Na4Ni5[(As1−xPx)O4]2[(As2yP2−2y)O7]2 (x = 0 27 and y = 0 295)

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Acta Cryst.(2004). E60, i1±i2 DOI: 10.1107/S1600536803027375 Ben Smail and Jouini Na₄Ni₅[(As_0.73P_0.27)O₄]₂[(As_0.59P_1.41)O₇]₂

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inorganic papers

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Na4Ni5[(As1

ÿx

P

x

)O4]2[(As2

y

P2

ÿ2y

)O7]2

(

x

= 0.27 and

y

= 0.295)

Ridha Ben Smaila,b_{and Tahar} Jouinia_*

a_{Laboratoire de MateÂriaux et Cristallochimie,}

DeÂpartement de Chimie, FaculteÂ des Sciences de Tunis, 2092 El Manar II, Tunis, Tunisie, and

b_{Institut SupeÂrieur des Sciences AppliqueÂes et de}

Technologie de GabeÁs, Route de Medenine, 6029 GabeÁs, Tunisie.

Correspondence e-mail: tahar.jouini@fst.rnu.tn

Key indicators Single-crystal X-ray study T= 293 K

Mean(Ni±O) = 0.003 AÊ Disorder in main residue Rfactor = 0.024 wRfactor = 0.065

Data-to-parameter ratio = 10.4

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Crystals of the title compound, tetrasodium pentanickel arsenic±phosphorus (2.64/3.36) docosaoxide, has been grown by a solid-state reaction and characterized by single-crystal X-ray diffraction. The structure is built up from corner- and edge-sharing (AsP)O4 tetrahedra, (AsP)2O7 groups, NiO6

octahedra and Ni2O9 units, giving rise to a polyhedral

connectivity having tunnels running along the [001] direction. It is isostructural with Na4Ni5(PO4)2(P2O7)2.

Comment

Phosphate and arsenate inorganic materials offer a consider-able variety of structures, giving rise to various potential applications. In the course of our investigations of the Na2O±

NiO±As2O5and K2O±NiO±As2O5ternary systems, in a search

for new materials likely to exhibit interesting magnetic or ionic conductivity properties, we have previously isolated four compounds: NaNi4(AsO4)3 (Ben Smail et al., 2002),

Na4Ni7(AsO4)6 (Ben Smailet al., 2004), K4Ni7(AsO4)6(Ben

Smail et al., 1999) and K3Ni(AsO4)(As2O7) (Ben Smail &

Jouini, 2000). Recently, during our investigation of the Na2O±

NiO±As2O5±P2O5 quaternary system, two compounds have

been isolated in the same preparation: Na3Ni2(As0.1P0.9

)-O4(As1.3P0.7)O7 (Ben Smail & Jouini, 2004) and Na4Ni5

-[(As0.73,P0.27)O4]2[(As0.59,P1.41)O7]2.

This paper reports the crystal structure of the latter compound. The asymmetric unit is illustrated in Fig. 1. This structure is isomorphous with that of Na4Ni5(PO4)2(P2O7)2

(Sanz et al., 1999). The structures of these compounds have channels running along c, in which alkali metal ions are

Received 18 November 2003 Accepted 28 November 2003 Online 12 December 2003

Figure 1

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located (Fig. 2). This solid solution phase differs from the phosphate-limiting phase Na4Ni5(PO4)2(P2O7)2 by the

split-ting of Na2 over two distinct sites (Na2 and Na20_{) separated by}

0.82 (4) AÊ.

Bond valence calculations (Brown & Shannon, 1973; Brown & Altermatt, 1985) con®rm the experimentally determined occupancies: 0.79 from bond valences (cf. 0.75 from X-ray experiment) for P1, 0.67 (cf.0.66) for P2 and 0.21 (cf.0.27) for P3.

This structure is determined with lowerR= 0.0241 andwR= 0.0653 values than the isotypic phosphate structure form,R= 0.0608 andwR= 0.1693.

Experimental

The preparation of the title compound is described elsewhere (Ben Smail & Jouini, 2004).

Crystal data

Na4Ni5[(As0.73P0.27)O4]2

-[(As0.59P1.41)O7]2

Mr= 1039.26

Monoclinic,P21=a

a= 10.676 (2) AÊ b= 6.716 (1) AÊ c= 12.812 (2) AÊ = 103.77 (1) V= 892.2 (3) AÊ3

Z= 2

Dx= 3.868 Mg mÿ3

MoKradiation Cell parameters from 25

re¯ections = 10.4±15 = 10.56 mmÿ1

T= 293 (2) K Parallelepiped, brown 0.200.080.02 mm

Data collection Enraf±Nonius CAD-4

diffractometer !/2scans

Absorption correction: scan (Northet al., 1968) Tmin= 0.368,Tmax= 0.784

2051 measured re¯ections 1942 independent re¯ections 1672 re¯ections withI> 2(I)

Rint= 0.012

max= 27.0

h= 0!13 k= 0!8 l=ÿ16!15 2 standard re¯ections

frequency: 120 min intensity decay: 1.0%

Re®nement Re®nement onF2

R[F2_{> 2(}_F2_{)] = 0.024}

wR(F2_{) = 0.065}

S= 1.10 1942 re¯ections 187 parameters

w= 1/[2₍_F

o2) + (0.0309P)2

+ 1.9015P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.032

max= 0.61 e AÊÿ3

min=ÿ0.72 e AÊÿ3

Extinction correction:SHELXL97 Extinction coef®cient: 0.0013 (2)

Table 1

Selected geometric parameters (AÊ).

As/P1ÐO8i _{1.528 (3)}

As/P1ÐO9ii _{1.554 (3)}

As/P1ÐO6iii _{1.555 (3)}

As/P1ÐO11 1.666 (3)

As/P2ÐO10iv _{1.556 (3)}

As/P2ÐO2v _{1.583 (3)}

As/P2ÐO7vi _{1.587 (3)}

As/P2ÐO11iv _{1.644 (3)}

As/P3ÐO4 1.633 (3)

As/P3ÐO3ii _{1.642 (3)}

As/P3ÐO1 1.677 (3)

As/P3ÐO5ii _{1.682 (3)}

Na1ÐO6vii _{2.287 (3)}

Na1ÐO8v _{2.364 (4)}

Na1ÐO7v _{2.366 (3)}

Na1ÐO4iv _{2.456 (3)}

Na1ÐO11iv _{2.523 (4)}

Na1ÐO2v _{2.805 (3)}

Na1ÐO9iv _{2.968 (4)}

Symmetry codes: (i)x;y;1z; (ii)xÿ1

2;12ÿy;z; (iii)xÿ1;y;z; (iv) 1ÿx;ÿy;1ÿz;

(v)1

2x;12ÿy;z; (vi) 1x;y;z; (vii)32ÿx;yÿ12;1ÿz.

The occupation factors of the As/P atoms in the tetrahedral sites have been re®ned, the sum of the occupation factors being ®xed at 1.0. Pairs of atoms at the same site were given the same coordinates and atomic displacement parameters. A residual Fourier peak (2.6 e AÊÿ3_{) still remained close to the Na2 site. It was re®ned as an}

alternative sodium position, the re®nement of the occupancy factors of the neighboring Na+ _{cations leading to a small improvement of}

reliability factors. Consequently, the Na2 sodium atom has been split into two positions (Na2 and Na20_{), with different occupancies. They}

are separated by 0.82 (4) AÊ.

Data collection:CAD-4EXPRESS(Duisenberg, 1992; MacõÂcÏek & Yordanov, 1992); cell re®nement:CAD-4EXPRESS; data reduction:

XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve struc-ture:SHELXS97 (Sheldrick, 1990); program(s) used to re®ne struc-ture:SHELXL97 (Sheldrick, 1997); molecular graphics:DIAMOND

(Brandenburg, 1998); software used to prepare material for

publi-cation:SHELXL97.

References

Ben Smail, R., Driss, A. & Jouini, T. (1999).Acta Cryst.C55, 284±286. Ben Smail, R. & Jouini, T. (2000).Acta Cryst.C56, 513±514. Ben Smail, R. & Jouini, T. (2004).Ann. Chim. Sci. Mat.Accepted. Ben Smail, R., Touati, A. & Jouini, T. (2004). In preparation.

Ben Smail, R., Zid, M. F. & Jouini, T. (2002).J. Soc. Chim. Tunisie,4, 1655± 1673.

Brandenburg, K. (1998). DIAMOND. Version 2.0. University of Bonn, Germany.

Brown, I. D. & Altermatt, D. (1985).Acta Cryst.B41, 244±247. Brown, I. D. & Shannon, R. D.. (1973).Acta Cryst.A29, 266±282. Duisenberg, A. J. M. (1992).J. Appl. Cryst.25, 92±96.

Harms, K. & Wocadlo, S. (1995).XCAD4. University of Marburg, Marburg, Germany.

MacõÂcÏek, J. & Yordanov, A. (1992).J. Appl. Cryst.25, 73±80.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.

Sanz, F., Parade, C., Rojo, J. M. & Ruiz-Valero, C. (1999).Chem. Mater.11, 2673±2679.

Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.

Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany.

Figure 2

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supporting information

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Acta Cryst. (2004). E60, i1–i2

supporting information

Acta Cryst. (2004). E60, i1–i2 [https://doi.org/10.1107/S1600536803027375]

Na

4

Ni

5

[(As

1−x

P

x

)O

4

]

2

[(As

2y

P

2−2y

)O

7

]

2

(

x

= 0.27 and

y

= 0.295)

Ridha Ben Smail and Tahar Jouini

tetrasodium pentanickel arsenic-phosphorus (2.67/3.35) twentytwooxide

Crystal data

Na4Ni5[(As0.73·P0.27)O4]2[(As0.59·P1.41)O7]2 Mr = 1039.26

Monoclinic, P21/a Hall symbol: -P 2yab a = 10.676 (2) Å b = 6.716 (1) Å c = 12.812 (2) Å β = 103.77 (1)° V = 892.2 (3) Å3 Z = 2

F(000) = 995 Dx = 3.868 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 25 reflections θ = 10.4–15°

µ = 10.56 mm−1 T = 293 K

Parallelepiped, brown 0.20 × 0.08 × 0.02 mm

Data collection Enraf-Nonius CAD-4

diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: ψ scan (North et al., 1968)

Tmin = 0.368, Tmax = 0.784 2051 measured reflections

1942 independent reflections 1672 reflections with I > 2σ(I) Rint = 0.012

θmax = 27.0°, θmin = 3.3° h = 0→13

k = 0→8 l = −16→15

2 standard reflections every 120 min intensity decay: 1.0%

Refinement Refinement on F2 R[F2_{> 2}_σ₍_F2_{)] = 0.024} wR(F2_{) = 0.065} S = 1.10 1942 reflections 187 parameters 4 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

w = 1/[σ2₍_F

o2) + (0.0309P)2 + 1.9015P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.032 Δρmax = 0.61 e Å−3 Δρmin = −0.72 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2_θ_)]-1/4 Extinction coefficient: 0.0013 (2)

Special details

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Refinement. Refinement of F2_{against ALL reflections. The weighted}_R_-factor_wR_{and goodness of fit}_S_{are based on}_F2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of}_F2_>_σ₍_F2_{) is used} only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq Occ. (<1) Ni1 0.0000 0.0000 0.5000 0.00915 (17)

Ni2 0.19757 (5) 0.01111 (8) 0.16483 (4) 0.01275 (15) Ni3 0.21707 (5) 0.23704 (7) 0.36451 (4) 0.00782 (14)

As1 0.08907 (7) 0.20966 (11) 0.91873 (6) 0.0093 (3) 0.25 (1) P1 0.08907 (7) 0.20966 (11) 0.91873 (6) 0.0093 (3) 0.75 (2) As2 0.93149 (6) 0.10195 (10) 0.24501 (5) 0.0071 (2) 0.34 (1) P2 0.93149 (6) 0.10195 (10) 0.24501 (5) 0.0071 (2) 0.66 (2) As3 0.27348 (4) 0.23408 (7) 0.58506 (4) 0.00626 (17) 0.73 (1) P3 0.27348 (4) 0.23408 (7) 0.58506 (4) 0.00626 (17) 0.27 (2) Na1 0.62987 (19) 0.0226 (3) 0.14797 (15) 0.0220 (4)

Na2 0.5442 (3) 0.0767 (7) 0.6627 (7) 0.0311 (14) 0.84 (2) Na2′ 0.5314 (17) 0.018 (4) 0.605 (4) 0.030 (8) 0.16 (2) O1 0.1336 (3) 0.2085 (4) 0.4930 (2) 0.0100 (6)

O2 0.3311 (3) 0.2314 (4) 0.2571 (2) 0.0114 (6) O3 0.7598 (3) 0.0742 (4) 0.6610 (2) 0.0120 (6) O4 0.3262 (3) 0.0379 (4) 0.6576 (2) 0.0121 (6) O5 0.8679 (3) 0.2285 (4) 0.4989 (2) 0.0103 (6) O6 0.9392 (3) 0.2021 (4) 0.8880 (3) 0.0178 (7) O7 0.0633 (3) 0.1958 (4) 0.2318 (2) 0.0120 (6) O8 0.1514 (3) 0.2014 (5) 0.0391 (2) 0.0188 (7) O9 0.6368 (3) 0.1135 (5) 0.8602 (3) 0.0219 (7) O10 0.0479 (3) 0.0556 (5) 0.6634 (2) 0.0136 (6) O11 0.1402 (3) 0.0038 (4) 0.8694 (2) 0.0139 (6)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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supporting information

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Acta Cryst. (2004). E60, i1–i2

O2 0.0132 (14) 0.0095 (14) 0.0130 (14) −0.0028 (11) 0.0061 (11) −0.0003 (11) O3 0.0138 (14) 0.0097 (13) 0.0128 (14) 0.0025 (12) 0.0037 (11) −0.0007 (12) O4 0.0143 (14) 0.0085 (14) 0.0138 (14) −0.0009 (11) 0.0037 (12) −0.0018 (11) O5 0.0102 (13) 0.0124 (14) 0.0080 (13) 0.0017 (11) 0.0019 (11) 0.0015 (11) O6 0.0168 (15) 0.0133 (15) 0.0216 (16) −0.0010 (12) 0.0010 (13) −0.0019 (12) O7 0.0108 (14) 0.0119 (14) 0.0130 (14) 0.0002 (11) 0.0023 (11) 0.0013 (11) O8 0.0233 (17) 0.0178 (16) 0.0143 (15) −0.0001 (13) 0.0029 (13) 0.0017 (12) O9 0.0254 (17) 0.0162 (16) 0.0238 (17) 0.0069 (14) 0.0051 (14) −0.0036 (13) O10 0.0128 (14) 0.0170 (15) 0.0105 (13) 0.0004 (12) 0.0017 (11) 0.0013 (12) O11 0.0121 (14) 0.0156 (15) 0.0146 (14) 0.0048 (12) 0.0041 (12) −0.0025 (12)

Geometric parameters (Å, º)

Ni1—O1i _{2.016 (3)} _As/P3—O4 _{1.633 (3)} Ni1—O1 2.016 (3) As/P3—O3iv _{1.642 (3)} Ni1—O10 2.068 (3) As/P3—O1 1.677 (3) Ni1—O10i _{2.068 (3)} _As/P3—O5iv _{1.682 (3)} Ni1—O5ii _{2.082 (3)} _Na1—O6ix _{2.287 (3)} Ni1—O5iii _{2.082 (3)} _Na1—O8vii _{2.364 (4)} Ni2—O8 2.023 (3) Na1—O7vii _{2.366 (3)} Ni2—O6iii _{2.042 (3)} _Na1—O4iii _{2.456 (3)} Ni2—O9iii _{2.049 (3)} _Na1—O11iii _{2.523 (4)} Ni2—O2 2.195 (3) Na1—O2vii _{2.805 (3)} Ni2—O7 2.217 (3) Na1—O9iii _{2.968 (4)} Ni2—O3iii _{2.243 (3)} _Na2—O3 _{2.307 (4)} Ni3—O2 2.042 (3) Na2—O4 2.327 (4) Ni3—O1 2.059 (3) Na2—O10vii _{2.469 (6)} Ni3—O5iv _{2.071 (3)} _Na2—O9 _{2.501 (9)} Ni3—O4v _{2.077 (3)} _Na2—O2iii _{2.542 (4)} Ni3—O7 2.081 (3) Na2—O5iv _{2.789 (5)} Ni3—O3iii _{2.139 (3)} _Na2—O1vii _{2.951 (6)} As/P1—O8vi _{1.528 (3)} _Na2′—O3 _{2.40 (2)} As/P1—O9iv _{1.554 (3)} _Na2′—O4 _{2.444 (18)} As/P1—O6ii _{1.555 (3)} _Na2′—O5iv _{2.580 (15)} As/P1—O11 1.666 (3) Na2′—O2iii _{2.619 (19)} As/P2—O10iii _{1.556 (3)} _Na2′—O1vii _{2.713 (16)} As/P2—O2vii _{1.583 (3)} _Na2′—O5ix _{2.72 (4)} As/P2—O7viii _{1.587 (3)} _Na2′—O1x _{2.82 (4)} As/P2—O11iii _{1.644 (3)} _Na2′—O10vii _{2.95 (4)}

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O10—Ni1—O5ii _{82.99 (11)} _{O2—Ni3—O3}iii _{76.70 (11)} O10i_—Ni1—O5ii _{97.01 (11)} _{O1—Ni3—O3}iii _{96.83 (11)} O1i_—Ni1—O5iii _{88.45 (11)} _O5iv_—Ni3—O3iii _{98.11 (11)} O1—Ni1—O5iii _{91.55 (11)} _O4v_—Ni3—O3iii _{163.68 (11)} O10—Ni1—O5iii _{97.01 (11)} _{O7—Ni3—O3}iii _{80.92 (11)} O10i_—Ni1—O5iii _{82.99 (11)} _O8vi_{—As/P1—O9}iv _{113.61 (18)} O5ii_—Ni1—O5iii _{180.000 (1)} _O8vi_{—As/P1—O6}ii _{115.41 (18)} O8—Ni2—O6iii _{99.18 (13)} _O9iv_{—As/P1—O6}ii _{109.80 (17)} O8—Ni2—O9iii _{100.89 (13)} _O8vi_{—As/P1—O11} _{104.45 (16)} O6iii_—Ni2—O9iii _{103.71 (13)} _O9iv_{—As/P1—O11} _{106.07 (16)} O8—Ni2—O2 90.41 (12) O6ii_{—As/P1—O11} _{106.69 (16)} O6iii_—Ni2—O2 _{166.58 (12)} _O10iii_{—As/P2—O2}vii _{112.59 (15)} O9iii_—Ni2—O2 _{83.45 (12)} _O10iii_{—As/P2—O7}viii _{112.37 (15)} O8—Ni2—O7 84.12 (12) O2vii_{—As/P2—O7}viii _{111.60 (15)} O6iii_—Ni2—O7 _{92.49 (12)} _O10iii_{—As/P2—O11}iii _{109.30 (16)} O9iii_—Ni2—O7 _{161.90 (12)} _O2vii_{—As/P2—O11}iii _{102.14 (15)} O2—Ni2—O7 79.10 (11) O7viii_{—As/P2—O11}iii _{108.24 (15)} O8—Ni2—O3iii _{155.06 (12)} _{O4—As/P3—O3}iv _{111.25 (14)} O6iii_—Ni2—O3iii _{96.33 (12)} _{O4—As/P3—O1} _{116.50 (14)} O9iii_—Ni2—O3iii _{94.21 (12)} _O3iv_{—As/P3—O1} _{107.91 (14)} O2—Ni2—O3iii _{71.59 (10)} _{O4—As/P3—O5}iv _{108.37 (14)} O7—Ni2—O3iii _{75.78 (10)} _O3iv_{—As/P3—O5}iv _{115.09 (14)} O2—Ni3—O1 167.81 (11) O1—As/P3—O5iv _{97.23 (13)} O2—Ni3—O5iv _{95.28 (11)}