catena-Poly[[[tetra-aqua-magnesium]-trans-μ-[(piperazine-1,4-diium-1,4-di-yl)bis-(methyl-ene)]di-phospho-nato] hemihydrate].

The structure of the title polymer, }[Mg(C6H14N2O6P2)(H2O)4]·0.5H2O} n , is based on centrosymmetric MgO6 octahedra, which are linked by [(piperazine-1,4-diium-1,4-di-yl)bis-(methyl-ene)]di-phospho-nate ligands, forming chains parallel to [1-1-1]. These chains are connected via hydrogen bonds primarily formed between the phospho-nate groups and water mol-ecules. The latter constitute four of the corners of the MgO6 polyhedra and bind to the O atoms of the phospho-nate groups of neighbouring chains. The lattice water molecule is disordered around an inversion centre, exhibiting an occupancy of 0.25.

Related literature

For related magnesium structures, see: Wharmby et al. (2012 ▶). For related N,N′-piperaziniumbis(methyl­ene­phospho­nates), see: Choi et al. (1994 ▶); Groves et al. (2005a ▶,b ▶); Groves, Stephens et al. (2006 ▶); Groves, Miller et al. (2006 ▶); LaDuca et al. (1996 ▶); Serre et al. (2006 ▶); Soghomonian et al. (1995 ▶); Wang et al. (2004 ▶); Wharmby et al. (2012 ▶). As a result of their flexible coordination behaviour, organic linker mol­ecules containing phospho­nate groups allow the synthesis of a multitude of inorganic-organic hybrid materials, see: Gagnon et al. (2012 ▶).

Experimental

Crystal data

[Mg(C6H14N2O6P2)(H2O)4]·0.5H2O

M = 377.51

Triclinic,

a = 6.6296 (5) Å

b = 6.8074 (6) Å

c = 8.7962 (7) Å

α = 94.579 (6)°

β = 103.326 (6)°

γ = 106.552 (6)°

V = 365.75 (5) Å3

Z = 1

Mo Kα radiation

μ = 0.40 mm−1

T = 293 K

0.21 × 0.12 × 0.04 mm

Data collection

Stoe IPSD-2 diffractometer

Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008 ▶) T min = 0.886, T max = 0.974

6973 measured reflections

1957 independent reflections

1727 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.080

S = 1.01

1957 reflections

103 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.43 e Å−3

Data collection: X-AREA (Stoe & Cie, 2008 ▶); 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: XP in SHELXTL (Sheldrick, 2008 ▶) and DIAMOND Brandenburg (2011 ▶); software used to prepare material for publication: XCIF in SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813018722/cq2003sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813018722/cq2003Isup2.hkl

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

[Mg(C6H14N2O6P2)(H2O)4]·0.5H2O	Z = 1
Mr = 377.51	F(000) = 199
Triclinic, P1	Dx = 1.714 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6296 (5) Å	Cell parameters from 1270 reflections
b = 6.8074 (6) Å	θ = 1.2–29.8°
c = 8.7962 (7) Å	µ = 0.40 mm−1
α = 94.579 (6)°	T = 293 K
β = 103.326 (6)°	Needle, colorless
γ = 106.552 (6)°	0.21 × 0.12 × 0.04 mm
V = 365.75 (5) Å3

Stoe IPSD-2 diffractometer	1957 independent reflections
Radiation source: fine-focus sealed tube	1727 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scan	θmax = 29.2°, θmin = 3.2°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2008)	h = −9→9
Tmin = 0.886, Tmax = 0.974	k = −9→9
6973 measured reflections	l = −12→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0352P)2 + 0.2734P] where P = (Fo2 + 2Fc2)/3
1957 reflections	(Δ/σ)max < 0.001
103 parameters	Δρmax = 0.43 e Å−3
0 restraints	Δρmin = −0.43 e Å−3

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)
Mg1	0.5000	0.5000	0.5000	0.01868 (16)
P1	0.36611 (6)	0.83891 (6)	0.71790 (4)	0.01741 (10)
O1	0.47100 (19)	0.67534 (18)	0.69031 (14)	0.0256 (2)
O2	0.22643 (18)	0.87610 (17)	0.56605 (13)	0.0228 (2)
O3	0.52336 (14)	1.04094 (13)	0.81824 (11)	0.0225 (2)
C1	0.17809 (14)	0.73201 (13)	0.83666 (11)	0.0218 (3)
H1A	0.2264	0.6279	0.8904	0.026*
H1B	0.0379	0.6240	0.8034	0.026*
N1	0.1348 (2)	0.89184 (19)	0.94153 (15)	0.0181 (2)
H1N1	0.2589	0.9558	1.0077	0.022*
C2	0.0614 (3)	1.0529 (2)	0.85892 (19)	0.0235 (3)
H2A	−0.0754	0.9870	0.7791	0.028*
H2B	0.1690	1.1225	0.8065	0.028*
C3	−0.0313 (3)	0.7900 (2)	1.02369 (19)	0.0218 (3)
H3A	0.0147	0.6857	1.0786	0.026*
H3B	−0.1695	0.7211	0.9461	0.026*
O4	0.30950 (18)	0.64149 (17)	0.34463 (13)	0.0236 (2)
H1O4	0.3778	0.7291	0.3008	0.028*
H2O4	0.2647	0.7153	0.3980	0.028*
O5	0.22487 (19)	0.26098 (18)	0.51161 (16)	0.0309 (3)
H1O5	0.2383	0.1488	0.5310	0.037*
H2O5	0.0957	0.2540	0.4922	0.037*
O6	0.5116 (13)	0.5606 (12)	1.0711 (9)	0.0620 (19)	0.25
H1O6	0.5284	0.5120	1.1538	0.093*	0.25
H2O6	0.5205	0.6822	1.0956	0.093*	0.25

	U11	U22	U33	U12	U13	U23
Mg1	0.0172 (3)	0.0181 (3)	0.0219 (3)	0.0073 (3)	0.0059 (3)	0.0011 (3)
P1	0.01580 (17)	0.01772 (18)	0.01999 (19)	0.00653 (13)	0.00637 (13)	0.00069 (13)
O1	0.0300 (6)	0.0285 (6)	0.0246 (6)	0.0176 (5)	0.0094 (5)	0.0020 (4)
O2	0.0203 (5)	0.0246 (5)	0.0244 (5)	0.0097 (4)	0.0047 (4)	0.0025 (4)
O3	0.0200 (5)	0.0213 (5)	0.0237 (5)	0.0037 (4)	0.0053 (4)	0.0010 (4)
C1	0.0228 (7)	0.0170 (6)	0.0276 (8)	0.0055 (5)	0.0121 (6)	0.0011 (6)
N1	0.0151 (5)	0.0194 (6)	0.0206 (6)	0.0052 (4)	0.0070 (5)	0.0019 (5)
C2	0.0269 (7)	0.0258 (7)	0.0246 (7)	0.0132 (6)	0.0127 (6)	0.0077 (6)
C3	0.0216 (7)	0.0205 (7)	0.0271 (7)	0.0066 (6)	0.0129 (6)	0.0060 (6)
O4	0.0245 (5)	0.0233 (5)	0.0252 (6)	0.0101 (4)	0.0075 (4)	0.0032 (4)
O5	0.0186 (5)	0.0240 (6)	0.0501 (8)	0.0059 (4)	0.0086 (5)	0.0106 (5)
O6	0.065 (5)	0.059 (4)	0.068 (5)	0.025 (4)	0.019 (4)	0.020 (4)

Mg1—O1i	2.0552 (11)	N1—H1N1	0.8600
Mg1—O1	2.0553 (11)	C2—C3ii	1.513 (2)
Mg1—O5	2.0991 (12)	C2—H2A	0.9700
Mg1—O5i	2.0992 (12)	C2—H2B	0.9700
Mg1—O4i	2.1209 (11)	C3—C2ii	1.513 (2)
Mg1—O4	2.1209 (11)	C3—H3A	0.9700
P1—O1	1.5027 (11)	C3—H3B	0.9700
P1—O2	1.5242 (12)	O4—H1O4	0.8199
P1—O3	1.5240 (10)	O4—H2O4	0.8201
P1—C1	1.8383	O5—H1O5	0.8200
C1—N1	1.5022 (15)	O5—H2O5	0.8200
C1—H1A	0.9700	O6—O6iii	1.395 (16)
C1—H1B	0.9700	O6—H1O6	0.8201
N1—C3	1.4925 (18)	O6—H2O6	0.8200
N1—C2	1.495 (2)
O1i—Mg1—O1	180.00 (6)	C3—N1—C2	108.49 (11)
O1i—Mg1—O5	90.35 (5)	C3—N1—C1	110.46 (10)
O1—Mg1—O5	89.65 (5)	C2—N1—C1	114.75 (11)
O1i—Mg1—O5i	89.65 (5)	C3—N1—H1N1	111.5
O1—Mg1—O5i	90.35 (5)	C2—N1—H1N1	106.5
O5—Mg1—O5i	180.00 (7)	C1—N1—H1N1	105.1
O1i—Mg1—O4i	89.80 (4)	N1—C2—C3ii	110.27 (12)
O1—Mg1—O4i	90.20 (4)	N1—C2—H2A	109.6
O5—Mg1—O4i	87.19 (5)	C3ii—C2—H2A	109.6
O5i—Mg1—O4i	92.81 (5)	N1—C2—H2B	109.6
O1i—Mg1—O4	90.20 (4)	C3ii—C2—H2B	109.6
O1—Mg1—O4	89.80 (4)	H2A—C2—H2B	108.1
O5—Mg1—O4	92.81 (5)	N1—C3—C2ii	111.06 (12)
O5i—Mg1—O4	87.19 (5)	N1—C3—H3A	109.4
O4i—Mg1—O4	180.0	C2ii—C3—H3A	109.4
O1—P1—O2	113.06 (7)	N1—C3—H3B	109.4
O1—P1—O3	114.25 (6)	C2ii—C3—H3B	109.4
O2—P1—O3	112.00 (6)	H3A—C3—H3B	108.0
O1—P1—C1	105.10 (6)	Mg1—O4—H1O4	115.4
O2—P1—C1	106.31 (6)	Mg1—O4—H2O4	108.1
O3—P1—C1	105.20 (5)	H1O4—O4—H2O4	99.6
P1—O1—Mg1	137.40 (7)	Mg1—O5—H1O5	119.2
N1—C1—P1	114.69 (7)	Mg1—O5—H2O5	130.9
N1—C1—H1A	114.7	H1O5—O5—H2O5	109.7
P1—C1—H1A	108.7	O6iii—O6—H1O6	119.9
N1—C1—H1B	102.6	O6iii—O6—H2O6	133.7
P1—C1—H1B	128.8	H1O6—O6—H2O6	106.3
H1A—C1—H1B	83.9

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3iv	0.86	1.84	2.6187 (16)	150
O4—H1O4···O3v	0.82	1.99	2.7956 (15)	166
O4—H2O4···O2	0.82	1.88	2.6733 (17)	164
O5—H1O5···O2vi	0.82	1.89	2.7032 (17)	172
O5—H2O5···O2vii	0.82	1.99	2.7667 (18)	158
C1—H1B···O4vii	0.97	2.48	3.4279 (15)	166
C2—H2B···O3	0.97	2.55	3.187 (2)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3i	0.86	1.84	2.6187 (16)	150
O4—H1O4⋯O3ii	0.82	1.99	2.7956 (15)	166
O4—H2O4⋯O2	0.82	1.88	2.6733 (17)	164
O5—H1O5⋯O2iii	0.82	1.89	2.7032 (17)	172
O5—H2O5⋯O2iv	0.82	1.99	2.7667 (18)	158

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .