Hexa­aqua­nickel(II) di­hydrogen hypodiphosphate

Gjikaj, M.; Wu, P.; Pook, N.-P.

doi:10.1107/S1600536813030717

inorganic compounds

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Volume 69| Part 12| December 2013| Page i83

doi:10.1107/S1600536813030717

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Hexaaquanickel(II) dihydrogen hypodiphosphate

Mimoza Gjikaj,^a ^* Peng Wu ^a and Niels-Patrick Pook ^a

^aInstitute of Inorganic and Analytical Chemistry, Clausthal University of Technology, Paul-Ernst-Strasse 4, D-38678 Clausthal-Zellerfeld, Germany
^*Correspondence e-mail: mimoza.gjikaj@tu-clausthal.de

(Received 1 November 2013; accepted 8 November 2013; online 13 November 2013)

The asymmetric unit of the title compound, [Ni(H₂O)₆](H₂P₂O₆), contains one-half of the hexaaquanickel(II) cation and one-half of the dihydrogen hypodiphosphate anion. In the complex cation, the Ni²⁺ atom is located on an inversion center and has an octahedral coordination sphere. The P—P distance in the centrosymmetric anion is 2.1853 (7) Å. In the crystal, discrete [Ni(H₂O)₆]²⁺ cations and (H₂P₂O₆)²⁻ anions are stacked in columns parallel to the c axis and are linked into a three-dimensional network by medium-strength O—H⋯O hydrogen bonds.

CCDC reference: 971020

Related literature

For the synthesis of hypodiphosphates, see: Leininger & Chulski (1953 ). For applications of hypodiphosphates, see: Bloss & Henzel (1967 ); Ruflin et al. (2007 ); Szklarz et al. (2011 ). For the crystal structures of transition metal hypodiphosphate 12-hydrates, see: Hagen & Jansen (1995 ); Haag et al. (2005 ). For the crystal structures of hydrogen hypodiphosphate compounds, see: Collin & Willis (1971 ); Szafranowska et al. (2012 ); Wu et al. (2012 ).

Experimental

Crystal data

[Ni(H₂O)₆](H₂P₂O₆)
M_r = 326.76
Monoclinic, P 2₁ /n
a = 9.3031 (14) Å
b = 5.8892 (8) Å
c = 9.7620 (12) Å
β = 96.111 (11)°
V = 531.80 (13) Å³
Z = 2
Mo Kα radiation
μ = 2.18 mm⁻¹
T = 223 K
0.29 × 0.25 × 0.22 mm

Data collection

Stoe IPDS-II diffractometer
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 1999 , 2001 ) T_min = 0.537, T_max = 0.619
8061 measured reflections
1601 independent reflections
1546 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.074
S = 1.16
1601 reflections
98 parameters
All H-atom parameters refined
Δρ_max = 0.44 e Å⁻³
Δρ_min = −1.08 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.92 (3)	1.68 (3)	2.5919 (15)	168 (3)
O4—H4A⋯O3ⁱⁱ	0.82 (3)	1.93 (3)	2.7293 (16)	165 (3)
O4—H4B⋯O2ⁱⁱⁱ	0.82 (3)	1.89 (3)	2.6822 (14)	162 (3)
O5—H5A⋯O1	0.81 (3)	1.98 (3)	2.7770 (15)	171 (3)
O5—H5B⋯O2^iv	0.84 (3)	2.04 (3)	2.8722 (16)	171 (3)
O6—H6A⋯O1^v	0.81 (2)	2.05 (2)	2.8163 (16)	159 (2)
O6—H6B⋯O1ⁱⁱ	0.84 (3)	2.08 (3)	2.9132 (17)	168 (3)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) -x+1, -y+1, -z+1; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (v) x, y+1, z.

Data collection: X-AREA (Stoe & Cie, 2002 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012 ); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 971020

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813030717/wm2784sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813030717/wm2784Isup2.hkl

checkCIF report

Comment top

Although main group hypodiphosphates have rather academic interest, the dihydrogen sodium and ammonium derivates, (M₂H₂P₂O₆ with M = Na⁺ and NH₄⁺) (Collin & Willis, 1971), respective their hydrates, have certain practical use. Ammonium dihydrogen hypodiphosphate-based powder material is applied as a green flame retardant and as a multipurpose extinguishing agent suitable for all classes of fire (Ruflin et al., 2007). Acidic Na₂H₂P₂O₆ solutions are applied for gravimetric precipitation and immobilization of uranium(IV) (Bloss & Henzel, 1967). The ferroelectricity of diammonium hypodiphosphate was discovered recently (Szklarz et al., 2011).

The crystal structures of transition metal hypodiphosphate 12-hydrates M₂P₂O₆^.12H₂O (M = Co und Ni) were determined by Hagen & Jansen (1995) and Haag et al. (2005). However, the crystal structures of transition metal dihydrogen hypodiphosphate hydrates have not been reported up to now.

The structure of the title compound, [Ni(H₂O)₆](H₂P₂O₆) is characterized by discrete [Ni(H₂O)₆]²⁺ cations and (H₂P₂O₆)^2- anions (Fig. 1). The Ni²⁺ ion is located on an inversion centre and is octahedrally coordinated by water molecules. In the (H₂P₂O₆)^2- anion, which is located about an inversion centre, the tetravalent phosphorus atom is surrounded by three oxygen atoms and one additional phosphorus atom with a P–P distance of 2.1854 (7) Å. The P–O bond lengths are ranging from 1.5050 (11) to 1.5816 (11) Å. All bond lengths and angles are well within the expected ranges (Wu et al., 2012) and are comparable to those found for Ni₂P₂O₆^. 12H₂O (2.1700 (13) Å for the P—P bond; Haag et al., 2005), however with a characteristically longer P—OH distance in comparison with the P—O distance.

The (H₂P₂O₆)^2– anions are joined to ribbons parallel to [010] by rather strong hydrogen bonds (O···O 2.5919 (15) Å). Anions and complex cations are stacked alternately in columns parallel to [001], held together by medium-strength O—H···O hydrogen bonds (Fig. 2). The O···O distances between water molecules and (H₂P₂O₆)^2– ions range from 2.6822 (14) to 2.9132 (17) Å (Table 1). All hydrogen bonding interactions considered, a three-dimensional network structure is established in the crystal.

Experimental top

Disodium dihydrogen hypodiphosphate was prepared using the procedure reported by Leininger & Chulski (1953). An aqueous solution of hypodiphosphoric acid was obtained by passing a saturated solution of disodium dihydrogen hypodiphosphate through a cation exchange resin (Dowex 50WX2 50-100). Single crystals of hexaaquanickel(II) dihydrogenhypodiphosphate were prepared by adding nickel hydroxide (148 mg) to a solution of hypodiphosphoric acid (40 mL).

Refinement top

All hydrogen atoms were located in a difference Fourier map and were refined isotropically with no restraints.

Related literature top

For the synthesis of hypodiphosphates, see: Leininger & Chulski (1953). For applications of hypodiphosphates, see: Bloss & Henzel (1967); Ruflin et al. (2007); Szklarz et al. (2011). For the crystal structures of transition metal hypodiphosphate 12-hydrates, see: Hagen & Jansen (1995); Haag et al. (2005). For the crystal structures of hydrogen hypodiphosphate compounds, see: Collin & Willis (1971); Szafranowska et al. (2012); Wu et al. (2012).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular entities in the title compound with atom labels and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii) -x, -y, -z + 1.]
	Fig. 2. The crystal structure of the title compound viewed along the b axis. Displacement ellipsoids are drawn at the 50% probability level. O—H···O hydrogen bonds are shown as dashed lines.

Hexaaquanickel(II) dihydrogen hypodiphosphate top

Crystal data top

[Ni(H₂O)₆](H₂P₂O₆)	F(000) = 336
M_r = 326.76	block, green
Monoclinic, P2₁/n	D_x = 2.041 Mg m⁻³
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.3031 (14) Å	Cell parameters from 8465 reflections
b = 5.8892 (8) Å	θ = 2.9–30.5°
c = 9.7620 (12) Å	µ = 2.18 mm⁻¹
β = 96.111 (11)°	T = 223 K
V = 531.80 (13) Å³	Block, green
Z = 2	0.29 × 0.25 × 0.22 mm

Data collection top

Stoe IPDS-II diffractometer	1601 independent reflections
Radiation source: fine-focus sealed tube	1546 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω–scans	θ_max = 30.5°, θ_min = 2.9°
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 1999, 2001)	h = −13→13
T_min = 0.537, T_max = 0.619	k = −8→8
8061 measured reflections	l = −13→13

Refinement top

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	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	All H-atom parameters refined
S = 1.16	w = 1/[σ²(F_o²) + (0.0423P)² + 0.1511P] where P = (F_o² + 2F_c²)/3
1601 reflections	(Δ/σ)_max = 0.001
98 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −1.08 e Å⁻³

Crystal data top

[Ni(H₂O)₆](H₂P₂O₆)	V = 531.80 (13) Å³
M_r = 326.76	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.3031 (14) Å	µ = 2.18 mm⁻¹
b = 5.8892 (8) Å	T = 223 K
c = 9.7620 (12) Å	0.29 × 0.25 × 0.22 mm
β = 96.111 (11)°

Data collection top

Stoe IPDS-II diffractometer	1601 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 1999, 2001)	1546 reflections with I > 2σ(I)
T_min = 0.537, T_max = 0.619	R_int = 0.056
8061 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.074	All H-atom parameters refined
S = 1.16	Δρ_max = 0.44 e Å⁻³
1601 reflections	Δρ_min = −1.08 e Å⁻³
98 parameters

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
Ni	0.5000	0.5000	0.5000	0.01306 (10)
P	0.06859 (3)	0.14612 (5)	0.53007 (3)	0.01116 (10)
O1	0.20361 (11)	0.05887 (19)	0.61176 (12)	0.0177 (2)
O2	0.08555 (10)	0.28724 (17)	0.40289 (10)	0.01404 (19)
O3	−0.02399 (12)	0.28534 (18)	0.62787 (11)	0.0185 (2)
O4	0.64678 (11)	0.6071 (2)	0.65421 (12)	0.0211 (2)
O5	0.48685 (12)	0.20885 (19)	0.61392 (12)	0.0204 (2)
O6	0.32539 (11)	0.62296 (19)	0.59655 (12)	0.0180 (2)
H3	−0.042 (3)	0.436 (5)	0.605 (3)	0.037 (7)*
H4A	0.620 (3)	0.681 (5)	0.719 (3)	0.037 (7)*
H4B	0.720 (3)	0.664 (5)	0.630 (3)	0.042 (7)*
H5A	0.407 (4)	0.154 (5)	0.607 (3)	0.045 (8)*
H5B	0.521 (3)	0.223 (5)	0.696 (3)	0.039 (7)*
H6A	0.296 (2)	0.750 (4)	0.581 (2)	0.019 (5)*
H6B	0.313 (3)	0.584 (5)	0.678 (3)	0.036 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni	0.01080 (13)	0.01511 (15)	0.01334 (15)	−0.00152 (7)	0.00159 (9)	−0.00086 (8)
P	0.00991 (15)	0.01073 (17)	0.01287 (17)	−0.00066 (9)	0.00128 (11)	0.00094 (10)
O1	0.0130 (4)	0.0173 (4)	0.0219 (5)	−0.0003 (4)	−0.0026 (4)	0.0023 (4)
O2	0.0140 (4)	0.0134 (4)	0.0151 (5)	−0.0015 (3)	0.0037 (3)	0.0017 (3)
O3	0.0251 (5)	0.0138 (4)	0.0179 (5)	0.0040 (4)	0.0086 (4)	0.0022 (4)
O4	0.0138 (4)	0.0332 (6)	0.0169 (5)	−0.0071 (4)	0.0043 (4)	−0.0090 (4)
O5	0.0194 (5)	0.0207 (5)	0.0204 (5)	−0.0044 (4)	−0.0005 (4)	0.0028 (4)
O6	0.0180 (5)	0.0194 (5)	0.0172 (5)	0.0040 (4)	0.0041 (4)	−0.0003 (4)

Geometric parameters (Å, º) top

Ni—O4	2.0226 (11)	P—O3	1.5814 (11)
Ni—O4ⁱ	2.0227 (11)	P—Pⁱⁱ	2.1853 (7)
Ni—O5ⁱ	2.0544 (11)	O3—H3	0.92 (3)
Ni—O5	2.0544 (11)	O4—H4A	0.82 (3)
Ni—O6	2.0922 (11)	O4—H4B	0.82 (3)
Ni—O6ⁱ	2.0922 (11)	O5—H5A	0.81 (3)
P—O1	1.5048 (10)	O5—H5B	0.84 (3)
P—O1	1.5048 (10)	O6—H6A	0.81 (2)
P—O2	1.5161 (10)	O6—H6B	0.84 (3)

O4—Ni—O4ⁱ	180.0	O1—P—O3	109.55 (6)
O4—Ni—O5ⁱ	93.91 (5)	O1—P—O3	109.55 (6)
O4ⁱ—Ni—O5ⁱ	86.09 (5)	O2—P—O3	108.73 (6)
O4—Ni—O5	86.09 (5)	O1—P—Pⁱⁱ	107.70 (5)
O4ⁱ—Ni—O5	93.91 (5)	O1—P—Pⁱⁱ	107.70 (5)
O5ⁱ—Ni—O5	179.999 (1)	O2—P—Pⁱⁱ	108.69 (5)
O4—Ni—O6	92.97 (5)	O3—P—Pⁱⁱ	103.32 (5)
O4ⁱ—Ni—O6	87.03 (5)	O1—O1—P	0 (10)
O5ⁱ—Ni—O6	92.80 (5)	P—O3—H3	116.7 (19)
O5—Ni—O6	87.20 (5)	Ni—O4—H4A	119.9 (19)
O4—Ni—O6ⁱ	87.03 (5)	Ni—O4—H4B	115 (2)
O4ⁱ—Ni—O6ⁱ	92.97 (5)	H4A—O4—H4B	109 (3)
O5ⁱ—Ni—O6ⁱ	87.20 (5)	Ni—O5—H5A	114 (2)
O5—Ni—O6ⁱ	92.80 (5)	Ni—O5—H5B	113 (2)
O6—Ni—O6ⁱ	180.0	H5A—O5—H5B	112 (3)
O1—P—O1	0.00 (11)	Ni—O6—H6A	119.9 (16)
O1—P—O2	117.86 (6)	Ni—O6—H6B	121.2 (19)
O1—P—O2	117.86 (6)	H6A—O6—H6B	111 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱⁱⁱ	0.92 (3)	1.68 (3)	2.5919 (15)	168 (3)
O4—H4A···O3^iv	0.82 (3)	1.93 (3)	2.7293 (16)	165 (3)
O4—H4B···O2ⁱ	0.82 (3)	1.89 (3)	2.6822 (14)	162 (3)
O5—H5A···O1	0.81 (3)	1.98 (3)	2.7770 (15)	171 (3)
O5—H5B···O2^v	0.84 (3)	2.04 (3)	2.8722 (16)	171 (3)
O6—H6A···O1^vi	0.81 (2)	2.05 (2)	2.8163 (16)	159 (2)
O6—H6B···O1^iv	0.84 (3)	2.08 (3)	2.9132 (17)	168 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.92 (3)	1.68 (3)	2.5919 (15)	168 (3)
O4—H4A···O3ⁱⁱ	0.82 (3)	1.93 (3)	2.7293 (16)	165 (3)
O4—H4B···O2ⁱⁱⁱ	0.82 (3)	1.89 (3)	2.6822 (14)	162 (3)
O5—H5A···O1	0.81 (3)	1.98 (3)	2.7770 (15)	171 (3)
O5—H5B···O2^iv	0.84 (3)	2.04 (3)	2.8722 (16)	171 (3)
O6—H6A···O1^v	0.81 (2)	2.05 (2)	2.8163 (16)	159 (2)
O6—H6B···O1ⁱⁱ	0.84 (3)	2.08 (3)	2.9132 (17)	168 (3)

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

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