DOCSLIB.ORG

Crystal Engineering Comes of Age

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Crystal Engineering Comes of Age books & arts Crystal engineering comes of age Crystal Engineering: What has happened since is crystal clear: meeting held in India because the authors A Textbook crystal engineering has facilitated the rapid are native Indians, and India has been at the development of new classes of compound cutting edge of crystal engineering research By Gautam R. Desiraju, that have practical utility, such as porous for more than two decades. Jagadese J. Vittal and coordination polymers — aka metal–organic As the title indicates, Crystal Engineering: Arunachalam Ramanan frameworks (MOFs) — and pharmaceutical A Textbook aims to serve as an introductory co-crystals, which today represent two of the textbook rather than a reference book. It IISC PRESS AND WORLD most active, high-impact areas in chemistry. comprises seven well-balanced chapters, SCIENTIFIC PUBLISHING: Pictured is MOF-5, in which ZnO4 each of which concludes with a set of 2011. 216PP. £65.00 tetrahedra are linked together by benzene problems that are suitable for use in dicarboxylate ligands, forming an extended teaching. The first chapter provides a 3D network with accessible pores. historical perspective that covers the development of crystal engineering and of nce upon a time, a certain well- cognate areas such as X-ray crystallography, known editor of a certain high-profile supramolecular chemistry and properties Ojournal opined on the subject of of crystals. This chapter reminds us that crystal structure prediction by asserting that the foundations of crystal engineering were it was scandalous that solid-state chemists not laid in 1989, and ensures giants such and materials scientists could not predict as Schmidt, Dunitz, Kitaigorodsky, Pauling crystal structures from a priori knowledge and Wöhler receive appropriate credit. of chemical composition (J. Maddox, Nature Chapters 2–4 are titled ‘Intermolecular 335, 201; 1988). Just one year later, almost as Interactions’, ‘Crystal Design Strategies’, if in response, Gautam Desiraju’s book titled and ‘Crystallization and Crystal Growth’, Crystal Engineering: The Design of Organic respectively. These chapters provide the Solids (Elsevier, 1989) was published. background knowledge that is needed to In hindsight, these two events were practice crystal engineering and could watershed moments for the immediate and stand alone for use in other courses. rapid development of crystal engineering, Chapters 5–7 cover three subjects of topical which, it should be noted, overlaps very little importance to contemporary materials with crystal structure prediction. Rather, SCIENTIFIC © WORLD science and are titled ‘Polymorphism’, crystal engineering focuses on the synthesis ‘Multi-Component Crystals’ and of new classes of crystalline materials from A sign that crystal engineering has ‘Coordination Polymers’, respectively. first principles through a strategy that uses come of age was the holding of the first These chapters make extensive use of molecules as if they were Lego building Gordon Research Conference on crystal case studies to highlight concepts and blocks. Desiraju’s definition of crystal engineering in June 2010. This meeting define nomenclature, but not in a manner engineering was apt in 1989 and it has boasted the highest ever first-time that takes sides where there is ambiguity stood the test of time well: “understanding attendance for a Gordon Conference and about terminology. The book concludes of intermolecular interactions in the demonstrated that crystal engineering with a glossary of terms, a tabulation of context of crystal packing and utilization covers all types of molecular building crystallographic space groups, a list of of such understanding in the design of block, that it is international in scope useful websites and a list of recommended new solids with desired physical and and that it has reached the ‘end of the reading. The latter is of note because chemical properties”. beginning’ as crystal engineers have citations are otherwise absent. developed a powerful toolbox in the The length of Crystal Engineering: A Crystal engineering has reached context of crystal design. The focus has Textbook, its modest price, its fair and naturally shifted from design to properties, balanced treatment of topics, and its the ‘end of the beginning’. and this means that there is now a need breadth and style make it perfectly suited to for crystal engineering to be more broadly serve as a one-semester course to introduce It would be fair to assert that there was taught and not just to the next generation crystal engineering to undergraduate or not a lot of respect for crystal engineering of crystal engineers. first-year graduate students in chemistry or back then. Indeed, most chemists and The second sign of the coming of age of materials science. It effectively addresses a materials scientists would have considered crystal engineering is represented by the need that has been created by the explosive even the idea of crystal engineering to be publication of the first textbook devoted to growth of crystal engineering research in an oxymoron as crystals were generally the subject. Crystal Engineering: A Textbook the past two decades. ❐ regarded as being a consequence of ‘nature was released on 28 June 2011 at the 20th abhors a vacuum’, and unusual features International Conference on the Chemistry REVIEWED BY MICHAEL J. ZAWOROTKO of crystal structure were often explained of the Organic Solid State (ICCOSS XX) away as being ‘the result of crystal in Bangalore, India. It is appropriate that Michael Zaworotko is a Professor of Chemistry at packing effects’. the book was released at an international the University of South Florida. NATURE CHEMISTRY | VOL 3 | SEPTEMBER 2011 | www.nature.com/naturechemistry 653 © 2011 Macmillan Publishers Limited. All rights reserved.
Load more

Recommended publications
  • Crystal Structures
    Crystal Structures Academic Resource Center Crystallinity: Repeating or periodic array over large atomic distances. 3-D pattern in which each atom is bonded to its nearest neighbors Crystal structure: the manner in which atoms, ions, or molecules are spatially arranged. Unit cell: small repeating entity of the atomic structure. The basic building block of the crystal structure. It defines the entire crystal structure with the atom positions within. Lattice: 3D array of points coinciding with atom positions (center of spheres) Metallic Crystal Structures FCC (face centered cubic): Atoms are arranged at the corners and center of each cube face of the cell. FCC continued Close packed Plane: On each face of the cube Atoms are assumed to touch along face diagonals. 4 atoms in one unit cell. a 2R 2 BCC: Body Centered Cubic • Atoms are arranged at the corners of the cube with another atom at the cube center. BCC continued • Close Packed Plane cuts the unit cube in half diagonally • 2 atoms in one unit cell 4R a 3 Hexagonal Close Packed (HCP) • Cell of an HCP lattice is visualized as a top and bottom plane of 7 atoms, forming a regular hexagon around a central atom. In between these planes is a half- hexagon of 3 atoms. • There are two lattice parameters in HCP, a and c, representing the basal and height parameters Volume respectively. 6 atoms per unit cell Coordination number – the number of nearest neighbor atoms or ions surrounding an atom or ion. For FCC and HCP systems, the coordination number is 12. For BCC it’s 8.
    [Show full text]
  • Quartz Crystal Division of Seiko Instruments Inc
    (1) Quartz Crystal Division of Seiko Instruments Inc. and affiliates, which is responsible for manufacturing the products described in this catalogue, holds ISO 9001 and ISO 14001 certification. (2) SII Crystal Technology Inc. Tochigi site holds IATF 16949 certification. Quartz Crystal Product Catalogue Electronic Components Sales Head Office 1-8, Nakase, Mihamaku, Chiba-shi, Chiba 261-8507, Japan Telephone:+81-43-211-1207 Facsimile:+81-43-211-8030 E-mail:[email protected] <Manufacturer> SII Crystal Technology Inc. 1110, Hirai-cho, Tochigi-shi, Tochigi 328-0054, Japan Released in February 2019 No.QTC2019EJ-02C1604 Creating Time - Optimizing Time - Enriching Time Seiko Instruments Inc. (SII), founded in 1937 as a member of the Seiko Group specializing in the manufacture of watches, has leveraged its core competency in high precision watches to create a wide range of new products and technologies. Over the years SII has developed high-precision processed parts and machine tools that pride themselves on their sub-micron processing capability, quartz crystals that came about as a result of our quartz watch R&D, and electronic components such as micro batteries. Optimizing our extensive experience and expertise, we have since diversified into such new fields as compact, lightweight, exceedingly quiet thermal printers, and inkjet printheads, a key component in wide format inkjet printers for corporate use. SII, in the years to come, will maintain an uncompromised dedication to its time-honored technologies and innovations of craftsmanship, miniaturization, and efficiency that meet the needs of our changing society and enrich the lives of those around us. SEIKO HOLDINGS GROUP 1881 1917 1983 1997 2007 K.
    [Show full text]
  • WHAT IS...A Quasicrystal?, Volume 53, Number 8
    ?WHAT IS... a Quasicrystal? Marjorie Senechal The long answer is: no one is sure. But the short an- diagrams? The set of vertices of a Penrose tiling does— swer is straightforward: a quasicrystal is a crystal that was known before Shechtman’s discovery. But with forbidden symmetry. Forbidden, that is, by “The what other objects do, and how can we tell? The ques- Crystallographic Restriction”, a theorem that confines tion was wide open at that time, and I thought it un- the rotational symmetries of translation lattices in two- wise to replace one inadequate definition (the lattice) and three-dimensional Euclidean space to orders 2, 3, with another. That the commission still retains this 4, and 6. This bedrock of theoretical solid-state sci- definition today suggests the difficulty of the ques- ence—the impossibility of five-fold symmetry in crys- tion we deliberately but implicitly posed. By now a tals can be traced, in the mineralogical literature, back great many kinds of aperiodic crystals have been to 1801—crumbled in 1984 when Dany Shechtman, a grown in laboratories around the world; most of them materials scientist working at what is now the National are metals, alloys of two or three kinds of atoms—bi- Institute of Standards and Technology, synthesized nary or ternary metallic phases. None of their struc- aluminium-manganese crystals with icosahedral sym- tures has been “solved”. (For a survey of current re- metry. The term “quasicrystal”, hastily coined to label search on real aperiodic crystals see, for example, the such theretofore unthinkable objects, suggests the website of the international conference ICQ9, confusions that Shechtman’s discovery sowed.
    [Show full text]
  • Crystal Structure of a Material Is Way in Which Atoms, Ions, Molecules Are Spatially Arranged in 3-D Space
    Crystalline Structures – The Basics •Crystal structure of a material is way in which atoms, ions, molecules are spatially arranged in 3-D space. •Crystal structure = lattice (unit cell geometry) + basis (atom, ion, or molecule positions placed on lattice points within the unit cell). •A lattice is used in context when describing crystalline structures, means a 3-D array of points in space. Every lattice point must have identical surroundings. •Unit cell: smallest repetitive volume •Each crystal structure is built by stacking which contains the complete lattice unit cells and placing objects (motifs, pattern of a crystal. A unit cell is chosen basis) on the lattice points: to represent the highest level of geometric symmetry of the crystal structure. It’s the basic structural unit or building block of crystal structure. 7 crystal systems in 3-D 14 crystal lattices in 3-D a, b, and c are the lattice constants 1 a, b, g are the interaxial angles Metallic Crystal Structures (the simplest) •Recall, that a) coulombic attraction between delocalized valence electrons and positively charged cores is isotropic (non-directional), b) typically, only one element is present, so all atomic radii are the same, c) nearest neighbor distances tend to be small, and d) electron cloud shields cores from each other. •For these reasons, metallic bonding leads to close packed, dense crystal structures that maximize space filling and coordination number (number of nearest neighbors). •Most elemental metals crystallize in the FCC (face-centered cubic), BCC (body-centered cubic, or HCP (hexagonal close packed) structures: Room temperature crystal structure Crystal structure just before it melts 2 Recall: Simple Cubic (SC) Structure • Rare due to low packing density (only a-Po has this structure) • Close-packed directions are cube edges.
    [Show full text]
  • Bubble Raft Model for a Paraboloidal Crystal
    Syracuse University SURFACE Physics College of Arts and Sciences 9-17-2007 Bubble Raft Model for a Paraboloidal Crystal Mark Bowick Department of Physics, Syracuse University, Syracuse, NY Luca Giomi Syracuse University Homin Shin Syracuse University Creighton K. Thomas Syracuse University Follow this and additional works at: https://surface.syr.edu/phy Part of the Physics Commons Recommended Citation Bowick, Mark; Giomi, Luca; Shin, Homin; and Thomas, Creighton K., "Bubble Raft Model for a Paraboloidal Crystal" (2007). Physics. 144. https://surface.syr.edu/phy/144 This Article is brought to you for free and open access by the College of Arts and Sciences at SURFACE. It has been accepted for inclusion in Physics by an authorized administrator of SURFACE. For more information, please contact [email protected]. Bubble Raft Model for a Paraboloidal Crystal Mark J. Bowick, Luca Giomi, Homin Shin, and Creighton K. Thomas Department of Physics, Syracuse University, Syracuse New York, 13244-1130 We investigate crystalline order on a two-dimensional paraboloid of revolution by assembling a single layer of millimeter-sized soap bubbles on the surface of a rotating liquid, thus extending the classic work of Bragg and Nye on planar soap bubble rafts. Topological constraints require crystalline configurations to contain a certain minimum number of topological defects such as disclinations or grain boundary scars whose structure is analyzed as a function of the aspect ratio of the paraboloid. We find the defect structure to agree with theoretical predictions and propose a mechanism for scar nucleation in the presence of large Gaussian curvature. Soft materials such as amphiphilic membranes, diblock any triangulation of M reads copolymers and colloidal emulsions can form ordered structures with a wide range of complex geometries and Q = X(6 ci)+ X (4 ci)=6χ , (1) − − topologies.
    [Show full text]
  • Crystal Structures and Symmetry 1 Crystal Structures and Symmetry
    PHYS 624: Crystal Structures and Symmetry 1 Crystal Structures and Symmetry Introduction to Solid State Physics http://www.physics.udel.edu/∼bnikolic/teaching/phys624/phys624.html PHYS 624: Crystal Structures and Symmetry 2 Translational Invariance • The translationally invariant nature of the periodic solid and the fact that the core electrons are very tightly bound at each site (so we may ignore their dynamics) makes approximate solutions to many-body problem ≈ 1021 atoms/cm3 (essentially, a thermodynamic limit) possible. Figure 1: The simplest model of a solid is a periodic array of valance orbitals embedded in a matrix of atomic cores. Solving the problem in one of the irreducible elements of the periodic solid (e.g., one of the spheres in the Figure), is often equivalent to solving the whole system. PHYS 624: Crystal Structures and Symmetry 3 From atomic orbitals to solid-state bands • If two orbitals are far apart, each orbital has a Hamiltonian H0 = εn, where n is the orbital occupancy ⇐ Ignoring the effects of electronic corre- lations (which would contribute terms proportional to n↑n↓). + +++ ... = Band E Figure 2: If we bring many orbitals into proximity so that they may exchange electrons (hybridize), then a band is formed centered around the location of the isolated orbital, and with width proportional to the strength of the hybridization PHYS 624: Crystal Structures and Symmetry 4 From atomic orbitals to solid-state bands • Real Life: Solids are composed of elements with multiple orbitals that produce multiple bonds. Now imagine what happens if we have several orbitals on each site (ie s,p, etc.), as we reduce the separation between the orbitals and increase their overlap, these bonds increase in width and may eventually overlap, forming bands.
    [Show full text]
  • Crystal Symmetry Groups
    X-Ray and Neutron Crystallography rational numbers is a group under Crystal Symmetry Groups multiplication, and both it and the integer group already discussed are examples of infinite groups because they each contain an infinite number of elements. ymmetry plays an important role between the integers obey the rules of In the case of a symmetry group, in crystallography. The ways in group theory: an element is the operation needed to which atoms and molecules are ● There must be defined a procedure for produce one object from another. For arrangeds within a unit cell and unit cells example, a mirror operation takes an combining two elements of the group repeat within a crystal are governed by to form a third. For the integers one object in one location and produces symmetry rules. In ordinary life our can choose the addition operation so another of the opposite hand located first perception of symmetry is what that a + b = c is the operation to be such that the mirror doing the operation is known as mirror symmetry. Our performed and u, b, and c are always is equidistant between them (Fig. 1). bodies have, to a good approximation, elements of the group. These manipulations are usually called mirror symmetry in which our right side ● There exists an element of the group, symmetry operations. They are com- is matched by our left as if a mirror called the identity element and de- bined by applying them to an object se- passed along the central axis of our noted f, that combines with any other bodies.
    [Show full text]
  • Quasicrystals a New Kind of Symmetry Sandra Nair First, Definitions
    Quasicrystals A new kind of symmetry Sandra Nair First, definitions ● A lattice is a poset in which every element has a unique infimum and supremum. For example, the set of natural numbers with the notion of ordering by magnitude (1<2). For our purposes, we can think of an array of atoms/molecules with a clear sense of assignment. ● A Bravais lattice is a discrete infinite array of points generated by linear integer combinations of 3 independent primitive vectors: {n1a1 + n2a2 + n3a3 | n1, n2, n3 ∈ Z}. ● Crystal structures = info of lattice points + info of the basis (primitive) vectors. ● Upto isomorphism of point groups (group of isometries leaving at least 1 fixed point), 14 different Bravais lattice structures possible in 3D. Now, crystals... ● Loosely speaking, crystals are molecular arrangements built out of multiple unit cells of one (or more) Bravais lattice structures. ● Crystallographic restriction theorem: The rotational symmetries of a discrete lattice are limited to 2-, 3-, 4-, and 6-fold. ● This leads us to propose a “functional” definition: A crystal is a material that has a discrete diffraction pattern, displaying rotational symmetries of orders 2, 3, 4 and 6. ● Note: Order 5 is a strictly forbidden symmetry → important for us. Tessellations aka tilings Now that we have diffraction patterns to work with, we consider the question of whether a lattice structure tiles or tessellates the plane. This is where the order of the symmetry plays a role. The crystals are special, as they display translational symmetries. As such, the tiling of their lattice structures (which we could see thanks to diffraction patterns) are periodic- they repeat at regular intervals.
    [Show full text]
  • Multidisciplinary Design Project Engineering Dictionary Version 0.0.2
    Multidisciplinary Design Project Engineering Dictionary Version 0.0.2 February 15, 2006 . DRAFT Cambridge-MIT Institute Multidisciplinary Design Project This Dictionary/Glossary of Engineering terms has been compiled to compliment the work developed as part of the Multi-disciplinary Design Project (MDP), which is a programme to develop teaching material and kits to aid the running of mechtronics projects in Universities and Schools. The project is being carried out with support from the Cambridge-MIT Institute undergraduate teaching programe. For more information about the project please visit the MDP website at http://www-mdp.eng.cam.ac.uk or contact Dr. Peter Long Prof. Alex Slocum Cambridge University Engineering Department Massachusetts Institute of Technology Trumpington Street, 77 Massachusetts Ave. Cambridge. Cambridge MA 02139-4307 CB2 1PZ. USA e-mail: [email protected] e-mail: [email protected] tel: +44 (0) 1223 332779 tel: +1 617 253 0012 For information about the CMI initiative please see Cambridge-MIT Institute website :- http://www.cambridge-mit.org CMI CMI, University of Cambridge Massachusetts Institute of Technology 10 Miller’s Yard, 77 Massachusetts Ave. Mill Lane, Cambridge MA 02139-4307 Cambridge. CB2 1RQ. USA tel: +44 (0) 1223 327207 tel. +1 617 253 7732 fax: +44 (0) 1223 765891 fax. +1 617 258 8539 . DRAFT 2 CMI-MDP Programme 1 Introduction This dictionary/glossary has not been developed as a definative work but as a useful reference book for engi- neering students to search when looking for the meaning of a word/phrase. It has been compiled from a number of existing glossaries together with a number of local additions.
    [Show full text]
  • Crystal Structure
    Physics 927 E.Y.Tsymbal Section 1: Crystal Structure A solid is said to be a crystal if atoms are arranged in such a way that their positions are exactly periodic. This concept is illustrated in Fig.1 using a two-dimensional (2D) structure. y T C Fig.1 A B a x 1 A perfect crystal maintains this periodicity in both the x and y directions from -∞ to +∞. As follows from this periodicity, the atoms A, B, C, etc. are equivalent. In other words, for an observer located at any of these atomic sites, the crystal appears exactly the same. The same idea can be expressed by saying that a crystal possesses a translational symmetry. The translational symmetry means that if the crystal is translated by any vector joining two atoms, say T in Fig.1, the crystal appears exactly the same as it did before the translation. In other words the crystal remains invariant under any such translation. The structure of all crystals can be described in terms of a lattice, with a group of atoms attached to every lattice point. For example, in the case of structure shown in Fig.1, if we replace each atom by a geometrical point located at the equilibrium position of that atom, we obtain a crystal lattice. The crystal lattice has the same geometrical properties as the crystal, but it is devoid of any physical contents. There are two classes of lattices: the Bravais and the non-Bravais. In a Bravais lattice all lattice points are equivalent and hence by necessity all atoms in the crystal are of the same kind.
    [Show full text]
  • The American Mineralogist Crystal Structure Database
    American Mineralogist, Volume 88, pages 247–250, 2003 The American Mineralogist crystal structure database ROBERT T. DOWNS* AND MICHELLE HALL-WALLACE Department of Geosciences, University of Arizona, Tucson, Arizona 85721-0077, U.S.A. ABSTRACT A database has been constructed that contains all the crystal structures previously published in the American Mineralogist. The database is called “The American Mineralogist Crystal Structure Database” and is freely accessible from the websites of the Mineralogical Society of America at http://www.minsocam.org/MSA/Crystal_Database.html and the University of Arizona. In addition to the database, a suite of interactive software is provided that can be used to view and manipulate the crystal structures and compute different properties of a crystal such as geometry, diffraction patterns, and procrystal electron densities. The database is set up so that the data can be easily incorporated into other software packages. Included at the website is an evolving set of guides to instruct the user and help with classroom education. INTRODUCTION parameters; (5) incorporating comments from either the origi- The structure of a crystal represents a minimum energy con- nal authors or ourselves when changes are made to the origi- figuration adopted by a collection of atoms at a given tempera- nally published data. Each record in the database consists of a ture and pressure. In principle, all the physical and chemical bibliographic reference, cell parameters, symmetry, atomic properties of any crystalline substance can be computed from positions, displacement parameters, and site occupancies. An knowledge of its crystal structure. The determination of crys- example of a data set is provided in Figure 1.
    [Show full text]
  • Crystal Engineering for Product and Process Design
    Crystal Engineering for Process and Product Design Michael F. Doherty Department of Chemical Engineering University of California Santa Barbara Pan American Study Institute on Emerging Trends in Process Systems Engineering1 Why Crystals? • Crystalline organic solids ubiquitous in ¾ chemicals & specialty chemicals ¾ home & personal care ¾ food and pharma • Almost 100% of small MW drugs are isolated as crystalline materials • Over 90% of ALL pharmaceutical products are formulated in particulate, generally crystalline form • Pharma industry worldwide > $500 billion/year sales 2 Why Modeling? “If you can’t model your process, you don’t understand it. If you don’t understand it, you can’t improve it. And, if you can’t improve it, you won’t be competitive in the 21st century.” Jim Trainham, DuPont/PPG 3 Conceptual Design You can’t understand the process if you don’t understand the chemistry 4 Role of Engineer in Industry To make, evaluate and justify technical decisions in support of business 5 Why Crystal Shape? • Crystal shape impacts: ¾ Downstream processing – filtering, washing, drying, etc (avoid needles and flakes) ¾ End use properties – bulk density, mechanical strength, flowability, dispersibility and stability of crystals in suspension, dissolution rate, bioavailability, catalytic properties ¾ Nano switches, ….. • The ability to predict and manipulate crystal shape enables optimized product & process design 6 Crystallization – Multiple Tasks • Separation and purification task ¾ crude separation followed by recrystallization ¾ crystal
    [Show full text]