 0.484513 1.016433 41.00000 0.10912 In this case, the bonds between atoms from different positions related by
PART 4 symmetry are not added to the connectivity list
C330 1 0.048908 0.282434 0.967174 51.00000 0.12264
...
C336 1 -0.057952 0.403523 1.025988 51.00000 0.11982
PART 0

9 10

FREE VARIABLES (fvar(x))

!
FVAR 0.21548 (osf – overall scale factor )
FREE VARIABLES (fvar(x))
!
!
Adding 10 means fixing the value
FVAR 0.38941 0.84781 (fvar(2))
!
!
C13 1 0.846522 0.708472 0.641399 11.00000 0.05817 C32 1 0.333780 1.086124 1.012517 21.00000 0.05754
C14 1 0.013860 0.409328 1.014577 10.50000 0.07252 C32A 1 0.319060 1.045344 0.986065 -21.00000 0.05797
X10 1 ………..... ……….… ……….… 10.33333 0.07252 !
X11 1 ………..... ……….… ……….… 10.16667 0.07252 !
X12 1 ………..... ……….… ……….… 10.25000 0.07252 The factor 21 is interpreted as 1 * fvar(2), whereas -21 means 1*
X13 1 ………..... ……….… ……….… 10.14000 0.07252 (1 – fvar(2)). Thus, the position of atom C32 is occupied from
C14 1 0.013860 0.409328 1.014577 10.50000 10.045 84.78 %, whereas that of C32A from 1-0.84781 = 15.22 %.
will fix the U-factor on value 0.045
C14 1 10.013860 10.409328 11.014577 10.50000
0.07252
will fix the coordinates of the atom
!
!

11 12
 How to recognize disordered atoms:
FREE VARIABLES (fvar(x)) !
! The Uij values after the anisotropic refinement are rather high and
FVAR 0.38941 0.84781 (fvar(2)) the ellipsoids point in wrong directions
! !
C32 1 0.333780 1.086124 1.012517 20.50000 0.05754 !
C32A 1 0.319060 1.045344 0.986065 -20.50000 0.05797 !
! !
! !
The factor 20.5 is interpreted as 0.5 * fvar(2), whereas -21 means !
0.5* (1 – fvar(2)). Thus, the position of atom C32 is occupied !
from 32.39 %, whereas that of C32A from 0.5*(1-0.84781) = !
7.61 %. From the *.lst file after anisotropic refinement:
!
0.3634 0.1439 0.0592 C7 may be split into 0.5577 1.1105 0.6695 and 0.5616 1.0966 0.6514
0.4153 0.1588 0.0569 C8 may be split into 0.5927 1.1963 0.6006 and 0.5949 1.1824 0.5805
0.4247 0.1590 0.0515 C9 may be split into 0.4794 1.1490 0.7174 and 0.4809 1.1370 0.6961

13 14

How to find the second orientation of a part or whole RIGID FIT of a highly disordered group or molecule
molecule? !
!
FRAG code [≥17] a b c α β γ allows to insert coordinates of a
From the residual electron density map
known well refined fragment or molecule into the *.ins file and use
!
them as coordinate source of a rigid model refinement using AFIX
From the *.lst file after anisotropic refinement
code command. Very useful for highly disordered solvent
!
molecules – e.g. hexane filling channels along a rotation axes.
refine the first part already with a free variable (this goes mostly
Command FEND has to be inserted immediately after the last atom
over 1 and then has to be again replaced by a number between
in FRAG.
0 and 1, the ideal compromise is 0.7) and use the original
coordinates of part 1 from the *.ins file as the coordinates for the
Code has to be higher than 16 and is then used in an AFIX code
second part in the *.res file
command. The AFIX command fits the following atoms identical
!
geometry to that of atoms specified between the FRAG and
Another approach can be the reduction of the occupancy of the
FEND commands. Only the atomic coordinates and not the
first domain (e.g. to 0.6, thus, the sof would be 10.6) and
atom types or sof’s are used.
refining the model. After the refinement, the second position can
!
become more obvious. After locating both positions, it is
a b c α β γ are the cell parameters of the original structure,
necessary to change the sof’s to use another free variable.
from which the coordinates for the rigid group were taken.
!
15 16
coordinates of the hexane molecule taken from: FISFET (A. Behrens, U. Behrens, E.
Nordlander, C. Bader, D. Rehder, Inorg.Chim.Acta 2005, 358, 1970.)
!
simu 0.01 c100 > c105 Treating of disorder mostly requires the use of constraints and
delu 0.005 c100 > c105 restraint
FRAG 17 17.0894 24.6097 34.4394 108.797 91.894 105.329
!
C1 1 0.948400 0.722000 0.930200 11.000000 0.05000
C2 1 0.971100 0.778600 0.917900 11.000000 0.05000 !
C3 1 0.904800 0.770600 0.883500 11.000000 0.05000 !
C4 1 0.925100 0.828400 0.872700 11.000000 0.05000 Excess of constraints and restraints at the beginning of the
C5 1 0.876000 0.868800 0.897900 11.000000 0.05000
C6 1 0.878300 0.918300 0.879300 11.000000 0.05000
refinement can help to stabilize the model
FEND !
PART -1 !
AFIX 176 6 means rigid group refinement !
C100 1 1.020875 0.992303 0.420537 10.33333 0.05 original
C101 1 1.019099 1.037722 0.483460 10.33333 0.05 coordinates After the refinement is finished, one can try to remove as many
C102 1 1.007147 0.947920 0.518204 10.33333 0.05 of a highly restraints and constraints as possible without jeopardizing the
C103 1 0.960218 0.969764 0.573774 10.33333 0.05 disordered stability or geometry of the model
C104 1 1.040012 0.979298 0.617371 10.33333 0.05 hexane
C105 1 0.984306 0.999276 0.672013 10.33333 0.05
PART 0
AFIX 0

17 18

Disorder on a general position

!
!
Data to parameters to restraints ratio: PART 1
! C300 1 -0.064112 0.493068 1.096790 21.00000 0.13197
Refining one molecule or its part, increases the amount of the ...
C306 1 0.102760 0.392121 1.045125 21.00000 0.12138
parameters to be refined PART 2
! C030 1 0.115824 0.229505 0.933867 -21.00000 0.10545
! ...
Data to parameters ratio > 10 for centrosymmetric and > 8 for C036 1 0.220975 0.318122 0.911817 -21.00000 0.12382
PART 0
noncentrosymmetric
!
!
Necessary to use a new FVAR
!
Disorder over 2 positions is mostly sufficient
!
!
Parameters to restraints ?
Recommended restraints:
SIMU and DELU or EADP
SADI or SAME

19 20
The SAME restraint The SAME restraint
!
SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2 SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2
x2 …. x2 ….
x3 …. x2 x2 x3 …. x2 x2
x4 …. x7 x4 …. x7
x3 x3 x7 x3 x3 x7
x5 …. x5 ….
x6 …. x6 ….
x7 …. x6 x6 x7 …. x6 x6
! x4 x4 ! x4 x4
x5 x5 x5 x5

21 22

The SAME restraint The SAME restraint

! !
SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2 SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2
x2 …. x2 ….
x3 …. x2 x2 x3 …. x2 x2
x4 …. x7 x7 x4 …. x7
x3 x3 x3 x3 x7
x5 …. x5 ….
x6 …. x6 ….
x7 …. x6 x6 x7 …. x6 x6
! x4 x4 ! x4 x4
x5 x5 x5 x5

23 24
The SAME restraint The SAME restraint
! !
SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2 SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2
x2 …. x2 ….
x3 …. x2 x2 x3 …. x2 x2
x4 …. x7 x4 …. x7
x3 x3 x7 x3 x3 x7
x5 …. x5 ….
x6 …. x6 ….
x7 …. x6 x6 x7 …. x6 x6
! x4 x4 ! x4 x4
x5 x5 x5 x5

25 26

The SAME restraint

! x2 x2 x2 x2
SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2 x3 x7 x3 x7 x3 x7 x3 x7

x2 ….
x3 …. x2 x2 x4
x6
x4
x6
x4
x6
x4
x6
x5 x5 x5 x5
x4 …. x7
x3 x3 x7
x5 …. x2 x2 x2 x2

x6 …. x3 x7 x3 x7 x3 x7 x3 x7

x7 …. x6 x6
! x4 x4 x4
x6
x4
x6
x4
x6
x4
x6
x5 x5 x5 x5
x5 x5
x2 x2 x2 x2
x3 x7 x3 x7 x3 x7 x3 x7

x6 x6 x6 x6
x4 x4 x4 x4
x5 x5 x5 x5

27 28
The SAME restraint The SAME restraint
!
SAME x3 x4 x5 x6 x7 x2 x3 > x7 x2 SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7
x2 …. x1 ….
x3 …. x2 x2 x2 …. x1 Y1
x4 …. x3 ….
x3 x7 x3 x7 x4 ….
x5 ….
x6 …. x5 …. x2 Y2
x7 …. x6 x6 x6 …. x3 x7 Y3 Y7
! x4 x4 x7 ….
x5 x5 !
x6 Y6
x4 Y4
x5 Y5
SADI x2 x3 x3 x4 x4 x5 x5 x6 x6 x7 x7 x2 1,2 distances
SADI x2 x4 x3 x5 x4 x6 x5 x7 x6 x2 x7 x3 1,3 distances

29 30

The SAME restraint The SAME restraint

SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7 SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7

x1 …. x1 ….
x2 …. x1 Y1 x2 …. x1 Y1
x3 …. x3 ….
x4 …. x4 ….
x5 …. x2 Y2 x5 …. x2 Y2
x6 …. x3 x7 Y3 Y7 x6 …. x3 x7 Y3 Y7
x7 …. x7 ….
! !
x6 Y6 x6 Y6
x4 Y4 x4 Y4
x5 Y5 x5 Y5

31 32
The SAME restraint The SAME restraint

SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7 SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7

x1 …. x1 ….
x2 …. x1 Y1 x2 …. x1 Y1
x3 …. x3 ….
x4 …. x4 ….
x5 …. x2 Y2 x5 …. x2 Y2
x6 …. x3 x7 Y3 Y7 x6 …. x3 x7 Y3 Y7
x7 …. x7 ….
! !
x6 Y6 x6 Y6
x4 Y4 x4 Y4
x5 Y5 x5 Y5

33 34

The SAME restraint The SAME restraint

SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7 SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7

x1 …. x1 ….
x2 …. x1 Y1 x2 …. x1 Y1
x3 …. x3 ….
x4 …. x4 ….
x5 …. x2 Y2 x5 …. x2 Y2
x6 …. x3 x7 Y3 Y7 x6 …. x3 x7 Y3 Y7
x7 …. x7 ….
! !
x6 Y6 x6 Y6
x4 Y4 x4 Y4
x5 Y5 x5 Y5

35 36
 Disordered THF molecule
The SAME restraint simu o6a > c82b
delu o6a > c82b
SAME esd12 esd13 Y1 Y2 Y3 Y4 Y5 Y6 Y7 same Li4 o6a c82a c81a c80a c79a compares chemically equivalent carbons of part
1 to each other
x1 …. same Li4 o6b > c82b compares part 1 to part 2
x2 …. x1 Y1 !
x3 …. Li4 3 0.600104 0.868969 0.413037 11.00000 0.02978
!
x4 ….
same o5 c75 c76 c77 c78 compares part 1 to another, non disordered molecule of
x5 …. x2 Y2 THF in the crystal
x6 …. x3 x7 Y3 Y7 !
x7 …. PART 1 O O
O6A 5 0.538681 0.864118 0.451985 21.00000 0.02039 6A 6B
82B
! C79A 1 0.541784 0.840075 0.506213 21.00000 0.03628 79A 82A 79B

x6 Y6 C80A 1 0.485634 0.787659 0.500091 21.00000 0.07055 80A 80B

x4 Y4 C81A 1 0.445027 0.806402 0.445724 21.00000 0.03171
81A 81B

C82A 1 0.472817 0.881507 0.429656 21.00000 0.03187

x5 Y5 PART 2
O6B 5 0.530172 0.877127 0.449133 -21.00000 0.02802
C79B 1 0.544344 0.835999 0.500698 -21.00000 0.03306
C80B 1 0.481354 0.807823 0.504918 -21.00000 0.02567
C81B 1 0.436804 0.839325 0.453336 -21.00000 0.03664
C82B 1 0.472484 0.835482 0.414827 -21.00000 0.01825
PART 0

37 38

Disordered tBu group Disorder between S and Se

simu 0.01 0.01 3 c37 > c40 these two numbers extend the “action radius” of simu to 3 Å
delu 0.005 c37 > c40a In this example, the ligand had composition iPr2P(S)NP(Se)iPr2, but the complex
same n4 c37a c38a c39a c40a compares part 1 to part 2 crystallize in P42/nbc with ¼ of the molecule in the asymmetric unit. Thus the ratio
same n4 c37 c39 c40 c38 tBu group rotated by 120 degree is compared to the original one between S and Se was not refined, instead the occupancy was set to 10.50000 for
! both atoms to correspond the composition of the complex
! !
! !
N4 3 -0.032124 0.683337 -0.010772 11.00000 0.03762 0.03601 = !
0.03841 0.00474 0.00054 0.00370 38 38A !
! 37
!
37A
PART 1 N
4
N EADP Se1 S1
4A 39A
39
C37 1 -0.018550 0.606462 -0.050888 21.00000 0.03854 !
C38 1 0.082735 0.629695 -0.081673 21.00000 0.04446 40 40A PART 1
C39 1 -0.117882 0.604528 -0.086345 21.00000 0.04367 S1 8 0.763946 0.877295 0.312845 10.50000 0.04243
C40 1 -0.006365 0.514161 -0.022331 21.00000 0.05048 part 2
PART 2
SE1 7 0.765700 0.879258 0.323944 10.50000 0.04243
C37A 1 0.012190 0.615090 -0.051010 -21.00000 0.04558
C38A 1 0.133919 0.624383 -0.060942 -21.00000 0.04514 PART 0
C39A 1 -0.050595 0.629562 -0.101915 -21.00000 0.04719 !
C40A 1 -0.008177 0.516932 -0.028818 -21.00000 0.04497 FOR EADP, THE ATOMS HAVE TO BE EITHER BOTH ANISOTROPIC OR BOTH
PART 0 ISOTROPIC BEFORE THE REFINEMENT !!!

39 40
 Disorder between S and Se Disorder of a Cp ring
sadi 0.01 al1 cl1 al1 cl1a simu 0.01 c36 > c40a
sadi al1 c6 al1 c6a delu 0.005 c36 > c40a
sadi cl1 c6 cl1a c6a or alternatively instead of all three SADI commands SAME Al1 Cl1a C6a same c36a > c40a Compares part 1 to part 2
same c37 > c40 c36 Cp ring rotated by 72 degree is compared to the original one
eadp c6 cl1a same c31 > c35 Compares part 1 to another not disordered Cp ring in the molecule
eadp c6a cl1
! 36 36A
!
! 37 40 37A 40A
!
! ! 38 39 39A
38A
! !
! PART 1
! C36 1 -0.050767 0.530283 0.060129 21.00000 0.03102
AL1 4 0.865452 0.084609 0.204755 11.00000 0.01767 0.01798 = C37 1 -0.077474 0.569771 0.090273 21.00000 0.02830
0.01942 0.00002 0.00821 0.00083 C38 1 -0.191303 0.644897 0.086818 21.00000 0.02462
PART 1 C39 1 -0.234748 0.651540 0.054649 21.00000 0.02684
C40 1 -0.149104 0.580595 0.037980 21.00000 0.03348
CL1 5 0.837573 -0.025664 0.203298 21.00000 0.02734
PART 2
C6 1 0.774936 0.129658 0.063453 21.00000 0.03677 C36A 1 -0.079019 0.540824 0.046444 -21.00000 0.03147
PART 2 C37A 1 -0.043685 0.542293 0.079179 -21.00000 0.03063
C6A 1 0.839970 -0.011185 0.213151 -21.00000 0.02734 C38A 1 -0.139914 0.614101 0.092564 -21.00000 0.03159
CL1A 5 0.768344 0.132777 0.045790 -21.00000 0.03677 C39A 1 -0.230818 0.659517 0.068172 -21.00000 0.02679
PART 0 C40A 1 -0.192015 0.614537 0.039519 -21.00000 0.02902
PART 0

41 42

Disorder on a special position Disorder of a Cp ring perpendicular to a m plane

!
Part -X simu 0.01 c22 > c26
! delu 0.005 c22 > c26
New FVAR is used only in a case of a heavy disorder same c23 > c26 c22 Cp ring rotated by 72 degree is compared to the original one
! same c21 c20 c19 c18 c17 Compares part 1 to another not disordered Cp ring in
Occupancy is reduced according to the type of the symmetry element the molecule
(multiplicity) !
! PART -1
Number of generated positions is a multiplication of the number of refined C22 1 0.401700 0.203469 0.388262 10.50000 0.01621
positions by the number of sites generated by the symmetry element C23 1 0.362900 0.196870 0.248598 10.50000 0.01589
! C24 1 0.348901 0.262542 0.193592 10.50000 0.01291
USE GROW IN XP BEFORE PICKING THE Q PEAKS! C25 1 0.374845 0.309199 0.299757 10.50000 0.01497
! C26 1 0.411771 0.273205 0.420197 10.50000 0.01646
Recommended restraints: PART 0
!
SIMU and DELU or EADP
!
SADI or SAME 22
! 23 26
In more difficult cases rigid group refinement: FRAG 17, FEND, AFIX 176
!
24 25
Any other restraint or constraint applicable

43 44
 Disorder of a Cp ring perpendicular to a m plane Disordered GaCl4- on a 42 axis
In this example, it was necessary to restrain the thermal ellipsoids, which were not
close to each other. This can be done by specifying two other parameters for the eadp cl1a cl1e makes the thermal ellipsoids for the equivalent chlorine atoms from
SIMU command. The first two are esd’s and the third is a “action radius” of a sphere both parts identical within the set ESd
around the atom, in which the atoms specified in SIMU should be restrained. eadp cl1b cl1f “
! eadp cl1c cl1g “
simu 0.02 0.04 3 c3 > cl3' eadp cl1d cl1h “
delu c3 > cl3' !
Cl 1 Cl
same c3 cl2 cl3 cl1 CCl3 moiety rotated by 120 degree
1' same ga2 Cl1e > cl1h Compares part 1 to part 2
is compared to the original one Cl 3 3' same ga2 cl1b cl1c cl1d cl1a Rotates the tetrahedron and compares it to the
Cl
same c3' > cl3' Compares part 1 to part 2
3 H 3' H original one
Cl 1A Cl
! 
 1E

Cl2 Cl2' GA2 6 0.250000 0.750000 0.500000 10.25000 0.04532 Cl

PART -1 PART -1 1B
Ga
2 Cl1D
Cl
1F
Ga
Cl1H
2
C3 1 0.168767 -0.001822 0.722731 20.50000 0.10908 CL1A 5 0.136194 0.831866 0.516781 20.25000 0.05278
CL1 6 0.287131 0.007146 0.816932 20.50000 0.11956 Cl 1C Cl 1G
CL1B 5 0.298156 0.701925 0.604291 20.25000 0.07820
CL2 6 0.112444 0.066898 0.608249 20.50000 0.12645 CL1C 5 0.349340 0.827951 0.446238 20.25000 0.09283
CL3 6 0.135872 -0.082675 0.639630 20.50000 0.10111 CL1D 5 0.216257 0.638238 0.432742 20.25000 0.04114
PART -2 PART -2
C3' 1 0.106533 -0.000099 0.631717 -20.50000 0.11905 CL1E 5 0.176769 0.849852 0.557953 -20.25000 0.05278
CL1' 6 0.068042 0.016528 0.462369 -20.50000 0.12573 CL1F 5 0.331206 0.673213 0.573000 -20.25000 0.07820
CL2' 6 0.204254 0.049018 0.742547 -20.50000 0.12840 CL1G 5 0.330917 0.811028 0.417285 -20.25000 0.09283
CL3' 6 0.126715 -0.089549 0.667264 -20.50000 0.12811 CL1H 5 0.156342 0.660832 0.451390 -20.25000 0.04114
PART 0
PART 0

45 46

Disorder over three positions

FREE VARIABLES (fvar(x)) and SUMP

!
FVAR 0.38941 0.57125 0.26158 0.16717
FREE VARIABLES (fvar(x))
! !
FVAR 0.38941 0.67125 (fvar(2)) SUMP 1 0.001 1 2 1 3 1 4
! !
And what if one atom does have more than two position? C32 1 0.333780 1.086124 1.012517 21.00000 0.05754
! C32A 1 0.319060 1.045344 0.986065 31.00000 0.05797
C32 1 0.333780 1.086124 1.012517 21.00000 0.05754 C32B 1 0.290140 1.003122 0.959255 41.00000 0.05797
C32A 1 0.319060 1.045344 0.986065 -21.00000 0.05797
!
C32B 1 0.290140 1.003122 0.959255 And what here?0.50000
0.05797 SUMP 1 0.001 1 2 1 3 1 4
! !
The principle of fvar and –fvar can describe only two positions! 1 * fvar(2) + 1 * fvar(3) + 1 * fvar(4)
!
!
is restrained to be 1 within esd 0.001

47 48
 DMSO disordered over three positions
SIMU 0.01 O8 > C91c
SUMP DELU 0.005 O8 > C91c
! SUMP 1.0000 0.00001 1 2 1 3 1 4
SAME Nd1 O7 S1 C88 C89 Compares part 1 to another DMSO molecule in the crystal
SUMP can be used for disorder over as many positions as SAME Nd1 O8 S2 C91 C90 Compares chemically equivalent atoms in part 1 to each other
necessary, but the question always is: is it reasonable? SAME Nd1 O8B > C91B Compares part 1 to part 2
90C C91 C90B C91B C90C C91C
SAME Nd1 O8C > C91C Compares part 1 to part 3 S2 S2B
! FVAR 0.30360 0.31239 0.15131 0.53631
S2C

SUMP can be used for balancing a charge ! O8 O8B O8C

! !
Nd1 7 0.502876 0.751498 0.771925 11.00000 0.02854
FVAR 0.38941 0.50000 0.37158 0.12842 PART 1
O8 4 0.579896 0.727324 0.922012 21.00000 0.06271
! S2 6 0.531937 0.695330 0.987343 21.00000 0.06905
SUMP 1.5 0.001 1 2 2 3 2 4 C90 1
C91 1
0.602239 0.733020 1.085633 21.00000 0.07867
0.605971 0.622193 1.009924 21.00000 0.08789
SUMP 1 0.001 1 2 1 3 1 4 PART 2
O8B 4 0.566657 0.715941 0.922105 31.00000 0.06464
! S2B 6 0.589511 0.649445 0.960142 31.00000 0.07166
Na1 1 0.333780 1.086124 1.012517 21.00000 0.05754 C90B 1 0.485045 0.637564 1.012894 31.00000 0.08274
C91B 1 0.708474 0.659977 1.052829 31.00000 0.08412
Ca1 1 0.319060 1.045344 0.986065 31.00000 0.05797 PART 3
Mg1 1 0.290140 1.003122 0.959255 41.00000 0.05797 O8C 4 0.578173 0.721340 0.926932 41.00000 0.06218
S2C 6 0.515978 0.704761 0.991897 41.00000 0.06278
! C90C 1 0.557339 0.763794 1.072327 41.00000 0.07054
or solving a disorder in a disorder C91C 1 0.593004 0.641301 1.051769 41.00000 0.08670
PART 0

49 50

AlCl4- disordered over three positions, two of them contaminated with AlCl3Me- AlCl4- disordered over three positions, two of them contaminated with AlCl3Me-
simu 0.01 0.02 5 al3 > cl4b
sump 0 0.0001 -1 2 1 3 1 4 Controls the sum of Cl3 and C03 to be equal to the free variable 2 delu 0.005 al3 > cl4b
! sump 0 0.0001 -1 2 1 3 1 4 Controls the sum of Cl3 and C03 to be equal to the free variable 2
sump 0 0.0001 -1 5 1 6 1 7 Controls the sum of Cl3a and C03a to be equal to the free variable 5 sump 0 0.0001 -1 5 1 6 1 7 Controls the sum of Cl3a and C03a to be equal to the free variable 5
!
sump 1 0.0001 1 2 1 5 1 8 Controls the sum PART 1, PART2 and PART 3 to be equal to 1 sump 1 0.0001 1 2 1 5 1 8 Controls the sum PART 1, PART2 and PART 3 to be equal to 1
! FVAR 0.10666 0.51632 0.23894 0.27739 0.36808 0.05178 0.31630
Cl3 Cl3A Cl3B
FVAR 0.11556
! C03 C03A
same 0.01 0.01 al3a > c03a Compares part 1 to part 2
! Cl4 Cl4A Cl4B same 0.01 0.01 al3b > cl4b Compares part 1 to part 3
Al3 Al3A Al3B
! same 0.01 0.01 al3 cl2 cl3 cl4 cl1 Compares chemically equivalent atoms in part 1 to each other
! Cl1
Cl2
Cl1A
Cl2A
Cl1B
Cl2B
same 0.01 0.01 al3 cl3 cl4 cl1 cl2 Compares chemically equivalent atoms in part 1 to each other
PART 1 PART 1
AL3 4 0.181774 1.106421 0.293674 21.00000 0.05422 AL3 4 0.181774 1.106421 0.293674 21.00000 0.05422
CL1 7 0.105045 1.024751 0.254989 21.00000 0.11579 CL1 7 0.105045 1.024751 0.254989 21.00000 0.11579
CL2 7 0.189959 1.233932 0.221799 21.00000 0.06049 CL2 7 0.189959 1.233932 0.221799 21.00000 0.06049
CL3 7 0.329641 1.021278 0.327548 31.00000 0.07295 CL3 7 0.329641 1.021278 0.327548 31.00000 0.07295
CL4 7 0.088811 1.154582 0.368685 21.00000 0.08375 CL4 7 0.088811 1.154582 0.368685 21.00000 0.08375
C03 1 0.312048 1.026816 0.323819 41.00000 0.06783 C03 1 0.312048 1.026816 0.323819 41.00000 0.06783
PART 2 PART 2
AL3A 4 0.196876 1.054417 0.331933 51.00000 0.06638 AL3A 4 0.196876 1.054417 0.331933 51.00000 0.06638
CL1A 7 0.127968 1.020176 0.259433 51.00000 0.13943 CL1A 7 0.127968 1.020176 0.259433 51.00000 0.13943
CL2A 7 0.297143 1.140608 0.289669 51.00000 0.11145 CL2A 7 0.297143 1.140608 0.289669 51.00000 0.11145
CL3A 7 0.277955 0.921741 0.396493 61.00000 0.08350 CL3A 7 0.277955 0.921741 0.396493 61.00000 0.08350
CL4A 7 0.077575 1.144310 0.378656 51.00000 0.07902 CL4A 7 0.077575 1.144310 0.378656 51.00000 0.07902
C03A 1 0.268492 0.936956 0.389800 71.00000 0.07972 C03A 1 0.268492 0.936956 0.389800 71.00000 0.07972
PART 3 PART 3
AL3B 4 0.169217 1.087813 0.311827 81.00000 0.06753 AL3B 4 0.169217 1.087813 0.311827 81.00000 0.06753
CL1B 7 0.081247 1.038605 0.257240 81.00000 0.04795 CL1B 7 0.081247 1.038605 0.257240 81.00000 0.04795
CL2B 7 0.234935 1.192973 0.251227 81.00000 0.06009 CL2B 7 0.234935 1.192973 0.251227 81.00000 0.06009
CL3B 7 0.288586 0.963621 0.361303 81.00000 0.06371 CL3B 7 0.288586 0.963621 0.361303 81.00000 0.06371
CL4B 7 0.071181 1.157821 0.376638 81.00000 0.05384 CL4B 7 0.071181 1.157821 0.376638 81.00000 0.05384
PART 0 PART 0

51 52
AlCl4- disordered over three positions, two of them contaminated with AlCl3Me-

“With the right restraints, you can fit an elephant to any data”
G. M. Sheldrick
!
!
R1
! = 5.47 C2 R1 = 5.67
H1a H1a
! C2
!
! C1
! C1
!
! H1b
H1b
! H1c H1c
!
!
flat 0.0001 c1 c2 h1a h1b h1c
DFIX 0.95 0.0001 C1 H1a C1 H1b C1 H1c
SADI 0.0001 C2 H1a C2 H1c
SADI 0.0001 H1b H1a H1b H1c
dfix 1.90 0.0001 H1a H1c
!
= Only 8 restraints!

53