Disodium calcium dinickel(II) bis­[diphosphate(V)] deca­hydrate

Cui, Y.-C.; Zhao, Y.-H.

doi:10.1107/S160053681100016X

inorganic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Pages i13-i14

doi:10.1107/S160053681100016X

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Disodium calcium dinickel(II) bis[diphosphate(V)] decahydrate

Yun-Cheng Cui ^a ^* and Yan-Hui Zhao ^a

^aDepartment of Chemistry, Jilin Normal University, Siping, Jilin 136000, People's Republic of China
^*Correspondence e-mail: yunchengc63@163.com

(Received 24 December 2010; accepted 4 January 2011; online 15 January 2011)

In the title compound, Na₂CaNi₂(P₂O₇)₂(H₂O)₁₀, there are two distinct P-atom sites, each tetrahedrally coordinated by four O atoms. The resulting phosphate tetrahedra link through a common O atom, forming a [P₂O₇]⁴⁻ diphosphate unit. The Ni—O coordination is square pyramidal with four O atoms from two diphosphate groups in equatorial positions and the vertex occupied by a water O atom. The (P₂O₇)(H₂O) units link the Ni atoms, forming a chain of pyramids and tetrahedra. As a result of the d-glide and twofold-axis symmetry of space group Fdd2, the chains propagate along [101] and [10 $[\overline{1}]$ ], and chains in adjacent layers are mutually orthogonal. The Ca cation, located on a rotation axis, and the Na cation are each octahedrally coordinated by four O atoms and two waters. The Ni-chain arrangement is stabilized by Ca and Na coordination and a network of O—H⋯O hydrogen bonds.

Related literature

For the isotypic copper(II)–diphosphate mineral wooldridgeite, see: Cooper & Hawthorne (1999 ). For the structure and magnetic properties of a diphosphate-bridged Cu^II complex, see: Kruger et al. (2001 ). For two other rare examples of Ni^II and Co^II coordination complexes with diphosphate ligands, see: Ikotun et al. (2007 ); Marino et al. (2008 ). Geometric calculatios and checking were performed with PLATON (Spek 2009 ).

Experimental

Crystal data

Na₂CaNi₂(P₂O₇)₂(H₂O)₁₀
M_r = 731.48
Orthorhombic, F d d 2
a = 11.9340 (11) Å
b = 32.774 (4) Å
c = 10.9860 (11) Å
V = 4296.9 (8) Å³
Z = 8
Mo Kα radiation
μ = 2.44 mm⁻¹
T = 290 K
0.15 × 0.13 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.705, T_max = 0.772
5540 measured reflections
2085 independent reflections
1999 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.049
S = 1.07
2085 reflections
150 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ), 974 Friedel pairs
Flack parameter: −0.011 (12)

Table 1
Selected bond lengths (Å)

Ca1—O8	2.254 (2)
Ca1—O8ⁱ	2.254 (2)
Ca1—O6ⁱⁱ	2.309 (2)
Ca1—O6ⁱⁱⁱ	2.309 (2)
Ca1—O10	2.428 (2)
Ca1—O10ⁱ	2.428 (2)
Ni1—O4	1.933 (2)
Ni1—O3	1.951 (2)
Ni1—O1	1.957 (2)
Ni1—O2	1.970 (2)
Ni1—O5	2.353 (3)
Na1—O3	2.342 (3)
Na1—O2	2.353 (2)
Na1—O9^iv	2.423 (3)
Na1—O10	2.450 (3)
Na1—O9	2.489 (4)
Na1—O11	2.902 (3)
Symmetry codes: (i) -x+1, -y, z; (ii) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (iv) $[x+{\script{1\over 4}}, -y+{\script{1\over 4}}, z+{\script{1\over 4}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H52⋯O11	0.94	1.89	2.803 (4)	163
O5—H51⋯O12^v	0.98	1.96	2.846 (4)	150
O9—H92⋯O4ⁱⁱⁱ	0.86	2.14	2.819 (4)	136
O9—H91⋯O11^vi	0.88	2.35	2.904 (4)	122
O10—H102⋯O1ⁱⁱⁱ	0.95	1.75	2.687 (3)	170
O10—H101⋯O12^vii	0.90	1.89	2.776 (3)	168
O11—H112⋯O8^v	0.99	1.85	2.834 (3)	175
O11—H111⋯O7ⁱⁱ	0.92	2.04	2.953 (3)	173
O12—H122⋯O5^viii	0.90	2.35	3.121 (4)	143
O12—H121⋯O6	0.93	1.87	2.772 (3)	162
Symmetry codes: (ii) $[-x+{\script{3\over 2}}, -y, z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (v) $[x+{\script{1\over 2}}, y, z+{\script{1\over 2}}]$ ; (vi) $[x-{\script{1\over 4}}, -y+{\script{1\over 4}}, z-{\script{1\over 4}}]$ ; (vii) x, y, z+1; (viii) $[-x+{\script{3\over 2}}, -y, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2003 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100016X/si2322sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681100016X/si2322Isup2.hkl

checkCIF report

Comment top

The design and synthesis of pyrophosphate-bridged coordination compounds have drawn considerable attention due to its ability to mediate electronic interactions between paramagnetic metal centers. The structure and magnetic properties of a pyrophosphate-bridged Cu(II) complex has been reported by Kruger et al. (2001). Two other rare examples of Ni^II (Mn^II) and Co^II coordination complexes with pyrophosphate ligands and their magnetic properties have been described by Ikotun et al. (2007) and Marino et al. (2008).

Wooldridgeite is a hydrated sodium-calcium-copper pyrophosphate mineral, Na₂CaCu²⁺₂(P₂O₇)₂(H₂O)₁₀, which is isotypic with the Ni²⁺ title pyrophosphate, described from the Judkins quarry, Nuneaton, Warwickshire, England (Cooper & Hawthorne, 1999). The geometric parameters of the copper mineral and the nickel title hydrate are very similar due to same space group and similar unit cell parameters. The vertex distances in the Wooldridgeite mineral (Cu—O4 and Cu—O4a) are described as 2.37 (2) Å and 3.39 (2) Å, respectively. Those for the nickel isotype are observed as Ni1—O5 = 2.353 (3) Å and Ni1—O5a = 3.355 (3) Å [calculated with PLATON (Spek, 2009)]. Relevant M—O distances (M = Ni, Ca, Na) of the title structure are presented in Table 1.

As shown in Fig. 1, there is one crystallographic Ni^II site surrounded by five O atoms in a square pyramidal or strongly distorted (4 + 1 + 1) octahedral arrangement, with Ni—O distances in the range of 1.933 (2) to 2.353 (3) Å, the long Ni—O distance is 3.355 (3) Å. Each Ni octahedron links through one trans pair of symmetry related vertices to other Ni octahedra to form a chain, this chain is decorated by [P₂O₇] groups to form a chain of octahedra and tetrahedra [Ni(P₂O₇)H₂O]_n (Fig. 2). These chains extend along [1 0 1] and [1 0 - 1] and linked into sheets by Na and Ca octahedra, the pattern of chains extending along [1 0 1] (Fig. 3). Together with the coordinated Ca and Na cations, a three-dimensional framework is generated by ten intermolecular O—H···O hydrogen bonds with water and phosphate oxygen atoms as acceptors (Table 2).

Related literature top

For the isotypic copper(II)–pyrophosphate mineral Wooldridgeite, see: Cooper & Hawthorne (1999). For the structure and magnetic properties of a pyrophosphate-bridged Cu^II complex, see: Kruger et al. (2001). For two other rare examples of Ni^II and Co^II coordination complexes with pyrophosphate ligands, see: Ikotun et al. (2007); Marino et al. (2008). Geometric calculatios and checking were performed with PLATON (Spek 2009).

Experimental top

A mixture of Na₄P₂O₇ (0.4476 g, 1.0 mmol), Ni(CH₃COO)₂ (0.2441 g, 0.98 mmol), Ca(CH₃COO)_2.H₂O (0.1763 g, 1.0 mmol), 2,2-Bipyridyl (0.1502 g, 0.96 mmol) and water (15 ml) was adjusted to pH 3.49 with H₂SO₄ (1 mol/L) solution. The filtration was allowed to stand over several days to give green block single crystals in 42% yield. Elementary Analysis calculated for Na₂CaNi₂(P₂O₇)₂(H₂O)₁₀: H 2.76, Ca 5.47, Na 6.29, Ni 16.05, O 52.50, P 16.94%; found: H 2.74, Ca 5.48, Na 6.28, Ni 16.07, O 52.52, P 16.95%.

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The local coordination feature of the title compound. Displacement ellipsoids are drawn at the 30% probability level (symmetry code: a = -1/4 + x, 1/4 + y, -1/4 + z, b = 1/4 + x, 1/4 - y, 1/4 + z).
	Fig. 2. A view of chain construct of the title compound. H, Ca, Na, and O12 atoms are omitted for clarity.
	Fig. 3. A view of a section of the three-dimensional structure of the title compound. H-bonds are drawn as black dashed lines.

Disodium calcium dinickel(II) bis[diphosphate(V)] decahydrate top

Crystal data top

Na₂CaNi₂(P₂O₇)₂(H₂O)₁₀	F(000) = 2960
M_r = 731.48	D_x = 2.261 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 937 reflections
a = 11.9340 (11) Å	θ = 1.8–26.5°
b = 32.774 (4) Å	µ = 2.44 mm⁻¹
c = 10.9860 (11) Å	T = 290 K
V = 4296.9 (8) Å³	Block, green
Z = 8	0.15 × 0.13 × 0.11 mm

Data collection top

Bruker CCD APEXII diffractometer	2085 independent reflections
Radiation source: fine-focus sealed tube	1999 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and ϕ scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→14
T_min = 0.705, T_max = 0.772	k = −40→40
5540 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.049	w = 1/[σ²(F_o²) + (0.0191P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2085 reflections	Δρ_max = 0.22 e Å⁻³
150 parameters	Δρ_min = −0.29 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 974 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.011 (12)

Crystal data top

Na₂CaNi₂(P₂O₇)₂(H₂O)₁₀	V = 4296.9 (8) Å³
M_r = 731.48	Z = 8
Orthorhombic, Fdd2	Mo Kα radiation
a = 11.9340 (11) Å	µ = 2.44 mm⁻¹
b = 32.774 (4) Å	T = 290 K
c = 10.9860 (11) Å	0.15 × 0.13 × 0.11 mm

Data collection top

Bruker CCD APEXII diffractometer	2085 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1999 reflections with I > 2σ(I)
T_min = 0.705, T_max = 0.772	R_int = 0.030
5540 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	H-atom parameters constrained
wR(F²) = 0.049	Δρ_max = 0.22 e Å⁻³
S = 1.07	Δρ_min = −0.29 e Å⁻³
2085 reflections	Absolute structure: Flack (1983), 974 Friedel pairs
150 parameters	Absolute structure parameter: −0.011 (12)
1 restraint

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Ca1	0.5000	0.0000	0.62448 (8)	0.01385 (17)
Ni1	0.86875 (3)	0.110744 (11)	0.47330 (3)	0.01615 (10)
Na1	0.71250 (14)	0.09782 (5)	0.71990 (15)	0.0492 (4)
P1	0.64133 (7)	0.07042 (2)	0.42464 (7)	0.01640 (16)
P2	0.79550 (6)	0.06891 (2)	0.22939 (7)	0.01653 (16)
O1	0.88590 (18)	0.08175 (6)	0.3187 (2)	0.0249 (5)
O2	0.73480 (18)	0.07854 (7)	0.51498 (19)	0.0238 (5)
O3	0.8414 (2)	0.14096 (6)	0.6234 (2)	0.0296 (5)
O5	0.9793 (3)	0.06393 (10)	0.5826 (3)	0.0684 (11)
H51	1.0545	0.0553	0.5590	0.082*
H52	0.9577	0.0581	0.6632	0.082*
O4	0.9895 (2)	0.14533 (6)	0.4175 (2)	0.0305 (5)
O6	0.83644 (18)	0.03723 (6)	0.14145 (19)	0.0221 (5)
O7	0.69943 (17)	0.04685 (6)	0.31024 (19)	0.0180 (4)
O8	0.55500 (18)	0.04126 (6)	0.4715 (2)	0.0246 (5)
O9	0.5427 (3)	0.13839 (8)	0.6683 (3)	0.0494 (8)
H91	0.5308	0.1648	0.6733	0.059*
H92	0.4990	0.1317	0.7274	0.059*
O10	0.58195 (19)	0.04368 (6)	0.7792 (2)	0.0275 (5)
H101	0.6151	0.0351	0.8478	0.033*
H102	0.5175	0.0595	0.7980	0.033*
O11	0.8778 (2)	0.03869 (7)	0.8000 (3)	0.0375 (6)
H111	0.8544	0.0120	0.7960	0.045*
H112	0.9425	0.0387	0.8564	0.045*
O12	0.6562 (2)	0.01268 (7)	0.0001 (2)	0.0369 (6)
H121	0.7193	0.0151	0.0491	0.044*
H122	0.6269	−0.0124	−0.0117	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ca1	0.0133 (4)	0.0136 (4)	0.0147 (4)	0.0007 (3)	0.000	0.000
Ni1	0.01661 (18)	0.01719 (17)	0.01464 (17)	−0.00632 (16)	0.00368 (16)	−0.00529 (14)
Na1	0.0593 (10)	0.0601 (9)	0.0283 (7)	−0.0349 (9)	0.0115 (8)	−0.0071 (8)
P1	0.0166 (4)	0.0160 (3)	0.0166 (4)	−0.0011 (3)	0.0018 (3)	0.0013 (3)
P2	0.0168 (4)	0.0169 (3)	0.0159 (3)	0.0026 (3)	0.0006 (3)	−0.0005 (3)
O1	0.0189 (12)	0.0328 (12)	0.0230 (12)	−0.0051 (10)	0.0009 (10)	−0.0112 (10)
O2	0.0220 (12)	0.0326 (11)	0.0169 (11)	−0.0081 (10)	0.0014 (9)	−0.0028 (9)
O3	0.0385 (14)	0.0263 (11)	0.0241 (12)	−0.0140 (11)	0.0132 (11)	−0.0087 (10)
O5	0.0506 (19)	0.108 (3)	0.0462 (18)	0.042 (2)	0.0165 (15)	0.0406 (18)
O4	0.0346 (14)	0.0267 (11)	0.0301 (13)	−0.0153 (11)	0.0136 (12)	−0.0113 (10)
O6	0.0208 (11)	0.0243 (10)	0.0212 (11)	0.0050 (10)	−0.0013 (9)	−0.0080 (9)
O7	0.0182 (11)	0.0160 (9)	0.0198 (10)	−0.0015 (9)	0.0020 (9)	−0.0029 (8)
O8	0.0219 (11)	0.0281 (11)	0.0238 (11)	−0.0075 (10)	0.0015 (10)	0.0040 (10)
O9	0.066 (2)	0.0474 (16)	0.0347 (14)	−0.0080 (15)	0.0152 (14)	0.0011 (12)
O10	0.0240 (12)	0.0317 (12)	0.0269 (13)	0.0031 (11)	−0.0025 (10)	−0.0016 (10)
O11	0.0377 (15)	0.0262 (11)	0.0487 (17)	−0.0059 (11)	−0.0046 (12)	0.0052 (12)
O12	0.0335 (15)	0.0386 (13)	0.0385 (16)	−0.0031 (12)	−0.0104 (11)	−0.0029 (12)

Geometric parameters (Å, º) top

Ca1—O8	2.254 (2)	Na1—O9^iv	2.423 (3)
Ca1—O8ⁱ	2.254 (2)	Na1—O10	2.450 (3)
Ca1—O6ⁱⁱ	2.309 (2)	Na1—O9	2.489 (4)
Ca1—O6ⁱⁱⁱ	2.309 (2)	Na1—O11	2.902 (3)
Ca1—O10	2.428 (2)	P1—O8	1.497 (2)
Ca1—O10ⁱ	2.428 (2)	P1—O3^v	1.508 (2)
Ca1—P2ⁱⁱⁱ	3.5191 (8)	P1—O2	1.517 (2)
Ca1—P2ⁱⁱ	3.5191 (8)	P1—O7	1.630 (2)
Ca1—Na1	4.2200 (15)	P2—O6	1.500 (2)
Ca1—Na1ⁱ	4.2200 (15)	P2—O4^v	1.511 (2)
Ni1—O4	1.933 (2)	P2—O1	1.518 (2)
Ni1—O3	1.951 (2)	P2—O7	1.621 (2)
Ni1—O1	1.957 (2)	P2—Ca1^vi	3.5191 (8)
Ni1—O2	1.970 (2)	O3—P1^iv	1.508 (2)
Ni1—O5	2.353 (3)	O4—P2^iv	1.511 (2)
Ni1—Na1	3.3160 (16)	O6—Ca1^vi	2.309 (2)
Na1—O3	2.342 (3)	O9—Na1^v	2.423 (3)
Na1—O2	2.353 (2)

O8—Ca1—O8ⁱ	83.63 (12)	O5—Ni1—Na1	79.34 (8)
O8—Ca1—O6ⁱⁱ	97.52 (8)	O3—Na1—O2	69.82 (9)
O8ⁱ—Ca1—O6ⁱⁱ	89.39 (8)	O3—Na1—O9^iv	92.02 (10)
O8—Ca1—O6ⁱⁱⁱ	89.39 (8)	O2—Na1—O9^iv	150.00 (11)
O8ⁱ—Ca1—O6ⁱⁱⁱ	97.52 (8)	O3—Na1—O10	167.19 (11)
O6ⁱⁱ—Ca1—O6ⁱⁱⁱ	170.74 (11)	O2—Na1—O10	97.58 (9)
O8—Ca1—O10	92.92 (7)	O9^iv—Na1—O10	98.45 (10)
O8ⁱ—Ca1—O10	173.07 (8)	O3—Na1—O9	96.27 (10)
O6ⁱⁱ—Ca1—O10	85.10 (8)	O2—Na1—O9	91.02 (10)
O6ⁱⁱⁱ—Ca1—O10	88.42 (7)	O9^iv—Na1—O9	115.25 (10)
O8—Ca1—O10ⁱ	173.07 (8)	O10—Na1—O9	85.97 (9)
O8ⁱ—Ca1—O10ⁱ	92.92 (7)	O3—Na1—O11	95.40 (10)
O6ⁱⁱ—Ca1—O10ⁱ	88.42 (7)	O2—Na1—O11	91.94 (9)
O6ⁱⁱⁱ—Ca1—O10ⁱ	85.10 (8)	O9^iv—Na1—O11	65.37 (9)
O10—Ca1—O10ⁱ	91.12 (11)	O10—Na1—O11	82.41 (8)
O8—Ca1—P2ⁱⁱⁱ	93.50 (5)	O9—Na1—O11	168.28 (10)
O8ⁱ—Ca1—P2ⁱⁱⁱ	115.28 (6)	O3—Na1—Ni1	35.32 (6)
O6ⁱⁱ—Ca1—P2ⁱⁱⁱ	153.99 (6)	O2—Na1—Ni1	35.82 (6)
O6ⁱⁱⁱ—Ca1—P2ⁱⁱⁱ	17.90 (5)	O9^iv—Na1—Ni1	119.28 (9)
O10—Ca1—P2ⁱⁱⁱ	70.83 (5)	O10—Na1—Ni1	131.87 (8)
O10ⁱ—Ca1—P2ⁱⁱⁱ	82.51 (6)	O9—Na1—Ni1	101.75 (8)
O8—Ca1—P2ⁱⁱ	115.28 (6)	O11—Na1—Ni1	87.18 (7)
O8ⁱ—Ca1—P2ⁱⁱ	93.50 (5)	O3—Na1—Ca1	137.79 (8)
O6ⁱⁱ—Ca1—P2ⁱⁱ	17.90 (5)	O2—Na1—Ca1	68.06 (6)
O6ⁱⁱⁱ—Ca1—P2ⁱⁱ	153.99 (6)	O9^iv—Na1—Ca1	127.04 (8)
O10—Ca1—P2ⁱⁱ	82.51 (6)	O10—Na1—Ca1	29.95 (6)
O10ⁱ—Ca1—P2ⁱⁱ	70.83 (5)	O9—Na1—Ca1	81.95 (7)
P2ⁱⁱⁱ—Ca1—P2ⁱⁱ	141.77 (4)	O11—Na1—Ca1	88.65 (6)
O8—Ca1—Na1	63.55 (6)	Ni1—Na1—Ca1	103.42 (4)
O8ⁱ—Ca1—Na1	144.66 (7)	O8—P1—O3^v	113.09 (14)
O6ⁱⁱ—Ca1—Na1	82.73 (6)	O8—P1—O2	113.15 (13)
O6ⁱⁱⁱ—Ca1—Na1	94.96 (6)	O3^v—P1—O2	112.81 (14)
O10—Ca1—Na1	30.25 (6)	O8—P1—O7	104.81 (11)
O10ⁱ—Ca1—Na1	121.07 (6)	O3^v—P1—O7	106.16 (12)
P2ⁱⁱⁱ—Ca1—Na1	81.25 (3)	O2—P1—O7	105.95 (12)
P2ⁱⁱ—Ca1—Na1	89.39 (3)	O6—P2—O4^v	113.05 (13)
O8—Ca1—Na1ⁱ	144.66 (7)	O6—P2—O1	112.14 (12)
O8ⁱ—Ca1—Na1ⁱ	63.55 (6)	O4^v—P2—O1	112.95 (13)
O6ⁱⁱ—Ca1—Na1ⁱ	94.96 (6)	O6—P2—O7	105.94 (11)
O6ⁱⁱⁱ—Ca1—Na1ⁱ	82.73 (6)	O4^v—P2—O7	106.24 (12)
O10—Ca1—Na1ⁱ	121.07 (6)	O1—P2—O7	105.81 (12)
O10ⁱ—Ca1—Na1ⁱ	30.25 (6)	O6—P2—Ca1^vi	28.24 (8)
P2ⁱⁱⁱ—Ca1—Na1ⁱ	89.39 (3)	O4^v—P2—Ca1^vi	131.10 (9)
P2ⁱⁱ—Ca1—Na1ⁱ	81.25 (3)	O1—P2—Ca1^vi	84.08 (9)
Na1—Ca1—Na1ⁱ	151.23 (5)	O7—P2—Ca1^vi	112.57 (7)
O4—Ni1—O3	95.47 (9)	P2—O1—Ni1	128.42 (13)
O4—Ni1—O1	86.08 (9)	P1—O2—Ni1	122.61 (13)
O3—Ni1—O1	175.96 (11)	P1—O2—Na1	126.15 (13)
O4—Ni1—O2	173.20 (10)	Ni1—O2—Na1	99.80 (9)
O3—Ni1—O2	86.53 (9)	P1^iv—O3—Ni1	132.45 (14)
O1—Ni1—O2	91.52 (9)	P1^iv—O3—Na1	126.69 (13)
O4—Ni1—O5	97.25 (11)	Ni1—O3—Na1	100.73 (10)
O3—Ni1—O5	89.63 (11)	P2^iv—O4—Ni1	129.96 (14)
O1—Ni1—O5	93.88 (11)	P2—O6—Ca1^vi	133.86 (13)
O2—Ni1—O5	89.25 (10)	P2—O7—P1	120.81 (12)
O4—Ni1—Na1	138.85 (7)	P1—O8—Ca1	147.13 (15)
O3—Ni1—Na1	43.95 (7)	Na1^v—O9—Na1	128.74 (13)
O1—Ni1—Na1	134.90 (7)	Ca1—O10—Na1	119.80 (10)
O2—Ni1—Na1	44.37 (6)

O4—Ni1—Na1—O3	11.86 (18)	O2—Ni1—O1—P2	40.92 (18)
O1—Ni1—Na1—O3	−174.48 (15)	O5—Ni1—O1—P2	130.27 (18)
O2—Ni1—Na1—O3	−159.31 (16)	Na1—Ni1—O1—P2	51.5 (2)
O5—Ni1—Na1—O3	100.70 (14)	O8—P1—O2—Ni1	173.16 (13)
O4—Ni1—Na1—O2	171.18 (15)	O3^v—P1—O2—Ni1	−56.86 (19)
O3—Ni1—Na1—O2	159.31 (16)	O7—P1—O2—Ni1	58.88 (17)
O1—Ni1—Na1—O2	−15.16 (14)	O8—P1—O2—Na1	−50.97 (19)
O5—Ni1—Na1—O2	−99.98 (13)	O3^v—P1—O2—Na1	79.01 (17)
O4—Ni1—Na1—O9^iv	−31.96 (17)	O7—P1—O2—Na1	−165.25 (12)
O3—Ni1—Na1—O9^iv	−43.83 (13)	O4—Ni1—O2—P1	23.7 (9)
O1—Ni1—Na1—O9^iv	141.70 (12)	O3—Ni1—O2—P1	130.99 (16)
O2—Ni1—Na1—O9^iv	156.86 (14)	O1—Ni1—O2—P1	−45.47 (16)
O5—Ni1—Na1—O9^iv	56.88 (12)	O5—Ni1—O2—P1	−139.33 (17)
O4—Ni1—Na1—O10	−168.76 (14)	Na1—Ni1—O2—P1	145.2 (2)
O3—Ni1—Na1—O10	179.38 (18)	O4—Ni1—O2—Na1	−121.5 (7)
O1—Ni1—Na1—O10	4.90 (17)	O3—Ni1—O2—Na1	−14.22 (11)
O2—Ni1—Na1—O10	20.07 (13)	O1—Ni1—O2—Na1	169.32 (10)
O5—Ni1—Na1—O10	−79.92 (15)	O5—Ni1—O2—Na1	75.45 (11)
O4—Ni1—Na1—O9	96.08 (14)	O3—Na1—O2—P1	−130.91 (17)
O3—Ni1—Na1—O9	84.22 (13)	O9^iv—Na1—O2—P1	173.25 (18)
O1—Ni1—Na1—O9	−90.26 (12)	O10—Na1—O2—P1	51.46 (17)
O2—Ni1—Na1—O9	−75.10 (12)	O9—Na1—O2—P1	−34.60 (16)
O5—Ni1—Na1—O9	−175.08 (11)	O11—Na1—O2—P1	134.06 (15)
O4—Ni1—Na1—O11	−91.57 (14)	Ni1—Na1—O2—P1	−143.5 (2)
O3—Ni1—Na1—O11	−103.44 (13)	Ca1—Na1—O2—P1	46.30 (13)
O1—Ni1—Na1—O11	82.09 (12)	O3—Na1—O2—Ni1	12.57 (9)
O2—Ni1—Na1—O11	97.25 (11)	O9^iv—Na1—O2—Ni1	−43.3 (2)
O5—Ni1—Na1—O11	−2.73 (11)	O10—Na1—O2—Ni1	−165.06 (10)
O4—Ni1—Na1—Ca1	−179.51 (11)	O9—Na1—O2—Ni1	108.87 (10)
O3—Ni1—Na1—Ca1	168.63 (13)	O11—Na1—O2—Ni1	−82.47 (10)
O1—Ni1—Na1—Ca1	−5.85 (11)	Ca1—Na1—O2—Ni1	−170.23 (10)
O2—Ni1—Na1—Ca1	9.31 (9)	O4—Ni1—O3—P1^iv	3.7 (2)
O5—Ni1—Na1—Ca1	−90.67 (10)	O1—Ni1—O3—P1^iv	−108.7 (13)
O8—Ca1—Na1—O3	−21.31 (14)	O2—Ni1—O3—P1^iv	−169.8 (2)
O8ⁱ—Ca1—Na1—O3	2.33 (19)	O5—Ni1—O3—P1^iv	100.9 (2)
O6ⁱⁱ—Ca1—Na1—O3	80.87 (14)	Na1—Ni1—O3—P1^iv	175.9 (3)
O6ⁱⁱⁱ—Ca1—Na1—O3	−108.14 (14)	O4—Ni1—O3—Na1	−172.19 (12)
O10—Ca1—Na1—O3	173.6 (2)	O1—Ni1—O3—Na1	75.5 (14)
O10ⁱ—Ca1—Na1—O3	164.60 (14)	O2—Ni1—O3—Na1	14.33 (11)
P2ⁱⁱⁱ—Ca1—Na1—O3	−119.68 (13)	O5—Ni1—O3—Na1	−74.94 (12)
P2ⁱⁱ—Ca1—Na1—O3	97.53 (13)	O2—Na1—O3—P1^iv	171.1 (2)
Na1ⁱ—Ca1—Na1—O3	167.93 (14)	O9^iv—Na1—O3—P1^iv	−33.4 (2)
O8—Ca1—Na1—O2	−25.22 (9)	O10—Na1—O3—P1^iv	−178.3 (5)
O8ⁱ—Ca1—Na1—O2	−1.58 (13)	O9—Na1—O3—P1^iv	82.3 (2)
O6ⁱⁱ—Ca1—Na1—O2	76.96 (9)	O11—Na1—O3—P1^iv	−98.82 (18)
O6ⁱⁱⁱ—Ca1—Na1—O2	−112.05 (9)	Ni1—Na1—O3—P1^iv	−176.2 (3)
O10—Ca1—Na1—O2	169.71 (14)	Ca1—Na1—O3—P1^iv	167.22 (12)
O10ⁱ—Ca1—Na1—O2	160.69 (9)	O2—Na1—O3—Ni1	−12.72 (10)
P2ⁱⁱⁱ—Ca1—Na1—O2	−123.59 (7)	O9^iv—Na1—O3—Ni1	142.82 (11)
P2ⁱⁱ—Ca1—Na1—O2	93.62 (7)	O10—Na1—O3—Ni1	−2.1 (6)
Na1ⁱ—Ca1—Na1—O2	164.03 (7)	O9—Na1—O3—Ni1	−101.50 (11)
O8—Ca1—Na1—O9^iv	−175.17 (13)	O11—Na1—O3—Ni1	77.37 (12)
O8ⁱ—Ca1—Na1—O9^iv	−151.54 (13)	Ca1—Na1—O3—Ni1	−16.59 (19)
O6ⁱⁱ—Ca1—Na1—O9^iv	−72.99 (12)	O3—Ni1—O4—P2^iv	4.3 (2)
O6ⁱⁱⁱ—Ca1—Na1—O9^iv	97.99 (12)	O1—Ni1—O4—P2^iv	−179.5 (2)
O10—Ca1—Na1—O9^iv	19.75 (14)	O2—Ni1—O4—P2^iv	111.1 (8)
O10ⁱ—Ca1—Na1—O9^iv	10.73 (13)	O5—Ni1—O4—P2^iv	−86.0 (2)
P2ⁱⁱⁱ—Ca1—Na1—O9^iv	86.45 (11)	Na1—Ni1—O4—P2^iv	−4.0 (3)
P2ⁱⁱ—Ca1—Na1—O9^iv	−56.33 (11)	O4^v—P2—O6—Ca1^vi	135.88 (17)
Na1ⁱ—Ca1—Na1—O9^iv	14.07 (10)	O1—P2—O6—Ca1^vi	6.8 (2)
O8—Ca1—Na1—O10	165.08 (13)	O7—P2—O6—Ca1^vi	−108.17 (17)
O8ⁱ—Ca1—Na1—O10	−171.28 (15)	O6—P2—O7—P1	174.81 (14)
O6ⁱⁱ—Ca1—Na1—O10	−92.74 (13)	O4^v—P2—O7—P1	−64.71 (18)
O6ⁱⁱⁱ—Ca1—Na1—O10	78.24 (13)	O1—P2—O7—P1	55.59 (17)
O10ⁱ—Ca1—Na1—O10	−9.02 (17)	Ca1^vi—P2—O7—P1	145.68 (11)
P2ⁱⁱⁱ—Ca1—Na1—O10	66.71 (11)	O8—P1—O7—P2	177.56 (14)
P2ⁱⁱ—Ca1—Na1—O10	−76.08 (11)	O3^v—P1—O7—P2	57.63 (18)
Na1ⁱ—Ca1—Na1—O10	−5.68 (11)	O2—P1—O7—P2	−62.54 (17)
O8—Ca1—Na1—O9	69.16 (9)	O3^v—P1—O8—Ca1	−132.5 (2)
O8ⁱ—Ca1—Na1—O9	92.80 (12)	O2—P1—O8—Ca1	−2.6 (3)
O6ⁱⁱ—Ca1—Na1—O9	171.34 (9)	O7—P1—O8—Ca1	112.4 (2)
O6ⁱⁱⁱ—Ca1—Na1—O9	−17.68 (9)	O8ⁱ—Ca1—O8—P1	−141.1 (3)
O10—Ca1—Na1—O9	−95.92 (13)	O6ⁱⁱ—Ca1—O8—P1	−52.6 (3)
O10ⁱ—Ca1—Na1—O9	−104.93 (9)	O6ⁱⁱⁱ—Ca1—O8—P1	121.2 (2)
P2ⁱⁱⁱ—Ca1—Na1—O9	−29.21 (7)	O10—Ca1—O8—P1	32.8 (2)
P2ⁱⁱ—Ca1—Na1—O9	−172.00 (7)	O10ⁱ—Ca1—O8—P1	158.4 (6)
Na1ⁱ—Ca1—Na1—O9	−101.60 (7)	P2ⁱⁱⁱ—Ca1—O8—P1	103.8 (2)
O8—Ca1—Na1—O11	−117.86 (9)	P2ⁱⁱ—Ca1—O8—P1	−50.3 (3)
O8ⁱ—Ca1—Na1—O11	−94.22 (12)	Na1—Ca1—O8—P1	25.4 (2)
O6ⁱⁱ—Ca1—Na1—O11	−15.68 (8)	Na1ⁱ—Ca1—O8—P1	−162.32 (17)
O6ⁱⁱⁱ—Ca1—Na1—O11	155.31 (9)	O3—Na1—O9—Na1^v	64.92 (15)
O10—Ca1—Na1—O11	77.06 (12)	O2—Na1—O9—Na1^v	−4.89 (15)
O10ⁱ—Ca1—Na1—O11	68.05 (10)	O9^iv—Na1—O9—Na1^v	160.14 (15)
P2ⁱⁱⁱ—Ca1—Na1—O11	143.77 (7)	O10—Na1—O9—Na1^v	−102.41 (16)
P2ⁱⁱ—Ca1—Na1—O11	0.98 (7)	O11—Na1—O9—Na1^v	−109.5 (5)
Na1ⁱ—Ca1—Na1—O11	71.38 (7)	Ni1—Na1—O9—Na1^v	29.56 (15)
O8—Ca1—Na1—Ni1	−31.08 (7)	Ca1—Na1—O9—Na1^v	−72.56 (14)
O8ⁱ—Ca1—Na1—Ni1	−7.44 (12)	O8—Ca1—O10—Na1	−13.35 (11)
O6ⁱⁱ—Ca1—Na1—Ni1	71.10 (7)	O8ⁱ—Ca1—O10—Na1	46.6 (7)
O6ⁱⁱⁱ—Ca1—Na1—Ni1	−117.91 (7)	O6ⁱⁱ—Ca1—O10—Na1	83.96 (12)
O10—Ca1—Na1—Ni1	163.84 (13)	O6ⁱⁱⁱ—Ca1—O10—Na1	−102.65 (12)
O10ⁱ—Ca1—Na1—Ni1	154.83 (7)	O10ⁱ—Ca1—O10—Na1	172.28 (15)
P2ⁱⁱⁱ—Ca1—Na1—Ni1	−129.45 (4)	P2ⁱⁱⁱ—Ca1—O10—Na1	−106.04 (11)
P2ⁱⁱ—Ca1—Na1—Ni1	87.76 (4)	P2ⁱⁱ—Ca1—O10—Na1	101.78 (11)
Na1ⁱ—Ca1—Na1—Ni1	158.16 (5)	Na1ⁱ—Ca1—O10—Na1	176.81 (6)
O6—P2—O1—Ni1	−163.26 (14)	O3—Na1—O10—Ca1	−19.7 (6)
O4^v—P2—O1—Ni1	67.6 (2)	O2—Na1—O10—Ca1	−9.63 (13)
O7—P2—O1—Ni1	−48.21 (19)	O9^iv—Na1—O10—Ca1	−164.18 (11)
Ca1^vi—P2—O1—Ni1	−160.03 (16)	O9—Na1—O10—Ca1	80.87 (12)
O4—Ni1—O1—P2	−132.71 (19)	O11—Na1—O10—Ca1	−100.59 (11)
O3—Ni1—O1—P2	−20.1 (15)	Ni1—Na1—O10—Ca1	−21.31 (17)

Symmetry codes: (i) −x+1, −y, z; (ii) −x+3/2, −y, z+1/2; (iii) x−1/2, y, z+1/2; (iv) x+1/4, −y+1/4, z+1/4; (v) x−1/4, −y+1/4, z−1/4; (vi) x+1/2, y, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H52···O11	0.94	1.89	2.803 (4)	163
O5—H51···O12^vii	0.98	1.96	2.846 (4)	150
O9—H92···O4ⁱⁱⁱ	0.86	2.14	2.819 (4)	136
O9—H91···O11^v	0.88	2.35	2.904 (4)	122
O10—H102···O1ⁱⁱⁱ	0.95	1.75	2.687 (3)	170
O10—H101···O12^viii	0.90	1.89	2.776 (3)	168
O11—H112···O8^vii	0.99	1.85	2.834 (3)	175
O11—H111···O7ⁱⁱ	0.92	2.04	2.953 (3)	173
O12—H122···O5^ix	0.90	2.35	3.121 (4)	143
O12—H121···O6	0.93	1.87	2.772 (3)	162

Symmetry codes: (ii) −x+3/2, −y, z+1/2; (iii) x−1/2, y, z+1/2; (v) x−1/4, −y+1/4, z−1/4; (vii) x+1/2, y, z+1/2; (viii) x, y, z+1; (ix) −x+3/2, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	Na₂CaNi₂(P₂O₇)₂(H₂O)₁₀
M_r	731.48
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	290
a, b, c (Å)	11.9340 (11), 32.774 (4), 10.9860 (11)
V (Å³)	4296.9 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.44
Crystal size (mm)	0.15 × 0.13 × 0.11

Data collection
Diffractometer	Bruker CCD APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.705, 0.772
No. of measured, independent and observed [I > 2σ(I)] reflections	5540, 2085, 1999
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.049, 1.07
No. of reflections	2085
No. of parameters	150
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.29
Absolute structure	Flack (1983), 974 Friedel pairs
Absolute structure parameter	−0.011 (12)

Computer programs: APEX2 (Bruker, 2003), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg & Berndt, 1999), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Ca1—O8	2.254 (2)	Ni1—O2	1.970 (2)
Ca1—O8ⁱ	2.254 (2)	Ni1—O5	2.353 (3)
Ca1—O6ⁱⁱ	2.309 (2)	Na1—O3	2.342 (3)
Ca1—O6ⁱⁱⁱ	2.309 (2)	Na1—O2	2.353 (2)
Ca1—O10	2.428 (2)	Na1—O9^iv	2.423 (3)
Ca1—O10ⁱ	2.428 (2)	Na1—O10	2.450 (3)
Ni1—O4	1.933 (2)	Na1—O9	2.489 (4)
Ni1—O3	1.951 (2)	Na1—O11	2.902 (3)
Ni1—O1	1.957 (2)

Symmetry codes: (i) −x+1, −y, z; (ii) −x+3/2, −y, z+1/2; (iii) x−1/2, y, z+1/2; (iv) x+1/4, −y+1/4, z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H52···O11	0.94	1.89	2.803 (4)	163
O5—H51···O12^v	0.98	1.96	2.846 (4)	150
O9—H92···O4ⁱⁱⁱ	0.86	2.14	2.819 (4)	136
O9—H91···O11^vi	0.88	2.35	2.904 (4)	122
O10—H102···O1ⁱⁱⁱ	0.95	1.75	2.687 (3)	170
O10—H101···O12^vii	0.90	1.89	2.776 (3)	168
O11—H112···O8^v	0.99	1.85	2.834 (3)	175
O11—H111···O7ⁱⁱ	0.92	2.04	2.953 (3)	173
O12—H122···O5^viii	0.90	2.35	3.121 (4)	143
O12—H121···O6	0.93	1.87	2.772 (3)	162

Symmetry codes: (ii) −x+3/2, −y, z+1/2; (iii) x−1/2, y, z+1/2; (v) x+1/2, y, z+1/2; (vi) x−1/4, −y+1/4, z−1/4; (vii) x, y, z+1; (viii) −x+3/2, −y, z−1/2.

Acknowledgements

The authors gratefully acknowledge financial support from the Youth Fund of Jilin Normal University.

References

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