Poly[bis-[μ(2)-(dimethyl-aza-nium-yl)methyl-enediphospho-nato]magnesium].

The title compound, [Mg(C(3)H(10)NO(6)P(2))(2)](n), synthesized by a hydro-thermal method, adopts a one-dimensional polymeric chain structure and is isotypic with the previously reported Cd complex based on the ligand N,N-dimethyl-amino-methane-1,1-diphospho-nic acid (H(4)L). The asymmetric unit contains one half Mg(2+) ion and one H(3)L(-) anion. The unique Mg(2+) ion lies on an inversion center and is octa-hedrally coordinated by O atoms from six phospho-nate groups of four different H(3)L(-) anions. Each H(3)L(-) anion, with one protonated N atom and two phospho-nate OH groups, serves as a tridentate ligand. Two of its six phospho-nate O atoms chelate to a Mg(2+) cation in a bidentate fashion, while a third O atom bridges to a neighbouring Mg(2+) ion. The inter-connection of Mg(2+) ions by the H(3)L(-)anions leads to the formation of a polymer chain along the a axis in which the adjacent Mg(2+) ions are doubly bridged by two equivalent H(3)L(-) anions. These discrete chains are further assembled into a three-dimensional supra-molecular network via O-H⋯O and N-H⋯O hydrogen bonds involving the non-coordin-ated phospho-nate O atoms and the protonated N atoms.

Related literature

For other metal complexes based on the N,N-dimethyl­amino­methane-1,1- diphospho­nate ligand, see: Du et al. (2009 ▶, 2010a ▶,b ▶). For bond-length data, see: Lutz & Muller (1995 ▶); Distler et al. (1999 ▶); Stock & Bein (2004 ▶).

Experimental

Crystal data

[Mg(C3H10NO6P2)2]

M = 460.43

Monoclinic,

a = 5.4507 (3) Å

b = 11.2166 (6) Å

c = 12.5770 (7) Å

β = 94.984 (1)°

V = 766.03 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.61 mm−1

T = 296 K

0.40 × 0.30 × 0.24 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.675, T max = 0.746

4801 measured reflections

1492 independent reflections

1447 reflections with I > 2σ(I)

R int = 0.014

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.066

S = 1.09

1492 reflections

115 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.33 e Å−3

Data collection: SMART (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811005976/sj5102sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005976/sj5102Isup2.hkl

Additional suppn class="Chemical">lementary materials: crystallographic information; 3D view; checkCIF report

[Mg(C3H10NO6P2)2]	F(000) = 476
Mr = 460.43	Dx = 1.996 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4647 reflections
a = 5.4507 (3) Å	θ = 2.4–29.4°
b = 11.2166 (6) Å	µ = 0.61 mm−1
c = 12.5770 (7) Å	T = 296 K
β = 94.984 (1)°	Block, colourless
V = 766.03 (7) Å3	0.40 × 0.30 × 0.24 mm
Z = 2

Bruker SMART APEX CCD area-detector diffractometer	1492 independent reflections
Radiation source: fine-focus sealed tube	1447 reflections with I > 2σ(I)
graphite	Rint = 0.014
φ and ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −6→6
Tmin = 0.675, Tmax = 0.746	k = −13→13
4801 measured reflections	l = −15→15

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)] = 0.024	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.0347P)2 + 0.6187P] where P = (Fo2 + 2Fc2)/3
1492 reflections	(Δ/σ)max = 0.001
115 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

Experimental. IR data (KBr, ν, cm-1): 3437 (m), 3137 (s), 3071 (m), 2986 (m), 2826 (m), 2280 (m), 1815 (m), 1473 (m), 1457 (m), 1421 (m), 1388 (m), 1256 (s), 1225 (s), 1200 (versus), 1155 (s), 1128 (s), 1088 (s), 1036 (s), 995 (s), 950 (s), 928 (s), 854 (m), 827 (m), 725 (m), 615 (m), 573 (s), 517 (m), 476 (m).

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
Mg1	0.0000	0.5000	0.5000	0.01237 (17)
P1	0.52519 (7)	0.34374 (3)	0.59421 (3)	0.01109 (12)
P2	0.34788 (7)	0.55738 (3)	0.72234 (3)	0.01225 (13)
N1	0.5807 (3)	0.35032 (12)	0.81729 (11)	0.0161 (3)
H1B	0.6307	0.2757	0.8007	0.019*
C1	0.4187 (3)	0.39596 (14)	0.72149 (12)	0.0126 (3)
H1A	0.2596	0.3565	0.7262	0.015*
C2	0.4447 (4)	0.33952 (16)	0.91574 (13)	0.0217 (4)
H2A	0.5545	0.3102	0.9737	0.032*
H2B	0.3096	0.2851	0.9024	0.032*
H2C	0.3831	0.4163	0.9341	0.032*
C3	0.8076 (3)	0.42374 (19)	0.84083 (15)	0.0264 (4)
H3A	0.9027	0.3918	0.9021	0.040*
H3B	0.7620	0.5045	0.8550	0.040*
H3C	0.9041	0.4221	0.7805	0.040*
O1	0.7774 (2)	0.38860 (10)	0.57970 (9)	0.0168 (3)
O2	0.3180 (2)	0.38023 (10)	0.51279 (9)	0.0160 (2)
O3	0.5417 (2)	0.20563 (10)	0.60652 (10)	0.0182 (3)
H3D	0.4114	0.1800	0.6253	0.027*
O4	0.5780 (2)	0.62560 (11)	0.68532 (9)	0.0177 (3)
H4A	0.5846	0.6161	0.6210	0.027*
O5	0.1277 (2)	0.57125 (10)	0.64393 (9)	0.0167 (3)
O6	0.3209 (2)	0.59441 (11)	0.83501 (9)	0.0187 (3)

	U11	U22	U33	U12	U13	U23
Mg1	0.0099 (4)	0.0144 (4)	0.0127 (4)	−0.0013 (3)	0.0006 (3)	0.0007 (3)
P1	0.0111 (2)	0.0108 (2)	0.0117 (2)	−0.00042 (14)	0.00234 (15)	0.00033 (14)
P2	0.0116 (2)	0.0127 (2)	0.0124 (2)	0.00185 (14)	0.00060 (15)	−0.00118 (14)
N1	0.0179 (7)	0.0157 (7)	0.0144 (6)	0.0044 (5)	−0.0008 (5)	0.0006 (5)
C1	0.0116 (7)	0.0146 (7)	0.0114 (7)	0.0011 (6)	0.0004 (6)	0.0000 (6)
C2	0.0286 (10)	0.0216 (9)	0.0150 (8)	0.0014 (7)	0.0029 (7)	0.0032 (6)
C3	0.0153 (9)	0.0371 (10)	0.0257 (9)	−0.0014 (8)	−0.0047 (7)	0.0022 (8)
O1	0.0137 (6)	0.0172 (6)	0.0200 (6)	−0.0027 (4)	0.0041 (4)	0.0022 (5)
O2	0.0142 (6)	0.0197 (6)	0.0141 (5)	0.0016 (4)	0.0008 (4)	0.0009 (4)
O3	0.0178 (6)	0.0122 (6)	0.0253 (6)	−0.0009 (4)	0.0067 (5)	0.0010 (5)
O4	0.0171 (6)	0.0191 (6)	0.0171 (5)	−0.0036 (5)	0.0022 (5)	−0.0025 (5)
O5	0.0147 (6)	0.0173 (6)	0.0174 (6)	0.0022 (4)	−0.0018 (5)	−0.0004 (4)
O6	0.0196 (6)	0.0217 (6)	0.0148 (6)	0.0060 (5)	0.0015 (5)	−0.0033 (5)

Mg1—O5i	2.0448 (11)	N1—C3	1.494 (2)
Mg1—O5	2.0448 (11)	N1—C2	1.502 (2)
Mg1—O1ii	2.0615 (11)	N1—C1	1.5196 (19)
Mg1—O1iii	2.0616 (11)	N1—H1B	0.9100
Mg1—O2	2.1879 (11)	C1—H1A	0.9800
Mg1—O2i	2.1879 (11)	C2—H2A	0.9600
P1—O1	1.4898 (12)	C2—H2B	0.9600
P1—O2	1.5134 (12)	C2—H2C	0.9600
P1—O3	1.5587 (12)	C3—H3A	0.9600
P1—C1	1.8451 (15)	C3—H3B	0.9600
P2—O5	1.4938 (12)	C3—H3C	0.9600
P2—O6	1.4961 (12)	O1—Mg1iv	2.0615 (11)
P2—O4	1.5737 (12)	O3—H3D	0.8200
P2—C1	1.8515 (16)	O4—H4A	0.8200
O5i—Mg1—O5	179.999 (1)	C3—N1—C1	112.68 (13)
O5i—Mg1—O1ii	88.62 (5)	C2—N1—C1	112.71 (13)
O5—Mg1—O1ii	91.38 (5)	C3—N1—H1B	107.1
O5i—Mg1—O1iii	91.38 (5)	C2—N1—H1B	107.1
O5—Mg1—O1iii	88.62 (5)	C1—N1—H1B	107.1
O1ii—Mg1—O1iii	180.0	N1—C1—P1	112.08 (10)
O5i—Mg1—O2	91.82 (4)	N1—C1—P2	115.59 (10)
O5—Mg1—O2	88.18 (4)	P1—C1—P2	113.39 (8)
O1ii—Mg1—O2	84.94 (4)	N1—C1—H1A	104.8
O1iii—Mg1—O2	95.06 (4)	P1—C1—H1A	104.8
O5i—Mg1—O2i	88.19 (4)	P2—C1—H1A	104.8
O5—Mg1—O2i	91.82 (4)	N1—C2—H2A	109.5
O1ii—Mg1—O2i	95.06 (4)	N1—C2—H2B	109.5
O1iii—Mg1—O2i	84.94 (4)	H2A—C2—H2B	109.5
O2—Mg1—O2i	180.00 (6)	N1—C2—H2C	109.5
O1—P1—O2	117.90 (7)	H2A—C2—H2C	109.5
O1—P1—O3	107.58 (7)	H2B—C2—H2C	109.5
O2—P1—O3	111.67 (7)	N1—C3—H3A	109.5
O1—P1—C1	111.24 (7)	N1—C3—H3B	109.5
O2—P1—C1	103.22 (7)	H3A—C3—H3B	109.5
O3—P1—C1	104.42 (7)	N1—C3—H3C	109.5
O5—P2—O6	117.19 (7)	H3A—C3—H3C	109.5
O5—P2—O4	111.67 (7)	H3B—C3—H3C	109.5
O6—P2—O4	106.96 (7)	P1—O1—Mg1iv	148.50 (8)
O5—P2—C1	104.71 (7)	P1—O2—Mg1	139.08 (7)
O6—P2—C1	108.34 (7)	P1—O3—H3D	109.5
O4—P2—C1	107.57 (7)	P2—O4—H4A	109.5
C3—N1—C2	109.91 (14)	P2—O5—Mg1	137.38 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3	0.91	2.57	3.0997 (18)	118
N1—H1B···O4v	0.91	2.31	3.1346 (18)	151
O3—H3D···O6vi	0.82	1.70	2.5011 (16)	166
O4—H4A···O2ii	0.82	1.81	2.6037 (16)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O3	0.91	2.57	3.0997 (18)	118
N1—H1B⋯O4i	0.91	2.31	3.1346 (18)	151
O3—H3D⋯O6ii	0.82	1.70	2.5011 (16)	166
O4—H4A⋯O2iii	0.82	1.81	2.6037 (16)	163

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