1, trans-trans, anti-anti 2, trans-cis, anti-anti 3, cis-cis, anti-anti 4, trans-trans, syn-anti 5, trans-cis

27 Pages·2012·14.09 MB·French

Electronic Supplementary Material (ESI) for CrystEngComm
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Electronic Supporting Information 1
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Possible geometrical isomers and conformers for 1,3-bis(cyanoxime)benzene.

NC CN
NC N N N
OH HO OH
N N N
HO OH HO CN CN CN
1, trans-trans, anti-anti 2, trans-cis, anti-anti 3, cis-cis, anti-anti
OH
NC CN
NC N N N
OH OH
N N N
OH OH OH CN CN CN
4, trans-trans, syn-anti 5, trans-cis, syn-anti 6, cis-cis, syn-anti
HO OH OH
NC CN
NC N N N
N N N
OH HO OH CN CN CN
7, trans-trans, syn-syn 8, trans-cis, syn-syn 9, cis-cis, syn-syn
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Electronic Supporting Information 2
______________________________________________________________________
Possible geometrical isomers and conformers for 1,4-bis(cyanoxime)benzene.

OH
N CN
CN OH
N
NC
NC
N
N
HO
HO
I, trans, anti-anti II. cis, anti-anti
HO
N CN
CN
N
NC
NC
OH
N
N
HO
HO
III, trans, syn-anti IV, cis, syn-anti
HO
N
CN
CN
N
NC
NC
OH
N
N
OH
OH
V, trans, syn-anti VI, cis, syn-anti
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Electronic Supporting Information 3
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Crystal data and structure refinement for the 1,3-BCO-monooxime.
_____________________________________________________________________________________
Empirical formula C H N O
10 7 3
Formula weight 185.19
Temperature 296(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P -1, #2
Unit cell dimensions a = 5.676(4) Å = 102.487(7)°.
b = 9.573(7) Å = 101.186(7)°.
c = 9.600(7) Å  = 106.568(7)°.
3
Volume, Z 469.6(6) Å , 2
3
Density (calculated) 1.310 Mg/m
-1
Absorption coefficient 0.090 mm
F(000) 192
Index ranges -6<=h<=6, -11<=k<=11, -11<=l<=11
Reflections collected 3673
Independent reflections 1764 [R(int) = 0.0462]
Completeness to theta = 25.67° 98.7 %
Max. and min. transmission 0.7454 and 0.4930
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 1764 / 0 / 139
Goodness-of-fit on F2 0.997
Final R indices [I>2sigma(I)] R1 = 0.0696, wR2 = 0.1575
R indices (all data) R1 = 0.1390, wR2 = 0.1938
Extinction coefficient 0.029(13)
-3
Largest diff. peak and hole 0.451 and -0.165 e.Å
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Hydrogen bonds for 1,3-BCO-monooxime [Å and °].
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D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
_____________________________________________________________________________________
O(1)-H(1O)...N(3)#1 1.09(6) 1.67(6) 2.749(4) 172(4)
_____________________________________________________________________________________
Symmetry transformations used to generate equivalent atoms: #1 -x+1,-y+1,-z
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Electronic Supporting Information 4
______________________________________________________________________
Molecular structure and numbering scheme for the 1,3-BCO-monooxime. An ORTEP
drawing at 50% thermal ellipsoids probability level. Selected bonds lengths (Å) are
indicated in yellow.

Actual TLC (MeOH/CHCl3) of all compounds involved into the synthesis of 1,3-BCO.
Rf = 0.69 
NC CN

NC
Rf = 0.39 
N CN
HO  
Rf = 0.16 
NC CN

N N
HO OH
Electronic Supplementary Material (ESI) for CrystEngComm
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s
n
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6
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Electronic Supplementary Material (ESI) for CrystEngComm
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s
w
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7 __ ed  
__ R
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____ etails
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on__ R e
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Ele___ 1H indi
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d
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8
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Electronic Supporting Information 9
______________________________________________________________________
UV-visible spectra of 1,3-BCO (top) and 1,4-BCO (nbottom) in different solvents upon
addition of KOH with the formation of dianion. Shown n→* and n→* (only for 1,3-
BCO) transitions in visible region of spectrum.
0,3 CN PrOH
OK MeOH
N
CHCN
3
EtOH
OK DMSO
NC N
0,2 DMF
e
c
n
a
b
or n *
s 0,1
b n *
A
0,0
400 500 600 700 800
Wavelength (nm)

1,00
MeOH
EtOH
PrOH
DMF
0,75
DMSO
e
c O- K+
n 0,50 N
a
b CN
r
o
bs n * NC
A
0,25
N
+K -O
0,00
400 500 600 700
Wavelength (nm)
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Electronic Supporting Information 10
______________________________________________________________________
Tables of H-bonding for studied bis-cyanoximes.

1,4-BCO · H O [Å and °].
2
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D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
____________________________________________________________________________
O(1)-H(1)...O(3S)#1 0.84 1.93 2.748(3) 165.5
O(3S)-H(1S)...N(4)#2 0.67(4) 2.20(4) 2.851(4) 167(5)
____________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x+3/4,y+1/4,z+3/4; #2 x,y,z+1

1,3-BCO · DMF [Å and °].
____________________________________________________________________________
D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
____________________________________________________________________________
O(1)-H(1)...O(1S) 0.84 1.83 2.664(2) 169.7
O(1)-H(1)...O(1S)#2 0.84 1.83 2.664(2) 169.7
____________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 x,y,-z+3/2 #2 x,y,-z+1/2

1,4-BCO [Å and °].
____________________________________________________________________________
D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
____________________________________________________________________________
O(1)-H(1)...N(2)#2 0.84 1.99 2.814(2) 165.6
____________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x+1,-y,-z+1 #2 -x-1/2,y+1/2,z

1,4-BCO · DMSO [Å and °].
____________________________________________________________________________
D-H...A d(D-H) d(H...A) d(D...A) <(DHA)
____________________________________________________________________________
O(1)-H(1)...O(1S)#2 0.92(2) 1.68(2) 2.6044(14) 176(2)
____________________________________________________________________________
Symmetry transformations used to generate equivalent atoms:
#1 -x+1,-y+2,-z+2 #2 x+1,y,z