Diammonium diaqua­bis(methyl­enediphospho­nato-κ2O,O′)cobaltate(II)

Van der Merwe, K.A.; Visser, H.G.; Venter, J.A.

doi:10.1107/S1600536809042159

metal-organic compounds

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Volume 65| Part 11| November 2009| Page m1394

https://doi.org/10.1107/S1600536809042159

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Diammonium diaquabis(methylenediphosphonato-κ²O,O′)cobaltate(II)

K. A. Van der Merwe,^a Hendrik G. Visser ^a ^* and J. A. Venter ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein, 9330, South Africa
^*Correspondence e-mail: visserhg.sci@ufs.ac.za

(Received 12 October 2009; accepted 14 October 2009; online 17 October 2009)

In the salt, (NH₄)₂[Co(CH₄O₆P₂)₂(H₂O)₂], the methylenediphosphonate acts as a bidentate ligand and the Co^II ion (site symmetry $[\overline 1]$ ) assumes an octahedral CoO₆ coordination geometry. The acid H atom of the ligand is distributed over two O atoms. In the crystal, a three-dimensional network is formed through O—H⋯O and N—H⋯O hydrogen bonds between the cations and anions.

Related literature

For related structures, see: DeLaMatter et al. (1973 ); Jurisson et al. (1983 ); Barthelet et al. (2002 ); Stahl et al. (2006 ).

Experimental

Crystal data

(NH₄)₂[Co(CH₄O₆P₂)₂(H₂O)₂]
M_r = 479.01
Triclinic, $[P \overline 1]$
a = 7.455 (5) Å
b = 7.560 (5) Å
c = 8.035 (5) Å
α = 88.282 (5)°
β = 62.450 (5)°
γ = 71.834 (5)°
V = 378.0 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.63 mm⁻¹
T = 103 K
0.28 × 0.16 × 0.11 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.739, T_max = 0.830
8419 measured reflections
1875 independent reflections
1735 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.097
S = 1.23
1875 reflections
134 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O5ⁱ	0.819 (18)	1.99 (2)	2.795 (3)	166 (4)
O1—H1B⋯O4ⁱⁱ	0.835 (19)	1.994 (19)	2.827 (3)	175 (4)
N1—H1N⋯O7ⁱⁱⁱ	0.825 (18)	2.09 (2)	2.892 (3)	166 (3)
N1—H2N⋯O6	0.825 (18)	1.98 (2)	2.796 (3)	171 (4)
N1—H3N⋯O3^iv	0.821 (18)	2.17 (2)	2.959 (3)	161 (3)
N1—H4N⋯O3^v	0.821 (18)	2.146 (19)	2.966 (3)	177 (3)
O6—H6A⋯O6^vi	0.82	1.66	2.463 (4)	165
O7—H7⋯O4^vii	0.82	1.66	2.435 (3)	156
Symmetry codes: (i) x-1, y, z+1; (ii) -x+1, -y+1, -z+2; (iii) -x+1, -y+1, -z+1; (iv) -x+2, -y, -z+1; (v) x, y, z-1; (vi) -x+1, -y, -z+1; (vii) x-1, y, z.

Data collection: SMART (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: DIAMOND (Brandenberg & Putz, 2005 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809042159/ng2665sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042159/ng2665Isup2.hkl

checkCIF report

Comment top

Diphosphonic acids are useful for the synthesis of metalorganic frameworks exhibiting microporous properties (Barthelet et al., 2002).

The Co^II ion in the title complex, (NH₄)₂[Co(C₂H₈O₁₂)₂(H₂O)₂], is in a slightly distorted octahedral environment with O—Co—O bonding angles ranging from 84.72 (8) to 95.28 (8) ^o. All the bonding distances and angles fall within the normal range observed for complexes of this nature (DeLaMatter et al., 1973; Jurisson et al., 1983 and Stahl et al., 2006). In the bidentate ligand, the distances of uncoordinated O atoms to their respective P atoms do not vary much with values ranging from 1.5304 (19) and 1.5469 (19) Å. This, together with the fact that the best fits of our data were obtained when a 50% positional disorder was applied to the hydrogen atoms bonded to these O atoms, probably is enough to validate the slight disorder. A three-dimensional network is provided by numerous hydrogen bonds between the oxygen atoms of the anionic species and the ammonium cations.

Related literature top

For related structures, see: DeLaMatter et al. (1973); Jurisson et al. (1983); Barthelet et al. (2002); Stahl et al. (2006).

Experimental top

CoCl₂.6H₂O (0,1696 g, 0,00071 mol) was dissolved in water (7 cm³) and heated to 70°C. The pH of the solution was 4,89 and deep pink in colour. Ammonium bicarbonate was added to raise the pH to 5,61 after which methylene disphosphonate (0,25 g, 0,00142 mol), dissolved in water (5 cm³) was added dropwise. The final pH of the solution was adjusted to 1.50 with ammonium bicarbonate. (Yield: 84.1%)

Structure description top

Diphosphonic acids are useful for the synthesis of metalorganic frameworks exhibiting microporous properties (Barthelet et al., 2002).

For related structures, see: DeLaMatter et al. (1973); Jurisson et al. (1983); Barthelet et al. (2002); Stahl et al. (2006).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenberg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. View of (I) (50% probability displacement ellipsoids). The ammonium cations have been omitted for clarity.

Diammonium diaquabis(methylenediphosphonato-κ²O,O')cobaltate(II) top

Crystal data top

(NH₄)₂[Co(CH₄O₆P₂)₂(H₂O)₂]	Z = 1
M_r = 479.01	F(000) = 237
Triclinic, P1	D_x = 2.069 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 7.455 (5) Å	Cell parameters from 4649 reflections
b = 7.560 (5) Å	θ = 3.2–28.3°
c = 8.035 (5) Å	µ = 1.63 mm⁻¹
α = 88.282 (5)°	T = 103 K
β = 62.450 (5)°	Rod, pink
γ = 71.834 (5)°	0.28 × 0.16 × 0.11 mm
V = 378.0 (4) Å³

Data collection top

Bruker SMART diffractometer	1875 independent reflections
Radiation source: sealed tube	1735 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 28.4°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.739, T_max = 0.830	k = −9→10
8419 measured reflections	l = −10→9

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.026	w = 1/[σ²(F_o²) + (0.0501P)² + 0.4031P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.097	(Δ/σ)_max < 0.001
S = 1.23	Δρ_max = 0.58 e Å⁻³
1875 reflections	Δρ_min = −0.48 e Å⁻³
134 parameters

Crystal data top

(NH₄)₂[Co(CH₄O₆P₂)₂(H₂O)₂]	γ = 71.834 (5)°
M_r = 479.01	V = 378.0 (4) Å³
Triclinic, P1	Z = 1
a = 7.455 (5) Å	Mo Kα radiation
b = 7.560 (5) Å	µ = 1.63 mm⁻¹
c = 8.035 (5) Å	T = 103 K
α = 88.282 (5)°	0.28 × 0.16 × 0.11 mm
β = 62.450 (5)°

Data collection top

Bruker SMART diffractometer	1875 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1735 reflections with I > 2σ(I)
T_min = 0.739, T_max = 0.830	R_int = 0.029
8419 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	6 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.23	Δρ_max = 0.58 e Å⁻³
1875 reflections	Δρ_min = −0.48 e Å⁻³
134 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.5	0	1	0.00601 (14)
P1	0.79673 (9)	0.26243 (8)	0.74506 (8)	0.00547 (16)
P2	0.40236 (9)	0.26654 (8)	0.71287 (8)	0.00548 (15)
C1	0.5577 (4)	0.3956 (3)	0.7338 (3)	0.0069 (4)
H51	0.4658	0.487	0.847	0.008*
H61	0.5984	0.465	0.6264	0.008*
O2	0.3230 (3)	0.1616 (2)	0.8790 (2)	0.0082 (3)
O3	0.7476 (3)	0.1227 (2)	0.8847 (2)	0.0079 (3)
O6	0.5476 (3)	0.1357 (2)	0.5238 (2)	0.0103 (4)
H6A	0.4935	0.058	0.5191	0.016*	0.5
O1	0.3253 (3)	0.2144 (3)	1.2321 (2)	0.0101 (4)
N1	0.8609 (4)	0.1904 (3)	0.1800 (3)	0.0114 (4)
O7	0.2170 (3)	0.4231 (2)	0.7030 (2)	0.0092 (3)
H7	0.1063	0.3971	0.7569	0.014*	0.5
O5	0.9736 (3)	0.1640 (2)	0.5452 (2)	0.0091 (3)
H5A	0.9708	0.0583	0.5301	0.014*	0.5
O4	0.8575 (3)	0.4110 (2)	0.8125 (2)	0.0083 (3)
H4	0.9866	0.3715	0.7787	0.013*	0.5
H1N	0.860 (5)	0.298 (3)	0.197 (4)	0.010 (8)*
H2N	0.779 (5)	0.165 (6)	0.282 (4)	0.029 (10)*
H3N	0.984 (3)	0.121 (4)	0.149 (5)	0.020 (9)*
H4N	0.829 (6)	0.175 (5)	0.098 (4)	0.020 (9)*
H1A	0.233 (5)	0.201 (5)	1.334 (3)	0.020 (9)*
H1B	0.274 (6)	0.323 (3)	1.212 (5)	0.027 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0060 (2)	0.0058 (2)	0.0061 (2)	−0.00256 (17)	−0.00242 (18)	0.00160 (16)
P1	0.0050 (3)	0.0051 (3)	0.0066 (3)	−0.0025 (2)	−0.0026 (2)	0.0016 (2)
P2	0.0056 (3)	0.0052 (3)	0.0062 (3)	−0.0025 (2)	−0.0028 (2)	0.0017 (2)
C1	0.0074 (11)	0.0060 (10)	0.0083 (10)	−0.0026 (8)	−0.0043 (9)	0.0013 (8)
O2	0.0077 (8)	0.0087 (8)	0.0093 (8)	−0.0042 (6)	−0.0043 (7)	0.0044 (6)
O3	0.0071 (8)	0.0083 (8)	0.0087 (8)	−0.0038 (6)	−0.0036 (6)	0.0034 (6)
O6	0.0115 (9)	0.0112 (8)	0.0081 (8)	−0.0071 (7)	−0.0023 (7)	−0.0008 (6)
O1	0.0107 (9)	0.0075 (8)	0.0085 (8)	−0.0032 (7)	−0.0017 (7)	0.0011 (6)
N1	0.0107 (11)	0.0102 (10)	0.0108 (10)	−0.0006 (8)	−0.0051 (9)	0.0010 (8)
O7	0.0077 (8)	0.0076 (8)	0.0147 (9)	−0.0033 (6)	−0.0069 (7)	0.0055 (6)
O5	0.0086 (8)	0.0067 (8)	0.0083 (8)	−0.0033 (6)	−0.0006 (6)	−0.0003 (6)
O4	0.0056 (8)	0.0087 (8)	0.0113 (8)	−0.0026 (6)	−0.0042 (7)	0.0002 (6)

Geometric parameters (Å, º) top

Co1—O2	2.0714 (18)	P2—C1	1.793 (2)
Co1—O2ⁱ	2.0714 (18)	C1—H51	0.97
Co1—O1ⁱ	2.102 (2)	C1—H61	0.97
Co1—O1	2.102 (2)	O6—H6A	0.82
Co1—O3ⁱ	2.135 (2)	O1—H1A	0.819 (18)
Co1—O3	2.135 (2)	O1—H1B	0.835 (19)
P1—O3	1.5166 (18)	N1—H1N	0.825 (18)
P1—O4	1.5304 (19)	N1—H2N	0.825 (18)
P1—O5	1.5403 (19)	N1—H3N	0.821 (18)
P1—C1	1.795 (3)	N1—H4N	0.821 (18)
P2—O2	1.5032 (18)	O7—H7	0.82
P2—O6	1.5363 (19)	O5—H5A	0.82
P2—O7	1.5469 (19)	O4—H4	0.82

O2—Co1—O2ⁱ	180	O2—P2—C1	111.74 (11)
O2—Co1—O1ⁱ	92.53 (8)	O6—P2—C1	106.30 (11)
O2ⁱ—Co1—O1ⁱ	87.47 (8)	O7—P2—C1	102.44 (12)
O2—Co1—O1	87.47 (8)	P2—C1—P1	116.96 (14)
O2ⁱ—Co1—O1	92.53 (8)	P2—C1—H51	108.1
O1ⁱ—Co1—O1	180.0000 (10)	P1—C1—H51	108.1
O2—Co1—O3ⁱ	84.72 (8)	P2—C1—H61	108.1
O2ⁱ—Co1—O3ⁱ	95.28 (8)	P1—C1—H61	108.1
O1ⁱ—Co1—O3ⁱ	88.91 (8)	H51—C1—H61	107.3
O1—Co1—O3ⁱ	91.09 (8)	P2—O2—Co1	126.71 (11)
O2—Co1—O3	95.28 (8)	P1—O3—Co1	133.61 (10)
O2ⁱ—Co1—O3	84.72 (8)	P2—O6—H6A	109.5
O1ⁱ—Co1—O3	91.09 (8)	Co1—O1—H1A	121 (2)
O1—Co1—O3	88.91 (8)	Co1—O1—H1B	117 (3)
O3ⁱ—Co1—O3	180.00 (7)	H1A—O1—H1B	106 (4)
O3—P1—O4	111.68 (11)	H1N—N1—H2N	108 (4)
O3—P1—O5	111.77 (11)	H1N—N1—H3N	105 (3)
O4—P1—O5	110.47 (11)	H2N—N1—H3N	108 (4)
O3—P1—C1	109.61 (11)	H1N—N1—H4N	114 (3)
O4—P1—C1	103.92 (11)	H2N—N1—H4N	111 (4)
O5—P1—C1	109.08 (11)	H3N—N1—H4N	110 (3)
O2—P2—O6	112.62 (11)	P2—O7—H7	109.5
O2—P2—O7	112.39 (10)	P1—O5—H5A	109.5
O6—P2—O7	110.73 (11)	P1—O4—H4	109.5

Symmetry code: (i) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5ⁱⁱ	0.82 (2)	1.99 (2)	2.795 (3)	166 (4)
O1—H1B···O4ⁱⁱⁱ	0.84 (2)	1.99 (2)	2.827 (3)	175 (4)
N1—H1N···O7^iv	0.83 (2)	2.09 (2)	2.892 (3)	166 (3)
N1—H2N···O6	0.83 (2)	1.98 (2)	2.796 (3)	171 (4)
N1—H3N···O3^v	0.82 (2)	2.17 (2)	2.959 (3)	161 (3)
N1—H4N···O3^vi	0.82 (2)	2.15 (2)	2.966 (3)	177 (3)
O6—H6A···O6^vii	0.82	1.66	2.463 (4)	165
O7—H7···O4^viii	0.82	1.66	2.435 (3)	156

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

Experimental details

Crystal data
Chemical formula	(NH₄)₂[Co(CH₄O₆P₂)₂(H₂O)₂]
M_r	479.01
Crystal system, space group	Triclinic, P1
Temperature (K)	103
a, b, c (Å)	7.455 (5), 7.560 (5), 8.035 (5)
α, β, γ (°)	88.282 (5), 62.450 (5), 71.834 (5)
V (Å³)	378.0 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.63
Crystal size (mm)	0.28 × 0.16 × 0.11

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.739, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	8419, 1875, 1735
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.097, 1.23
No. of reflections	1875
No. of parameters	134
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.48

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenberg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5ⁱ	0.819 (18)	1.99 (2)	2.795 (3)	166 (4)
O1—H1B···O4ⁱⁱ	0.835 (19)	1.994 (19)	2.827 (3)	175 (4)
N1—H1N···O7ⁱⁱⁱ	0.825 (18)	2.09 (2)	2.892 (3)	166 (3)
N1—H2N···O6	0.825 (18)	1.98 (2)	2.796 (3)	171 (4)
N1—H3N···O3^iv	0.821 (18)	2.17 (2)	2.959 (3)	161 (3)
N1—H4N···O3^v	0.821 (18)	2.146 (19)	2.966 (3)	177 (3)
O6—H6A···O6^vi	0.82	1.66	2.463 (4)	164.6
O7—H7···O4^vii	0.82	1.66	2.435 (3)	156.1

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

Acknowledgements

We thank the University of the Free State for financial support and Professor A. Roodt for helpful discussions.

References

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