Diaqua-bis{[1-hydr-oxy-2-(1H-imidazol-3-ium-1-yl)ethane-1,1-di-yl]bis-(hydrogen phospho-nato)}manganese(II).

In the title compound, [Mn(C(5)H(9)N(2)O(7)P(2))(2)(H(2)O)(2)], the Mn(II) atom (site symmetry ) is coordinated by four phos-pho-n-ate O atoms from a pair of partially deprotonated 1-hydr-oxy-2-(imidazol-3-yl)ethane-1,1-bis-phophonic acid ligands (imhedpH(3) (-)) and two water mol-ecules, resulting in a slightly distorted trans-MnO(6) octa-hedral geometry for the metal ion. In the ligands, the imidazole units are protonated and two of the hydr-oxy O atoms of the phospho-nate groups are deprotonated and chelate the Mn(II), thus forming the neutral mol-ecule of the title compound. The two protonated O atoms within the phospho-nate groups of one imhedpH(3) (-) ligand act as hydrogen-bond acceptors for a bifurcated hydrogen bond originating from the coordinated water mol-ecule. The phospho-nate units of neigboring mol-ecules are connected with their equivalents in neighboring mol-ecules via two types of inversion-symmetric hydrogen-bonding arrangements with four and two strong O-H⋯O hydrogen bonds, respectively. The two inter-actions connect mol-ecules into infinite chains along [111] and [110], in combination forming a tightly hydrogen-bonded three-dimensional supra-molecular network. This network is further stabilized by additional hydrogen bonds between the protonated imidazole units and one of the coordinated P-O O atoms and by additional O-H⋯O hydrogen bonds between the water mol-ecules and the P=O O atoms of neigboring mol-ecules.

Related literature

For a review of the structures and applications of lanthanide phospho­nates, see: Mao (2007 ▶). For other complexes based on the imhedpH4 ligand, see: Cao et al. (2007 ▶, 2008 ▶). For the structures and properties of some metal organophospho­nates, see: Rao et al. (2004 ▶); Yang et al. (2009 ▶).

Experimental

Crystal data

[Mn(C5H9N2O7P2)2(H2O)2]

M = 633.14

Triclinic,

a = 7.4408 (17) Å

b = 8.566 (2) Å

c = 9.680 (2) Å

α = 105.366 (4)°

β = 110.865 (4)°

γ = 97.461 (4)°

V = 538.4 (2) Å3

Z = 1

Mo Kα radiation

μ = 1.00 mm−1

T = 153 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.788, T max = 0.825

2637 measured reflections

1829 independent reflections

1543 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.135

S = 0.99

1829 reflections

175 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.46 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680905065X/zl2255sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680905065X/zl2255Isup2.hkl

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

[Mn(C5H9N2O7P2)2(H2O)2]	Z = 1
Mr = 633.14	F(000) = 323
Triclinic, P1	Dx = 1.953 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4408 (17) Å	Cell parameters from 584 reflections
b = 8.566 (2) Å	θ = 2.4–24.6°
c = 9.680 (2) Å	µ = 1.00 mm−1
α = 105.366 (4)°	T = 153 K
β = 110.865 (4)°	Block, light pink
γ = 97.461 (4)°	0.25 × 0.20 × 0.20 mm
V = 538.4 (2) Å3

Bruker SMART APEXII diffractometer	1829 independent reflections
Radiation source: fine-focus sealed tube	1543 reflections with I > 2σ(I)
graphite	Rint = 0.029
ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −8→4
Tmin = 0.788, Tmax = 0.825	k = −10→10
2637 measured reflections	l = −9→11

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.0806P)2 + 0.0364P] where P = (Fo2 + 2Fc2)/3
1829 reflections	(Δ/σ)max < 0.001
175 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.46 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.7059 (7)	0.0407 (6)	0.4433 (6)	0.0313 (11)
H1	0.5957	−0.0541	0.3933	0.038*
C2	0.9765 (8)	0.2242 (6)	0.6170 (6)	0.0411 (13)
H2	1.0898	0.2812	0.7125	0.049*
C3	0.9192 (7)	0.2695 (6)	0.4880 (5)	0.0330 (12)
H3	0.9850	0.3632	0.4743	0.040*
C4	0.6265 (7)	0.1604 (6)	0.2269 (5)	0.0263 (10)
H4A	0.5289	0.0511	0.1646	0.032*
H4B	0.7133	0.1768	0.1719	0.032*
C5	0.5147 (6)	0.2977 (5)	0.2313 (5)	0.0186 (9)
Mn1	0.0000	0.0000	0.0000	0.0188 (3)
N1	0.7483 (5)	0.1543 (4)	0.3809 (4)	0.0231 (8)
N2	0.8436 (7)	0.0832 (5)	0.5856 (5)	0.0393 (11)
H2A	0.8485	0.0279	0.6511	0.047*
O1	0.2208 (4)	0.1161 (3)	−0.0561 (3)	0.0218 (7)
O2	0.5292 (4)	0.2914 (3)	−0.0465 (3)	0.0212 (7)
O3	0.2772 (4)	0.4247 (4)	0.0239 (4)	0.0236 (7)
H3A	0.355 (7)	0.511 (6)	0.031 (5)	0.028*
O4	0.1983 (4)	0.1153 (4)	0.2449 (3)	0.0256 (7)
O5	0.4729 (4)	0.3069 (4)	0.5030 (3)	0.0258 (7)
O6	0.2356 (5)	0.4203 (4)	0.3166 (3)	0.0258 (7)
H6A	0.316 (7)	0.515 (6)	0.369 (6)	0.031*
O7	0.6604 (5)	0.4552 (4)	0.3074 (4)	0.0274 (8)
H7A	0.616 (7)	0.534 (6)	0.347 (6)	0.033*
O8	−0.1140 (6)	0.2247 (5)	−0.0097 (5)	0.0421 (10)
H8A	−0.232 (9)	0.226 (7)	−0.018 (7)	0.051*
H8B	−0.021 (9)	0.314 (7)	0.028 (7)	0.051*
P1	0.37848 (16)	0.27554 (13)	0.02248 (13)	0.0187 (3)
P2	0.34950 (16)	0.27977 (13)	0.33400 (12)	0.0203 (3)

	U11	U22	U33	U12	U13	U23
C1	0.032 (3)	0.032 (3)	0.038 (3)	0.011 (2)	0.017 (2)	0.020 (2)
C2	0.041 (3)	0.036 (3)	0.030 (3)	0.008 (3)	−0.003 (2)	0.011 (2)
C3	0.031 (3)	0.029 (3)	0.030 (3)	0.001 (2)	0.004 (2)	0.011 (2)
C4	0.027 (3)	0.030 (3)	0.020 (2)	0.013 (2)	0.008 (2)	0.006 (2)
C5	0.015 (2)	0.020 (2)	0.016 (2)	0.0023 (18)	0.0028 (18)	0.0052 (17)
Mn1	0.0177 (5)	0.0178 (5)	0.0178 (5)	0.0005 (4)	0.0058 (4)	0.0047 (4)
N1	0.021 (2)	0.025 (2)	0.022 (2)	0.0057 (16)	0.0065 (17)	0.0092 (16)
N2	0.052 (3)	0.045 (3)	0.031 (2)	0.016 (2)	0.017 (2)	0.026 (2)
O1	0.0219 (17)	0.0240 (17)	0.0183 (16)	0.0013 (13)	0.0098 (13)	0.0051 (13)
O2	0.0197 (16)	0.0242 (16)	0.0232 (16)	0.0056 (13)	0.0111 (13)	0.0099 (13)
O3	0.0211 (17)	0.0222 (17)	0.0342 (18)	0.0055 (13)	0.0143 (15)	0.0155 (14)
O4	0.0316 (18)	0.0241 (17)	0.0153 (16)	−0.0009 (14)	0.0062 (14)	0.0061 (13)
O5	0.0251 (17)	0.0299 (18)	0.0168 (16)	0.0001 (14)	0.0063 (14)	0.0057 (13)
O6	0.0223 (18)	0.0273 (18)	0.0225 (17)	0.0041 (14)	0.0080 (14)	0.0027 (14)
O7	0.0222 (17)	0.0244 (18)	0.0294 (18)	0.0004 (14)	0.0095 (15)	0.0035 (14)
O8	0.023 (2)	0.026 (2)	0.077 (3)	0.0073 (16)	0.021 (2)	0.0163 (19)
P1	0.0175 (6)	0.0197 (6)	0.0188 (6)	0.0028 (5)	0.0078 (5)	0.0065 (5)
P2	0.0211 (6)	0.0205 (6)	0.0162 (6)	0.0009 (5)	0.0073 (5)	0.0038 (5)

C1—N2	1.309 (6)	Mn1—O4	2.159 (3)
C1—N1	1.334 (6)	Mn1—O4i	2.159 (3)
C1—H1	0.9500	Mn1—O8i	2.213 (4)
C2—N2	1.345 (6)	Mn1—O8	2.213 (4)
C2—C3	1.347 (6)	N2—H2A	0.8800
C2—H2	0.9500	O1—P1	1.489 (3)
C3—N1	1.363 (6)	O2—P1	1.505 (3)
C3—H3	0.9500	O3—P1	1.565 (3)
C4—N1	1.462 (5)	O3—H3A	0.85 (5)
C4—C5	1.526 (6)	O4—P2	1.499 (3)
C4—H4A	0.9900	O5—P2	1.499 (3)
C4—H4B	0.9900	O6—P2	1.571 (3)
C5—O7	1.437 (5)	O6—H6A	0.84 (5)
C5—P2	1.850 (4)	O7—H7A	0.85 (5)
C5—P1	1.854 (4)	O8—H8A	0.86 (6)
Mn1—O1	2.116 (3)	O8—H8B	0.85 (6)
Mn1—O1i	2.116 (3)
N2—C1—N1	107.7 (4)	O1—Mn1—O8	84.33 (13)
N2—C1—H1	126.2	O1i—Mn1—O8	95.67 (13)
N1—C1—H1	126.2	O4—Mn1—O8	93.01 (13)
N2—C2—C3	107.3 (4)	O4i—Mn1—O8	86.99 (13)
N2—C2—H2	126.3	O8i—Mn1—O8	180.0
C3—C2—H2	126.3	C1—N1—C3	108.7 (4)
C2—C3—N1	106.5 (4)	C1—N1—C4	125.9 (4)
C2—C3—H3	126.8	C3—N1—C4	125.4 (4)
N1—C3—H3	126.8	C1—N2—C2	109.9 (4)
N1—C4—C5	114.6 (3)	C1—N2—H2A	125.1
N1—C4—H4A	108.6	C2—N2—H2A	125.1
C5—C4—H4A	108.6	P1—O1—Mn1	134.48 (17)
N1—C4—H4B	108.6	P1—O3—H3A	111 (3)
C5—C4—H4B	108.6	P2—O4—Mn1	132.06 (17)
H4A—C4—H4B	107.6	P2—O6—H6A	110 (3)
O7—C5—C4	107.3 (3)	C5—O7—H7A	113 (3)
O7—C5—P2	111.1 (3)	Mn1—O8—H8A	121 (4)
C4—C5—P2	112.1 (3)	Mn1—O8—H8B	113 (4)
O7—C5—P1	108.2 (3)	H8A—O8—H8B	123 (5)
C4—C5—P1	104.7 (3)	O1—P1—O2	115.48 (17)
P2—C5—P1	113.0 (2)	O1—P1—O3	108.67 (17)
O1—Mn1—O1i	180.00 (17)	O2—P1—O3	110.18 (16)
O1—Mn1—O4	88.32 (11)	O1—P1—C5	108.75 (17)
O1i—Mn1—O4	91.68 (11)	O2—P1—C5	107.50 (18)
O1—Mn1—O4i	91.68 (11)	O3—P1—C5	105.82 (18)
O1i—Mn1—O4i	88.32 (11)	O5—P2—O4	115.53 (17)
O4—Mn1—O4i	180.00 (17)	O5—P2—O6	111.28 (17)
O1—Mn1—O8i	95.67 (13)	O4—P2—O6	107.09 (18)
O1i—Mn1—O8i	84.33 (13)	O5—P2—C5	109.22 (18)
O4—Mn1—O8i	86.99 (13)	O4—P2—C5	107.87 (18)
O4i—Mn1—O8i	93.01 (13)	O6—P2—C5	105.31 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O4ii	0.88	1.85	2.718 (5)	167
O7—H7A···O5iii	0.85 (5)	2.07 (5)	2.889 (4)	162 (5)
O6—H6A···O5iii	0.84 (5)	1.82 (5)	2.653 (4)	167 (5)
O3—H3A···O2iv	0.85 (5)	1.74 (5)	2.573 (4)	167 (5)
O8—H8A···O2v	0.86 (6)	1.88 (6)	2.707 (5)	162 (5)
O8—H8B···O3	0.85 (6)	2.32 (6)	3.042 (5)	143 (5)
O8—H8B···O6	0.85 (6)	2.59 (6)	3.124 (5)	122 (5)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O4i	0.88	1.85	2.718 (5)	167
O7—H7A⋯O5ii	0.85 (5)	2.07 (5)	2.889 (4)	162 (5)
O6—H6A⋯O5ii	0.84 (5)	1.82 (5)	2.653 (4)	167 (5)
O3—H3A⋯O2iii	0.85 (5)	1.74 (5)	2.573 (4)	167 (5)
O8—H8A⋯O2iv	0.86 (6)	1.88 (6)	2.707 (5)	162 (5)
O8—H8B⋯O3	0.85 (6)	2.32 (6)	3.042 (5)	143 (5)
O8—H8B⋯O6	0.85 (6)	2.59 (6)	3.124 (5)	122 (5)

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