Coordination polymers constructed from tetrahedral-shaped adamantane tectons

Article abstract of DOI:10.1039/C6CE02146H

Two rigid tetrahedral organic linkers derived from adamantane have been employed in constructing a 3-D, 4-fold interpenetrated framework featuring a PtS topology, [CuL¹(H₂O)₂](BF₄)₂·8H₂O (1

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Coordination polymers constructed from tetrahedral shaped
adamantane tectons†
Teodora Mocanu,a Lidia Pop,b Niculina D. Hădade,b Sergiu Shova,c Ion Grosu,b,*and Marius
Andruha,*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Two rigid tetrahedral organic linkers derived from adamantane (pyridine,10 triazole,11 and tetrazole8,12-13 fragments, cyano
have been employed in constructing a 3-D, 4-fold interpenetrated groups2,14). Tetra-substituted adamantane derivatives are
framework featuring a PtS topology, [CuL1(H2O)2](BF4)2∙8H2O (1) useful tectons in generating robust porous structures showing
(L1= 1,3,5,7-tetrakis{4-(4-pyridyl)phenyl}adamantane), and a 2-fold high connectivity topologies.6-8,12,14c In spite of the fact that
interpenetrated grid–like coordination polymer, [Mn(hfac)2(L2)0.5
(2) (L2= 1,3,5,7-tetrakis(4-cyano-phenyl)adamantane).
]
rigid organic tetrahedral tectons are encoded to orient the
donor atoms towards the vertices of a regular tetrahedron,
thus extending the molecular assembling into three
dimensions, 2-D layered comprising organic ligands with Td
symmetry have also been described.6a,14
Tetrahedral divergent ligands played an important role in
crystal engineering.1 By developing the “node-and-spacer”
approach, Robson has shown that coordination polymers
featuring a diamond-like topology can be rationally obtained
by combining two tectons: a metal ion with a preference for Td
coordination geometry, and an organic molecule with
tetrahedrally-disposed coordination groups.2 Several other
basic inorganic structures are constructed from tetrahedral
tectons (mainly metal ions): lonsdaleite (lon), quartz (qtz),
Herein, we report the crystal structures of two new
coordination polymers constructed from copper(II) ions and
{MnII(hfac)2} entities acting as nodes: [CuL1(H2O)2](BF4)2∙8H2O
1
and [Mn(hfac)2(L2)0.5 , where L1 and L2 are tetrahedral
] 2
spacers having four phenyl-pyridyl (L1) or phenyl-cyano
moieties (L2) attached to an adamantane backbone (Scheme
1). The two assembling species have been chosen from the
following reasons: CuII adopts various coordination numbers
and geometries, but, only rarely tetrahedral; {MnII(hfac)2} has
two positions available for the interaction with the spacer
(either cis or trans). In the first case, CuII, the topology of the
resulting coordination polymer cannot be easily predicted. In
the second case, a 3-D coordination polymer is expected, if the
donor atoms arising from the spacer occupy the trans
positions at the manganese ion, and a 2-D coordination
polymer, when the donor atoms from the spacer occupy the
cis positions.
SrAl2 (sra) (tetrahedral nodes – uni- or binodal nets), PtS (pts
(a combination of tetrahedral and square planar nodes), Ge3N4
(tetrahedral and trigonal nodes in a 3:4 ratio), fluorite (flu
)
)
(tetrahedral and cubic centres) etc.3 Even though a rich
diversity of topologies can be envisioned, the number of
coordination polymers described in the literature and relying
upon tetrahedral spacers is quite low.4 The network topologies
are different from the diamondoid one when the metal ions
have other stereochemical preferences.
The coordinating-prone units attached to tetrahedral skeletons
(methane, silane or adamantane derivatives) can be anionic
(carboxylate,5 sulfonate,6 phosphonate7-9 groups), or neutral
a.Inorganic Chemistry Laboratory, Faculty of Chemistry, University of Bucharest, Str.
Dumbrava Rosie no. 23, 020464, Bucharest, Romania
E-mail: mariusandruh@dnt.ro
b.Centre of Supramolecular Organic and Organometallic Chemistry (CCSOOM),
Department of Chemistry, Faculty of Chemistry and Chemical Engineering, Babeş-
Bolyai University, 11 Arany Janos, 400028, Cluj-Napoca, Romania
c. ‘‘Petru Poni’’ Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda,
41A, 700487 Iasi, Romania
†Electronic Supplementary Information (ESI) available: details of synthetic
procedures, crystallographic data, figures of asymmetric units, spectral data, TGA
curve and experimental and calculated powder diffraction patterns. CCDC
1508551 and 1508552. For ESI and X-ray crystallographic data in CIF or other
electronic format see DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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Scheme 1
Figure 1. Perspective view of the coordination polymer in
crystal with atom numbering scheme.
1
The two adamantane derivatives, L1 and L2, have been already
described in the literature.15,8 In the case of
tetrapyridyladamantane
L1
(Scheme
S1),
relevant
improvements of the synthesis, compared to the method
reported by Müller,15 were elaborated. The employment of
PdCl2(dppf) instead of Pd(PPh3)4 lead to an increase of the
yields from 27 to 41%, a reducing of the reaction time from 72
to 12 h, and an easier chromatographic separation of the
target compound.‡
The reaction of L1 with copper(II) tetrafluoroborate, in the
presence of monoethanolamine, affords blue-green single
crystals of [CuL1(H2O)2](BF4)2∙8H2O 1.‡ The investigation of the
Figure 2. Perspective view of the 3-D coordination framework
of and the corresponding representation of platinum sulfide
1
topology.
crystal structure§ of
four copper(II) ions (Figure 1) in a 3-D network (Figure 2). The
copper ions display distorted octahedral coordination
1
reveals that each L1 molecule connects
a
geometry with four nitrogen atoms in the equatorial plane
arising from four organic linker molecules (Cu1 – N1 = 2.026(8)
Å) and two semi-coordinated water molecules in trans
positions (Cu1 – O1W= 2.626(16) Å). The Cu∙∙∙Cu distances are
18.130 Å (Cu1∙∙∙Cu1a, a = 1+x, 1+y, z), and 20.744 Å (Cu1∙∙∙Cu1b,
b
= 0.5+x, 2.5-y, 0.5+z). The 3-D cationic framework can be
described as
a binodal (4,4)-connected network with a
platinum sulfide topology, where L1 molecules play the role of
tetrahedral sulfide nodes while the equatorial CuN4 units
replace platinum square planar centres. The analysis of the
packing diagram shows the interpenetration of four
independent 3-D nets of 1 (Figure 3). The structural changes of
L1, in comparison with the homolog derived from methane,10b
are reflected in an increase of the interpenetration degree. To
the best of our knowledge, this is the highest interpenetration
degree encountered for molecular assemblies built from a rigid
organic linker with Td symmetry bearing pyridine moieties. The
Figure 3. Crystal packing diagram in crystal 1, showing the
four-fold interpenetration.
molecules could not be directly determined by the
crystallographic measurements, we estimated the presence of
eight water molecules per formula (ESI†) from the data
obtained by elemental and thermogravimetric analyses. The
-
void space resulting upon interpenetration is filled by BF4
anions and solvent molecules. Since the number of the water
diffuse reflectance electronic spectrum of 1 (Figure S3) shows
a band at 604 nm, due to the hexacoordinated CuII ions.
Compound [Mn(hfac)2(L2)0.5
] 2 crystallizes in the tetragonal
centrosymmetric I41/a space group.§ Taking into consideration
the weak coordinating ability of nitrile containing molecules,
we have employed
a hexafluoroacetylacetonate metal
complex, as the electron-withdrawing F atoms increase the
Lewis acidity of the metal ion, thus favouring the coordination
of the nitrile groups to the manganese ion, by replacing the
weakly bounded aqua ligands. A neutral coordination structure
is assembled by reacting [Mn(hfac)2(H2O)2] with L2 (Hhfac =
1,1,1,5,5,5-hexafluoro-2,4-pentanedione).‡
The {Mn(hfac)2} nodes are linked by L2 molecules resulting in
neutral (4,4)-connected grid-like layers. The MnII ions adopt a
slightly distorted octahedral geometry with two chelating hfac-
ligands (Mn – O1 = 2.128(4) Å, Mn – O2 = 2.154(5) Å) and two
nitrogen ligand atoms disposed in cis positions (Mn – N1 =
2.239(7) Å) (Figure 4). Since L2 acts as a 4-connecting knot, the
low dimensionality of
2 can be ascribed exclusively to the cis-
2 | J. Name., 2012, 00, 1-3
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5
(a) B. Chen, M. Eddaoudi, T. M. Reineke, J. W. Kampf, M.
Notes and references
Okeeffe and O. M. Yaghi, J. Am. Chem. Soc., 2000, 122
,
11559; (b) J. Kim, B. Chen, T. M. Reineke, H. Li, M. Eddaoudi,
D. B. Moler, M. Okeeffe and O. M. Yaghi, J. Am. Chem. Soc.,
2001, 123, 8239; (c) M. Zhang, Y.-P. Chen, M. Bosch, T.
Gentle, K. Wang, D. Feng, Z. U. Wang and H.-C. Zhou, Angew.
Chem., Int. Ed., 2014, 53, 815; (d) H. Chun, D. Kim, D. N.
Dybtsev and K. Kim, Angew. Chem. Int. Ed., 2004, 43, 971; (e)
‡ Synthesis of L1: To a 100 mL three-necked round-bottom flask
equipped with a reflux condenser were added 4-pyridylboronic acid
(0.258 g, 2.11 mmol), Pd(dppf)Cl2 (0.043 g, 0.05 mmol), and Na2CO3
(0.452 g, 4.27 mmol) in dioxane/water (2.5:1 v/v, 35 mL) and the
solution was flushed with argon for 20 min, after 1,3,5,7-tetrakis(4-
iodophenyl)adamantane (0.25 g, 0.26 mmol) was added under
argon atmosphere, and the reaction mixture was stirred at 80˚C for
12 h. The solvent was evaporated, and the crude product was
dissolved in chloroform and washed with water (2×50 mL) and satd.
NH4Cl solution (2×50 mL). The separated organic layer was dried
over MgSO4, filtered and concentrated under vacuum. After
L. Wen, P. Cheng and W. Lin, Chem. Commun., 2012, 48
2846; (f) L. Wen, P. Cheng and W. Lin, Chem. Sci., 2012,
,
3
,
2288; (g) C. Tan, S. Yang, N. R.Champness, X. Lin, A. J. Blake,
W. Lewis and M. Schröder, Chem. Commun., 2011, 47, 4487;
(h) Y. E. Cheon and M. P. Suh, Chem. Commun., 2009, 2296;
(i) L. Ma, A. Jin, Z. Xieand W. Lin, Angew. Chem. Int. Ed.,
2009, 48, 9905; (j) M. Zhang, Y.-P. Chen and H.-C. Zhou,
CrystEngComm, 2013, 15, 9544; (k) R. P. Davies, R. Less, P. D.
Lickiss, K. Robertson and A. J. P. White, Cryst. Growth Des.,
2010, 10, 4571; (l) J. M. Gotthardt, K. F. White, B. F.
Abrahams, C. Ritchie and C. Boskovic, Cryst. Growth Des.,
2012, 12, 4425; (m) D. Liu,Z. Xie,L. Ma and W. Lin, Inorg.
Chem., 2010, 49, 9107; (n) G. A. Senchyk, A. B. Lysenko, H.
Krautscheid, E. B. Rusanov, A. N. Chernega, K. W. Krämer, S.-
X. Liu, S. Decurtins and K. V. Domasevitch, Inorg. Chem.,
2013, 52, 863.
(a) D. J. Hoffart, A. P. Côté and G. K. H. Shimizu, Inorg. Chem.,
2003, 42, 8603; (b) D. J. Hoffart, S. A. Dalrymple and G. K. H.
Shimizu, Inorg. Chem., 2005, 44, 8868.
(a) J. M. Taylor, A. H. Mahmoudkhani and G. K. H. Shimizu,
Angew. Chem. Int. Ed., 2007, 46, 795; (b) M. V. Vasylyev, E. J.
Wachtel, R. Popovitz-Biro and R. Neumann, Chem.Eur. J.,
2006, 12, 3507; (c) M. Vasylyev and R. Neumann, Chem.
Mater., 2006, 18, 2781.
purification
pentane/DCM/MeOH: 1.5:1:0.2, Rf= 0.45) the product was isolated
as white solid (0.082 g, 41% yield). Tetrakis(p-
cyanophenyl)adamantane L2 was obtained (Scheme S2) in good
yields (80%) starting from 1,3,5,7-tetrakis(p-
by
column
chromatography
(silica
gel,
iodophenyl)adamantane applying the procedure described in the
literature.8
Synthesis of 1: A methanol solution (4 mL) of Cu(BF4)2∙6H2O (0.0024
g, 0.007 mmol) was reacted with 0.0018
g (0.029 mmol)
monoethanolamine in 4 mL methanol and the resulting mixture was
left to slowly diffuse through an ethanol layer (5 mL) into 5 mL
CHCl3 of L1 (0.0019 g, 0.0025 mmol). Blue green single crystals
suitable for X-ray measurements appeared in two-three weeks.
Yield (based on L1): 0.0013 g, 46%. Selected IR data (KBr): 3315 (m),
3068 (w), 3033 (w), 2929 (w), 2897 (w), 2849 (w), 1664 (s), 1614
(vs), 1542 (m), 1493 (s), 1431(m), 1401 (w), 1356 (w), 1295 (w),
1236 (w), 1123 (s), 1073 (s), 1028 (s), 1007 (s), 1025 (m), 825 (w),
792 (s), 739 (w), 667 (w), 637 (w).
6
7
Synthesis of 2: [Mn(hfac)2(H2O)2] H2O (0.0038 g, 0.0072 mmol) was
solubilized in 4 mL boiling n-heptane. Upon cooling to room
temperature, 4 mL of CH2Cl2 were added and the solution was
carefully layered on top of 2 mL CH2Cl2 solution of L2 (0.002g,
0.0037 mmol) in a test tube. Yellow single crystals were formed in
few days. Yield (based on L2): 0.0015 g, 28%. Selected IR data (KBr):
3401 (m), 2939 (w), 2858 (w), 2262 (m), 2224 (m), 1647 (s),
1606(w), 1523 (w), 1493 (s), 1405 (w), 1369 (w), 1252 (s), 1196 (s),
1149 (vs), 1096 (w), 836 (w), 794 (w), 764 (w), 665(w).
8
9
I. Boldog, K. V. Domasevitch, I. A. Baburin, H. Ott, B. Gil-
Hernández, J. Sanchiz and C. Janiak, CrystEngComm, 2013,
15, 1235.
A. Bulut, Y. Zorlu, E. Kirpi, A. Çetinkaya, M. Wörle, J.
Beckmann and G. Yücesan, Cryst. Growth Des., 2015, 15
,
5665.
10 (a) K. Matsumoto, M. Kannami, D. Inokuchi, H. Kurata, T.
Kawase and M. Oda, Org. Lett., 2007, , 2903; (b) C. B.
9
§Crystal data for [CuL1(H2O)2](BF4)2∙8H2O (1): C54H64CuB2F8N4O10 , M
= 1166.26, T = 293(2) K, tetragonal, space group I422, a =
12.8199(9), c = 32.617(4) Å, V = 5360.5(1) Å3, Dc = 1.310 gcm-3, ꢀ =
1.218 mm-1, Z = 4, Flack parameter = 0.42(7), reflections collected =
Caputo, V. N. Vukotic, N. M. Sirizzotti and S. J. Loeb, Chem.
Commun., 2011, 47, 8545; (c) F. Geyer, F. Rominger, M.
Vogtland and U. H. F. Bunz, Cryst. Growth Des., 2015, 15
3539; (d) S. Shankar, R. Balgley, M. Lahav, S. R Cohen, R.
,
6049, independent reflection
= 1932 [Rint = 0.0566]. Before
Popovitz-Biro and M. E. van der Boom, J. Am. Chem. Soc.,
2015, 137, 226; (e) X.-Y. Chen, H.-Y. Shi, R.-B. Huang, L.-S.
Zheng and J. Tao, Chem. Commun., 2013, 49, 10977; (f) X.-Y.
Chen, R.-B. Huang, L.-S. Zheng and J. Tao, Inorg. Chem., 2014,
53, 5246.
SQUEEZE: R indices [I > 2σ(I)]: R1 = 0.1033, wR2 = 0.2671, R indices
(all data): R1 = 0.1507, wR2 = 0.3199, GoF = 1.086 with ꢁρmin/ꢁρmax =
-0.244/1.258 eÅ-3. After SQUEEZE: R indices [I > 2σ(I)]: R1 = 0.0750,
wR2 = 0.1876, R indices (all data): R1 = 0.1138, wR2 = 0.2237, GoF =
0.938 with ꢁρmin/ꢁρ
max = -0.216/0.939 eÅ-3.
11 (a) G. A. Senchyk, A. B. Lysenko, I. Boldog, E. B. Rusanov, A. N.
Chernega, H. Krautscheid and K. V. Domasevitch, Dalton
Trans., 2012, 41, 8675; (b) G. A. Senchyk, A. B. Lysenko, E. B.
Rusanov, A. N. Chernega, J. Jezierska, K. V. Domasevitch and
A. Ozarowski, Eur. J. Inorg. Chem., 2012, 5802; (c) A. B.
Lysenko, G. A. Senchyk, J. Lincke, D. Lässig, A. A. Fokin, E. D.
Butova, P. R. Schreiner, H. Krautscheid and K. V.
Crystal data for [Mn(hfac)2(L2)0.5] (2): C29H16MnF12N2O4, M = 739.38,
T = 293(2) K, tetragonal, space group I41/a, a = 11.645(5), c =
52.700(5) Å, V = 7146(6) Å3, Dc = 1.374 gcm-3, ꢀ = 0.465 mm-1, Z = 8,
reflections collected = 32305, independent reflection = 3122 [Rint
=
0.2541]. R indices [I > 2σ(I)]: R1 = 0.0604, wR2 = 0.1342, R indices (all
data): R1 = 0.1674. wR2 = 0.1807, GoF = 0.885 with ꢁρmin/ꢁρmax = -
0.249/0.534 eÅ-3.
Domasevitch, Dalton Trans., 2010, 39, 4223.
1
(a) R. Robson, J. Chem. Soc., Dalton Trans., 2000, 3735; (b) R.
Robson, Dalton Trans., 2008, 5113; (c) G. R. Desiraju, Angew.
Chem., Int. Ed. Engl., 1995, 34, 2311.
12 (a) I. Boldog, K. V. Domasevitch, J. Sanchiz, P. Mayerd and C.
Janiak, Dalton Trans., 2014, 43, 12590; (b) I. Boldog, K.
Domasevitch, J. K. Maclaren, C. Heering, G. Makhloufi and C.
Janiak, CrystEngComm, 2014, 16, 148.
2
3
B. F. Hoskins and R. Robson, J. Am. Chem. Soc., 1990, 112
1546.
S. R. Batten, S. M. Neville and D. R. Turner, Coordination
,
13 M. Dincă, A. Dailly and J. R. Long, Chem. Eur. J., 2008, 14
10280.
14 (a) D. Venkataraman, S. Lee, J. S. Moore, P. Zhang, K. A.
,
polymers: Design, analysis and applications, Royal Society of
Chemistry, Cambridge, 2008.
See, for example T. Muller and S. Bräse, RSC Adv., 2014, 4,
6886 and references therein.
Hirsch, G. B. Gardner, A. C. Covey and C. L. Prentice, Chem.
Mater., 1996, , 2030; (b) F.-Q. Liu and T. D. Tilley, Inorg.
Chem., 1997, 36, 5090; (c) K. M. Patil,M. E. Dickinson,T.
4
8
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Tremlett, S. C. Moratti and L. R. Hanton, Cryst. Growth Des.,
2016, 16, 1038.
15 C. I. Schilling, O. Plietzsch, M. Nieger, T. Muller and S. Bräse,
Eur. J. Org. Chem., 2011, 1743.
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Two coordination polymers with different dimensionalities have been constructed using
rigid tetrahedral organic tectons derived from adamantane.