Hemipotassium hemirubidium digallium(III) manganese(II) tris(phos­phate) dihydrate

Abstract

The title manganese(II) substituted gallophosphate, K_0.5Rb_0.5[Ga₂Mn(PO₄)₃(H₂O)₂], features a three-dimensional network built of PO₄ tetra­hedra, GaO₅ trigonal bipyramids and MnO₆ octa­hedra. The Rb^I and K^I ions, which are disordered with respect to each other in a 1:1 ratio, occupy sites within the channels of the framework. The Rb^I/K^I and Mn^II atoms occupy positions of 2 symmetry, as does one of the two P atoms. The Rb^I/K^I site is surrounded by six O atoms [2.996 (2)–3.178 (4) Å] in an irregularly-shaped coordination environment. O—H⋯O hydrogen bonds between the water molecules and phosphate O atoms consolidate the crystal packing.

Related literature

For isotypic NH₄[Ga₂Mn(PO₄)₃(H₂O)₂], see: Chippindale et al. (1998 ▶).

Experimental

Crystal data

• K_0.5Rb_0.5[Ga₂Mn(PO₄)₃(H₂O)₂]

• M _r = 577.61

• Monoclinic,

• a = 13.5504 (12) Å

• b = 10.2965 (9) Å

• c = 8.9072 (8) Å

• β = 108.527 (1)°

• V = 1178.34 (18) ų

• Z = 4

• Mo Kα radiation

• μ = 8.31 mm⁻¹

• T = 295 K

• 0.45 × 0.40 × 0.35 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.118, T _max = 0.159

• 6267 measured reflections

• 1348 independent reflections

• 1239 reflections with I > 2σ(I)

• R _int = 0.037

Refinement

• R[F ² > 2σ(F ²)] = 0.023

• wR(F ²) = 0.065

• S = 1.04

• 1348 reflections

• 103 parameters

• 2 restraints

• H-atom parameters constrained

• Δρ_max = 0.63 e Å⁻³

• Δρ_min = −0.75 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H1⋯O3i	0.84 (3)	1.97 (2)	2.790 (3)	166 (4)
O1w—H2⋯O6ii	0.84 (3)	2.10 (2)	2.913 (3)	165 (4)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

Microporous aluminium phosphates are readily synthesized by using the hydrothermal route; studies on these compounds have led to improvements in the synthesis of the related gallophosphates. The structure of NH₄[Ga₂Mn(PO₄)₃(H₂O)₂] features PO₄ tetrahedra, GaO₅ trigonal bipyramids and MnO₆ octahedra that are linked together to form a three-dimensional network (Chippindale et al., 1998). The title compound has a similar structure (Fig. 1); however, the rubidium and potassium atoms that occupy the channels within the network rattle in the cavities, as noted from the irregular nature of the polyhedron surrounding the atoms. The coordination number is much higher when longer interactions are considered.

Experimental

The compound was synthesized from a mixture of gallium oxide (0.037 g), boric acid (0.035 g), rubidium carbonate (0.023 g), potassium carbonate (0.138 g), manganese dichloride tetrahydrate (0.397 g), phosphoric acid (0.15 ml) and water (1.8 ml) (molar ratio of 2:5:1:10:20:20:1000). This mixture was sealed in 25 ml, Teflon-lined, stainless-steel Parr bomb. The bomb was heated at 468 K for 7 days. Colorless block-shaped crystals were isolated.

Refinement

The water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H 0.84±0.01 Å; their temperature factors were tied to those of the O atom by a factor of 1.5 times.

The potassium and rubidium atoms share the same site, a special position of 2 site symmetry. As the occupancy of each refined to nearly 1/2, the occupancies were then fixed as exactly 1/2. The temperature factors of K1 and Rb1 were restrained to be identical.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of a portion of the polymeric structure of K0.5Rb0.5[Ga2Mn(PO4)3(H2O)2] at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The potassium atoms are disordered with respect to the rubidium atoms in a 1:1 ratio. Symmetry codes: (i) x + 1/2, -y + 3/2, z + 1/2; (ii) -x + 1/2, -y + 3/2, -z + 1; (iii) -x + 1, y, -z + 3/2; (iv) -x + 1/2, y + 1/2, -z + 1/2; (v) x + 1/2, y + 1/2, z + 1; (vi) x, -y + 1, z + 1/2; (vii) -x + 1, -y + 1, -z + 1; (viii) x, -y + 1, z - 1/2; (ix) -x, y, -z + 1/2; (x) x - 1/2, -y + 1/2, z - 1/2.

Crystal data

K0.5Rb0.5[Ga2Mn(PO4)3(H2O)2]	F(000) = 1104
Mr = 577.61	Dx = 3.256 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4099 reflections
a = 13.5504 (12) Å	θ = 2.5–28.6°
b = 10.2965 (9) Å	µ = 8.31 mm−1
c = 8.9072 (8) Å	T = 295 K
β = 108.527 (1)°	Block, colorless
V = 1178.34 (18) Å3	0.45 × 0.40 × 0.35 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	1348 independent reflections
Radiation source: fine-focus sealed tube	1239 reflections with I > 2σ(I)
graphite	Rint = 0.037
ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→17
Tmin = 0.118, Tmax = 0.159	k = −13→13
6267 measured reflections	l = −11→11

Refinement

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)] = 0.023	Hydrogen site location: difference Fourier map
wR(F2) = 0.065	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0391P)2 + 2.8102P] where P = (Fo2 + 2Fc2)/3
1348 reflections	(Δ/σ)max = 0.001
103 parameters	Δρmax = 0.63 e Å−3
2 restraints	Δρmin = −0.75 e Å−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Rb1	0.5000	0.86132 (6)	0.7500	0.03306 (18)	0.50
Ga1	0.32950 (2)	0.57498 (3)	0.42741 (3)	0.01061 (11)
Mn1	0.0000	0.28198 (6)	0.2500	0.01443 (15)
K1	0.5000	0.86132 (6)	0.7500	0.03306 (18)	0.50
P1	0.5000	0.49997 (9)	0.7500	0.0106 (2)
P2	0.21012 (6)	0.37336 (7)	0.17422 (8)	0.01171 (16)
O1	0.44106 (16)	0.59068 (19)	0.6149 (2)	0.0150 (4)
O2	0.42851 (16)	0.40472 (19)	0.8014 (2)	0.0154 (4)
O3	0.29213 (16)	0.41300 (18)	0.3344 (2)	0.0146 (4)
O4	0.10038 (17)	0.3988 (2)	0.1749 (3)	0.0198 (4)
O5	0.23416 (16)	0.22845 (19)	0.1603 (2)	0.0156 (4)
O6	0.22740 (16)	0.45222 (19)	0.0373 (2)	0.0148 (4)
O1w	−0.11223 (19)	0.3043 (2)	0.0069 (3)	0.0263 (5)
H1	−0.146 (3)	0.237 (3)	−0.033 (5)	0.039*
H2	−0.154 (3)	0.366 (3)	−0.001 (5)	0.039*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Rb1	0.0418 (4)	0.0181 (3)	0.0425 (4)	0.000	0.0179 (3)	0.000
Ga1	0.01323 (18)	0.01036 (17)	0.00716 (17)	0.00043 (10)	0.00172 (12)	0.00000 (10)
Mn1	0.0166 (3)	0.0129 (3)	0.0145 (3)	0.000	0.0059 (2)	0.000
K1	0.0418 (4)	0.0181 (3)	0.0425 (4)	0.000	0.0179 (3)	0.000
P1	0.0127 (4)	0.0117 (4)	0.0067 (4)	0.000	0.0021 (3)	0.000
P2	0.0142 (4)	0.0121 (3)	0.0088 (3)	−0.0013 (3)	0.0036 (3)	−0.0006 (2)
O1	0.0181 (10)	0.0163 (10)	0.0072 (9)	−0.0007 (8)	−0.0010 (7)	0.0015 (7)
O2	0.0182 (10)	0.0134 (9)	0.0165 (10)	−0.0009 (8)	0.0081 (8)	0.0005 (8)
O3	0.0213 (11)	0.0110 (9)	0.0101 (9)	−0.0030 (8)	0.0028 (8)	−0.0027 (7)
O4	0.0176 (10)	0.0203 (10)	0.0232 (11)	0.0004 (8)	0.0088 (9)	0.0042 (9)
O5	0.0202 (10)	0.0115 (9)	0.0147 (9)	−0.0038 (8)	0.0048 (8)	−0.0038 (7)
O6	0.0196 (10)	0.0146 (9)	0.0118 (9)	0.0006 (8)	0.0072 (8)	0.0026 (7)
O1w	0.0286 (13)	0.0226 (11)	0.0204 (11)	0.0018 (10)	−0.0025 (9)	−0.0040 (9)

Geometric parameters (Å, °)

Rb1—O1	3.040 (2)	Mn1—O2ix	2.264 (2)
Rb1—O1i	3.040 (2)	Mn1—O2x	2.264 (2)
Rb1—O4ii	3.613 (2)	Mn1—O4	2.079 (2)
Rb1—O4iii	2.996 (2)	Mn1—O4xi	2.079 (2)
Rb1—O4iv	2.996 (2)	Mn1—O1w	2.228 (2)
Rb1—O5v	3.555 (2)	Mn1—O1wxi	2.228 (2)
Rb1—O5vi	3.555 (2)	P1—O1	1.532 (2)
Rb1—O6vii	3.451 (2)	P1—O1i	1.532 (2)
Rb1—O6ii	3.451 (2)	P1—O2	1.546 (2)
Rb1—O4vii	3.613 (2)	P1—O2i	1.546 (2)
Rb1—O1wii	3.178 (3)	P2—O4	1.512 (2)
Rb1—O1wvii	3.178 (3)	P2—O5	1.541 (2)
Ga1—O1	1.870 (2)	P2—O6	1.543 (2)
Ga1—O2viii	2.015 (2)	P2—O3	1.558 (2)
Ga1—O3	1.860 (2)	O1w—H1	0.84 (3)
Ga1—O5ii	1.850 (2)	O1w—H2	0.84 (3)
Ga1—O6vi	1.952 (2)
O4iv—Rb1—O4iii	68.95 (8)	O4iii—Rb1—O4ii	95.69 (5)
O4iv—Rb1—O1	138.43 (6)	O1—Rb1—O4ii	73.69 (5)
O4iii—Rb1—O1	139.75 (6)	O1i—Rb1—O4ii	118.48 (5)
O4iv—Rb1—O1i	139.75 (6)	O1wii—Rb1—O4ii	51.14 (5)
O4iii—Rb1—O1i	138.43 (6)	O1wvii—Rb1—O4ii	131.83 (5)
O1—Rb1—O1i	47.11 (7)	O6vii—Rb1—O4ii	134.28 (5)
O4iv—Rb1—O1wii	68.68 (6)	O6ii—Rb1—O4ii	40.88 (5)
O4iii—Rb1—O1wii	131.90 (6)	O5vi—Rb1—O4ii	77.00 (5)
O1—Rb1—O1wii	70.81 (6)	O5v—Rb1—O4ii	106.30 (5)
O1i—Rb1—O1wii	89.44 (6)	O4iv—Rb1—O4vii	95.69 (5)
O4iv—Rb1—O1wvii	131.90 (6)	O4iii—Rb1—O4vii	74.01 (6)
O4iii—Rb1—O1wvii	68.68 (6)	O1—Rb1—O4vii	118.48 (5)
O1—Rb1—O1wvii	89.44 (6)	O1i—Rb1—O4vii	73.69 (5)
O1i—Rb1—O1wvii	70.81 (6)	O1wii—Rb1—O4vii	131.83 (5)
O1wii—Rb1—O1wvii	158.73 (9)	O1wvii—Rb1—O4vii	51.14 (5)
O4iv—Rb1—O6vii	65.17 (5)	O6vii—Rb1—O4vii	40.88 (5)
O4iii—Rb1—O6vii	88.43 (6)	O6ii—Rb1—O4vii	134.28 (5)
O1—Rb1—O6vii	127.06 (5)	O5vi—Rb1—O4vii	106.30 (5)
O1i—Rb1—O6vii	83.95 (5)	O5v—Rb1—O4vii	77.00 (5)
O1wii—Rb1—O6vii	93.74 (5)	O4ii—Rb1—O4vii	167.72 (7)
O1wvii—Rb1—O6vii	92.00 (5)	O5ii—Ga1—O3	123.61 (9)
O4iv—Rb1—O6ii	88.43 (6)	O5ii—Ga1—O1	116.06 (9)
O4iii—Rb1—O6ii	65.17 (5)	O3—Ga1—O1	120.26 (9)
O1—Rb1—O6ii	83.95 (5)	O5ii—Ga1—O6vi	91.40 (9)
O1i—Rb1—O6ii	127.06 (5)	O3—Ga1—O6vi	87.64 (9)
O1wii—Rb1—O6ii	92.00 (5)	O1—Ga1—O6vi	93.74 (9)
O1wvii—Rb1—O6ii	93.74 (5)	O5ii—Ga1—O2viii	88.85 (8)
O6vii—Rb1—O6ii	148.53 (7)	O3—Ga1—O2viii	88.85 (9)
O4iv—Rb1—O5vi	131.58 (5)	O1—Ga1—O2viii	89.78 (9)
O4iii—Rb1—O5vi	76.41 (5)	O6vi—Ga1—O2viii	175.95 (8)
O1—Rb1—O5vi	63.43 (5)	O4—Mn1—O4xi	109.28 (12)
O1i—Rb1—O5vi	88.32 (5)	O4—Mn1—O1w	86.67 (9)
O1wii—Rb1—O5vi	118.20 (5)	O4xi—Mn1—O1w	86.48 (9)
O1wvii—Rb1—O5vi	55.36 (5)	O4—Mn1—O1wxi	86.48 (9)
O6vii—Rb1—O5vi	147.08 (4)	O4xi—Mn1—O1wxi	86.67 (9)
O6ii—Rb1—O5vi	45.70 (4)	O1w—Mn1—O1wxi	168.14 (13)
O4iv—Rb1—O5v	76.41 (5)	O4—Mn1—O2x	157.23 (8)
O4iii—Rb1—O5v	131.58 (6)	O4xi—Mn1—O2x	93.49 (8)
O1—Rb1—O5v	88.32 (5)	O1w—Mn1—O2x	94.61 (8)
O1i—Rb1—O5v	63.43 (5)	O1wxi—Mn1—O2x	95.46 (8)
O1wii—Rb1—O5v	55.36 (5)	O4—Mn1—O2ix	93.49 (8)
O1wvii—Rb1—O5v	118.20 (5)	O4xi—Mn1—O2ix	157.23 (8)
O6vii—Rb1—O5v	45.70 (4)	O1w—Mn1—O2ix	95.46 (8)
O6ii—Rb1—O5v	147.08 (4)	O1wxi—Mn1—O2ix	94.61 (8)
O5vi—Rb1—O5v	149.86 (6)	O2x—Mn1—O2ix	63.75 (10)
O4iv—Rb1—O4ii	74.01 (6)

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1···O3x	0.84 (3)	1.97 (2)	2.790 (3)	166 (4)
O1w—H2···O6xii	0.84 (3)	2.10 (2)	2.913 (3)	165 (4)

Symmetry codes: (x) x−1/2, −y+1/2, z−1/2; (xii) −x, −y+1, −z.