supplementary revised defclaudio pettinari,*a alfonso venzod adept. of chemical sciences, via s....
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Synthesis, characterization, crystal structure and preliminary reactivity behaviour of new heteropolytopic ligands based on the 1,3,5-triazine spacer and pyrazolyl, tris-pyrazolylmethyl and tris-pyrazolylethoxy bonding fragments. Corrado Di Nicola,a Federica Garau,b Fabio Marchetti,a Magda Monari,*c Luciano Pandolfo,*b Claudio Pettinari,*a Alfonso Venzod aDept. of Chemical Sciences, Via S. Agostino, 1, University of Camerino, I-62032 Camerino (MC), Italy. E-mail: [email protected]; Fax:+39 0737 637345; Tel: +39 0737 402234 bDept. of Chemical Sciences, University of Padova, Via Marzolo, 1, I-35131 Padova, Italy. E-mail: [email protected]; Fax:+39 049 8275161; Tel: +39 049 8275157 cDept. of Chemistry “G. Ciamician”, University of Bologna, Via Selmi, 2, I-40126 Bologna, Italy. E-mail: [email protected]; Fax:+39 051 2099456; Tel: +39 051 2099559 dCNR – ISTM University of Padova, Via Marzolo, 1, I-35131 Padova, Italy.
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011
N
NC''
NC'
Cl
NN
N C3
C4C5
H5
H4
H3
N N N
NN
N
HN CH2
NH
N3
NN3
N
N1N
N
N
C5 C4
C3N2
H5H4
H3
N
N
N'
N
NN
N N
N1
N
NN
N2
C3C4
C5
N
NNN
N
N
H5
H4 H3
N N
N
N
N'
N
NN
N N
N1
N
NN
N2
C3C4
C5
N
NNN
N
N
H5
H4 H3
N N
O O
OH2C
1 2
3 4 Chart S1 – Numbering scheme for NMR signals assignments. NB The numbering of 3 doesn’t correspond to the labels indicated in the crystal structure figure.
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011
N
N
N
Cl
Cl Cl
N
N
N
Nu
Cl Cl
N
N
N
Nu
Cl Nu'
N
N
N
Nu
Nu" Nu'
+ Nu'H, T2
-HCl
+ NuH, T1
+ Nu"H, T3
-HCl
-HCl
T1 < T2 < T3
Scheme S1 – Scheme describing the so-called Moffat rule.
Figure S1 – View of the molecular structure of 3 bisected by a plane containing the triazine ring.
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011
Figure S2 – Space-filling view of 3 along the crystallographic a axis evidencing small, irregular, channels running along the same axis.
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011
Figure S3 – ESI-MS of L3.
m700 720 740 760 780 800
Norm.
0
20
40
60
80
100
*MSD1 SPC, time=0.247:0.266 of PT\10020904.D API-ES, Pos, Scan, 30
Max: 69460 803
.5 8
04.5
805
.5
740
.3
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011
m/z0 200 400 600 800 1000 1200 1400
Norm.
0
20
40
60
80
100
*MSD1 SPC, time=0.367:0.496 of SNAPSHOT.D API-ES, Pos, Scan
Max: 122626 830
.8 8
31.8
227
.3
740
.8
446
.4
832
.8
202
.2
a
m/z0 200 400 600 800 1000 1200 1400
Norm.
0
20
40
60
80
100
*MSD1 SPC, time=0.293:0.423 of PT\08121902.D API-ES, Pos, Scan, 300
Max: 24816 227
.3
159
.1 1
32.1
224
.2
53.
2 7
9.2
536
.5
267
.3
202
.2
310
.3
147
.2
468
.5
830
.8
51.
2
106
.2
400
.4
242
.2
160
.1
335
.3
537
.5
198
.1
54.
2
b Figure S4 – ESI-MS of L4 at different [(a) 30, (b) 300] “fragmentor energy”, (see text).
[L4 + Na + 2H]3+ calcd m/z = 277.4
[4 + Na]+ calcd m/z = 830.3
[L4 - pz]+ calcd m/z = 740.3
[4 + Na + 2H]3+ calcd m/z = 277.4
[L4 + Na]+ calcd m/z = 830.3
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m/z450 500 550 600 650 700 750 800 850
Norm.
0
20
40
60
80
*MSD1 SPC, time=0.181:0.274 of PT\09111200.D API-ES, Pos, Scan, 30
Max: 24302
589
.2
483
.3
590
.2
545
.2
484
.2
733
.0
592
.2
547
.2
505
.2
593
.2
792
.2
734
.1
548
.2 5
57.0
m/z1050 1100 1150 1200 1250 1300 1350
Norm.
0
5
10
15
20
25
30
35
*MSD1 SPC, time=0.181:0.274 of PT\09111200.D API-ES, Pos, Scan, 30
Max: 24302
132
9.3
107
3.4
107
1.4
102
7.3
128
5.3
133
1.2
107
4.3
102
8.4
128
6.3
132
8.3
Figure S5 – ESI-MS of 2.
N
NN
N
N
NH
N
NN
NN
N
N
HN
N
N
H+
N
NN
N
N
NH
N
NN
NN
N
N
HN
N
NAg+
N
NN
N
N
NH
N
NN
NN
N
N
HN
N
N
Ag+
N
NN
N
N
HN
N
N
N
NN
N
N
NH
N
N
N
NN
N
N
NH
N
NN
NN
N
N
HN
N
N
Ag+
N
NN
N
N
HN
N
N
N
NN
N
N
NH
N
N
Ag+
CF3SO3
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011
m/z200 400 600 800 1000 1200 1400
Norm.
0
20
40
60
80
100
*MSD1 SPC, time=0.194:0.268 of PT\09111203.D API-ES, Pos, Scan, 30
Max: 19513 272
.6
544
.2
607
.2
273
.5
130
.1
609
.2
546
.2
306
.6
513
.7 5
45.2
580
.2
307
.5
65.
2
346
.5
102
.2
514
.3
384
.6
108
9.4
434
.5
593
.2
288
.6
909
.2
551
.5
733
.2
692
.1
125
6.3
344
.4
230
.1
794
.2
m/z50 100 150 200 250 300 350 400 450
Norm.
0
20
40
60
80
100
*MSD1 SPC, time=0.194:0.268 of PT\09111203.D API-ES, Pos, Scan, 30
Max: 19513 272
.6 2
73.5
130
.1
306
.6 3
07.5
65.
2
346
.5
102
.2
384
.6
113
.5
434
.5
422
.5
450
.0
334
.9
288
.6 2
78.6
358
.5
344
.4
230
.1
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011
m/z500 550 600 650 700 750 800
Norm.
0
10
20
30
40
50
60
70
*MSD1 SPC, time=0.194:0.268 of PT\09111203.D API-ES, Pos, Scan, 30
Max: 19513
544
.2
607
.2 6
09.2
546
.2
513
.7
608
.2
545
.2
580
.2
593
.7
514
.3
551
.5
733
.2
692
.1
584
.2
598
.2
610
.2
794
.2
m/z900 950 1000 1050 1100 1150 1200 1250 1300
Norm.
0
2.5
5
7.5
10
12.5
15
17.5
*MSD1 SPC, time=0.194:0.268 of PT\09111203.D API-ES, Pos, Scan, 30
Max: 19513
108
9.4
109
1.4
909
.2
931
.3
125
6.3
Figure S6 – ESI-MS of 3.
N
NN
N
N
NH
N
NN
NN
N
N
N
N
NCu++
N
NN
N
N
NH
N
NN
NN
N
N
HN
N
NCu++ NO3
N
NN
N
N
NH
N
NN
NN
N
N
HN
N
N
N
NN
N
N
HN
N
N
N
NN
N
N
NH
N
N
Cu++ NO3
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Figure S7 – Molecular structure of compound 9, [Zn(TPM)2](CF3SO3)2. Symmetry operations to generate equivalent atoms: 1-x, -y, 2-z.
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Table S1. Crystal data and experimental details for 9. The structure determination was carried out on a crystal of poor quality and these data are preliminary.
Compound 7 Formula C22H20F6N12O6S2Zn M 791.99 T/ K 293(2) Crystal symmetry Triclinic Space group P-1 a/ Å 7.957(2) b/ Å 9.891(2) c/ Å 10.939(2) α/ ° 68.19(3) β/ ° 83.31(3) γ/ ° 82.96(3)
V/ Å3 790.9(3)
Z 1 Dc/ Mg m-3 1.663 μ(Mo-Kα)/ mm-1 1.002 F(000) 400 Crystal size/ mm 0.07 x 0.07 x 0.10 θ limits/ ° 2.40-21.86 Reflections collected 3488 Unique obs. reflections 1764 Goodness-of-fit-on F2 0.982
R1 (F)a, wR2 (F2)b 0.1522, 0.3184
Largest diff. peak and h l Å 3
0.658 and –0.767 a R1 = Σ||Fo|-|Fc||/Σ|Fo|.b wR2 = [Σw(Fo
2-Fc2)2/Σw(Fo
2)2]1/2 where w = 1/[σ2(Fo
2) + (aP)2 + bP] where
P = (Fo2 + Fc
2)/3. Table S2. Selected bond lengths (Å) and angles (deg) for 9. Zn-N(1) 2.12(2) Zn-N(5) 2.11(2) Zn-N(3) 2.21(2) S-O(1) 1.42 (2) S-O(3) 1.36(2) S-O(2) 1.41(2) S-C(10) 1.71(4) N(5)-Zn-N(5)#1 180.000(3) N(5)-Zn-N(1) 85.9(7) N(5)#1-Zn-N(1) 94.1(7) N(5)-Zn-N(3) 82.1(9) N(5)#1-Zn-N(3) 97.9(9) N(1)-Zn-N(3) 82.8(7) N(1)#1-Zn-N(3) 97.2(7) Symmetry code #1 = 1-x, -y, 2-z
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Figure S8 – Arbitrary view of the dication of 9 surrounded by ten triflate ions interacting with it through more or less weak “non-conventional” H-bonds (red dashed lines), all of the type C(Y)-H(Y)···O(X), pertaining to the triflate oxygen atoms and some pyrazolate or methinic hydrogens.
Figure S9 – Crystal packing of 9 viewed along the crystallographic a axis. The space filling representation evidences the small channels, running parallel to the same axis, having section dimensions of about. 2.7x1 Å, taking into account the appropriate vdW radii.
Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2011