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DaltonTransactionsAn international journal of inorganic chemistry

1477-9226(2010)39:1;1-K

www.rsc.org/dalton Volume 39 | Number 3 | 21 January 2010 | Pages 657–964

Volume 39 | N

umber 3 | 2010

Dalton Transactions

Pages 657–964

PAPERManzano et al.Experimental and computational study of the interplay between C–H/p and anion–p interactions

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This journal is © The Royal Society of Chemistry [2011] Dalton Trans., [2011], [vol], 00–00 | 1

Structural relationships among LiNaMg[PO4]F and Na2M[PO4]F (M = Mn-Ni, and Mg), and the magnetic structure of LiNaNi[PO4]F

Hamdi Ben Yahiaa,*, Masahiro Shikanoa,*, Hironori Kobayashia, Maxim Avdeevb, Samuel Liuc, Chris D. Lingc

Received (in XXX, XXX) Xth XXXXXXXXX 2011, Accepted Xth XXXXXXXXX 20XX 5

DOI: 10.1039/b000000x

The new compound LiNaMg[PO4]F has been synthesized by wet chemical reaction route. Its crystal structure was determined from single-crystal X-ray diffraction data. LiNaMg[PO4]F crystallizes with the monoclinic pseudomerohedrally twinned LiNaNi[PO4]F structure, space group P21/c, a = 6.772(4), b = 11.154(6), c = 5.021(3) Å, β = 90.00(1) ° and Z = 4. The structure contains [MgO3F]n chains made up of 10

zigzag edge-sharing MgO4F2 octahedra. These chains are interlinked by PO4 tetrahedra forming 2D-Mg[PO4]F layers. The alkali metal atoms are well ordered in between these layers over two atomic positions. The use of group-subgroup transformation schemes in the Bärnighausen formalism enabled us to determine precise phase transition mechanisms from LiNaNi[PO4]F- to Na2M[PO4]F-type structures (M = Mn-Ni, and Mg) (see video clip1 and 2). The crystal and magnetic structure and properties of the 15

parent LiNaNi[PO4]F phase were also studied by magnetometry and neutron powder diffraction. Despite rather long interlayer distance, dmin(Ni+2-Ni+2)~6.8 Å, the material develops long-range magnetic order below 5 K. The magnetic structure can be viewed as antiferromagnetically coupled ferromagnetic layers with moments parallel to the b-axis.

1. Introduction 20

There have been a number of studies on compounds of the formula AMPO4, where A is an alkali atom and M is a transition metal.1and ref. therein The crystal structures of AMPO4 depend strongly on the size of the monovalent A+ cation. With A = Li, the AMPO4 compounds adopt the olivine-type structure. Since the 25

study of its electrochemical properties by Goodenough et al.,2 LiFePO4 has been extensively studied among the olivine series LiMPO4. Several studies have shown that LiFePO4 is a promising high-potential cathode material for rechargeable Li-ion batteries.3-

5 With A = Na, the AMPO4 (M = Mn-Co) compounds have the 30

maricite-type structure.6 When the LiMPO4 (M = Mg, Co, Ni) compounds are mixed with LiF, the Li2MPO4F fluorophosphates are formed and they crystallize with the 3D-Li2NiPO4F-type structure. 7-8 The Li2MPO4F (M = Mn, Fe) phases could not be synthesised using 35

conventional synthesis routes. However, these phases could be

*,aResearch Institute for Ubiquitous Energy Devices, National Institute ofAdvanced Industrial Science and Technology (AIST), Midorigaoka 1-8-31, Ikeda, Osaka 563-8577, Japan. Fax: +81-72-751-9609; Tel: +81-72-751-7932;E-mail:benyahia.hamdi@voila.fr,shikano.masahiro@aist.go.jp.bBragg Institute, B87, Australian Nuclear Science and TechnologyOrganisation, Locked Bag 2001 Kirrawee DC NSW 2232, Australia. c School of Chemistry, The University of Sydney, Sydney, NSW 2006,Australia. † Electronic Supplementary Information (ESI) available: SeeDOI: 10.1039/b000000x/

obtained by electrochemical ion exchange starting from the Na2MnPO4F and by lithium intercalation into the tavorite LiFePO4F.9-11 When the NaMPO4 (M = Mn-Ni and Mg) compounds are mixed with NaF, the Na2MPO4F fluorophosphates 40

are formed and they crystallize with three different layered structures strongly related to each other. 12 and ref. therein Since, the crystal structures of the A2MPO4F compounds are very sensitive to any volume change, related to the size of the alkali metal or the transition metal atoms, our research group has 45

recently focused on the synthesis and the study of the physical properties of new compositions. Indeed, we succeeded to discover several phases (LiNaCo[PO4]F, Li2-xNaxFe[PO4]F, LiNaFe1-xMnx[PO4]F, and Li2Mg[PO4]F crystallizing with the Li2Ni[PO4]F-type structure and LiNaMg[PO4]F, LiNaNi[PO4]F, 50

and Na2Ni[PO4]F crystallizing with two different layered structures).12-16 Furthermore, we discovered Li9Mg3[PO4]4F3 which crystallizes with a new structure type closely related to Na2Mn[PO4]F and which exhibits a high ionic conductivity σ of 10−4 S cm−1 at 300 °C.17 55

In this paper, we report the crystal structure study of the new compound LiNaMg[PO4]F and discuss in details its structural relationship to the Na2M[PO4]F (M = Mn-Ni, and Mg) compounds. We also characterized the parent LiNaNi[PO4]F phase by powder neutron diffraction and magnetic susceptibility 60

measurements. This work is a complement to the previously studied Li2-xNaxNi[PO4]F system.

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1. Synthesis

polycrystallinNaNi[PO4]F woichiometric mbtained by heaNH4)H2PO4 at 3

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ne (powder) swere prepared bmixture of NaFating a 1:2:2 350 °C for 6 1) (LiNi[PO4]

O3, NiO, and (Nand at 850 °C fhanol for 2 h inied, pelletized

was also preparemixture of L. The starting mthen left stirrinThe obtained

C for 8 h in a pMg[PO4]F as adentified impurind fired at 1000rate of 15 °C/h

colorless singleidentified in th

e X-ray (ED) analyses.

croprobe analy

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sitions of the cNaMg[PO4]F (ot sufficient to

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amples of Liby direct solid-sF, LiMg[PO4] mixture of Lh and at 750 was obtained b

NH4)H2PO4 at for 18 h). The mn a planetary ba

and fired at ed by a wet cheLiF, NaNO3, materials were dng for a few ho

powder was thplatinum cruciba major phaseties. This mixtu

0 °C, then slowh. After washine crystals of Lhe sample using

DX) and sing

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es of differenon the diffractoanalyzer installscope (SEM). Tarbon coated m(Fig. 2). The determine the l

stry [2011]

d experimenta

iNaMg[PO4]F state reaction f

(LiMg[PO4] i2CO3, MgO, °C for 24 h) by heating a 1350 °C for 6 hmixtures were wall-mill. The mi

580 °C for 4emical route fro

NH4H2PO4, dissolved in boiours until the when pelletized ble under air. T

alongside a ure was placed

wly cooled to rong the mixture w

iNaMg[PO4]F g a combination

gle crystal X

nt single crysometer were carled a JSM-500The experimentmaterial were c

resolution of lithium content.

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check the purider XRD measuom temperatureep size of 0actometer operahing refinemeram.18 The bacion, and the pe The refined u

974(7), c = 5.0n good agreeme S1. ngle crystals oted on the baaction spots. DaX (Bruker) diessing and all reram. A Gaussiahape was deterction details, se

Magnetic susce

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ment with the si

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eptibility measu

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tem (PPMS) M) probe. The

rans., [2011], [v

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NaMg[PO4]F pperformed. Data

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urements

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LiNaMg[PO4]F

powder, routina were collected 2θ 80 ° with-TTR (Rigakun. Full patternthe Jana2006

ng a Legendrgt function (Fig 6.8144(4), b =

d V = 382.70(6ata presented in

for XRD werharpness of thut on a SMARTradiation. Datith the Jana2006was applied andscope. For dat

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2

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the zero field-cunder the field

2.5. Neutron p

Neutron powdhigh-resolution(Lucas HeightsÅ. For the meainto a 6 mm diabetween 3 and using a closedwas performedscattering lengt

3. RESULT

3.1. Structure

The cell paraorthorhombic absences were group. Therefospace group P1the sir2004 prodifference-Four(18 atoms). Tprograms,20 wemonoclinic spstructural modereduced the nuof two. Using the residual fa0.532 for 37 residual factor0.5116 for 82 metal occupanthe expected vawere well-behfactors and thsymmetry probsuite program wThe two-fold twinning eleme(-1 0 0, 0 -1 0,residuals immeTable S1. Thconsequence owhich lead to tInspection of LiNaNi[PO4]F.ADP are givenon the structFachinformatioLeopoldshafen Crystallogramonoclinic spextremely rare we have atteexamining the possible to us

© The Royal S

cooled mode oof 100 Oe.

powder diffrac

der diffraction n diffractometes, Australia) usasurements, ~2 ameter cylindri6 K, i.e., above

d-cycle refrigerd using the Fullths and Ni2+ ma

TS AND DIS

refinement

ameters determsymmetry; h

not consistent wore, we first s1. Most of the ogram.19 After rier syntheses,

Then, using the determined thpace group Pel and changing

umber of indepisotropic atom

actors convergerefined parames did not decrerefined param

ncies did not shalues. At this staved, although

he goodness-ofblem, most likewas used to tesaxis parallel t

ent, and on this , 0 0 1). By incediately droppehere are three f the coset decthe same refine

databases rev.12 The refined

n in Tables 1 anture refinemenonszentrum K, by quoting the

aphers and otpace group P2

and usually indempted to costructure. Indeee the Pnma sp

Society of Chem

ver the temper

tion

(NPD) data wer Echidna at sing neutrons og of the powde

ical vanadium ce and below therator. Rietveld lprof Suite withagnetic form-fa

SCUSSION

mined for LiNowever, the with any knownolved the struatomic positionfew refinementhe whole struc

he Platon suitehat a higher symP21/c. Starting g the space groendent atomic

mic displacemened to R(F) = 0eters. With anease, R(F) = 0

meters. The refihow any signiftage of the refin

h the high valuf-fit (s = 7.6) ely twinning. Tst possible twinto c was idenbasis we introd

corporating thised drastically to

other possiblomposition) wh

ement result; 2[

vealed a structd atomic positnd S2,† respectnts may be

Karlsruhe, D-e Registry No. Cthers will not21/c with the βdicates higher snfirm the syed, in theoreticpace group to

mistry [year]

rature range 2–

were collected othe OPAL f

of wavelength 2er sample was lcan and data cole magnetic trananalysis of th

h the default nctor.

NaMg[PO4]F suapparent systen orthorhombiccture in the trns were locatednt cycles followcture was detere of crystallogmmetry exists w

from the troup from P1 topositions by a

nt parameters (A0.2617 and wRnisotropic ADP0.2473 and wRnement of the

ficant deviationnement, all the ues of the reli

clearly hintedTherefore, the nning of the struntified as a poduced the twin ms twinning optioo the values lisle twin matrixhich can be use

100], m[100], and tural relationshions and anisotively. Further dobtained from

-76344 EggenCSD-426199. te that we uβ = 90 ° whsymmetry. Thermmetry by cal point of viewsolve the stru

–300 K

on the facility 2.4395 loaded llected

nsition, he data neutron

uggest ematic

c space riclinic d using wed by rmined graphic with a

riclinic o P21/c

factor (ADP), (F2) =

Ps, the (F2) = alkali

n from atoms

iability d at a Platon ucture. ossible matrix on, the sted in xes (a ed and m[001].

hip to otropic details m the nstein-

used a hich is refore, closely w, it is ucture,

howtheordPnm95

postheof rTaLiN75

AtoLiNaMgP O1O2O3O4F

3.2

LiNLiNa mMg125

thecoooctruntetr130

lithX, a

Fig(00(1095

wever in this ce 8d atomic posdered structure ma to P21/c. sition into 2 × 4e ordered Mg aref. 12). ble 1. Atom

NaMg[PO4]F. om x

0.7408(5)0.51155(1

g 0.01886(10.75454(90.5429(2)0.8905(3)0.8051(3)0.7828(3)0.1990(2)

2. Crystal struc

NaMg[PO4]F wNaNi[PO4]F, wmonoclinic pseug[PO4]F layers e interlayer spacordinated to ftahedra share enning along therahedra to formhium and sodiuand P-O are list

g. 3. Projection01) plane (a) an00) plane (b).

Dalton

ase a Na/Mg ssition. Thereforit is necessaryThis induces

4e (P21/c) atomnd Na atoms (F

m positions a

y) 0.9196(3) 15) 0.83455(9)12) 0.17115(7)9) 0.08170(5)) 0.12366(16) 0.17177(16) 0.07394(15) 0.95910(14) 0.28708(13

cture

was thereby fhich crystallize

udomerohedrallwith lithium ance (Fig. 3a). Mfour oxygen andges (via 1F ae c axis. Thes

m Mg[PO4]F laym atoms. The ted in Table 2.

view of the stnd projection vie

Trans., [2013]

statistical disorre, in order to

y to decrease ththe splitting o

mic positions, inFor more detai

and isotopic

z 0.7635(7)

) 0.2530(2) ) 0.76322(16) 0.27092(126) 0.2405(3) 6) 0.1317(4) 5) 0.5700(4) 4) 0.1428(3) 3) 0.9647(3)

found to be es with a layerely twinned strucnd sodium atom

Magnesium atomand two fluoriand 1O) and fose chains are cyers (Fig. 3b) binteratomic dis

tructure of LiNiew of the Mg[P

, [vol], 00–00

der is observedobtain a perfec

he symmetry frof the 8d atom

n which are locails see section 3

ADPs (Å2)

Ueq (Å2)

0.0068(12)0.0199(4)

6) 0.0082(2)2) 0.00751(1

0.0143(5)0.0143(5)0.0126(5)0.0119(5)0.0137(4)

isostructural wed structure.12 Icture consistingms well-ordered

ms are octahedraine atoms. Th

orm infinite chaconnected by Pbetween whichstances Na-X, M

NaMg[PO4]F in PO4]F layer on

| 3

d at ctly rom mic ated 3.4.

for

)

9)

with It is g of d in ally

hese ains PO4 h lie Mg-

the the

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CREATED USING THE RSC ARTICLE TEMPLATE (VER. 3.0) - SEE WWW.RSC.ORG/ELECTRONICFILES FOR DETAILS

ARTICLE TYPE www.rsc.org/xxxxxx | XXXXXXXX

4 | Dalton Trans., [2013], [vol], 00–00 This journal is © The Royal Society of Chemistry [year]

Table 2. Interatomic distances (in Å) and bond valence sums (BVS) for LiNaMg[PO4]F. Average distances are given in brackets. distance BV distance BV Li-F 1.922(4) 0.219 Na-O4 2.384(2) 0.208 Li-O1 1.994(4) 0.240 Na-O1 2.396(2) 0.201 Li-O4 1.977(4) 0.251 Na-F 2.4878(18) 0.112 Li-O3 2.034(4) 0.215 Na-O3 2.550(2) 0.133 Li-F 2.722(4) 0.025 Na-O1 2.550(2) 0.133 Li-O2 2.766(4) 0.030 Na-O1 2.613(2) 0.112 <Li-X> 1.982[4] 0.925[4] a Na-F 2.6372(18) 0.075 Mg-F 1.9937(16) 0.390 <Na-X> 2.5168[7] 0.974[7] a Mg-O4 2.0464(19) 0.385 Mg-O2 2.047(2) 0.384 P-O1 1.5252(18) 1.282 Mg-F 2.0554(17) 0.330 P-O4 1.5313(17) 1.261 Mg-O3 2.063(2) 0.368 P-O2 1.5393(19) 1.234 Mg-O2 2.076(2) 0.355 P-O3 1.5438(19) 1.219 <Mg-X> 2.0469[6] 2.212[6] a <P-O> 1.5349[4] 4.996[4] a a bond valence sum, BV = exp{(r0–r)/b} with the following parameters: b = 0.37, r0 (LiI–O) = 1.466, r0 (LiI–F) = 1.36, r0 (NaI–O) = 1.803, r0 (NaI–F) = 1.677, r0 (MgII–O) = 1.693, r0 (MgII–F) = 1.645 and r0 (P

V–O) = 1.617 Å.21, 22

In LiNaMg[PO4]F, the MgO4F2 octahedra are regular in shape 5

with Mg-X distances ranging from 1.9937 to 2.076 Å and an average value of 2.0469 Å. No significant difference in Mg coordination is observed compared to Li2Mg[PO4]F and Na2Mg[PO4]F, although the latter structures belong to a different structure types.17, 23 The PO4 tetrahedra are also quite regular, 10

with P-O distances ranging from 1.5252 to 1.5438 Å with an average value of 1.5349 Å, only slightly lower than the value of 1.55 Å estimated from the effective ionic radii of the four-coordinated P5+ and O2-.24 The sodium atoms are coordinated to five oxygen and two fluorine atoms (Fig. 4a). The Na-X distances 15

range from 2.384 and 2.6372 Å with an average value of 2.5168 Å. This sodium environment is similar to sodium polyhedra in LiNaNi[PO4]F (Fig. 4b). The lithium atoms are four coordinated to three oxygen and one fluorine atoms (Fig. 4a). The Li-X distances range from 1.922 and 2.034 Å with an average value of 20

1.982 Å. The BVS of 0.925, 0.974, 2.212, and 4.996 are in very good agreement with the expected value of +1, +1, +2, and +5 for Li+, Na+, Mg2+, and P5+, respectively.

Fig. 4. Surrounding of the sodium and lithium atoms in LiNaMg[PO4]F (a), and LiNaNi[PO4]F (b). 25

3.3. Structural relationship of A2M[PO4]F (A = Li and Na; M = Mn-Ni, and Mg) to other known oxides.

In the supplementary information section, we have demonstrated that each Na2M[PO4]F unit cell is a supercell of an orthorhombic subcell, similar to LiNaNi[PO4]F (Table S3).25-44 Consequently, 30

starting from an orthorhombic subcell (ao1 ~ 6.75 Å, bo1 ~ 5 Å, and co1 ~ 11 Å) and using the geometric relationships given in Fig. 5q, it is possible to build an orthorhombic supercell (ao2 = ~ 13.5 Å, bo2 = bo1 ~ 5 Å, and co2 = co1 ~ 11 Å) (Fig. 5o) or a monoclinic supercell (am = ~ 13.5 Å, bm= bo1 ~ 5 Å, and cm= ~ 12.9Å) (Fig. 35

5p) which are very similar to the Na2M[PO4]F unit cells Fig. 5a-c. A projection view of the fluorophosphates along the short axis (~5 Å) shows the layered character of the structures (Fig. 5a-e). In all cases, the structures are built of M[PO4]F layers with the interlayer spaces filled by the alkali metal atoms. The only 40

exception is the manganese phase, for which a mixture of manganese and sodium atoms is observed in and between the layers. A projection view perpendicular to the layers provide more structural details (Fig. 5f-j). LiNaM[PO4]F (M = Ni and Mg) contains infinite chains of edge-sharing octahedra (Fig. 5j), 45

whereas Na2M[PO4]F (M = Mn-Ni, and Mg) contain infinite chains of dimer units (face-sharing octahedra) sharing corners (Fig. 5f-i). Depending on the size of the transition metal, the dimer units point to different directions (Fig. 5k-n). In Na2M[PO4]F(M = Fe, Co, and Mg) all the dimer units point to the 50

same direction (Fig. 5k), whereas in Na2M[PO4]F(M = Ni and Mn), we observe an alternation of two chains with the dimer units pointing to the right and two chains with the dimer units pointing to the left (Fig. 5l, m). The structural transition from edge- to face-sharing octahedra is mainly due to the tilting of a few PO4 55

tetrahedra. Furthermore, since the tilted tetrahedra are different from phase to phase, this induces different orientations for the dimer units built of face-sharing octahedra (Fig. 5k-n). From a theoretical point of view, it would also be possible to build a theoretical structure in which one chain with the dimer units 60

pointing to the right alternates with one chain with the dimer units pointing to the left (Fig. 5d, i, n). The predicted crystallographic data of this theoretical phase are given in Table 3.

Table 3. Crystallographic data of the A2M[PO4]F theoretical structure (P21212, Z = 4, a = 5.1991 Å, b = 11.6557 Å, c = 6.8489 65

Å, and V = 415.04 Å3).

Atom Wyck. x y z A1 4c 0.25367 0.83112 0.75500 A2 4c 0.24405 0.57990 0.49245 M 4c 0.78012 0.92680 0.97370 P 4c 0.29525 0.83807 0.23435 O1 4c 0.08875 0.64283 0.79617 O2 4c 0.65387 0.59587 0.92930 O3 4c 0.74525 0.79147 0.78667 O4 4c 0.71836 0.61910 0.56725 F1 2a 1/2 1/2 0.24880 F2 2b 0 1/2 0.18910

70

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mistry [year]

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Dalton

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Trans., [2013], [vol], 00–00 | 5

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4.1. LiNaNi[PO

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4.2. LiNaNi[Powder diffracti

xamination of vealed additionig. 7a). 46 This

ata which suggeffraction peaks ll doubled alon/2, 0, 0). For toup, the magne

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The Royal Soc

ructure and pr

O4]F magnetic

f magnetic suare presenteds a function of transition at T1 curve follows 0-300 K yieldsB. The fo

c (AFM) interacue for S = 1 Nall AFM nature ion temperatureerature on cooliially develops the long-range

our is fully conrmined from thelow.

susceptibility tion of temperas the linear fit w

PO4]F magneion data

the NPD pattenal diffraction s is consistent ested an AFM tr

of magnetic ong a axis, i.e., the 4e(x, y, z) etic representatirreducible repr

e associated basment between ebtained for ththe P21’/c S

er 14.3.88). Fshowed no

magnetic momre only the parained. The Rie

ciety of Chemis

roperties of LiN

properties

usceptibility md in Fig. 6f temperature reT ~ 5 K. Abo

the Curie-Weis = -16.5 K

ormer indicatections in the sy

Ni2+.45 It is alsof the magneti

e, the rise of thing below ~30 Kshort-range fe

e AFM structurnsistent with te neutron powd

χ, its inverse χature for LiNaNwith the Curie-W

etic structure

erns collected peaks due to with the magn

ransition at ~ 5origin could be

with the propaWyckoff site o

tion decomposeresentations (IRsis vectors are lxperimental an

he 1 (GxFyGShubnikov grourthermore, ex

o evidence oment componenameter definingetveld plot an

stry [2011]

NaNi[PO4]F

measurements 6. The magnevealed a signaove ~ 170 K ss law. A linea

K and an effeces predomina

ystem and the laso noteworthy ically ordered she χ·T product K suggests that

erromagnetic (Fre sets in at TN

the bulk magnder diffraction d

χ-1, and χT prodNi[PO4]F. The Weiss function.

e from neut

at 3 K and 6magnetic ordenetic susceptib K (Fig. 6). Allindexed by a

agation vector of the P21/c spes in terms of fR) as = 31 + isted in Table S

nd calculated NGz) representaoup, Opechowxamination of of the scattents along the ag the moment ald crystallograp

for netic ature

the ar fit ctive antly atter that

state as a t the FM) ~ 5

netic data

duct red

.

tron

6 K ering bility l the unit k =

pace four 32

S8.† NPD ation wski-

the ering or c long phic

informThe dexpec75

the m= 0 fmome Thintere85

alongchaindistansuperexpec90

Th(Fig.chainin AFthe tw115

appeacouplplanesuppointera120

orient

Fig. 7at 3 KindicaLiNaN90

mation are presdetermined valucted for d8 Ni2+

magnetization asfor S = 1 and Tent, similarly cl

he magnetic stesting combinag c, b, and a axens running alonces (~3.1Å)rexchange viacted from the Ghe magnetic mo

8), which is ns.49 Super-supeFM coupling; hwo Ni-O---O ars to be severlled ferromagnee (Fig. 8a, b).orted likely by actions which tation in the FM

7. LiNaNi[PO4

K and 6 K. Addated with asteNi[PO4]F neutr

Dalton Tra

sented in Fig. 7ue of the mome+. Assuming Bs a function of tTN = 5 K yieldlose to the theorructure of LiNation of progres. The NiO3F zng the c axis) are orde

common oxyGoodenough-Ka

ments are perpea typical case

erexchange via however, in the angles in eachly bent to ~98°etically, formin Finally, the a combination is consistent

M quasi-layers f

]F neutron powditional peaks oberisk symbols ron powder dif

rans., [2011], [v

7b and Table S9ent, 1.87(4) B,

Brillouin functiotemperature, exds 2.12 B as toretical value. NaNi[PO4]F arressively weakzigzag edge-shas with the shoered ferromaygen and fluoanamori rules.47

endicular to thefor (quasi-)iso

phosphate groue case of LiNaNh M-O---O-M ° and as a resulng FM quasi-la

order betweenof exchange an

with the in-favoured by the

wder diffractionbserved at low (a). Rietveldffraction data c

vol], 00–00 | 6

9,† respectively, is close to thaon behaviour oxtrapolation to Tthe ground stat

rises due to anker interactionaring octahedraortest Ni2+-Ni2

agnetically byrine atoms, a

7, 48 e chain directionolated magnetiups often resultNi[PO4]F one o

interchain linklt the chains arayers in the b-n the layers ind dipole-dipol-plane momen

e latter49,50.

n data collectedtemperature ar

d plot for thcollected at 3 K

6

y. at of T te

n ns al 2+ y

as

n c ts of k

re c is e

nt

d re he K

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10

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25

This journal is

(b). The red crobserved andrespectively. Tdiffraction peak10.6%.46 The b

Fig. 8. Views ox = 0 (a), and LiNaNi[PO4]F layers (c).

4. Conclusio

The crystal strux 2) led to thand LiNaMgLi2Ni[PO4]F anthe different relationships amNa; M = Mn-NCa3[SiO4]O. transformation Mn-Ni, and MThe main diffeorientations o(Na2Mn[PO4]Ftransition-metasize of the transtructure of LiN

© The Royal S

rosses and blacd calculated The tick marks. Rp = 4.89%

blue curve in the

of the ferromagd x = 1 (b) and

with antiferr

ons

ucture study ofhe discovery ofg[PO4]F. Thesnd LiNaNi[PO4

crystallograpmong the fluoroNi, and Mg) an

More interschemes show

Mg) phases can ference betweenof the PO4 F), a permutatal atoms. This nsition-metal anNaNi[PO4]F as

Society of Chem

ck and green sopatterns and

rks indicate t%, Rwp = 6.68%

e inset shows m

gnetically ordered view of the mromagnetic co

f the Li2-xNaxMf two new compse phases ar

4]F, respectivelphic databaseophosphates A2

nd oxides suchrestingly, th

wed that all thebe described a

n these compotetrahedra plution between difference is m

nd alkali-metal s determined fr

mistry [year]

olid lines indicad their diffehe position o, RF = 2.99%, R

magnetic contrib

ed Ni[PO4]F laymagnetic structupling betwee

Mg[PO4]F systempounds Li2Mg[re isostructurly. The inspects revealed M[PO4]F (A = L

h as β-Nb[PO4]he group-sube Na2M[PO4]F as layered strucunds is the dif

us, in some the alkali- an

mainly related atoms. The maom NPD data c

ate the erence, of the Rmag = bution.

yers at ture of en the

m (0 [PO4]F ral to tion of strong Li and O and

bgroup (M =

ctures. fferent

cases nd the to the

agnetic can be

desshaphocha50

Ac

ThiProCDCo55

R

1 H2

3 K50

4 R

5 Y55

6 E

7 S

8 M60

9 S

10 65

11 N

12

13 75

14

80

15

16

17 75

18

19

20 85

21 I22 N 23 24 90

25

26 M95

27 H28

110

29 F

scribed as AFMaring octahedraosphate groupsain direction an

cknowledgm

is work was finomotion of SciDL received sup

uncil – Discove

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Dalton Transactions

Cite this: DOI: 10.1039/c0xx00000x

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Synopsis

This journal is © The Royal Society of Chemistry [2011] Dalton Trans., [2012], [vol], 00–00 | 1

Structural relationships among LiNaMg[PO4]F and Na2M[PO4]F (M =

Mn-Ni, and Mg), and the magnetic structure of LiNaNi[PO4]F

Hamdi Ben Yahiaa,*, Masahiro Shikano

a,*, Hironori Kobayashi

a, Maxim Avdeev

b, Samuel Liu

c, Chris D.

Lingc

Received (in XXX, XXX) Xth XXXXXXXXX 2011, Accepted Xth XXXXXXXXX 20XX 5

DOI: 10.1039/b000000x

Synopsis

10

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