The Crystal Structure of Baca(CO3)2 (Barytocalcite)
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JOURNAL O F RESEARCH of the National Bureau of Standards - A. Physics and Chemistry Vol. 75A, No.3, May - June 1971 The Crystal Structure of BaCa(C03)2 (barytocalcite) B. Dickens and J. S. Bowen* Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234 (February 3, 1971) The barytocal c ite phase of BaCa(CO,,), c rysta llizes in the monoclinic unit cell a= 8.092(1) A, b = 5.2344(6) A, c= 6.544(1) A, (3 = 106.05(1t at 25 °C with cell conte nts of 2[B aCa(CO,,), I. The Slru et ure pre viou s ly reported by Aim is correct in its coarse details but has been rede te rmined he re and re fin ed to R w = 0.028 , R = 0.023 in space-gro up P2 1 / m using 1652 observed re Rections. Correcti ons we re made for absorption, isotropic extin cti on, a nd ano ma lous di s pe rsio n. The struc ture of barytocalc ite has an ... AB C ABC ... s tackin g of cati on layers a nd re peat e very 3 la yers. The cal cite phase of CaCO:1 has an AB C c ati on layer seque nce a nd re peats every 6 layers. The orie ntations of th e CO:1 gro ups in barytocalcite a re like th e CO:1 gro up ori entati o n in th e a ragonit e phase of CaCO:1 , and are rotate d a bout 30 ° from t he CO" group ori entati on in calcite. The cation layer seque nce in a ragonite is. ABAB. and th e s tructure re peats eve ry 2 laye rs. The Ca ion in barytocalcit e is coordinat,ed to seve n o*ygens, in c lu ding a n edge of a CO" group, with Ca .. ° di s tances in the ra nge 2. 305(2) A to 2.518(2) A. The Ba io n is coordin ated to fiv e edges a nd one apex of the CO:1 groups with Ba . .. ° di stances ra ngin g from 2.729(3) A to 3. 14;0(2) A. The di ~ lances of th e C atoms in the CO:1 ~r o up s fro m the pl anes of the °a toms are 0.025(5) A a nd 0.022(4) A for C(l ) and C(2), respectivel y. Key words : Aragonite; barium calcium carbonate; calcium carbonate; crys ta l structure; single crys tal x-ray diffraction. 1. Introduction standard deviations on any para meters and used limited film data. The structure of barytocalcite was, The crystal s tructure of th e baryto calcite phase of therefore, poorl y known by modern s tandards, and BaCa(CO:lh has been redetermined in our program of has been redetermined he re. structural investi gations [Ili on calcium carbonates, calcium phos phates, associated hydrates, and related 2. Data Collection and Structure Refinement compounds. The structural features in these com pounds have important applications in understanding The crystal used in the data collection is an ap· possible epitaxy, syntaxy, and substitutional solid proximate sphere, radius 0.094(3) mm , ground from a solution in biological min erals such as hydroxyapatite crystal from mineral sample R1 3868 (from Cumberland, (Ca5(P04 h OH) and calcite, aragonite and vaterite, England) obtained from the National Museum of the three phase of anhydrous CaC03 . Natural History, Smithsonian Institution, Washington, From a consideration of the morphologies, d'spacings D.C., and supplied by J. S. White, Jr. It was mounted and possible space·groups of barytocalcite and calcite, in our usual way [4]. Gossner and Mussgnug [2J gave a structure for baryto· calcite whi ch is a rearrangement of the calcite struc· formula (i deal): BaCa(CO:1}2 (barytocalcite phase). ture. They assumed the space·group to be P21 . AIm [3] cell: monoclinic used a relatively large (0.3 mm) single crystal of baryto· a=8.092(1) A at25°C calcite and unfiltered Cu radiation to s:o]] ect photo· b = 5.2344(6) graphic data from the hOl , hll, hkO and hkh levels. He A c = 6.544(1) A also assumed the space·group to be P21 , rather than f3 = 106.05 (l) ~ P21/m , on steri c consid erations which are inva"ltd. The volume = 266.4 A3 structure he gave for barytocalcite differs from that space·group P2,/m; cell contents 2(BaCa(C03 h] given by Gossner and Mussgnu g in the orientations of reciprocal lattice extinctions, OkO :k= 2n + 1 the CO:3 groups. However, AIm made no correcti ons for calculated density 3.72 g' cm- 3 ; observed density what mu s t have been considerable absorption, gave no 3.71 g' cm- 3 [5]. *Hcscarch Associate of tlu' Americ an Dt 'll lal Associa tion at the National Bureau of S ta ndard s. \Va s hillj.!ton. D.C. 202:,4. In the determination of the unit cell and in the col· I Fi gures in b,'aekct s indic at e 11 1(' lit erature refe re nces a t the e nd of thi s pa pe r. lection and processing of data, the general procedure 197 , l in reference [4] was followed. In the present case, minimized lw(lFol-IFcl)t, and included those un 3379 reflections were collected from the ±h+k+l and observed reflections for which F hkl calculated more ±h-k+l quadrants and merged into a unique set of than 2u-(F hkl). 1772, of which 1652 are "observed" and 120 are The highest peak in an electron density difference "unobserved." The R factor o;;ynthesis calculated after anisotropic refinement was equivalent to about 1/3 of an electron and was 0.49 A L IFI;kl-F~kll/LF';kl hkl from Ba. When the space-group is assumed to be P2 1 the largest correlation coefficients are 0.90 to 0.95 with i < j between pairs F ~kl and F I,kl of observed between (i) x of 0(1) and x of 0(2), (ii) z of 0(1) and z of equivalent reflections F hkl was 0.018 calculated over 0(2), (iii) x of 0(4) and x of 0(5) and (iv) z of 0(4) and 1189 pairs. i and j are the sequence numbers in the z of 0(5); 0.80 to 0.90 between (i) B I I of 0(1) and B II of list of equivalent reflections. Absorption corrections 0(2), (ii) B 13 of 0(4) and B 13 of 0(5), and (iii) B23 of 0(4) for a sphere with fL=85.6 cm- 1 were applied. The and B23 of 0(5). There are 48 correlation coefficients maximum and minimum transmission factors were greater than 0.50. 0.347 and 0.317, respectively. The isotropic extinction parameter, r , where The 0 - 20 scans were carried out on an automated F2 = F~n c (l + f3rF~nC> and F unc is the structure factor Picker t diffractometer at 2°/ min for ZIJ; backgrounds uncorrected for extinction, was then refined together were counted for 20 s each. Because the least signifi· with the structural and scale parameters using the cant digit in all counts was dropped by the Picker least-squares program RFINE written by L. W. Finger hardware, standard deviations, u- hkl, of the structure of the Carnegie Institution of Washington; these refine factors , Fhkl, were estimated from U-II",I=Fllkd5.7 for ments included only the observed reflections. The F'lkl < 5.7; U-IIk{= 1 for 5.7 < Fhkl < 30; andu-IIkl=Fllkd30 resulting R values were R w=0.027, R=0.022. The for Fhkl > 30 where Fmax on this arbitrary scale is 113. structure obtained had essentially the symmetry The scattering factors used were those for the neutral P21 /m; subsequent anisotropic refinement in P2 1 /m atoms in reference 6 for the x·ray 67 refinements and gave Rw= 0.036, R = 0.028 without extinction refine those in references 7 and 8 for the extinction and ment and R w= 0.028, R = 0.025 in refinements in anomalous dispersion refinements. which r refined to 0.000100(4) cm. All unconstrained The quasi·normalized structure factor statistics on parameters were varied. Finally, three cycles of refine our barytocalcite data indicate that the structure is ment including corrections for anomalous dispersion acentric, since < IE I > = 0.885, < £t > = 1.00 (fixed), and extinction gave R w=0.028, R=0.023; r became < lEt - 11 > = 0.709; the corres ponding . theoretical 0.000100(5) em. The largest chalJge in the other param values are 0.886, 1.000, 0.736 for the acentric case and eters was an increase of ~ 0.1 At in allB ii parameters 0.798, 1.000, 0.968 for the centric case. E is the quasi of Ca. In the final cycle, the average shift/error was normalized structure factor [9] . The fraction of E 0.02, and the standard deviation of an observation of values greater than 1.0,2.0 and 3.0, respectively, was unit weight, [lw(Fo-Fc)2 / (1652-56)]1/2, was 0.43. found to be 0.405 , 0.0027 and 0.0000; the corresponding The final Rw values for the centric and acentric cases theoretical values are 0.368, 0.0183 , 0.0001 for the are near the limit of the experimental data.