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The Crystal Structure of [Mg (H O) (HCO ) ]+Cl–, Containing A

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The Crystal Structure of [Mg (H O) (HCO ) ]+Cl–, Containing A + – The Crystal Structure of [Mg2(H2O)6(HCO3)3] Cl , Containing a Magnesium-based Hetero-polycation Robert E. Dinnebier and Martin Jansen Max-Planck Institut f¨ur Festk¨orperforschung, Heisenbergstraße 1, D-70569 Stuttgart, Germany Reprint requests to Prof. Dr. R. Dinnebier. Fax: +49-(0)711-6891139. E-mail: [email protected] Z. Naturforsch. 2008, 63b, 1347 – 1351; received September 12, 2008 The crystal structure of di-magnesium hexahydrate trihydrogencarbonate chloride, [Mg (H O) - + − 2 2 6 (HCO3)3] Cl , has been determined from high-resolution laboratory powder diffraction data (lattice parameters at r. t.: a = 8.22215(2), c = 39.5044(2) A,˚ V = 2312.85(2) A˚ 3, space group R3¯c, Z =6). The crystal structure of [Mg (H O) (HCO ) ]+Cl− is built up of alternating sheets of Cl− anions 2 2 6+ 3 3 and complex [Mg2(H2O)6(HCO3)3] cations consisting of two Mg(OH2)3O3 octahedra intercon- nected by three disordered hydrogen carbonate groups. The packing can be described as a cubic close + − packing of [Mg2(H2O)6(HCO3)3] cations with the Cl anions filling all octahedral voids. In the temperature range from r. t. up to decomposition, which takes place in the range 398 K < T < 413 K, no structural phase transition occurs. Key words: Powder Diffraction, Hetero-polycation, Magnesium Chloride Carbonate Hydrate Introduction If Mg(OH)2,MgCl2 and water are mixed, the high quality Sorel cements are formed with many applica- The quaternary system Mg(OH)2-MgCl2-MgCO3- tions in industrial flooring [11]. In the ternary phase H2O contains a variety of technologically important diagram of magnesium oxychlorides, four compounds phases. In particular the binary components mag- have been identified so far, which are defined by nesium carbonate MgCO3 (magnesite)[1]and the number of Mg(OH)2 in their formulas: 2Mg- · · · · magnesium hydroxide Mg(OH)2 (brucite) [2] are well (OH)2 MgCl2 4H2O (F2-phase); 3Mg(OH)2 MgCl2 investigated. While magnesite is mainly used to pro- 8H2O (F3-phase) [12], 5Mg(OH)2·MgCl2·8H2O(F5- duce magnesium metal and basic refractory bricks, as phase) [13], and 9Mg(OH)2·MgCl2·5H2O (F9-phase). a drying agent for hands in rock climbing, gymnastics, Among these four phases, only the F3 and the F5 rep- and weight lifting, as well as in flooring, fireproofing, resentatives are stable at r. t. and constitute the major fire extinguishing compositions, cosmetics, dusting binder phases in Sorel cements [14]. powder, and toothpaste, brucite has applications as a Some of these materials react with carbon dioxide fire retardant, an antacid to neutralize stomach acid, a in air forming magnesium oxychlorocarbonates. The laxative, a non antiperspirant armpit deodorant, and is only confirmed compound so far is chlorartinite which used in bleaching solutions to whiten clothes and as a is of key importance for the quality of Sorel cements non-hazardous alkali to neutralize acidic wastewaters. and occurs when the wet F3 phase is exposed to air. Several hydrated forms of magnesite exist as The timescale of the binding reactions spans from sec- minerals, like the di-, tri-, and pentahydrates known onds to years. Chlorartinite also occurs as a volcanic as barringtonite (MgCO3·2H2O) [3], nesque- exhalation product in Kamchatka, and its crystal struc- honite (MgCO3·3H2O) [4], and lansfordite (Mg- ture was recently solved from high-resolution powder CO3·5H2O) [5], respectively. Some basic forms diffraction data [15, 16]. Chloratinite forms a zeolite- such as artinite (MgCO3 ·Mg(OH)2 ·3H2O) [6], like honeycomb framework structure. hydromagnestite (4MgCO3·Mg(OH)2·4H2O) [7], A second magnesium chloride carbonate hydrate dypingite (4MgCO3·Mg(OH)2·5H2O) [8], gior- compound with unknown crystal structure was re- giosite (Mg5(CO3)4(OH)2·5H2O) [9], and pokrovskite ported by Schmittler [17] with the possible formula (Mg2(CO3)(OH)2·0.5H2O) [10] occur as minerals. Mg2Cl2CO3·7H2O. It can be expected that many more 0932–0776 / 08 / 1200–1347 $ 06.00 c 2008 Verlag der Zeitschrift f¨ur Naturforschung, T¨ubingen · http://znaturforsch.com + − 1348 R. E. Dinnebier – M. Jansen · Crystal Structure of [Mg2(H2O)6(HCO3)3] Cl + phases exist in this quaternary system with interest- Table 1. Crystallographic data for [Mg2(H2O)6(HCO3)3] Cl ing crystal structures and properties. In the course of at 298 K. + − a further examination of this system, we have synthe- Compound [Mg2(H2O)6(HCO3)3] Cl + sized the new ionic compound [Mg2(H2O)6(HCO3)3] Temperature, K 298 −1 Cl−. Since single crystals of sufficient size and quality Formula weight, g mol 375.21 Space group R3¯c (no. 167) for single crystal diffraction could not be obtained, the Z 6 determination of the crystal structure was performed a, A˚ 8.22214(3) by means of high-resolution laboratory X-ray powder c, A˚ 39.5044(2) V, A˚ 3 2312.84(2) diffraction. −1 µ(CuKα1), cm 37.8 ρ −3 Experimental Section calc,gcm 1.61 λ, A˚ 1.54059 a Synthesis Rp , % 2.94 a Rwp , % 3.88 At adding 7.5 mL of dest. H2O to a mixture of 20.2 mg a RF2 , % 2.71 MgCl2·6H2O and 17.4 mg Mg(OH)2, a white suspension Starting angle 2θ,deg 2 formed. The slurry was sealed in a glass ampoule and kept Final angle 2θ,deg 92 for 1 month at r. t. After heating to 100 ◦C for 24 h, the am- Step width 2θ, deg 0.009 poule was opened and kept under atmospheric conditions un- Time/scan, hrs. 24 til a white residue remained. The product was filtered off and No. of variables 48 No. of reflections 225 placed for 12 h at slightly reduced pressure in an exsiccator, a R , R ,andR as defined in TOPAS (Bruker AXS). where it showed no noticeable change in consistency. The p wp F2 ◦ sample was then kept at 35 C for one week. For filling cap- refinements [19]. From volume increments Z was determined illaries for X-ray diffraction, the waxy sample was levigated as 6. with glass powder. The peak profiles and precise lattice parameters were de- termined by a LeBail fit [20] using the fundamental param- Laboratory powder diffraction eter (FP) approach of TOPAS [21]. Due to the fact that the High-resolution X-ray powder diffraction patterns of geometry of the V˚antag-1 PSD is not fully characterized by + − [Mg2(H2O)6(HCO3)3] Cl were recorded at different tem- FP’s, fine tuning of the available parameters was performed peratures on a powder diffractometer (D-8, Bruker-AXS, by using refined values of the FPs from a precise measure- CuKα1 radiation from a primary Ge(111) Johanson-type ment of the NIST line profile standard SRM 660a (LaB6)in monochromator; V˚antag-1 position sensitve detector (PSD) a 0.1 mm capillary over the full 2θ range of the diffractome- with an opening angle of 6◦ in Debye-Scherrer geome- ter. The refinements converged quickly. try) with the sample sealed in a borosilicate glass capil- No related crystal structure could be found in the ICSD lary of 0.5 mm diameter (Hilgenberg glass no. 50). For database (FIZ Karlsruhe). Therefore, structure determination the measurements at elevated temperature, a water-cooled was performed in space group R3¯c by the global optimiza- capillary heating stage (mri Physikalische Ger¨ate GmbH) tion method of simulated annealing (SA) as implemented in with a temperature stability ≤ 1 K was used. All samples TOPAS [22]. Since the exact number of atoms was not known were spun during measurement for better particle statistics. apriori, 2 magnesium atoms, 2 chlorine atoms and 6 oxy- + − At r. t., data of [Mg2(H2O)6(HCO3)3] Cl were taken in gen atoms with a merging radius of 0.6 A˚ for each kind of steps of 2θ = 0.009◦ from 2θ = 2.0 – 92.0◦ at a scanning atoms were introduced to the simulated annealing run. After speed of 0.05◦ min−1. In the range 323 ≤ T ≤ 533 K, data several runs, a meaningful crystal structure was found. As + − for [Mg2(H2O)6(HCO3)3] Cl were taken in increments main structural motif, groups of two MgO6 octahedra facing of 15 K with a step width of 2θ = 0.009◦ from 2θ =4.0– each other were identified with additional electron density 64.0◦ for 3 h each. For structure determination and refine- between the octahedra, completing triangles of oxygen atoms ment, the program TOPAS 4.0 (Bruker AXS) was used. with a central atom of lower scattering power, thus suggest- Indexing of the diffraction data collected at T = 298 K ing the existence of CO3 groups as linking elements. Consec- was performed by iterative use of singular value decompo- utive Rietveld refinements confirmed this idea and revealed sition (LSI) as implemented in the program TOPAS [18], the presence of disorder for the CO3 groups in a sense that leading to a rhombohedral unit cell with lattice parameters the two oxygen atoms connecting to the two MgO6 octahedra a = 8.22214(3), and c = 39.5044(2) A.˚ The most probable have the function of the hinges of a swinging door, leaving space groups could be determined as R3c (no. 161), or R3¯c the third unconnected oxygen atom with a large displacement (no. 167) from the observed extinction rules of which the lat- parameter in the direction of the swing. Thus, the introduc- ter could subsequently be confirmed by successful Rietveld tion of a slack soft constraint for that particular C–O bond + − R. E. Dinnebier – M.
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