Ab initio structure determination of anhydrous sodium alendronate from laboratory powder X-ray diffraction data

Asnani, Minakshi; Vyas, K.; Bhattacharya, Apurba; Devarakonda, Surya; Chakraborty, Subrata; Mukherjee, Alok K.

doi:10.1002/jps.21561

Cited by 17 publications

(34 citation statements)

References 21 publications

(25 reference statements)

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“…[5][6][7] These structures also verify the development of 3-D hydrogen bonded networks in these materials through interactions of the pendant cationic alkylammonium group, the phosphonate residues and the lattice water molecules. [5][6][7] More recently, studies of metal coordination compounds of alendronate and related 1,1-bisphosphonate ligands have led to new strategies for their use in the treatment of cancer 8 and other medicinal applications, 9 as well as developing new materials with magnetic, photochromic, and electrocatalytic properties. [10][11][12] In this current contribution we have investigated the syntheses and structures of a series of new coordination polymers of alendronic acid (LH 5 , Scheme 1) with a particular focus on cations from the group 1 metals potassium, rubidium and caesium.…”

Section: Introductionmentioning

confidence: 68%

Coordination Polymers of Increasing Complexity Derived from Alkali Metal Cations and (4-Amino-1-hydroxybutylidine)-1,1-bisphosphonic Acid (Alendronic Acid): The Competitive Influences of Coordination and Supramolecular Interactions

Deacon

Forsyth

Greenhill

et al. 2015

Crystal Growth & Design

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Reactions of (4-amino-1-hydroxybutylidine)-1,1-bisphosphonic acid (alendronic acid = LH 5 ) with one equivalent of the group 1 metal bases KOH, KHCO 3 , Rb 2 CO 3 , RbOH or Cs 2 CO 3 in aqueous solution at pH 4-5 gave the corresponding complexes [M(LH 4 )(H 2 O) n ].m(H 2 O), M = K (1), Rb (2) or Cs (3). Crystallisation of the products under varying conditions yielded differing hydrates and/or polymorphic phases. Rapid crystallisation of the potassium complex 1 from water/EtOH or water/DMSO gave 2[K(LH 4 )].3(H 2 O) (1a) whereas slow crystallisation from water or water/DMSO gave [K 2 (LH 4 ) 2 (H 2 O) 2 ].2H 2 O (1b phase I). For the rubidium complex 2, rapid crystallisation from water/EtOH gave the analogous [Rb 2 (LH 4 ) 2 (H 2 O) 2 ].2H 2 O (2b phase I) whereas slow crystallisation from water/DMSO also gave 2b, but as a mixture of phase I and the structural polymorph [Rb(LH 4 )(H 2 O)].H 2 O (2b phase II). In contrast, only [Cs(LH 4 )(H 2 O)].H 2 O (3b phase II) was obtained for the caesium complex 3 under all crystallisation conditions. A second complex type [M(LH 4 )(LH 5 )].2H 2 O (M = Rb 4, Cs 5), incorporating an additional coordinated alendronic acid molecule was also observed for the larger metals Rb and Cs as a minor product in some syntheses and isolated by fractional crystallisation for 4, but as the sole product from Cs(O 2 CH) and LH 5 for 5. The crystal structures of the complexes [M(LH 4 )(H 2 O) n ].m(H 2 O) 1a, 2b (phase II) and 3b (phase II) comprise edge-shared or corner-shared polyhedral chains that are linked by bridging bisphosphonate ligands into 2-D sheets. The 4-ammoniobutylidene chains protrude above and below the coordination layers and interact with neighbouring layers through hydrogen bonding of the terminal ammonium group forming distinctive supramolecular 3-D arrays. The phase I structure of 1b and 2b comprises ribbons of parallel M 4 (LH 4 ) 4 (H 2 O) 4 subunits arranged in a more close packed 3-D supramolecular network. For [M(LH 4 )(LH 5 )].2H 2 O (M = Rb 4, Cs 5), isolated M + cations, bridged by bisphosphonate ligands, are arranged into 2-D sheets, with the pendant 4-ammoniumbutylidene chains resulting in a 3-D lamellar network similar to those of 1a and 2b/3b (phase II). All of the [M(LH 4 )(H 2 O) n ].m(H 2 O) and [M(LH 4 )(LH 5 )].2H 2 O structures display strong PO-H…O(phosphonate) and N-H…O(phosphonate/water) hydrogen bond motifs which significantly impact upon the observed structures. Reactions of LH 5 with two equivalents of the group 1 metal bases MOH (M = Na, K, Rb, Cs) at pH 9-10 gave the di-metallated complexes [M 2 (LH 3 )(H 2 O) n ].(H 2 O) m (M = Na 6, K 7, Rb 8, Cs 9). Crystallisation of 6 from water/MeOH gave [Na 2 (LH 3 )(H 2 O) 4 ].H 2 O (6a) as a single phase. For 7, crystallisation from water/MeOH gave K 2 (LH 3 ).3(H 2 O) (7a) as the bulk product, whereas crystals of [K 2 (LH 3 )(H 2 O) 6 ] (7b) were grown from water/DMSO solutions. On standing, the crystals of 7b were converted into the bulk product 7a. The structures of 6a and 7b are chain rather than ...

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Section: Introductionmentioning

confidence: 68%

Coordination Polymers of Increasing Complexity Derived from Alkali Metal Cations and (4-Amino-1-hydroxybutylidine)-1,1-bisphosphonic Acid (Alendronic Acid): The Competitive Influences of Coordination and Supramolecular Interactions

Deacon

Forsyth

Greenhill

et al. 2015

Crystal Growth & Design

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“…The 3D molecular self-assemblies of alendronate salts are distinguishable. The structures revealed one-dimensional and two-dimensional pseudo-coordination (1) polymeric architectures and in structure (1) has intermediate character between the anhydrous polymorph determined from the powder data [13] and hydrated sodium salts [14,15]. The R 2 2 (20) synthon is observed in all sodium alendronate salts.…”

Section: Resultsmentioning

confidence: 90%

“…The P-C bond distances 1.834(3) and 1.864(3) Å and P-C-P bond angle of As has already been reported, these systems demonstrate diverse complexity, which increases with the central cation radius. Lithium alendronate salts revealed four-coordinate tetrahedral Li + cation [16]; sodium salts, six-coordinate octahedral Na + [13][14][15]; potassium salts, seven-coordinated K + [14]; and rubidium, 6/7/8-coordinated Rb + [14]; while cesium, 7/8/9-coordinated Cs + [14]. Surprisingly, Na + cation in (1) is surrounded by a fivecoordinated sphere through three of the hydroxyl (-OH) and two oxygen atoms of the phosphonate (P=O) groups.…”

Section: Resultsmentioning

confidence: 99%

“…search of literature and the Cambridge Crystal Structure Database (CSD Version 5.38, May 2017 release) [12] revealed the following salts with alkali cations such as the following: sodium, represented by CSD reference codes-UTOKAQ [13], PUQHAM, TEHWOS01 [14], TEHWOS [15]; lithium-EJEZUP [16]; potassium-PUQFOY, PUQFUE, PUQHEQ [14]; rubidium-PUQGAL, PUQGAL01, PUQGOZ, PUQHIU, PUQHOA [14]; and cesium-PUQGIT, PUQGUF, PUQHUG, PUQJAO [14]. Besides, alendronic acid crystal structures signed by CSD reference codes GOWZEX [17] and KOJGUL [18] were included into the analysis.…”

Section: Introductionmentioning

confidence: 99%

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Analysis of supramolecular interactions in alendroniate alkali metal salts: synthesis, structure, and properties of novel sodium alendronate polymorph

2018

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A new polymorph of anhydrous sodium alendronate, C 4 H 12 NO 7 P 2 Na, has been synthesized and characterized by single crystal X-ray diffraction as well as infrared spectroscopy and thermal analysis. The title compound crystallizes in the monoclinic P2 1 /c space group. Asymmetric unit consists of one alendronic anion and one sodium cation. An interplay of classical strong O-H O hydrogen bonds creates 3D framework in the crystal. Contrary to previously reported sodium alendronate salts, in which Na + cation is surrounded by six-coordinated sphere, in compound (1), the Na + cation is fivecoordinated in a distorted trigonal-bipyramidal geometry. In order to provide a detailed investigation of the molecular arrangement in view of intermolecular interactions, the title compound was compared with alendronic acid and other known alkali metal alendronate salts, retrieved from the Cambridge Crystal Structure Database. The intercontacts were qualitatively and quantitatively compared using Hirshfeld surface analysis. It highlights that strong O

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“…109 Both crystal forms crystallized in the monoclinic P2 1 /n space group, with the structure of the anhydrate featuring a two-dimensional molecular sheet in the (011) plane and the trihydrate featuring a one-dimensional chain along the (010) direction. A multidisciplinary characterization of the 1:1 methanol, 2:1 ethanol, 2:1 dichloroethane, and monohydrate solvatomorphs of aripiprazole has been conducted to study the various molecular packing in the various forms.…”

Section: Solvatomorphic Systemsmentioning

confidence: 99%

Polymorphism and Solvatomorphism 2009

Brittain¹

2011

Journal of Pharmaceutical Sciences

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Ab initio structure determination of anhydrous sodium alendronate from laboratory powder X-ray diffraction data

Cited by 17 publications

References 21 publications

Coordination Polymers of Increasing Complexity Derived from Alkali Metal Cations and (4-Amino-1-hydroxybutylidine)-1,1-bisphosphonic Acid (Alendronic Acid): The Competitive Influences of Coordination and Supramolecular Interactions

Coordination Polymers of Increasing Complexity Derived from Alkali Metal Cations and (4-Amino-1-hydroxybutylidine)-1,1-bisphosphonic Acid (Alendronic Acid): The Competitive Influences of Coordination and Supramolecular Interactions

Analysis of supramolecular interactions in alendroniate alkali metal salts: synthesis, structure, and properties of novel sodium alendronate polymorph

Polymorphism and Solvatomorphism 2009

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