Non-centrosymmetric Na(3)Nb(4)As(3)O(19).

A new non-centrosymmetric compound, tris-odium tetra-niobium triarsenic nona-deca-oxide, Na(3)Nb(4)As(3)O(19), has been synthesized by a solid-state reaction at 1123 K. The structure consists of AsO(4) tetra-hedra and NbO(6) octa-hedra sharing corners to form a three-dimensional framework containing two types of tunnels running along the c axis, in which the sodium ions are located. Na(+) cations occupying statistically several sites, respectively, are surrounded by seven, six and four O atoms at distances ranging from 2.08 (1) to 2.88 (4) Å. The title structure is compared with those containing the same groups, viz.M(2)XO(13) and M(2)X(2)O(17) (M = transition metal, and X = As or P).

Related literature

For physical properties of this class of compound, see: Masquelier et al. (1995 ▶); Daidouh et al. (1997 ▶, 1998 ▶, 1999 ▶); Sanz et al. (1999 ▶, 2001 ▶); Baies et al. (2006 ▶); Ravez et al. (1972 ▶, 1974 ▶); Torardi et al. (1985 ▶); Krol et al. (1980 ▶); Blasse et al. (1992 ▶). For synthetic details, see: Zid et al. (1988 ▶, 1989 ▶); Ben Amor & Zid (2005 ▶, 2006 ▶); Hizaoui et al. (1999a ▶, b ▶); Haddad et al. (1988 ▶); Harrison et al. (1994 ▶); Chérif et al. (2011 ▶). For related structures, see: Guyomard et al. (1991 ▶); Serra & Hwu (1992 ▶); Ben Amor & Zid (2006 ▶); Ledain et al. (1996 ▶); Leclaire et al. (1994 ▶); Amos & Sleight (2001 ▶). For details of the bond-valences method, see: Brown & Altermatt, (1985 ▶).

Experimental

Crystal data

Na3Nb4As3O19

M = 969.37

Orthorhombic,

a = 13.014 (2) Å

b = 24.170 (3) Å

c = 5.0880 (9) Å

V = 1600.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 9.13 mm−1

T = 298 K

0.35 × 0.25 × 0.16 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.083, T max = 0.230

2116 measured reflections

1757 independent reflections

1516 reflections with I > 2σ(I)

R int = 0.041

2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.076

S = 1.03

1757 reflections

159 parameters

2 restraints

Δρmax = 0.75 e Å−3

Δρmin = −0.91 e Å−3

Absolute structure: Flack (1983 ▶), 718 Friedel pairs

Flack parameter: 0.019 (16)

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812010537/ru2026sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010537/ru2026Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Na3Nb4As3O19	F(000) = 1792
Mr = 969.37	Dx = 4.023 Mg m−3
Orthorhombic, C2221	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 25 reflections
a = 13.014 (2) Å	θ = 10–15°
b = 24.170 (3) Å	µ = 9.13 mm−1
c = 5.0880 (9) Å	T = 298 K
V = 1600.4 (3) Å3	Prism, colourless
Z = 4	0.35 × 0.25 × 0.16 mm

Enraf–Nonius CAD-4 diffractometer	1516 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.041
Graphite monochromator	θmax = 27.0°, θmin = 3.0°
ω/2θ scans	h = −1→16
Absorption correction: ψ scan (North et al., 1968)	k = −1→30
Tmin = 0.083, Tmax = 0.230	l = −6→6
2116 measured reflections	2 standard reflections every 120 min
1757 independent reflections	intensity decay: 1%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029	w = 1/[σ2(Fo2) + (0.0368P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.076	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.75 e Å−3
1757 reflections	Δρmin = −0.91 e Å−3
159 parameters	Absolute structure: Flack (1983), 718 Friedel pairs
2 restraints	Flack parameter: 0.019 (16)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Nb1	0.09989 (4)	0.61182 (2)	0.98822 (12)	0.00837 (14)
Nb2	0.5000	0.55734 (4)	0.7500	0.0191 (2)
Nb3	0.5000	0.66841 (3)	0.2500	0.0147 (2)
As1	0.28249 (5)	0.61930 (3)	0.51616 (17)	0.00926 (16)
As2	0.0000	0.73103 (4)	0.2500	0.0116 (2)
Na1	0.2677 (4)	0.5000	0.0000	0.066 (3)	0.937 (16)
Na2	0.0494 (12)	0.5000	0.5000	0.044 (4)	0.68 (3)
Na3	0.184 (4)	0.5000	0.5000	0.027 (18)*	0.092 (18)
Na4	0.105 (7)	0.5000	0.5000	0.029 (17)*	0.11 (3)
Na5	0.771 (3)	0.7465 (10)	0.753 (13)	0.014 (11)*	0.12 (2)
Na6	0.742 (4)	0.7414 (15)	0.629 (18)	0.022 (14)*	0.11 (3)
Na7	0.7659 (13)	0.7594 (7)	0.006 (11)	0.010 (5)*	0.191 (16)
Na8	0.7726 (19)	0.7525 (11)	0.892 (12)	0.018 (8)*	0.17 (2)
O1	0.3557 (4)	0.6722 (2)	0.3978 (9)	0.0126 (11)
O2	0.0000	0.4110 (3)	0.7500	0.0139 (14)
O3	0.2178 (4)	0.64941 (19)	0.7635 (11)	0.0148 (10)
O4	0.1043 (4)	0.6949 (2)	0.1612 (10)	0.0151 (10)
O5	0.2132 (4)	0.5923 (2)	0.2719 (12)	0.0156 (11)
O6	0.6461 (4)	0.56446 (17)	0.8803 (9)	0.0096 (10)
O7	0.4590 (5)	0.5000	0.0000	0.0149 (14)
O8	0.1235 (4)	0.5478 (2)	0.8340 (10)	0.0151 (10)
O9	−0.0435 (4)	0.7711 (2)	0.0017 (15)	0.0264 (14)
O10	0.0000	0.6408 (3)	0.7500	0.0150 (15)
O11	0.4634 (4)	0.61482 (19)	0.0053 (14)	0.0234 (13)

	U11	U22	U33	U12	U13	U23
Nb1	0.0069 (3)	0.0093 (3)	0.0089 (3)	−0.00043 (19)	0.0005 (4)	−0.0009 (2)
Nb2	0.0102 (4)	0.0107 (4)	0.0364 (6)	0.000	−0.0103 (5)	0.000
Nb3	0.0139 (4)	0.0088 (4)	0.0212 (4)	0.000	0.0098 (4)	0.000
As1	0.0060 (3)	0.0116 (3)	0.0101 (4)	0.0003 (2)	0.0005 (3)	0.0015 (3)
As2	0.0091 (5)	0.0072 (4)	0.0186 (5)	0.000	−0.0002 (5)	0.000
Na1	0.012 (3)	0.036 (4)	0.150 (8)	0.000	0.000	0.036 (6)
Na2	0.045 (8)	0.024 (4)	0.063 (7)	0.000	0.000	−0.026 (5)
O1	0.007 (2)	0.015 (3)	0.015 (3)	0.000 (2)	−0.0004 (19)	0.004 (2)
O2	0.010 (3)	0.020 (3)	0.012 (3)	0.000	−0.006 (3)	0.000
O3	0.013 (2)	0.014 (2)	0.017 (3)	−0.0008 (19)	0.004 (3)	−0.003 (2)
O4	0.008 (2)	0.015 (2)	0.022 (3)	0.000 (2)	−0.001 (2)	−0.005 (2)
O5	0.010 (2)	0.018 (2)	0.019 (3)	−0.002 (2)	−0.007 (2)	0.000 (2)
O6	0.011 (2)	0.002 (2)	0.016 (3)	−0.0010 (19)	−0.005 (2)	0.0001 (18)
O7	0.012 (3)	0.012 (3)	0.020 (4)	0.000	0.000	0.009 (4)
O8	0.016 (2)	0.010 (2)	0.020 (2)	0.002 (2)	0.001 (2)	−0.006 (2)
O9	0.016 (3)	0.022 (3)	0.041 (4)	−0.003 (2)	−0.001 (3)	0.025 (3)
O10	0.014 (3)	0.016 (3)	0.015 (4)	0.000	−0.005 (4)	0.000
O11	0.011 (2)	0.023 (3)	0.037 (3)	−0.0011 (18)	−0.004 (3)	−0.016 (4)

Nb1—O8	1.762 (5)	Na2—O8x	2.270 (9)
Nb1—O10	1.910 (3)	Na2—O2xiii	2.580 (7)
Nb1—O2i	1.941 (3)	Na2—O2	2.580 (7)
Nb1—O5ii	2.117 (6)	Na2—O8xiii	2.667 (14)
Nb1—O3	2.119 (5)	Na2—O8xiv	2.667 (14)
Nb1—O4ii	2.194 (5)	Na3—O8x	2.202 (19)
Nb2—O7iii	1.955 (2)	Na3—O8	2.202 (19)
Nb2—O7ii	1.955 (2)	Na3—O5	2.542 (9)
Nb2—O11ii	1.961 (6)	Na3—O5x	2.542 (9)
Nb2—O11iv	1.961 (6)	Na3—O6v	2.77 (4)
Nb2—O6v	2.021 (5)	Na3—O6xii	2.77 (4)
Nb2—O6	2.021 (5)	Na4—O8	2.069 (11)
Nb3—O11	1.859 (6)	Na4—O8x	2.069 (11)
Nb3—O11iv	1.859 (6)	Na4—O2xiii	2.85 (4)
Nb3—O9vi	2.024 (6)	Na4—O2	2.85 (4)
Nb3—O9vii	2.024 (6)	Na4—O5	2.88 (4)
Nb3—O1	2.025 (5)	Na4—O5x	2.88 (4)
Nb3—O1iv	2.025 (5)	Na5—O3v	2.35 (3)
As1—O5	1.669 (6)	Na5—O1xv	2.38 (2)
As1—O3	1.680 (6)	Na5—O4xv	2.62 (2)
As1—O6v	1.702 (4)	Na5—O9xvi	2.80 (5)
As1—O1	1.705 (5)	Na6—O3v	2.35 (4)
As2—O4viii	1.676 (5)	Na6—O1xv	2.56 (4)
As2—O4	1.676 (5)	Na6—O4xv	2.59 (4)
As2—O9viii	1.690 (6)	Na6—O9vi	2.68 (6)
As2—O9	1.690 (6)	Na7—O9xvii	2.496 (17)
Na1—O8ix	2.360 (7)	Na7—O4vii	2.523 (18)
Na1—O8x	2.360 (7)	Na7—O3xv	2.57 (4)
Na1—O7	2.489 (8)	Na7—O1iv	2.681 (17)
Na1—O5	2.718 (6)	Na8—O9xvi	2.50 (3)
Na1—O5xi	2.718 (6)	Na8—O4xv	2.55 (2)
Na1—O6iv	2.726 (6)	Na8—O1xv	2.58 (3)
Na1—O6xii	2.726 (6)	Na8—O3v	2.62 (4)
Na2—O8	2.270 (9)
O8—Nb1—O10	99.1 (2)	O6v—Nb2—O6	170.2 (2)
O8—Nb1—O2i	99.9 (3)	O11—Nb3—O11iv	91.6 (4)
O10—Nb1—O2i	94.80 (12)	O11—Nb3—O9vi	177.1 (3)
O8—Nb1—O5ii	89.2 (2)	O11iv—Nb3—O9vi	90.5 (3)
O10—Nb1—O5ii	171.3 (2)	O11—Nb3—O9vii	90.5 (3)
O2i—Nb1—O5ii	86.28 (18)	O11iv—Nb3—O9vii	177.1 (3)
O8—Nb1—O3	90.6 (2)	O9vi—Nb3—O9vii	87.5 (4)
O10—Nb1—O3	89.64 (18)	O11—Nb3—O1	92.5 (2)
O2i—Nb1—O3	167.8 (2)	O11iv—Nb3—O1	91.2 (2)
O5ii—Nb1—O3	87.7 (2)	O9vi—Nb3—O1	89.5 (2)
O8—Nb1—O4ii	168.0 (2)	O9vii—Nb3—O1	86.7 (2)
O10—Nb1—O4ii	86.4 (2)	O11—Nb3—O1iv	91.2 (2)
O2i—Nb1—O4ii	90.2 (2)	O11iv—Nb3—O1iv	92.5 (2)
O5ii—Nb1—O4ii	85.0 (2)	O9vi—Nb3—O1iv	86.7 (2)
O3—Nb1—O4ii	78.75 (19)	O9vii—Nb3—O1iv	89.5 (2)
O7iii—Nb2—O7ii	89.72 (14)	O1—Nb3—O1iv	174.8 (3)
O7iii—Nb2—O11ii	178.2 (2)	O5—As1—O3	117.2 (3)
O7ii—Nb2—O11ii	90.3 (2)	O5—As1—O6v	102.7 (2)
O7iii—Nb2—O11iv	90.3 (2)	O3—As1—O6v	112.3 (3)
O7ii—Nb2—O11iv	178.2 (2)	O5—As1—O1	109.4 (3)
O11ii—Nb2—O11iv	89.8 (4)	O3—As1—O1	102.7 (2)
O7iii—Nb2—O6v	95.9 (2)	O6v—As1—O1	112.8 (2)
O7ii—Nb2—O6v	91.0 (2)	O4viii—As2—O4	117.2 (3)
O11ii—Nb2—O6v	85.9 (2)	O4viii—As2—O9viii	111.6 (3)
O11iv—Nb2—O6v	87.2 (2)	O4—As2—O9viii	103.2 (2)
O7iii—Nb2—O6	91.0 (2)	O4viii—As2—O9	103.2 (2)
O7ii—Nb2—O6	95.9 (2)	O4—As2—O9	111.6 (3)
O11ii—Nb2—O6	87.2 (2)	O9viii—As2—O9	110.0 (4)
O11iv—Nb2—O6	85.9 (2)