Na3Co2(As0.52P0.48)O4(As0.95P0.05)2O7.

The title compound, trisodium dicobalt(II) (arsenate/phosphate) (diarsenate/diphosphate), was prepared by a solid-state reaction. It is isostructural with Na3Co2AsO4As2O7. The framework shows the presence of CoX22O12 (X2 is statistically disordered with As0.95P0.05) units formed by sharing corners between Co1O6 octa-hedra and X22O7 groups. These units form layers perpendicular to [010]. Co2O6 octa-hedra and X1O4 (X1 = As0.54P0.46) tetra-hedra form Co2X1O8 chains parallel to [001]. Cohesion between layers and chains is ensured by the X22O7 groups, giving rise to a three-dimensional framework with broad tunnels, running along the a- and c-axis directions, in which the Na(+) ions reside. The two Co(2+) cations, the X1 site and three of the seven O atoms lie on special positions, with site symmetries 2 and m for the Co, m for the X1, and 2 and m (× 2) for the O sites. One of two Na atoms is disordered over three special positions [occupancy ratios 0.877 (10):0.110 (13):0.066 (9)] and the other is in a general position with full occupancy. A comparison between structures such as K2CdP2O7, α-NaTiP2O7 and K2MoO2P2O7 is made. The proposed structural model is supported by charge-distribution (CHARDI) analysis and bond-valence-sum (BVS) calculations. The distortion of the coordination polyhedra is analyzed by means of the effective coordination number.

Related literature

For isotypic structures, see: Ben Smail & Jouini (2005 ▶); Guesmi & Driss (2012 ▶). For related structures, see: Ben Smail & Jouini (2004 ▶); Boughzala et al. (1997 ▶); Faggiani & Calvo (1976 ▶); Leclaire et al. (1988 ▶); Geoffroy et al. (2011 ▶); Rissouli et al. (1996 ▶); Zid et al. (2003 ▶). For bond-valence analysis, see: Brown (2002 ▶); Adams (2003 ▶). For the charge distribution method, see: Nespolo et al. (2001 ▶); Nespolo (2001 ▶); Guesmi et al. (2006 ▶).

Experimental

Crystal data

Na3Co2(As0.52P0.48)O4(As0.95P0.05)2O7

M = 562.32

Monoclinic,

a = 10.3982 (9) Å

b = 16.087 (2) Å

c = 6.4421 (6) Å

β = 120.425 (9)°

V = 929.21 (17) Å3

Z = 4

Mo Kα radiation

μ = 12.44 mm−1

T = 298 K

0.26 × 0.18 × 0.16 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.077, T max = 0.138

2212 measured reflections

1052 independent reflections

974 reflections with I > 2σ(I)

R int = 0.027

2 standard reflections every 120 reflections intensity decay: 1.4%

Refinement

R[F 2 > 2σ(F 2)] = 0.020

wR(F 2) = 0.049

S = 1.15

1052 reflections

105 parameters

3 restraints

Δρmax = 0.61 e Å−3

Δρmin = −0.61 e Å−3

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 & Putz, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813032029/br2232sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813032029/br2232Isup2.hkl

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

As2.42Co2Na3O11P0.57	F(000) = 1055
Mr = 562.32	Dx = 4.020 Mg m−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 25 reflections
a = 10.3982 (9) Å	θ = 10–15°
b = 16.087 (2) Å	µ = 12.44 mm−1
c = 6.4421 (6) Å	T = 298 K
β = 120.425 (9)°	Prism, pink
V = 929.21 (17) Å3	0.26 × 0.18 × 0.16 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	974 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
Graphite monochromator	θmax = 27.0°, θmin = 2.5°
ω/2θ scans	h = −13→13
Absorption correction: ψ scan (North et al., 1968)	k = −20→1
Tmin = 0.077, Tmax = 0.138	l = −8→8
2212 measured reflections	2 standard reflections every 120 reflections
1052 independent reflections	intensity decay: 1.4%

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)] = 0.020	w = 1/[σ2(Fo2) + (0.012P)2 + 5.1693P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.049	(Δ/σ)max < 0.001
S = 1.15	Δρmax = 0.61 e Å−3
1052 reflections	Δρmin = −0.61 e Å−3
105 parameters	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
3 restraints	Extinction coefficient: 0.00084 (13)

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)
As1	0.61047 (7)	0.5000	0.82497 (11)	0.0066 (2)	0.519 (5)
P1	0.61047 (7)	0.5000	0.82497 (11)	0.0066 (2)	0.481 (6)
As2	0.11976 (4)	0.33459 (2)	0.26883 (6)	0.00837 (13)	0.953 (4)
P2	0.11976 (4)	0.33459 (2)	0.26883 (6)	0.00837 (13)	0.047 (4)
Co1	0.5000	0.32278 (4)	0.5000	0.00767 (18)
Co2	0.30246 (7)	0.5000	0.58620 (11)	0.00979 (18)
O1	0.2677 (3)	0.30726 (17)	0.2518 (4)	0.0159 (5)
O2	0.4973 (3)	0.42032 (15)	0.7288 (4)	0.0125 (5)
O3	0.7294 (4)	0.5000	0.7420 (6)	0.0130 (7)
O4	0.7069 (4)	0.5000	1.1130 (6)	0.0175 (8)
O5	0.1483 (3)	0.40165 (15)	0.4838 (4)	0.0137 (5)
O6	0.0000	0.3895 (2)	0.0000	0.0126 (7)
O7	0.0195 (3)	0.25247 (17)	0.2544 (4)	0.0204 (6)
Na1	0.1865 (3)	0.16850 (11)	0.0966 (3)	0.0443 (6)
Na2A	0.0524 (3)	0.5000	0.7917 (8)	0.0361 (12)	0.871 (10)
Na2B	0.0000	0.5000	0.5000	0.0361 (12)	0.111 (12)
Na2C	0.038 (4)	0.5000	0.643 (13)	0.0361 (12)	0.071 (9)

	U11	U22	U33	U12	U13	U23
As1	0.0072 (3)	0.0073 (4)	0.0058 (3)	0.000	0.0037 (3)	0.000
P1	0.0072 (3)	0.0073 (4)	0.0058 (3)	0.000	0.0037 (3)	0.000
As2	0.00761 (19)	0.0082 (2)	0.00724 (19)	−0.00078 (13)	0.00228 (14)	−0.00001 (13)
P2	0.00761 (19)	0.0082 (2)	0.00724 (19)	−0.00078 (13)	0.00228 (14)	−0.00001 (13)
Co1	0.0072 (3)	0.0082 (3)	0.0074 (3)	0.000	0.0036 (2)	0.000
Co2	0.0096 (3)	0.0113 (3)	0.0094 (3)	0.000	0.0055 (3)	0.000
O1	0.0096 (11)	0.0173 (13)	0.0166 (12)	0.0020 (10)	0.0035 (10)	−0.0054 (10)
O2	0.0133 (11)	0.0115 (12)	0.0147 (11)	−0.0007 (10)	0.0086 (10)	−0.0013 (10)
O3	0.0176 (17)	0.0123 (17)	0.0101 (16)	0.000	0.0078 (14)	0.000
O4	0.0177 (18)	0.027 (2)	0.0113 (17)	0.000	0.0101 (15)	0.000
O5	0.0154 (12)	0.0144 (12)	0.0121 (11)	−0.0043 (10)	0.0075 (10)	−0.0042 (10)
O6	0.0122 (15)	0.0100 (16)	0.0091 (14)	0.000	0.0008 (13)	0.000
O7	0.0276 (14)	0.0179 (13)	0.0121 (12)	−0.0130 (12)	0.0074 (11)	0.0016 (11)
Na1	0.0860 (17)	0.0175 (9)	0.0239 (9)	0.0096 (10)	0.0238 (10)	−0.0010 (7)
Na2A	0.0202 (14)	0.0243 (15)	0.054 (3)	0.000	0.0117 (15)	0.000
Na2B	0.0202 (14)	0.0243 (15)	0.054 (3)	0.000	0.0117 (15)	0.000
Na2C	0.0202 (14)	0.0243 (15)	0.054 (3)	0.000	0.0117 (15)	0.000

As1—O3	1.577 (4)	Na1—O1vii	2.549 (3)
As1—O4	1.601 (3)	Na1—O7viii	2.573 (3)
As1—O2	1.635 (2)	Na1—O2ix	2.609 (3)
As1—O2i	1.635 (2)	Na1—O5iii	2.613 (3)
As2—O1	1.656 (2)	Na1—O4x	2.717 (2)
As2—O7	1.656 (3)	Na2A—O4vi	2.255 (5)
As2—O5	1.659 (2)	Na2A—O6xi	2.449 (4)
As2—O6	1.773 (2)	Na2A—O6xii	2.449 (4)
Co1—O7ii	2.082 (2)	Na2A—O5xiii	2.501 (4)
Co1—O7iii	2.082 (2)	Na2A—O5xii	2.501 (4)
Co1—O1	2.131 (2)	Na2A—O3vi	2.696 (5)
Co1—O1iv	2.131 (2)	Na2B—O5xiii	2.249 (2)
Co1—O2	2.163 (2)	Na2B—O5i	2.249 (2)
Co1—O2iv	2.163 (2)	Na2B—O5xii	2.249 (2)
Co2—O3v	1.967 (3)	Na2B—O4vi	2.794 (4)
Co2—O4vi	1.989 (4)	Na2B—O4xiv	2.794 (4)
Co2—O5	2.106 (2)	Na2C—O4vi	2.30 (4)
Co2—O5i	2.106 (2)	Na2C—O5xiii	2.31 (3)
Co2—O2i	2.169 (2)	Na2C—O5xii	2.31 (3)
Co2—O2	2.169 (2)	Na2C—O5i	2.46 (5)
O3—As1—O4	104.73 (18)	O1iv—Co1—O2	88.54 (10)
O3—As1—O2	114.16 (11)	O7ii—Co1—O2iv	82.19 (10)
O4—As1—O2	110.33 (11)	O7iii—Co1—O2iv	168.43 (10)
O3—As1—O2i	114.16 (11)	O1—Co1—O2iv	88.54 (10)
O4—As1—O2i	110.33 (11)	O1iv—Co1—O2iv	101.27 (9)
O2—As1—O2i	103.25 (17)	O2—Co1—O2iv	86.97 (13)
O1—As2—O7	111.36 (14)	O3v—Co2—O4vi	169.21 (16)
O1—As2—O5	116.62 (12)	O3v—Co2—O5	88.62 (9)
O7—As2—O5	114.01 (13)	O4vi—Co2—O5	84.28 (10)
O1—As2—O6	106.49 (9)	O3v—Co2—O5i	88.62 (9)
O7—As2—O6	103.40 (12)	O4vi—Co2—O5i	84.28 (10)
O5—As2—O6	103.39 (12)	O5—Co2—O5i	97.39 (14)
O7ii—Co1—O7iii	108.88 (16)	O3v—Co2—O2i	93.91 (11)
O7ii—Co1—O1	82.59 (10)	O4vi—Co2—O2i	94.79 (11)
O7iii—Co1—O1	89.58 (10)	O5—Co2—O2i	167.36 (10)
O7ii—Co1—O1iv	89.58 (10)	O5i—Co2—O2i	95.05 (9)
O7iii—Co1—O1iv	82.59 (10)	O3v—Co2—O2	93.91 (11)
O1—Co1—O1iv	166.54 (15)	O4vi—Co2—O2	94.79 (11)
O7ii—Co1—O2	168.43 (10)	O5—Co2—O2	95.05 (9)
O7iii—Co1—O2	82.19 (10)	O5i—Co2—O2	167.36 (10)
O1—Co1—O2	101.27 (9)	O2i—Co2—O2	72.44 (13)

Cation	q(i).sof(i)	V(i).sof(i)	Q(i)	CN(i)	ECoN(i)	dmoy(i)	dmed(i)
M1	5,000	5,131	5,146	4	3,966	1,611	1,610
M2	5,000	4,967	4,927	4	3,884	1,686	1,677
Co1	2,000	1,945	2,030	6	5,948	2,125	2,122
Co2	2,000	2,152	2,022	6	5,672	2,084	2,164
Na1	1,000	0,965	0,989	7	6,571	2,606	2,577
Na2A	0,882	0,969	0,846	6	5,412	2,475	2,430
Na2B	0,056	0,067	0,055	6	4,374	2,430	2,268
Na2C	0,071	0,086	0,069	5	4,817	2,366	2,351