Discrete spirobicyclic silicate anions with SiO2N2C, SiN2S2C and SiO4C frameworks

Article abstract of DOI:10.1080/10426500601015633

Bis(2-aminobenzoato)phenylsilicate (1), bis(2-aminothiophenoxy) phenylsilicate (2), and bis(2-hydroxybenzoato) phenylsilicate (3) anions were obtained as their triethylammonium salts from the reactions of phenylsilane with appropriate ligands in the presence of triethylamine. The compounds were characterized by IR, multinuclear (¹H, ¹³C, and ²⁹Si) NMR, and FAB mass spectral data. Th X-ray crystal structure of 1.CH₂Cl₂ revealed slightly distorted trigonal bipyramidal geometry around silicon. The spirobicyclic silicate anions are the first examples with silicon-heteroatom linkages having six-membered (1) and five-membered (2) rings on silicon. Copyright Taylor & Francis Group, LLC.

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Discrete Spirobicyclic Silicate
Anions with SiO2N2C, SiN2S2C
and SiO4C Frameworks
Suraj P. Narula a , Meenu Puri b , Neena Garg a
Jugal K. Puri a & Raj K. Chadha c
,
a Department of Chemistry , Panjab University ,
Chandigarh, India
b University Institute of Engineering and
Technology , Panjab University , Chandigarh, India
c Department of Chemistry , Scripps Research
Institute , La Jolla, California, USA
Published online: 30 Jan 2007.
To cite this article: Suraj P. Narula , Meenu Puri , Neena Garg , Jugal K. Puri & Raj
K. Chadha (2007) Discrete Spirobicyclic Silicate Anions with SiO2N2C, SiN2S2C and
SiO4C Frameworks, Phosphorus, Sulfur, and Silicon and the Related Elements, 182:3,
569-587, DOI: 10.1080/10426500601015633
To link to this article: http://dx.doi.org/10.1080/10426500601015633
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Phosphorus, Sulfur, and Silicon, 182:569–587, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500601015633
Discrete Spirobicyclic Silicate Anions with SiO2N2C,
SiN2S2C and SiO4C Frameworks
Suraj P. Narula
Department of Chemistry, Panjab University, Chandigarh, India
Meenu Puri
University Institute of Engineering and Technology, Panjab University,
Chandigarh, India
Neena Garg
Jugal K. Puri
Department of Chemistry, Panjab University, Chandigarh, India
Raj K. Chadha
Department of Chemistry, Scripps Research Institute, La Jolla,
California, USA
Bis(2-aminobenzoato)phenylsilicate (1), bis(2-aminothiophenoxy)phenylsilicate (2),
and bis(2-hydroxybenzoato) phenylsilicate (3) anions were obtained as their triethy-
lammonium salts from the reactions of phenylsilane with appropriate ligands in the
presence of triethylamine. The compounds were characterized by IR, multinuclear
1
13
29
( H, C, and Si) NMR, and FAB mass spectral data. Th X-ray crystal structure
of 1.CH Cl revealed slightly distorted trigonal bipyramidal geometry around sili-
2
2
con. The spirobicyclic silicate anions are the first examples with silicon-heteroatom
linkages having six-membered (1) and five-membered (2) rings on silicon.
Keywords Discrete silicate; heteroatom; spirobicyclic
INTRODUCTION
Ionic complexes have assumed a special place among hypervalent sil-
icon compounds. Besides unique chemical features,1 developments re-
lating to new structural varieties of these silicates have also come to
light.2−5 Cationic complexes were known for a long time,6 although
Received March 29, 2006; accepted July 27, 2006.
The authors are thankful to Prof. M. F. Lappert, FRS, University of Sussex, Brighton,
U.K., for 29Si NMR spectra and Dr. K. C. Molloy, University of Bath, U.K., for FAB mass
spectra. Financial assistance from CSIR, India, is gratefully acknowledged.
Address correspondence to Meenu, University Institute of Engineering and Technol-
ogy, Panjab University, Chandigarh 160014, India. E-mail: meenuchem@yahoo.com
569

570
S. P. Narula et al.
the authors have demonstrated their use as precursors to hexacoordi-
nate bicyclic silicate dianions.7 The authors have reported earlier penta
and hexacoordinate silicate anions with SiO4N and SiO4N2 skeletons,
respectively, where silicon–nitrogen linkage was derived from acyclic
substituent(s).8 Although Pframmer and Tacke,9 Bertermann et al.,10
and Seiler et al.11 have reported many zwitterionic silicates with nitro-
gen and sulfur atoms in a spirosilicate framework, discrete silicate an-
ions with silicon-heteroatom linkages are not known. The present com-
munication reports the preparation and structure elucidation of penta-
coordinate silicates with a SiO2N2C, SiS2N2C, and SiO4C framework.
These complexes incorporate six-membered (1, 3) and five-membered
(2) ring systems on silicon atoms. The details are reported in this article.
RESULTS AND DISCUSSION
Compounds 1–3 were prepared by a single step reaction between
phenylsilane and an appropriate ligand in the presence of triethyl
amine at 0 to 10◦C (Scheme 1).
Ph
X
Y
X
Y
XH
YH
CH3CN
[HNEt3]+
Si
+ 3 H2
+
NEt3
PhSiH3
+
2
0–10oC, 3–5 h
Y= NH, X= C(O)O (1)
Y= NH, X= S
( )
2
Y= O, X= C(O)O
(3)
SCHEME 1
Effervescence on the addition of phenylsilane to the other reactants
indicated progress of the reaction and the evolution of hydrogen. 1 was
precipitated out from the reaction mixture, while 2 and 3 were isolated
after work-up of the reaction mixture using diethyl ether. All these
complexes were soluble in dichloromethane, chloroform, methanol, and
DMSO. Elemental analyses and molar conductance (see the Experimen-
tal section) of these compounds suggest the composition and formula
as assigned.
Spectral Studies
IR spectra of 1 and 3 revealed νCO (carboxylate) absorptions due to
benzoate groups at 1641 and 1634 cm−1, respectively. These absorptions
were shifted by 40–50 cm−1 toward lower frequency compared to those

Spirobicyclic Silicate Anions
571
of free acids, suggesting attachment of the ligands to silicon. νNH vi-
brations were observed at 3110 cm−1 in spectra of 1 and 2. νSi-Ph ab-
sorption was identified at 1119–1130 cm−1 in the spectra of all three
complexes. Absorption bands at 2703–2657 cm−1 were due to quart-
ernization of nitrogen in a triethyl ammonium cation.
1H NMR spectra of 1–3 depicted signals for aromatic and triethyl
ammonium protons in a desired intensity ratioed as expected for the
composition assigned (see the Experimental section). 13C NMR spec-
tra revealed signals due to phenyl and bidentate ligands besides those
due to the cation (see the Experimental section). Only one set of signals
was observed for the two substituents (C6H4XY) forming the spirocyclic
framework around silicon, thus suggesting their equivalent position.
29Si NMR spectra revealed a sharp single peak in each case at −112.5,
−49.8, and −121.0 ppm for 1, 2, and 3, respectively, and are sugges-
tive of pentacoordination around the silicon atom. These chemical shift
values are within the range for the respective complexes.
Attempts to obtain good quality crystals for 1 were successful, while
for 2 and 3, attempts failed. FAB mass spectral data have been fre-
quently used for the elucidation of bonding in ionic compounds. Selected
FAB mass spectral data of 1–3 are given in Table I. The anion of 1 was
identified from a peak at m/z 375 in the negative ion mode. Similarly,
the spectra of 2 and 3 exhibited peaks in the negative ion mode corre-
sponding to an anion/anionic cluster/fragmented anion. The spectra of
1–3 in positive ion mode depicted a peak at m/z 102, thus identifying
cation [HNEt3]+ in each case.
X-ray Crystal Structure of 1.CH2Cl2
X-ray quality crystals were grown by refrigerating a solution of 1 in
dry CH2Cl2. The atomic coordinates, selected bond lengths, and bond
angles are recorded in Tables II and III, respectively. The crystal system
TABLE I Selected FAB Mass Spectral Data (in 3-nitrobenzyl alcohol
[NBA]) of 1–3
Positive Ion Mode
Assignment
Negative Ion Mode
Assignment
Compound (m/z)
(m/z)
1
102 [HNEt3]+
375 [(C6H4(COO)NH)2SiPh]−
528 [(C6H4(COO)NH)2SiPh]−.NBA
351 [(C6H4(S)NH)2SiPh]−
255 [HNEt3]+. NBA
102 [HNEt3]+
2
3
228 [HNEt3]+.C6H4NH2SH 459 [(C6H4(S)NH)2SiPh]−.C6H5CH2OH
504 [(C6H4(S)NH)2SiPh]−.NBA
102 [HNEt3]+
581 [(C6H4(COO)O)2SiPh]−.2NBA

572
S. P. Narula et al.
TABLE II Crystal Data and Structure Refinement
Empirical formula
Formula weight
Temperature
C27H33Cl2N3O4Si
562.55
173 (2 ) K
˚
Wavelength
0.71073 A
Crystal system
Space group
Triclinic
P1(No. 2, Cil)
◦
˚
˚
˚
Unit cell dimensions
a = 11.259 (2) A; alpha = 77.506 (4) ;
◦
b = 11.473 (2) A; beta = 76.646 (4) ;
◦
c = 23.589 (5) A; gamma = 70.883 (4) ;
3
˚
Volume, z
2768.3 (10) A , 4
Density (calculated)
Absorption coefficient
F (000)
1.350 Mg/m3
0.316 mm−1
1184
Crystal size
θ range for data collection
Limiting indices
0.36 × 0.32 × 0.24 mm
0.90–25.00◦
−13 ≤ h ≤ 13, −13 ≤ k ≤ 13, −28 ≤ l ≤ 27
20,545
Reflections collected
Independent reflections
Completeness to θ = 25.000
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [1 > 2σ(I)]
R indices (all data)
9717 (Rint = 0.0364)
99.5%
Empirical
0.9280 and 0.8948
Full-matrix least-squares on F2
9717/0/740
1.126
R l = 0.0630, wR2 = 0.1472
R l = 0.0788, wR2 = 0.1551
−3
˚
0.415 and -0.317 e A
Largest diff. peak and hole
R l = (ꢀ ꢀꢀFo ꢀ − ꢀ Fc ꢀ ꢀ / ꢀ ꢀ Foꢀ), wR2 = ꢀw (F20 -Fc2)2 / ꢀw[(F02)2]1/2
s = [ꢀw(F20 -F2c )2 / (n-p)]1/2
,
is triclinic with the P1(2Ci1) space group. The unit cell dimensions are
◦
˚
a = 11.259 (2), b = 11.473 (2), c = 23.589 (2) A, and α = 77.506 , β =
76.646(4)◦, γ =70.883 (4)◦ with Z = 4. The atomic labeling scheme is
shown in the ORTEP plot (Figure 1).
Figure 1 clearly depicts the presence of two similar but crystallo-
graphically independent anions with their cations Et3NH+ and a sol-
vent molecule (CH2Cl2) each in a unit cell. Thus, the compound seems
to exist as solvate 1.CH2Cl2 in the crystal. (For the sake of clarity, the
anions have been designated as A and B in the figure and data for
both the molecules that are given. A marginal difference in the bond
parameters of the two anions was observed, thus giving them a sep-
arate identity [Table III]). A silicon coordination polyhedron was ob-
served as a slightly distorted trigonal bipyramid with each of the axial
positions occupied by oxygen atoms. The two nitrogen atoms and the
phenyl group were at equatorial positions. Si N bond lengths in both

Spirobicyclic Silicate Anions
573
FIGURE 1 Crystal structure of 1.CH2Cl2 (ORTEP plot with probability level
30%), showing atomic labeling scheme. The two crystallographically inde-
pendent molecules presented in a single crystal are shown with the solvent
(CH2Cl2) molecules.
˚
anions fell in the range 1.730(3)–1.744(3) A, and all Si O bond lengths
◦
˚
were observed between 1.796(2) and 1.838(2) A. NSiN were 122.44(13)
and 125.24(15)◦, and NSiO fell in the range 85.71(12)◦–92.71(11)◦,
while OSiO were 179.05(11)◦ and 176.73(12)◦ (Table III). The bond
parameters are comparable to similar zwitterionic silicates incorpo-
rating five-membered rings around silicon.4 In spite of the presence
◦
˚
TABLE III Selected Bond Lengths (A) and Bond Angles ( ) of 1
Si (1A)-N (1A)
Si (1A)-N (2A)
1.730 (3)
1.744 (3)
Si (1B)-N (1B)
Si (1B)-N (2B)
1.742 (3)
1.732 (3)
Si (1A)-O (1A)
1.796 (2)
Si (1B)-O (1B)
1.809 (2)
Si (1A)-O (3A)
1.838 (2)
Si (1B)-O (3B)
1.804 (2)
Si (1A)-C (1A)
1.875 (3)
Si (1B)-C (1B)
1.876 (4)
N (1A)-Si (1A)-N (2A)
N (1A)-Si (1A)-O (1A)
N (1A)-Si (1A)-O (3A)
N (2A)-Si (1A)-O (1A)
N (2A)-Si (1A)-O (3A)
N (1A)-Si (1A)-C (1A)
N (2A)-Si (1A)-C (1A)
O (1A)-Si (1A)-O (3A)
O (1A)-Si (1A)-C (1A)
O (3A)-Si (1A)-C (1A)
122.44 (13)
92.71 (11)
86.47 (12)
88.39 (12)
91.64 (11)
120.18 (14)
117.29 (14)
179.05 (11)
91.73 (12)
89.10 (12)
N (1B)-Si (1B)-N (2B)
N (1B)-Si (1B)-O (1B)
N (1B)-Si (1B)-O (3B)
N (2B)-Si (1B)-O (1B)
N (2B)-Si (1B)-O (3B)
N (1B)-Si (1B)-C (1B)
N (2B)-Si (1B)-C (1B)
O (1B)-Si (1B)-O (3B)
O (1B)-Si (1B)-C (1B)
O (3B)-Si (1B)-C (1B)
125.24 (15)
91.59 (12)
85.71 (12)
88.06 (12)
91.99 (12)
116.58 (15)
118.17 (15)
176.73 (12)
91.42 (13)
91.44 (13)

574
S. P. Narula et al.
TABLE IV Analysis of Potential Hydrogen Bonds
. . .
. . .
. . .
. . .
H A
No.
Donor H. . . Acceptor
(ARU)
D
H
H
A
D
A
D
. . .
1
2
3
4
5
6
7
N(1A)—H(1A) O(3B)
(2666.02)
(2775.02)
(2566.01)
(2666.02)
(2666.01)
(Intra)
0.7961
0.8065
0.8600
0.9300
0.9700
0.9700
0.9700
2.3962
2.2553
2.4614
2.5853
2.3650
2.3939
2.5440
3.1627
3.0321
3.2284
3.3901
3.2324
3.0088
3.3076
161.95
161.86
148.87
145.10
148.57
120.85
135.63
. . .
N(1B)—H(1B) O(4B)
. . .
N(2A)—H(2A) O(3B)
. . .
C(6A)—H(6A) O(3B)
. . .
C(21A)—H(21A) O(2B)
. . .
C(21B)—H(21C) O(1B)
. . .
C(21B)—H(21D) O(3B)
(Intra)
Equivalent position code: (2556) = −x, 1−y, 1−z; (2666) = 1−x, 1−y, 1−z; (2775) =
2−x, 2−y, −z;
. . .
For C—H acceptor interactions, see: Th. Steiner, Cryst. Rev., 6, 1 (1996).
For H-bond classification, see G. A. Jeffery, H. Maluszynska, and J. Mitra, Int. J. Biol.
Macromol., 7, 336 (1985).
of six-membered rings around silicon in 1, bond angles were more to-
ward those for ideal trigonal bipyramidal (tbp) geometry [ N Si O
91.64(11), N Si C 120.18(14), O Si O 179.05 (11), O Si C 91.73
(12), O Si C 89.10 (12)]. The widest O Si O reported for such zwit-
terions was 177.01◦.4 Bond lengths represented five normal covalent
bonds thus justifying the formation of a stable discrete pentacoordi-
nate anion with SiO2N2C framework incorporating six-membered rings
around silicon. Additional geometric data revealed the involvement of
all the oxygen atoms of anion B in inter- and intramolecular hydrogen
bonding (Table IV).
Conclusion
The X-ray crystal structure of 1 and spectral data of 1, 2, and 3 estab-
lished the formation of new discrete silicate anions incorporating un-
symmetrical ligands with different heteroatoms and ring sizes around
a silicon atom.
EXPERIMENTAL
Materials and Analyses
All operations were carried out under a dry nitrogen atmosphere
using an all-glass vacuum line. Solvents were dried by refluxing over
P2O5 (acetonitrile, dichloromethane) or sodium metal (diethyl ether)
and were freshly distilled prior to use. Triethyl amine (Merck) was
purified by being refluxed over KOH pallets followed by distillation
under nitrogen. PhSiCl3 (Aldrich) and LiAlH4(Aldrich) were used
as received. PhSiH3 was prepared by the reaction of PhSiCl3 with

Spirobicyclic Silicate Anions
575
LiAlH4in diethylether. o-aminobenzoic acid, o-aminothiophenol, and
salicylic acid (o-hydroxybenzoic acid) (Qualigens) were purified by
conventional procedures.
Infrared spectra were routinely obtained as thin films or Nujol mulls
using KBr plates on FTIR model RX-I. 1H and 13C NMR were recorded
on a Bruker 300 Mz instrument, while 29Si NMR spectra were taken on
a Bruker (AMX 500) or Jeol 300 MHz instrument. FAB mass spectra
were obtained on MAT 95 of a finniganan MAT spectrometer using a
3-nitrobenzyl alcohol (NBA) matrix. C, H, and N analyses were carried
out on a Perkin-Elmer Model 2400 CHN elemental analyzer, while Si
content was estimated gravimetrically.
X-ray Crystallography
A colorless, block-shaped crystal (0.24 × 0.32 × 0.36 mm) was mounted
with the largest dimension, and data were collected with a Bruker
SMART APEX diffractometer equipped with a molybdenum sealed tube
and a highly oriented graphite monochromator. Frame data were ac-
quired with SMART software using a three-axis stage. The chi axis on
this stage was fixed at 54.74◦, and the CCD detector was maintained
at −40◦C. Cell constants were determined from 1200 10s frames at the
detector resolution of 512 × 512 pixels. A total of 1800 frames were
collected in three sets. The frames were then processed on an IBM-
compatible PC using SAINT+ software to give an hkl file corrected by
Lp/decay and absorption. There were no systematic absences in the
data. Therefore, the space group was assumed and later confirmed by
successful refinement of the structure. The structure was solved by
direct methods using SHELXTL-PC. All non-hydrogen atoms were re-
fined anisotropically by the full-matrix least-squares method. Hydrogen
atoms were included in the ideal positions with fixed isotropic U values
equal to 1.2 times that of the atom they were attached to. There was
no evidence of secondary extinction; therefore it was not applied for. All
calculations were done using SMART (data collection), SAINT+ (data
reduction), SADABS (absorption correction), and SHELTX-PC.13
Preparations
Triethylammonium bis(aminobenzoato)phenylsilicate(1)
PhSiH3 (0.7 g, 0.8 mL, 6.4 mmol) was added dropwise to a solution
of aminobenzoic acid (1.7 g, 12.8 mmol) and triethyl amine (0.9 mL,
6.4 mmol) in acetonitrile (35 mL) at 0◦C. Effervescence started after
the complete addition of PhSiH3, and a white solid was precipitated
out. The solution was stirred for 3 h while maintaining the temper-
ature of reactants between 0–10◦C. The solution was concentrated

576
S. P. Narula et al.
to 70% of its volume. The solid was filtered under reduced pressure,
washed first with cold acetonitrile and then with diethylether, and
dried under vacuum. Yield: 2.0 g (68%). M.p.: 98◦C. M (ꢁ−1 cm2mol−1
,
CH3CN): 81.5. Anal. calcd. for C26H31N3O4Si: C, 65.40; H, 6.49; N, 8.80;
Si, 5.87. Found: C, 64.80; H, 6.02; N, 8.59; Si, 5.79. IR (Nujol, KBr,
cm−1): 3110 (νNH), 1638 (νC=O, carboxylate), 1120 (νSi-Ph). δ1H NMR
(CDCl3): 0.9 (t, 9H, CH3), 2.6 (q, 6H, NCH2), 7.1, 7.2, 7.4 (2H, 1H,
2H, d, t, t, phenyl ring), 6.6, 6.7, 7.2, 7.9 (2H, 2H, 2H, 2H, d, t, d, t,
aminobenzoate rings), 4.8 (br, NH). δ13C NMR (CDCl3): 8.2 (CH3, tri-
ethylammonium), 45.4 (NCH2, triethylammonium), 126.9 (C1 & C3/C5,
Ph), 130.8 (C4), 133.6 (C2/C6, Ph), 113.3 (C1, aminobenzoate), 116.3
(C3, aminobenzoate), 118.1 (C5, aminobenzoate), 131.4 (C6, aminoben-
zoate), 133.6 (C4, aminobenzoate), 150.2 (C2, aminobenzoate), 168.6
(COO, aminobenzoate). δ29Si NMR (CDCl3): −112.5 ppm.
Triethylammonium bis(2-aminothiophenoxy)phenylsilicate (2)
PhSiH3 (0.4 g, 0.5 mL, 4.0 mmol) was added dropwise to a solution of
aminothiophenol (1.0 g, 0.8 mL, 8.0 mmol) and triethyl amine (0.5 mL,
4.0 mmol) in acetonitrile (35 mL) at 0◦C. Effervescence started after
the complete addition of PhSiH3.The solution was stirred for 4 h while
maintaining the temperature of reactants between 0–10◦C. Thereafter,
the solvent was evaporated, and diethyl ether (25 mL) was added. A
white solid was precipitated out after stirring the reaction mixture for
5–6 h. The solid was filtered under reduced pressure, washed with di-
ethylether, and dried under vacuum to isolate 2 as a dirty white solid.
Yield: 1.08 g (60%). M.p.: 108◦C.
(ꢁ−1 cm2mol−1, CH3CN): 64.5.
M
Anal. calcd. for C24H31N3S2Si: C, 63.57; H, 6.84; N, 9.27; S, 14.12; Si,
6.18. Found: C, 63.20; H, 6.82; N, 9.19; S, 14.00; Si, 6.21. IR (Nujol,
KBr, cm−1): 3115 (νNH), 1120 (νSi-Ph), 761 (νC S). δ1H NMR (CDCl3):
1.3 (t, 9H, CH3), 2.8 (q, 6H, NCH2), 7.0, 7.2, 7.5 (d, t, t, 2H, 1H, 2H
phenyl ring), 6.8, 7.4, 7.8, 8.1 (2H, 2H, 2H, 2H, d, d, t, t, aminothio-
phenoxy rings), 4.4 (br, NH). δ13C NMR (CDCl3): 11.1 (CH3, triethy-
lammonium), 45.6 (NCH2, triethylammonium), 128.6 (C1, Ph), 128.9
(C3/C5, Ph), 130.8 (C4), 136.1 (C2/C6, Ph), 114.6 (C3, aminothiophe-
noxy), 116.8 (C4, aminothiophenoxy), 126.6 (C5, aminothiophenoxy),
133.9 (C6, aminothiophenoxy), 135.5 (C1, aminothiophenoxy), 149.2
(C2, aminothiophenoxy). δ29Si NMR (CDCl3): −49.8 ppm.
Triethylammonium bis(2-hydroxybenzoato)phenylsilicate (3)
PhSiH3 (0.5 g, 0.6 mL, 4.8 mmol) was added dropwise to a solu-
tion of o-hydroxybenzoic acid (1.3 g, 9.6 mmol) and triethyl amine
(0.6 mL, 4.8 mmol) in acetonitrile (40 mL) at 0–10◦C. Effervescence
started. The solution was stirred for 4 h at r.t. at 25◦C. Thereafter, the

Spirobicyclic Silicate Anions
577
solvent was evaporated, and diethyl ether (25 mL) was added. A white
solid was precipitated out. The reaction mixture was stirred for 5–
6 h. The solid obtained was filtered under reduced pressure, washed
with diethylether, and dried under vacuum. Yield: 1.49 g (65%). m.p.:
125◦C. M (ꢁ−1 cm2mol−1, CH3CN): 110. Anal. calcd. for C26H29NO6Si:
C, 65.10; H, 6.05; N, 2.90; Si, 5.84. Found: C, 64.61; H, 6.07; N, 3.13;
Si, 6.01. IR (Nujol, KBr, cm−1): 1634 (νC=O), 1113 (νSi-Ph), 1259, 1243
(νC O aromatic), 877 (νSi O). δ1H NMR (CDCl3): 1.1 (t, 9H, CH3),
3.0 (q, 6H, NCH2), 7.1, 7.2, 7.4 (d, t, t, 2H, 1H, 2H phenyl ring), 6.9,
7.9, 8.2, 8.4 (2H, 2H, 2H, 2H, t, t, d, d hydroxybenzoate rings), 4.6 (br,
NH). δ13C NMR (CDCl3): 8.2 (CH3, triethylammonium), 45.4 (NCH2, tri-
ethylammonium), 128.0 (C1, Ph), 129.6 (C3/C5, Ph), 130.4 (C4), 136.4
(C2/C6, Ph), 115.2 (C1, hydroxybenzoate), 116.6 (C3, hydroxybenzoate)
119.2 (C5, hydroxybenzoate), 130.1 (C6, hydroxybenzoate), 134.1 (C4,
hydroxybenzoate), 161.4 (C2, hydroxybenzoate), 173.1 (COO, hydroxy-
benzoate). δ29Si NMR (CDCl3): −121.0 ppm.
REFERENCES
[1] C. Chuit, R. J. P. Corriu, C. Reye, and J. C. Young, Chem. Rev., 93, 1371 (1993).
[2] R. R. Holmes, Chem. Rev., 96, 927 (1996).
[3] D. Kost and I. Kalikhman, In Chemistry of Organic Silicon Compounds, Z. Rapport
and Y. Apeloig, eds. Vol. 2, p. 1339 (John Wiley & Sons, Chichester, U.K., 1998).
[4] R. Tacke, M. Pulm, and B. Wagner, Adv. Organomet. Chem., 44, 221 (1999).
[5] D. Kost and I. Kalikhman, Adv. Organomet. Chem., 50, 1 (2001).
[6] D. Kummer and T. Seshadri, Chem. Ber., 110, 2355 (1977), and references cited
therein.
[7] (a) S. P. Narula, R. Shankar, M. Kumar, and Meenu, Inorg. Chem., 33, 2716 (1994);
(b) S. P. Narula, R. Shankar, Meenu, and R. D. Anand, Polyhedron, 18, 2055 (1999);
(c) S. P. Narula, M. Puri, N. Garg, and J. K. Puri, Main Group Metal Chemistry, 25,
655 (2001).
[8] (a) S. P. Narula, R. Shankar, M. Puri, and J. K. Puri, Phosphorus, Sulfur, and Silicon,
158, 1 (2000); (b) S. P. Narula, R. Shankar, and Meenu, Phosphorus, Sulfur, and
Silicon, 113, 237 (1996); (c) S. P. Narula, R. Shankar, Meenu, J. K. Puri, and R. D.
Anand, Main Gp. Metal Chem., 23, 405 (2000).
[9] E. Breitmaier and W. Voelter, Carbon-13 NMR spectroscopy, 3rd ed., p. 261, (VCH,
Weinheim, Germany, 1987).
[10] (a) B. Pframmer and R. Tacke, Eu. J. Inorg. Chem., 415 (1998); [Au – Pls. provide
vol. no.] (b) D. Kost, I. Kalikhman, S. Krivonos, R. Bertermann, C. Burschka, R. E.
Neugebauer, et al., Organometallics, 10, 1083 (2000).
[11] R. Bertermann, A. Biller, M. Kaupp, M. Penka, O. Seiler, and R. Tacke,
Organometallics, 22, 4104 (2003).
[12] O. Seiler, M. Buttner, M. Penka, and R. Tacke, Organometallics, 24, 6059 (2005).
[13] (a) SMART (Version 5.624), (Bruker X-ray Analytical Instruments, Madison, WI,
1995), (b) SAINT+ (Version 5.6), (Bruker X-ray Analytical Instruments, Madison,
WI, 1995); (c) G. M. Sheldrick, SADABS (Version 2.03), (Bruker X-ray Analytical
Instruments, Inc. Madison, WI, 1999); (d) G. M. Sheldrick, SHELXTL-PC (Version
6.0), (Bruker X-ray Analytical Instruments, Madison, WI, 1990).

578
S. P. Narula et al.
SUPPLEMENTARY TABLE I Torsional Angles [◦]
N(1A)-Si(1A)-O(1A)-C(7A)
O(3A)-Si(1A)-O(1A)-C(7A)
N(1A)-Si(1A)-O(3A)-C(14A)
O(1A)-Si(1A)-O(3A)-C(14A)
N(2A)-Si(1A)-N(1A)-C(9A)
O(3A)-Si(1A)-N(1A)-C(9A)
N(1A)-Si(1A)-N(2A)-C(16A)
O(3A)-Si(1A)-N(2A)-C(16A)
N(1A)-Si(1A)-C(1A)-C(2A)
O(1A)-Si(1A)-C(1A)-C(2A)
N(1A)-Si(1A)-C(1A)-C(6A)
O(1A)-Si(1A)-C(1A)-C(6A)
C(6A)-C(1A)-C(2A)-C(3A)
C(1A)-C(2A)-C(3A)-C(4A)
C(3A)-C(4A)-C(5A)-C(6A)
C(2A)-C(1A)-C(6A)-C(5A)
Si(1A)-O(1A)-C(7A)-O(2A)
O(2A)-C(7A)-C(8A)-C(9A)
O(2A)-C(7A)-C(8A)-C(13A)
C(13A)-C(8A)-C(9A)-N(1A)
C(13A)-C(8A)-C(9A)-C(10A)
N(1A)-C(9A)-C(10A)-C(11A)
C(9A)-C(10A)-C(11A)-C(12A)
C(11A)-C(12A)-C(13A)-C(8A)
C(7A)-C(8A)-C(13A)-C(12A)
Si(1A)-O(3A)-C(14A)-C(15A)
O(3A)-C(14A)-C(15A)-C(20A)
O(3A)-C(14A)-C(15A)-C(16A)
Si(1A)-N(2A)-C(16A)-C(15A)
C(14A)-C(15A)-C(16A)-C(2A)
C(14A)-C(15A)-C(16A)-C(17A)
C(15A)-C(16A)-C(17A)-C(18A)
C(17A)-C(18A)-C(19A)-C(20A)
C(16A)-C(15A)-C(20A)-C(19A)
N(2B)-Si(1B)-O(1B)-C(7B)
O(3B)-Si(1B)-O(1B)-C(7B)
N(2B)-Si(1B)-O(3B)-C(14B)
O(1B)-Si(1B)-O(3B)-C(14B)
N(2B)-Si(1B)-N(1B)-C(9B)
O(1B)-Si(1B)-N(1B)-C(9B)
N(1B)-Si(1B)-N(2B)-C(16B)
O(1B)-Si(1B)-N(2B)-C(16B)
N(2B)-Si(1B)-C(1B)-C(6B)
O(3B)-Si(1B)-C(1B)-C(6B)
N(2B)-Si(1B)-C(1B)-C(2B)
O(3B)-Si(1B)-C(1B)-C(2B)
C(6B)-C(1B)-C(2B)-C(3B)
C(1B)-C(2B)-C(3B)-C(4B)
C(3B)-C(4B)-C(5B)-C(6B)
11.9(3)
43(7)
113.7(3)
83(7)
−94.7(3)
175.6(3)
−76.1(3)
10.7(3)
164.1(2)
−101.8(3)
−13.8(3)
80.4(3)
N(2A)-Si(1A)-O(1A)-C(7A)
C(1A)-Si(1A)-O(1A)-C(7A)
N(2A)-Si(1A)-O(3A)-C(14A)
C(1A)-Si(1A)-O(3A)-C(14A)
O(1A)-Si(1A)-N(1A)-C(9A)
C(1A)-Si(1A)-N(1A)-C(9A)
O(1A)-Si(1A)-N(2A)-C(16A)
C(1A)-Si(1A)-N(2A)-C(16A)
N(2A)-Si(1A)-C(1A)-C(2A)
O(3A)-Si(1A)-C(1A)-C(2A)
N(2A)-Si(1A)-C(1A)-C(6A)
O(3A)-Si(1A)-C(1A)-C(6A)
Si(1A)-C(1A)-C(2A)-C(3A)
C(2A)-C(3A)-C(4A)-C(5A)
C(4A)-C(5A)-C(6A)-C(1A)
Si(1A)-C(1A)-C(6A)-C(5A)
Si(1A)-O(1A)-C(7A)-C(8A)
O(1A)-C(7A)-C(8A)-C(9A)
O(1A)-C(7A)-C(8A)-C(13A)
C(7A)-C(8A)-C(9A)-N(1A)
C(7A)-C(8A)-C(9A)-C(10A)
C(8A)-C(9A)-C(10A)-C(11A)
134.3(3)
−108.4(3)
−8.7(3)
−126.0(3)
−4.9(3)
88.7(3)
−168.3(3)
100.5(3)
−12.7(3)
78.7(3)
169.5(3)
−99.2(3)
−178.0(3)
−0.7(6)
0.8(6)
177.1(3)
−9.7(4)
−1.8(4)
−179.2(3)
7.6(5)
−171.7(3)
−5.2(5)
3.2(6)
−1.9(5)
−178.5(2)
5.6(5)
−175.0(3)
171.0(3)
178.4(3)
−0.8(5)
0.0(5)
0.7(6)
−0.1(6)
−0.8(5)
172.4(2)
176.0(3)
−1.4(5)
−175.1(3)
5.7(5)
175.6(3)
0.8(5) C(10A)-C(11A)-C(12A)-C(13A)
−2.6(6)
175.5(3)
3.3(5)
C(9A)-C(8A)-C(13A)-C(12A)
Si(1A)-O(3A)-C(14A)-O(4A)
O(4A)-C(14A)-C(15A)-C(20A)
O(4A)-C(14A)-C(15A)-C(16A)
Si(1A)-N(2A)-C(16A)-C(17A)
−176.2(3)
3.2(5)
−8.2(5) C(20A)-C(15A)-C(16A)-N(2A)
−1.0(5) C(20A)-C(15A)-C(16A)-C(17A)
179.8(3) N(2A)-C(16A)-C(17A)-C(18A) −177.7(3)
1.5(5) C(16A)-C(17A)-C(18A)-C(19A)
0.8(6) C(18A)-C(19A)-C(20A)-C(15A)
0.1(5) C(14A)-O(15A)-C(20A)-O(19A)
−1.6(6)
−0.1(5)
179.5(3)
−5.7(3)
111.0(3)
−149.4(3)
94.1(3)
176.2(3)
−94.3(3)
12.2(3)
−80.5(3)
−161.2(3)
106.3(3)
17.2(4)
−75.3(3)
−176.7(3)
2.1(7)
−130.9(3)
N(1B)-Si(1B)-O(1B)-C(7B)
C(1B)-Si(1B)-O(1B)-C(7B)
N(1B)-Si(1B)-O(3B)-C(14B)
C(1B)-Si(1B)-O(3B)-C(14B)
O(3B)-Si(1B)-N(1B)-C(9B)
C(1B)-Si(1B)-N(1B)-C(9B)
O(3B)-Si(1B)-N(2B)-C(16B)
C(1B)-Si(1B)-N(2B)-C(16B)
N(1B)-Si(1B)-C(1B)-C(6B)
O(1B)-Si(1B)-C(1B)-C(6B)
N(1B)-Si(1B)-C(1B)-C(2B)
O(1B)-Si(1B)-C(1B)-C(2B)
Si(1B)-C(1B)-C(2B)-C(3B)
C(2B)-C(3B)-C(4B)-C(5B)
C(2B)-C(1B)-C(6B)-C(5B)
−40(2)
−24.2(3)
−115(2)
86.8(3)
−1.9(3)
98.3(3)
−171.1(3)
17.8(4)
−75.2(3)
−163.8(3)
103.1(3)
1.7(6)
−2.9(7)
−0.4(7)
0.0(6)

Spirobicyclic Silicate Anions
579
SUPPLEMENTARY TABLE I Torsional Angles [◦] (Continued)
Si(1B)-C(1B)-C(6B)-C(5B)
178.4(3)
−168.0(2)
−8.8(5)
C(4B)-C(5B)-C(6B)-C(1B)
Si(1B)-O(1B)-C(7B)-C(8B)
O(1B)-C(7B)-C(8B)-C(13B)
O(1B)-C(7B)-C(8B)-C(9B)
Si(1B)-N(1B)-C(9B)-C(8B)
C(7B)-C(8B)-C(9B)-N(1B)
C(7B)-C(8B)-C(9B)-C(10B)
C(8B)-C(9B)-C(10B)-C(11B)
−0.7(6)
10.3(5)
173.0(3)
−7.1(5)
3.7(5)
Si(1B)-O(1B)-C(7B)-O(2B)
O(2B)-C(7B)-C(8B)-C(13B)
O(2B)-C(7B)-C(8B)-C(9B)
171.1(3)
−176.4(3)
−179.2(3)
0.9(5)
Si(1B)-N(1B)-C(9B)-C(10B)
C(13B)-C(8B)-C(9B)-C(1B)
C(13B)-C(8B)-C(9B)-C(10B)
N(1B)-C(9B)-C(10B)-C(11B)
C(9B)-C(10B)-C(11B)-C(12B)
C(11B)-C(12B)-C(13B)-C(8B)
C(7B)-C(8B)-C(13B)-C(12B)
Si(1B)-C(3B)-C(14B)-C(15B)
O(3B)-C(14B)-C(15B)-C(20B)
O(3B)-C(14B)-C(15B)-C(16B)
Si(1B)-N(2B)-C(16B)-C(15B)
C(14B)-C(15B)-C(16B)-N(2B)
C(14B)-C(15B)-C(16B)-C(17B)
C(15B)-C(16B)-C(17B)-C(18B)
C(17B)-C(18B)-C(19B)-C(20B)
C(16B)-C(15B)-C(20B)-N(19B)
C(25A)-N(3A)-C(21A)-C(22A)
C(21A)-N(3A)-C(23A)-C(24A)
C(21A)-N(3A)-C(25A)-C(26A)
C(23B)-N(3B)-C(21B)-N(22B)
C(21B)-N(3B)-C(23B)-C(24B)
C(21B)-N(3B)-C(25B)-C(26B)
C(25B)-N(3B)-C(21B)-C(22B)
C(25B)-N(3B)-C(23B)-C(24B)
C(21B)-N(3B)-C(25B)-C(26B)
0.9(5)
−179.0(3)
−1.3(5)
0.8(6)
178.8(3)
0.5(6) C(10B)-C(11B)-C(12B)-C(13B)
−1.2(6)
C(9B)-C(8B)-C(13B)-C(12B)
Si(1B)-O(3B)-C(14B)-O(4B)
0.3(5)
−179.8(3)
−161.6(2)
21.6(5) O(4B)-C(14B)-C(15B)-C(20B)
−2.2(5)
174.5(3) O(4B)-C(14B)-C(15B)-C(16B) −178.9(3)
−2.1(5)
Si(1B)-N(2B)-C(16B)-C(17B)
178.7(3)
176.1(3)
−3.4(5)
−0.8(5) C(20B)-C(15B)-C(16B)-N(2B)
−7.3(5) C(20B)-C(15B)-C(16B)-C(17B)
173.2(3) N(2B)-C(16B)-C(17B)-C(18B) −175.5(3)
4.0(5) C(16B)-C(17B)-C(18B)-C(19B)
−1.9(6)
−1.1(6) C(18B)-C(19B)-C(20B)-C(15B)
1.7(6)
0.5(5) C(14B)-C(15B)-C(20B)-C(19B) −176.1(3)
62.7(4) C(23A)-N(3A)-C(21A)-C(22A)
−54.9(4) C(25A)-N(3A)-C(23A)-C(24A)
164.7(3) C(23A)-N(3A)-C(25A)-C(26A)
154.1(9) C(25B)-N(3B)-C(21B)-C(22B)
23.7(10) C(25B)-N(3B)-C(23B)-C(24B)
146.8(7) C(23B)-N(3B)-C(25B)-C(26B)
171.4(17) C(23B)-N(3B)-C(21B)-C(22B)
62.7(15) C(21B)-N(3B)-C(23B)-C(24B)
24.1(17) C(23B)-N(3B)-C(25B)-C(26B)
−64.8(4)
177.5(3)
−66.7(4)
5.1(13)
172.5(7)
−3.8(10)
56.5(19)
177.1(13)
137.8(13)

580
S. P. Narula et al.
SUPPLEMENTARY TABLE II Anisotropic Displacement Parameters
˚
[A2x103]. The Anisotropic Displacement Factor Exponent Takes the
Form: −2p2[(h2a* 2U11 + k2b* 2U22 + I2c* 2U33 + 2hka*b*U12 +
2hla*c*U13 + 2klb*c*U23]
U11
U22
U33
U23
U13
U12
−5(1)
Si(1A)
O(1A)
O(2A)
O(3A)
O(4A)
N(1A)
N(2A)
C(1A)
C(2A)
C(3A)
C(4A)
C(5A)
C(6A)
C(7A)
C(12A)
C(13A)
C(14A)
C(15A)
C(16A)
C(17A)
C(18A)
C(19A)
C(20A)
Si(1B)
O(1B)
O(2B)
O(3B)
O(4B)
N(1B)
N(2B)
C(1B)
C(2B)
C(3B)
C(4B)
C(7B)
C(8B)
C(9B)
C(10B)
C(11B)
C(12B)
C(13B)
C(14B)
C(15B)
C(16B)
23(1)
23(1)
36(1)
32(1)
49(1)
28(1)
34(1)
30(2)
30(2)
26(2)
46(2)
49(2)
31(2)
31(2)
25(2)
31(2)
22(2)
21(2)
20(2)
34(2)
41(2)
42(2)
31(2)
26(1)
32(1)
47(1)
28(1)
38(1)
31(1)
27(1)
34(2)
40(2)
42(2)
71(3)
27(2)
25(2)
20(2)
28(2)
29(2)
34(2)
34(2)
33(2)
33(2)
30(2)
16(1)
22(1)
29(1)
15(1)
21(1)
20(1)
19(1)
22(2)
28(2)
50(2)
46(2)
25(2)
22(2)
16(2)
50(2)
43(2)
20(2)
19(2)
19(2)
24(2)
21(2)
18(2)
26(2)
24(1)
25(1)
33(1)
28(1)
32(1)
28(2)
25(1)
33(2)
53(2)
87(3)
74(3)
27(2)
26(2)
34(2)
38(2)
39(2)
25(2)
32(2)
26(2)
26(2)
24(2)
17(1)
21(1)
20(1)
21(1)
22(1)
18(1)
16(1)
14(2)
29(2)
34(2)
30(2)
33(2)
27(2)
16(2)
36(2)
25(2)
23(2)
25(2)
24(2)
27(2)
32(2)
33(2)
24(2)
17(1)
21(1)
25(1)
20(1)
25(1)
19(1)
22(2)
19(2)
38(2)
53(3)
47(3)
24(2)
29(2)
25(2)
33(2)
53(2)
61(3)
39(2)
16(2)
18(2)
17(2)
−2(1)
−6(1)
−8(1)
−3(1)
−7(1)
−7(1)
−3(1)
−5(1)
−5(2)
−11(2)
−6(2)
2(2)
−4(1)
−4(1)
−5(1)
−4(1)
−5(1)
−5(1)
−6(1)
−2(1)
−10(2)
−6(2)
−1(2)
−8(2)
−6(1)
−1(1)
3(2)
−4(1)
−7(1)
−4(1)
−7(1)
−7(1)
−6(1)
−10(1)
−6(2)
−14(2)
−31(2)
−16(2)
−7(1)
−8(1)
−1(2)
−6(2)
−6(1)
−4(1)
−5(1)
−3(2)
−3(2)
−3(2)
−6(1)
−8(1)
−6(1)
−18(1)
−10(1)
−17(1)
−8(1)
−11(1)
−15(2)
−10(2)
−21(2)
−40(3)
−14(1)
−12(1)
−9(1)
−7(2)
−3(2)
−4(2)
−12(2)
−12(1)
−12(1)
−8(1)
−4(1)
1(1)
−14(2)
−12(2)
−5(1)
−3(1)
−2(1)
0(1)
0(2)
−3(1)
−3(1)
−1(1)
−14(2)
−13(2)
−9(2)
−2(1)
−3(1)
1(1)
−4(1)
−3(1)
−4(1)
−1(1)
−3(1)
−5(1)
−12(2)
−18(2)
−22(2)
−8(1)
−11(1)
−6(1)
−6(2)
−9(2)
−16(2)
−13(2)
−6(1)
−4(1)
−7(1)
5(2)
−5(2)
−7(1)
1(1)
4(1)
9(1)
5(1)
4(1)
3(1)
3(1)
3(1)
−10(2)
−17(3)
−12(2)
3(1)
0(1)
−5(2)
−7(2)
−19(2)
−8(2)
1(2)
−2(1)
−5(1)
−6(1)

Spirobicyclic Silicate Anions
581
SUPPLEMENTARY TABLE II Anisotropic Displacement Parameters
˚
[A2x103]. The Anisotropic Displacement Factor Exponent Takes the
Form: −2p2[(h2a∗ 2U11 + k2b∗ 2U22 + I2c∗ 2U33 + 2hka∗b∗U12 +
2hla∗c∗U13 + 2klb∗c∗U23] (Continued)
U11
U22
U33
U23
U13
U12
C(17B)
C(18B)
C(19B)
C(20B)
N(3A)
C(21A)
C(22A)
C(23A)
C(24A)
C(25A)
C(21B)
C(22B)
C(23B)
C(24B)
C(25B)
C(26B)
N(3B)
C(21B)
C(22B)
C(23B)
C(24B)
C(25B)
C(26B)
C1(1A)
C1(2A)
C(27A)
C1(1B)
C1(2B)
C(27B)
32(2)
30(2)
40(2)
39(2)
24(1)
26(2)
49(2)
32(2)
57(2)
31(2)
30(3)
48(4)
48(3)
58(5)
28(3)
44(4)
33(5)
82(10)
19(6)
59(8)
70(11)
49(7)
22(5)
52(1)
38(1)
37(1)
47(2)
38(1)
28(2)
26(2)
30(2)
25(2)
24(2)
23(1)
28(2)
33(2)
37(2)
45(2)
40(2)
47(4)
34(4)
36(3)
38(4)
34(3)
73(5)
36(5)
38(7)
56(10)
71(9)
57(12)
71(9)
49(7)
35(1)
28(1)
33(2)
57(1)
58(1)
46(2)
26(2)
37(2)
36(2)
29(2)
20(1)
30(2)
42(2)
21(2)
36(2)
27(2)
60(4)
90(7)
29(3)
36(5)
34(3)
64(5)
1(4)
42(8)
57(10)
43(7)
61(12)
70(9)
34(6)
51(1)
58(1)
52(2)
42(1)
40(1)
51(2)
−5(1)
−9(2)
−4(2)
−1(2)
−1(1)
−4(2)
−3(2)
−9(2)
−8(2)
−11(2)
8(3)
−10(4)
−4(3)
−10(4)
−4(3)
1(4)
−4(1)
−5(2)
−13(2)
−8(2)
−3(1)
−1(2)
−11(2)
1(1)
−7(2)
−4(2)
−5(3)
−12(5)
−8(3)
−4(4)
−5(2)
−5(4)
−4(3)
6(7)
−11(1)
−5(2)
−2(2)
−11(2)
−7(1)
−2(1)
−4(2)
−11(2)
−28(2)
−11(2)
−1(3)
−10(3)
−12(3)
−25(4)
−4(2)
−21(4)
−9(4)
−15(4)
4(6)
−13(7)
−6(6)
−4(7)
−29(7)
5(10)
−31(7)
−25(5)
−12(1)
−3(1)
8(2)
−15(1)
−13(1)
−11(2)
−20(6)
5(6)
−32(7)
−22(9)
−5(7)
−38(9)
−31(7)
−8(5)
−7(1)
−6(1)
−17(2)
0(1)
−2(5)
0(1)
−11(1)
−15(2)
−25(1)
−20(1)
−11(2)
−6(1)
−8(2)

582
S. P. Narula et al.
◦
˚
SUPPLEMENTARY TABLE III Bond Lengths [A] and Bond Angles [ ]
Si(lA)-N(lA)
Si(lA)-O(lA)
Si(lA)-C(lA)
O(2A)-C(7A)
O(4A)-C(14A)
N(2A)-C(16A)
C(lA)-C(6A)
C(3A)-C(4A)
C(5A)-C(6A)
1.730(3)
1.796(2)
1.875(3)
1.233(4)
1.244(4)
1.377(4)
1.400(4)
1.377(5)
1.384(5)
1.401(5)
1.400(5)
1.389(6)
1.474(4)
1.412(5)
1.375(5)
1.374(5)
1.742(3)
1.809(2)
1.298(4)
1.311(4)
1.383(4)
1.384(5)
1.384(6)
1.364(6)
1.472(5)
1.405(5)
1.374(5)
1.369(5)
1.388(5)
1.392(5)
1.386(5)
1.493(4)
1.510(4)
1.501(5)
1.425(8)
1.490(8)
1.517(12)
1.526(15)
1.553(17)
1.49(3)
Si(lA)-N(2A)
Si(lA)-O(3A)
O(lA)-C(7A)
O(3A)-C(14A)
N(lA)-C(9A)
C(lA)-C(2A)
C(2A)-C(3A)
C(4A)-C(5A)
C(7A)-C(8A)
C(8A)-C(13A)
C(10A)-C(11A
C(12A)-C(13A)
C(15A)-C(20A)
C(16A)-C(17A)
C(18A)-C(19A)
Si(lB)-N(2B)
Si(lB)-O(3B)
Si(lB)-C(lB)
O(2B)-C(7B)
1.744(3)
1.838(2)
1.299(4)
1.297(4)
1.378(4)
1.388(4)
1.390(5)
1.378(5)
1.475(5)
1.402(4)
1.365(5)
1.370(5)
1.396(4)
1.408(4)
1.391(5)
1.732(3)
1.804(2)
1.876(4)
1.239(4)
1.229(4)
1.382(4)
1.394(5)
1.360(7)
1.387(6)
1.403(5)
1.403(5)
1.397(6)
1.472(4)
1.413(5)
1.385(5)
1.374(5)
1.494(4)
1.509(5)
1.496(5)
1.451(8)
1.392(11)
1.420(9)
1.533(15)
1.323(19)
1.478(18)
1.750(4)
1.752(4)
92.71(11)
86.47(12)
179.05(11)
117.29(14)
89.10(12)
134.6(2)
130.5(2)
120.6(2)
C(8A)-C(9A)
C(9A)-C(10A)
C(11A)-C(12A)
C(14A)-C(15A)
C(15A)-C(16A)
C(17A)-C(18A)
C(19A)-C(20A)
Si(lB)-N(lB)
Si(lB)-O(lB)
O(lB)-C(7B)
O(3B)-C(14B)
N(lB)-C(9B)
C(1B)-C(6B)
O(4B)-C(14B)
N(2B)-C(16B)
C(1B)-C(2B)
C(3B)-C(4B)
C(5B)-C(6B)
C(2B)-C(3B)
C(4B)-C(5B)
C(7B)-C(8B)
C(8B)-C(9B)
C(8B)-C(13B)
C(9B)-C(10B)
C(11B)-C(12B)
C(14B)-C(15B)
C(15B)-C(16B)
C(17B)-C(18B)
C(19B)-C(20B)
N(3A)-C(25A)
C(21A)-C(22A)
C(25A)-C(26A)
N(3B)-C(23B)
C(21B)-C(22B)
C(25B)-C(26B)
N(3B)-C(21B)
C(21B)-C(22B)
C(25B)-C(26B)
C1(2A)-C(27A)
C1(2B)-C(27B)
N(1A)-Si(1A) O(lA)
N(1A)-Si(lA)-O(3A)
O(lA)-Si(lA)-O(3A)
N(2A)Si.(lA)-C(lA)
O(3A)-Si(lA)-C(lA)
C(14A)-O(3A)-Si(1A)
C(16A)-N(2A)-Si(1A)
C(2A)-C(1A)-Si(1A)
C(10BC(11B)
C(12B)-C(13B)
C(15B)-C(20B)
C(16B)-C(17B)
C(18B)-C(19B)
N(3A)-C(21A)
N(3A)-C(23A)
C(23A)-C(24A)
N(3B)-C(21B)
N(3B)-C(25B)
C(23B)-C(24B)
N(3B)-C(25B)
N(3B)-C(23B)
C(23B)(24B)
C1(1A)-C(27A)
Cl(lB)-C(27B)
N(lA)-Si(lA)-N(2A)
N(2A)-Si(1A)-O(1A)
N(2A)-Si(lA)-O(3A)
N(lA)-Si(lA)-C(1A)
O(lA)-Si(lA)-C(lA)
C(7A)-O(lA)-Si(lA)
C(9A)-N(1A)-Si(1A)
C(2A)-C(1A)-C(6A)
1.748(4)
1.770(4)
122.44(13)
88.39(12)
91.64(11)
120.18(14)
91.73(12)
134.8(2)
130.0(2)
117.1(3)

Spirobicyclic Silicate Anions
583
◦
˚
SUPPLEMENTARY TABLE III Bond Lengths [A] and Bond Angles [ ]
(Continued)
C(6A)-C(1A)-Si(1A)
C(4A)-C(3A)-C(2A)
C(4A)-C(5A)-C(6A)
O(2A)-C(7A)-O(lA)
O(lA)-C(7A)-C(8A)
122.3(2)
120.5(3)
120.3(3)
120.6(3)
117.2(3)
121.6(3)
122.5(3)
118.0(3)
120.5(3)
120.4(4)
121.8(3)
120.0(3)
120.9(3)
123.1(3)
121.2(3)
118.9(3)
125.24(15)
85.71(12)
91.59(12)
118.17(15)
91.44(13)
135.2(2)
131.4(2)
116..6(4)
121.3(3)
120.5(4)
119.8(4)
120.3(3)
118.0(3)
119.4(3)
120.0(3)
118.1(3)
120.4(4)
121.8(4)
122.0(3)
120.6(3)
120.8(3)
122.9(3)
120.9(3)
118.1(3)
111.8(3)
111.7(3)
114.2(3)
121.1(6)
116.0(5)
116.5(6)
107.1(9)
106.0(10)
108.7(14)
112.3(2)
C(lA)-C(2A)-C(3A)
C(5A)-C(4A)-C(3A)
C(5A)-C(6A)-C(lA)
121.3(3)
119.3(3)
121.5(3)
122.2(3)
119.9(3)
118.5(3)
119.4(3)
121.2(3)
119.7(3)
119.8(3)
118.4(3)
119.2(3)
119.4(3)
117.5(3)
120.9(3)
121.5(3)
91.99(12)
88.06(12)
176.73(12)
116.58(15)
91.42(13)
133.5(2)
129.7(2)
122.1(3)
121.2(4)
119.9(4)
122.0(4)
121.7(3)
119.4(3)
121.3(3)
121.9(3)
121.5(4)
118.9(3)
120.8(3)
117.1(3)
118.5(3)
119.9(3)
117.2(3)
121.5(3)
121.5(3)
113.6(3)
114.2(3)
113.8(3)
115.6(5)
130.3(7)
123.0(6)
107.8(9)
127.4(13)
130.1(12)
112.0(2)
O(2A)-C(7A)-C(8A)
C(9A)-C(8A)-C(13A)
C(13A)-C(8A)-C(7A)
N(lA)-C(9A)-C(10A)
C(11A)-C(10A)-C(9A)
C(13A)-C(12A)-C(11A)
O(4A)-C(14A)0(3A)
O(3A)-C(14A)-C(15A)
C(20A)-C(15A)-C(14A)
N(2A)-C(16A)-C(17A)
C(17A)-C(16A)-C(15A)
C(17A)-C(18A)-C(19A)
C(19A)-C(20A)-C(15A)
N(2B)-Si(lB)-O(3B)
N(2B)-Si(lB)-O(lB)
O(3B)-Si(lB)-O(lB)
N(lB)-Si(lB)-C(1B)
O(lB)-Si(lB)-C(lB)
C(14B)-O(3B)-Si(lB)
C(16B)-N(2B)-Si(lB)
C(6B)-C(lB)-Si(lB)
C(3B)-C(2B)-C(lB)
C(3B)-C(4B)-C(5B)
C(lB)-C(6B)-C(5B)
C(9A)-C(8A)-C(7A)
N(lA)-C(9A)-C(8A)
C(8A)-C(9A)-C(10A)
C(10A)-C(11A)-C(12A)
C(12A)-C(13A)-C(8A)
O(4A)-C(14A)-C(15A)
C(20A)-C(15A)-C(16A)
C(16A)-C(15A)-C(14A)
N(2A)-C(16A)-C(15A)
C(18A)-C(17A)-C(16A)
C(20A)-C(19A)-C(18A)
N(2B)-Si(lB)-N(lB)
N(lB)-Si(lB)-O(3B)
N(lB)-Si(lB)-O(lB)
N(2B)-Si(lB)-C(lB)
O(3B)-Si(lB)-C(lB)
C(7B)-O(lB)-Si(lB)
C(9B)-N(lB)-Si(lB)
C(6B)-C(lB)-C(2B)
C(2B)-C(lB)-Si(lB)
C(4B)-C(3B)-C(2B)
C(4B)-C(5B)-C(6B)
O(2B)-C(7B)-O(lB)
O(lB)-C(7B)-C(8B)
O(2B)-C(7B)-C(8B)
C(13B)-C(8B)-C(9B)
C(9B)-C(8B)-C(7B)
N(lB)-C(9B)-C(8B)
C(13B)-C(8B)-C(7B)
N(lB)-C(,9B)-C(10B)
C(10B)-C(9B)-C(8B)
C(10B)-C(11B)-C(12B)
C(12B)-C(13B)-C(8B)
O(4B)-C(14B)-C(15B)
C(20B)-C(15B)-C(16B)
C(16B)-C(15B)-C(14B)
N(2B)-C(16B)-C(15B)
C(18B)-C(17B)(16B)
C(20B)-C(19B)(18B)
C(21A)-N(3A)-C(25A)
C(25A)-N(3A)-C(23A)
C(24A)-C(23A)-N(3A)
C(21B)-N(3B)-C(23B)
C(23B)-N(3B)-C(25B)
N(3B)-C(23B)-C(24B)
C(25B)-N(3B)-C(21B)
C(21B)-N(3B)-C(23B)
C(24B)-C(23B)-N(3B)
C1(lA)-C(27A)-Cl(2A)
C(11B)-C(10B)-C(9B)
C(13B)-C(12B)-C(11B)
O(4B)-C(14B)-O(3B)
O(3B)-C(14B)-C(15B)
C(20B)-C(15B)-C(14B)
N(2B)-C(16B)-C(17B)
C(17B)-C(16B)-C(15B)
C(19B)-C(18B)-C(17B)
C(19B)-C(20B)-C(15B)
C(21A)-N(3A)-C(23A)
N(3A)-C(21A)-C(22A)
N(3A)-C(25A)-C(26A)
C(21B)-N(3B)-C(25B)
C(22B)-C(21B)-N(3B)
C(26B)-C(25B)-N(3B)
C(25B)-N(3B)-C(23B)
C(22B)-C(21B)-N(3B)
C(26B)-C(25B)-N(3B)
Cl(2B)-C(27B)-Cl(lB)

584
S. P. Narula et al.
SUPPLEMENTARY TABLE IV Atomic Coordinates (× 104) and
Equivalent Isotropic Displacement Parameters (× 103). U(eq) is
ꢀ ꢀ
∗
Defined as U(eq) = 1/3
Uij ai aj∗ ai aj
i
j
X
Y
Z
U(eq)
Si(1A)
O(1A)
O(2A)
O(3A)
O(4A)
N(1A)
N(2A)
C(1A)
C(2A)
C(3A)
C(4A)
C(5A)
C(6A)
C(7A)
C(8A)
C(9A)
C(10A)
C(11A)
C(12A)
C(13A)
C(14A)
C(15A)
C(16A)
C(17A)
C(18A)
C(19A)
C(20A)
Si(1B)
O(1B)
O(2B)
O(3B)
O(4B)
N(1B)
N(2B)
C(1B)
C(2B)
C(3B)
C(4B)
C(5B)
C(6B)
C(7B)
C(8B)
C(9B)
C(10B)
9187(1)
9629(2)
10653(2)
8760(2)
8131(2)
10750(2)
8499(2)
8134(3)
6819(3)
6022(3)
6522(4)
7825(4)
8620(3)
10661(3)
11932(3)
11845(3)
13025()
14120(3)
14090(3)
12963(3)
8299(3)
7953(3)
8058(3)
7706(3)
7303(3)
7201(3)
7527(3)
8325(1)
8604(2)
8383(2)
8042(2)
8223(2)
7325(3)
9963(2)
7540(3)
6306(4)
5705(4)
6329(4)
7542(4)
8136(4)
8160(3)
7363(3)
6970(3)
6194(3)
8420(1)
7700(2)
6486(2)
9162(2)
10526(2)
7988(2)
9827(2)
7405(3)
7868(3)
7140(4)
5938(4)
5457(3)
6175(3)
6938(3)
6682(3)
7261(3)
7098(3)
6319(4)
5678(4)
5875(3)
10305(3)
11307(3)
11027(3)
12034(3)
13247(3)
13517(3)
12548(3)
3027(1)
4178(2)
5903(2)
1941(2)
145(2)
3979(1)
3327(1)
2655(1)
4644(1)
5229(1)
4089(1)
3557(1)
4353(1)
4390(2)
4681(2)
4949(2)
4919(2)
4623(2)
3083(1)
3325(1)
3788(1)
3941(2)
3681(2)
3251(2)
3066(2)
4748(1)
4253(1)
3686(1)
3236(2)
3342(2)
3902(2)
4349(2)
969(1)
19(1)
22(1)
28(1)
23(1)
31(1)
22(1)
23(1)
22(1)
29(1)
35(1)
37(1)
36(1)
27(1)
22(1)
22(1)
21(1)
26(1)
36(1)
39(1)
34(1)
22(1)
22(1)
22(1)
29(1)
33(1)
32(1)
28(1)
23(1)
29(1)
36(1)
27(1)
32(1)
28(1)
26(1)
29(1)
43(1)
58(1)
57(1)
51(1)
38(1)
25(1)
25(1)
25(1)
33(1)
336(1)
−308(1)
1626(1)
2224(1)
1378(1)
929(1)
551(2)
439(2)
156(2)
4183(3)
2440(3)
2357(3)
2969(4)
2443(5)
1334(5)
714(4)
1221(3)
5380(3)
6085(3)
5470(3)
6202(3)
−42(2)
54(2)
351(2)
206(2)
681(2)
1242(2)
1671(2)

Spirobicyclic Silicate Anions
585
SUPPLEMENTARY TABLE IV Atomic Coordinates (× 104) and
Equivalent Isotropic Displacement Parameters (× 103). U(eq) is
ꢀ ꢀ
∗
Defined as U(eq) = 1/3
Uij ai aj∗ ai aj (Continued)
i
j
X
Y
Z
U(eq)
C(11B)
C(12B)
C(13B)
C(14B)
C(15B)
C(16B)
C(17B)
C(18B)
C(19B)
C(20B)
N(3A)
C(21A)
C(22A)
C(23A)
C(24A)
C(25A)
C(26A)
N(3B)
C(21B)
C(22B)
C(23B)
C(24B)
C(25B)
C(26B)
N(3B)
C(21B)
C(22B)
C(23B)
C(24B)
C(25B)
C(26B)
Cl(1A)
Cl(2A)
C(27A)
Cl(1B)
Cl(2B)
C(27B)
5844(3)
6249(3)
6986(3)
8727(3)
10120(3)
10675(3)
12002(3)
12739(3)
12190(3)
10881(3)
2049(2)
769(3)
7483(4)
8094(3)
7394(3)
845(3)
1554(2)
998(2)
571(2)
40(1)
40(1)
34(1)
24(1)
24(1)
23(1)
27(1)
33(1)
35(1)
31(1)
23(1)
30(1)
43(1)
30(1)
42(1)
32(1)
49(1)
46(2)
51(2)
58(3)
38(2)
41(3)
34(1)
62(2)
21(2)
60(4)
44(4)
54(4)
59(7)
60(4)
33(3)
49(1)
42(1)
40(1)
46(1)
43(1)
41(1)
1849(1)
1656(1)
1232(1)
1119(2)
1386(2)
1787(2)
1922(2)
3947(1)
4054(2)
3674(2)
3338(2)
3179(2)
4090(2)
4146(2)
1310(3)
1323(3)
1144(5)
1719(3)
1979(5)
1117(3)
1341(4)
1553(4)
1018(6)
918(8)
1583(6)
2077(11)
1417(6)
1011(5)
2935(1)
2974(1)
2735(2)
2489(1)
1862(1)
2016(2)
531(3)
1365(3)
1061(3)
−53(3)
−889(3)
−574(3)
1637(2)
2573(3)
3829(4)
1275(3)
809(4)
671(4)
2406(3)
1445(4)
3067(3)
4283(4)
1103(5)
−125(6)
−462(9)
1297(6)
131(9)
2210(5)
3369(6)
1034(10)
831(14)
−249(13)
93(12)
290(20)
2389(12)
3522(9)
5643(1)
749(1)
7234(3)
4851(1)
4041(1)
5341(3)
2040(3)
1013(4)
5697(5)
6593(6)
7879(8)
4535(5)
4084(9)
6214(5)
5665(8)
5852(10)
6882(12)
7739(17)
5099(13)
4030(20)
4991(13)
5242(11)
8739(1)
6276(1)
7879(3)
3021(1)
1559(1)
1880(4)
Structure occupancy factor is 0.65 and 0.35 respectively for atoms N(3B) to C(26B).

586
S. P. Narula et al.
SUPPLEMENTARY TABLE V Coordinates (× 104) and isotopic
2
3
˚
displacement parameters (A × 10 )
X
Y
Z
U(eq)
H(1AA)
H(2AA)
H(2AB)
H(3AA)
H(4AA)
H(5AA)
H(6AA)
H(10A)
H(11A)
H(12A)
H(13A)
H(17A)
H(18A)
H(19A)
H(20A)
H(1BA)
H(2BA)
H(2BB)
H(6BA)
H(10B)
H(11B)
H(12B)
H(13B)
H(17B)
H(18B)
H(19B)
H(20B)
H(3AA)
H(21A)
H(21B)
H(22A)
H(22B)
H(22C)
H(23A)
H(23B)
H(24A)
H(24B)
H(24C)
H(25A)
H(25B)
H(26A)
H(26B)
H(26C)
H(3BA)
H(21C)
10863
8421
6457
5126
5975
8178
9517
13063
14909
14848
12948
7747
7091
6912
7460
6986
10409
5870
8978
5904
5323
6016
7250
12406
13643
12703
10487
2000
563
8278
9760
8698
7474
5445
4629
5827
7538
6215
5105
5463
11873
13911
14356
12726
3897
2895
3761
776
5803
7957
8980
7806
1626
−249
−1657
−1125
917
2689
2236
4376
3724
4204
2009
616
450
1504
168
2383
2718
1322
728
315
5388
6285
4383
3203
4211
4696
5152
5103
4602
4231
3795
3085
2760
2853
3029
3973
4732
1734
679
26
27
34
42
45
43
32
31
43
47
40
35
40
38
33
33
31
52
45
40
48
48
41
33
39
41
37
28
36
36
52
52
52
36
36
51
51
51
38
38
58
58
58
55
61
558
419
2050
1853
918
191
856
1293
1963
2203
4211
4473
3983
3753
3257
3764
3046
3311
2813
3122
3497
4466
3778
4272
3763
4438
969
120
−204
896
1260
2519
3237
1808
675
1225
2742
3252
4879
4662
4102
1150
−578
1102

Spirobicyclic Silicate Anions
587
SUPPLEMENTARY TABLE V Coordinates (× 104) and isotopic
2
3
˚
displacement parameters (A × 10 ) (Continued)
X
Y
Z
U(eq)
H(21D)
H(22D)
H(22E)
H(22F)
H(23C)
H(23D)
H(24D)
H(24E)
H(24F)
H(25C)
H(25D)
H(26D)
H(26E)
H(26F)
H(3BA)
H(21C)
H(21D)
H(22D)
H(22E)
H(22F)
H(23C)
H(23D)
H(24D)
H(24E)
H(24F)
H(25C)
H(25D)
H(26D)
H(26E)
H(26F)
H(27A)
H(27B)
H(27C)
H(27D)
−550
−1250
224
−597
1648
1953
393
−287
−465
2437
1892
4052
3592
3264
898
1439
1143
−227
−967
−352
−797
249
6483
8147
8097
8300
4635
3875
3241
4071
4650
6252
7089
5955
4754
5905
6177
7352
6445
8552
7514
7786
5644
4780
3648
4341
3415
4677
4266
4878
6146
4869
8174
8029
2179
1102
1740
980
843
61
69
69
69
45
45
50
50
50
40
40
74
74
74
26
72
72
52
52
52
64
64
71
71
71
72
72
40
40
40
48
48
49
49
1484
2048
1514
2200
1661
2245
683
1193
1069
1380
1727
1899
1001
670
976
1191
511
1649
1206
2149
2434
1973
1805
1291
1206
903
−399
289
1112
2665
2284
4270
3377
3670
7787
7478
5843
5902
655
2906
2300
1642
2203