A new calcium trimellitate coordination polymer with a chain-like structure

Solid State Sciences 9 (2007) 455e458 www.elsevier.com/locate/ssscie

A new calcium trimellitate coordination polymer with a chain-like structure Christophe Volkringer a, Thierry Loiseau a,*, Ge´rard Fe´rey a, John E. Warren b, David S. Wragg c, Russell E. Morris c a

Institut Lavoisier, UMR CNRS 8180, Universite´ de Versailles Saint Quentin, 45, avenue des Etats-Unis, 78035 Versailles, France b CCLRC Daresbury Laboratory, Warrington, Cheshire WA4 4AD, UK c School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, UK Received 5 March 2007; received in revised form 28 March 2007; accepted 3 April 2007 Available online 10 April 2007

Abstract The calcium trimellitate, Ca(H2O)[(O2C)2eC6H3eCO2H], was hydrothermally synthesized from a mixture of calcium hydroxide, 1,2,4benzenetricarboxylic (or trimellitic) acid and water at 180  C for 24 h (under autogenous pressure). Its crystal structure has been determined by single-crystal X-ray diffraction analysis using synchrotron radiation (station 9.8, SRS Daresbury, UK). It consists of infinite chains of calcium bicapped trigonal prismatic polyhedra connected to each other through the 1,2,4-benzenetricarboxylate ligand. The eight-fold coordinated calcium cation is bonded to one terminal water molecule, two carboxylate groups with a chelating conformation and three carboxylate groups in a monodentating mode. One of the monodentate carboxylate is terminal with the occurrence of protonated CeOH bonding. ˚ , b ¼ 6.9917(4) A ˚ , c ¼ 10.3561(6) A ˚ , a ¼ 87.178(1) , b ¼ 83.233(1) , g ¼ 69.576(1) , Triclinic space group P-1 with a ¼ 6.9073(4) A 3 ˚ V ¼ 465.41(5) A . Ó 2007 Elsevier Masson SAS. All rights reserved. Keywords: Calcium; 1,2,4-Benzenetricarboxylate ligand; Hydrothermal synthesis; Crystal structure

1. Introduction In the last decade, there has been a growing interest for the elaboration of metaleorganic frameworks (MOF) or coordination polymers exhibiting porosity properties [1e6]. This emerging class of materials found many potential applications in the areas of adsorption, gas storage, catalysis, magnetism, luminescence [7,8]. Most often, these compounds possess open architectures combining metallic centers connected to each other through organic ligands (or spacer), containing amine or carboxylate functionalities. The use of carboxylate species involving benzene cycle has received much attention since rigid three-dimensional porous networks have been generated. Intensive works have been carried out with different divalent * Corresponding author. Tel.: þ33 1 39 25 43 73; fax: þ33 1 39 25 43 58. E-mail address: [email protected] (T. Loiseau). 1293-2558/$ - see front matter Ó 2007 Elsevier Masson SAS. All rights reserved. doi:10.1016/j.solidstatesciences.2007.04.002

transition metals such as copper or zinc, but there are fewer reports on the synthesis of coordination polymers involving alkaline-earth cations, such as magnesium or calcium. The preparation of magnesium carboxylates has recently been considered in order to get relatively low dense open-frameworks in view of gas storage applications [9e12]. Calcium carboxylates are less studied with this perspective, but different contributions have already described the reactivity with aromatic carboxylic acids. Up to now, several phases are known with the ligands 1,4-benzenedicarboxylic acid [13,14], 1,3-benzenedicarboxylic acid [15], 1,3,5-benzenetricarboxylic acid [16e18], 1,3,5-benzenetriacetic acid [19], 1,2,4,5-benzenetetracarboxylic acid [20], 1,4,5,8-naphthalenetetracarboxylic acid [21]. In this paper, we report our investigations on the hydrothermal synthesis of a new calcium-based coordination polymer Ca(H2O)[(O2C)2eC6H3eCO2H] involving the molecule 1,2,4benzenetricarboxylate (or trimellitate). Its crystal structure was

456

C. Volkringer et al. / Solid State Sciences 9 (2007) 455e458 Table 2 Atomic coordinates (104) and equivalent isotropic displacement parameters ˚ 2  103) for Ca(H2O)[(O2C)2eC6H3eCO2H] (A

Fig. 1. SEM image of the calcium trimellitate Ca(H2O)[(O2C)2eC6H3e CO2H)] (photograph width: 100 mm).

solved from synchrotron single-crystal X-ray diffraction. It is built up from one-dimensional chain of calcium polyhedra linked to each other via the carboxylate ligands.

Ca(1) O(1) O(2) O(3) O(4) O(5) O(6) OW C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) H(6) H(1W) H(2W) H(3) H(2) H(1)

x

y

z

U (eq)

12,490(1) 13,914(2) 11,594(2) 9017(2) 10,731(2) 13,982(2) 13,181(2) 15,286(2) 11,278(3) 9855(3) 10,543(3) 7804(3) 7126(3) 6452(3) 9176(3) 15,645(3) 9963(3) 13,910(70) 15,650(60) 16,320(50) 11,960(40) 7240(50) 5120(50)

2617(1) 852(2) 906(2) 3763(2) 2750(2) 3941(2) 2328(3) 2604(2) 2543(3) 2540(3) 2312(3) 2775(3) 2559(3) 2773(3) 2352(3) 2444(3) 2311(3) 2360(60) 3660(60) 1550(50) 2250(40) 2910(50) 2930(50)

10,445(1) 11,051(1) 8777(1) 9307(1) 12,610(1) 8504(2) 13,932(2) 11,731(1) 13,707(2) 14,889(2) 6126(2) 4772(2) 7105(2) 5872(2) 7228(2) 8271(2) 8528(2) 13,170(40) 11,690(40) 11,580(30) 6210(20) 3990(30) 5810(30)

11(1) 16(1) 17(1) 15(1) 17(1) 16(1) 20(1) 14(1) 13(1) 13(1) 13(1) 14(1) 11(1) 13(1) 11(1) 11(1) 11(1) 50(11) 49(11) 23(7) 13(6) 21(7) 24(7)

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

2. Experimental 2.1. Synthesis of Ca(H2O)[(O2C)2eC6H3eCO2H] All reactants were commercially available and used as received without further purification. Ca(OH)2 (95þ%) and 1,2,4-benzenetricarboxylic acid (97%) were purchased from Aldrich, HNO3, from Prolabo (Rectapur). The reactions were performed in Teflon-lined Parr autoclaves under

Table 3 ˚ ] and angles [ ] for Ca(H2O)[(O2C)2eC6H3eCO2H] Bond lengths [A

Table 1 Crystal data and structure refinement for Ca(H2O)[(O2C)2eC6H3eCO2H]

Ca(1)eO(1) Ca(1)eO(3)#1 Ca(1)eO(2) Ca(1)eO(4) Ca(1)eO(5) Ca(1)eOW Ca(1)eO(3) Ca(1)eO(1)#2

2.3605(15) 2.3918(14) 2.4017(15) 2.4108(15) 2.4401(15) 2.4694(16) 2.6492(15) 2.6895(15)

Identification code Empirical formula Formula weight Temperature Wavelength Crystal system, space group Unit cell dimensions

O(1)eC(8)#2 O(2)eC(9) O(3)eC(9) O(4)eC(1) O(5)eC(8) O(6)eC(1)

1.250(2) 1.254(2) 1.266(2) 1.226(2) 1.262(2) 1.318(2)

C(1)eC(2) C(2)eC(4)#3 C(2)eC(3)#3 C(3)eC(7) C(3)eC(2)#4 C(4)eC(6) C(4)eC(2)#4 C(5)eC(6) C(5)eC(7) C(5)eC(8)#5 C(7)eC(9) C(8)eO(1)#2 C(8)eC(5)#6

1.477(3) 1.387(3) 1.401(3) 1.388(3) 1.401(3) 1.385(3) 1.387(3) 1.393(3) 1.393(3) 1.506(3) 1.505(3) 1.250(2) 1.506(3)

Volume Z, Calculated density Absorption coefficient F(000) Crystal size Theta range for data collection Limiting indices Reflections collected/unique Completeness to theta ¼ 31.04 Refinement method Data/parameters Goodness-of-fit on F2 Final R indices [I > 2s(I )] R indices (all data) Largest diff. peak and hole

Ca(H2O)[(O2C)2eC6H3eCO2H] C18H12Ca2O14 532.44 150(2) K ˚ 0.69110 A Triclinic, P-1 ˚ , a ¼ 87.178(1) a ¼ 6.9073(4) A ˚ , b ¼ 83.233(1) b ¼ 6.9917(4) A ˚ , g ¼ 69.576(1) c ¼ 10.3561(6) A ˚3 465.41(5) A 1, 1.900 Mg/m3 0.698 mm1 272 0.060  0.020  0.005 mm 3.02 e31.04 10  h  10, 9  k  10, 15  l  15 5425/2873 [R(int) ¼ 0.0513] 88.7% Full-matrix least-squares on F2 2873/178 1.029 R1 ¼ 0.0519, wR2 ¼ 0.1416 R1 ¼ 0.0579, wR2 ¼ 0.1469 ˚ 3 0.554 and 0.584 e A

Symmetry transformations used to generate equivalent atoms: #1: x þ 2, y þ 1,z þ 2; #2: x þ 3,y,z þ 2; #3: x, y, z þ 1; #4: x, y, z  1; #5: x  1, y, z; #6: x þ 1, y, z.

C. Volkringer et al. / Solid State Sciences 9 (2007) 455e458

O1

C8

457

O5 H2W

O5

C8

O1

H1W

OW

O2

H6

CA1

O6

C9 O4 O3

C1

O3 C9 O2

(a)

(b)

Fig. 2. The coordination geometries of calcium. (a) ORTEP-type drawing (50%) showing the connection scheme of the 1,2,4-benzenetricarboxylate with calcium with the chelating and monodentate conformation. Hydrogen bond interaction (dotted) is also indicated between the hydrogen H6 and the terminal water molecule OW. (b) Representation of the bicapped trigonal prismatic polyhedron around the calcium cation.

autogenous pressure. The solid was synthesized from the reaction of Ca(OH)2 (211.0 mg, 2.7 mmol), 1,2,4-benzenetricarboxylic acid (283.2 mg, 1.3 mmol), HNO3 4 M (1 ml, 4 mmol) in water (5 ml, 277.8 mmol). The mixture was heated at 180  C for 24 h. The final pH value was 1. The powdered samples were collected by filtration, washed with purified water and dried at room temperature. SEM image (Fig. 1) indicates that the title compound crystallizes with a plate-like morphology (60e10 mm length).

The structure was solved using the direct methods program SHELXS and refined with the full matrix least squares routine SHELXL [23] to give final R factors of 0.0519 (I > 2s(I )) and 0.0579 (all data). Hydrogen atoms were located using difference Fourier maps and refined isotropically without restraints. Atomic coordinates and selected interatomic distances are given in Tables 2 and 3, respectively.

2.2. Single-crystal X-ray diffraction

The structure of the coordination polymer Ca(H2O) [(O2C)2eC6H3eCO2H] is built up from infinite chains of calcium polyhedra interconnected to each other through the trimellitate ligands. Calcium (Figs. 2 and 3) is bonded to seven oxygen atoms from the carboxylate groups and one water mol˚ ). Two of ecule in terminal position (Ca1eOW ¼ 2.469(2) A the five carboxylate anions coordinate with calcium in a chelate fashion (Ca1eO2 ¼ 2.402(2), Ca1eO3 ¼ 2.649(2) ˚ ) whereas and Ca1eO1 ¼ 2.689(2), Ca1eO5 ¼ 2.440(2) A

The crystals were too small for a conventional lab diffractometer, so diffraction data were collected at station 9.8 of the SRS, Daresbury UK [22]. A plate-like microcrystal of 60  20  5 mm was selected and mounted on a two stage glass fiber. Data were collected on a modified Bruker Nonius APEXII diffractometer with CCD area detector. The crystal was indexed with a triclinic unit cell (see Table 1 for crystal data) and a full sphere of data was collected. The intensities were integrated and scaled using the Bruker SAINT software.

OW

H6 O6

CA1

O4

C3 C6

H2

O3

H3

C1 C2 C4

C9 O2

C7 C5

H1

3. Results and discussion

O5 C8

O1

c a Fig. 3. Coordination of calcium with the carboxylate groups from five distinct 1,2,4-benzenetricarboxylate species.

b

Fig. 4. View of the chains of the CaO7(H2O) bicapped trigonal prisms running along the [110] axis, connected via the 1,2,4-benzenetricarboxylate species with the chelate and monodentate bridging modes.

C. Volkringer et al. / Solid State Sciences 9 (2007) 455e458

458

100 90

Weigth loss (%)

80 70 60 50 40 30 20 10 0

b a c

0

100

200

300

400

500

600

700

800

Temperature (°C) Fig. 6. TG curve of Ca(H2O)[(O2C)2eC6H3eCO2H] under N2 (1  C/min).

Fig. 5. View of the structure of Ca(H2O)[(O2C)2eC6H3eCO2H].

three others are in a monodentate bridging mode (Ca1e ˚ ). O1 ¼ 2.361(2), Ca1eO3 ¼ 2.392(1) & Ca1eO4 ¼ 2.411(2) A Two of the latter carboxylates groups also bridge two calcium cations via the oxygen atoms O1 and O3 and adopt alternatively a chelating or monodentating conformation for two adjacent calcium atoms. One of the monodendate configuration in the para position, has a terminal CeO bonding with a longer ˚ ) corresponding to a CeO distance (C1eO6 ¼ 1.318(2) A protonated state of the carboxylate group. This is confirmed by IR spectroscopy showing a vibration band at 1690 cm1 due to the nCeO of free non-bonded carboxylic acid group (eCOOH). A strong hydrogen bond interaction (OW/ ˚ ) occurs between the proton H6 of the termiH6 ¼ 1.724(1) A nal nonodentate ReCO2H and terminal water molecule attached to the calcium. Other CeO bridging bond distances ˚. are typically ranging between 1.226(2) and 1.266(2) A The Ca1eO bond distances are in the range 2.361(2)e ˚ , which is similar to those observed in other 2.689(2) A calcium carboxylates accepting an eight-fold coordination [13e15,19,20]. It defines a bicapped trigonal prism polyhedron, which is connected to each other through a common edge and this results in the formation of straight chains running along the [110] direction (Fig. 4). The file of calcium polyhedra are linked to each other via the trimellitate species ensuring the three-dimensional cohesion of the structure (Fig. 5). Adjacent chains are linked along [100] by two carboxylates in position 1,2 and along [001] by two carboxylates in position 4. It is noted that the calcium 1,2,4-benzenetricarboxylate assembling is not dominated by the pep interactions ˚ are observed between two adjacent since distances of z4.0 A benzene rings. Thermogravimetric analysis (under N2, 1  C min1, TA Instrument 2050) indicates that the calcium trimellitate is stable up to 210  C and then different weight loss events are observed from 210 to 800  C (Fig. 6). Between 210 and

510  C, the first weight loss with two sub-steps is assigned to the decomposition of the trimellitate species into calcium carbonate CaCO3 (obs: 37.1%; calc: 37.6%). The formation of the CaCO3 was confirmed by powder X-ray diffraction. The latter is stable up to 660  C and then decomposes into CaO with the departure of one CO2 (obs: 21.0%; calc: 21.05%). Similar thermal behavior was previously reported for the calcium 1,4,5,8-naphthalenetetracarboxylate [21]. References [1] S.R. Batten, R. Robson, Angew. Chem. Int. Ed. 37 (1998) 1460. [2] B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629. [3] O.M. Yaghi, M. O’Keeffe, N.W. Ockwig, H.K. Chae, M. Eddaoudi, J. Kim, Nature 423 (2003) 705. [4] G. Fe´rey, C. Mellot-Draznieks, C. Serre, F. Millange, Acc. Chem. Res. 38 (2005) 217. [5] S. Kitagawa, R. Kitaura, S.-I. Noro, Angew. Chem. Int. Ed. 43 (2004) 2334. [6] D. Bradshaw, J.B. Claridge, E.J. Cussen, T.J. Prior, M.J. Rosseinsky, Acc. Chem. Res. 38 (2005) 273. [7] C. Janiak, Dalton Trans. (2003) 2781. [8] U. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastre´, J. Mater. Chem. 16 (2006) 626. [9] M. Dinca, J.R. Long, J. Am. Chem. Soc. 127 (2005) 9376. [10] J.A. Rood, B.C. Noll, K.W. Henderson, Inorg. Chem. 45 (2006) 5521. [11] I. Senkovska, S. Kaskel, Eur. J. Inorg. Chem. (2006) 4565. [12] S. Ma, J.A. Fillinger, M.W. Ambrogio, J.-L. Zuo, H.-C. Zhou, Inorg. Chem. Commun. 10 (2007) 220. [13] R.H. Groeneman, J.L. Atwood, Cryst. Eng. 2 (1999) 241. [14] S.H. Dale, M.R. Elsegood, Acta Crystallogr. E59 (2003) m586. [15] S.H. Dale, M.R. Elsegood, Acta Crystallogr. C59 (2003) m540. [16] M.J. Platers, R.A. Howie, A.J. Roberts, Chem. Commun. (1997) 893. [17] M.J. Plater, A.J. Roberts, J. Marr, E.E. Lachowski, R.A. Howie, J. Chem. Soc., Dalton Trans. (1998) 797. [18] Y.-Y. Yang, Z.-Q. Huang, L. Szeto, W.-T. Wong, Appl. Organometal. Chem. 18 (2004) 97. [19] H.-F. Zhu, Z.-H. Zhang, W.-Y. Sun, T. Okamura, N. Ueyama, Cryst. Growth Des. 5 (2005) 177. [20] C. Robl, Z. Naturforsch. 43b (1988) 993. [21] R.K.B. Nielsen, K.O. Kongshaug, H. Fjellvag, Solid State Sci. 8 (2006) 1237. [22] R.J. Cernik, W. Clegg, C.R.A. Catlow, G. Bushnell-Wye, J.V. Flaherty, G.N. Greaves, H. Hamichi, I. Burrows, D.J. Taylor, S.J. Teat, J. Synchrotron Radiat. 4 (1997) 279. [23] G.M. Sheldrick, Univeristy of Go¨ttingen, Germany, release 97-2.