Poly[tri-μ-aqua-di­aqua-μ-phosphono­formato-cobalt(II)sodium]

The title complex, [CoNa(CO₅P)(H₂O)₅]_n, was obtained by reacting sodium phosphono­formate with cobalt nitrate. The complex contains cobalt(II) and sodium ions, which are bridged by the O atoms of two aqua ligands. The Co^II ion is octahedrally coordinated by three phosphonoformato ligands (one bi- and the other monodentate) and by two O atoms from the bridging aqua ligands. The sodium cation is hexa­coordinated by six O atoms from four bridging and two terminal aqua ligands. The complex mol­ecules are linked to give a three-dimensional structure by phosphono­formate ligands bridging Co^II atoms and water mol­ecules establishing cobalt–sodium bridges. O—H...O hydrogen bonding between the aqua ligands and all O atoms of the phosphono­formato ligand and neighbouring aqua ligands help to consolidate the packing.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](O-C) = 0.004 Å
• R factor = 0.035
• wR factor = 0.066
• Data-to-parameter ratio = 10.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H    Uiso(max)/Uiso(min) ..        5.0 Ratio
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.812
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         10

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite         15
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          3
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            O7  -CO1 -O4  -C1   -118.40  0.60   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         33
            O4  -CO1 -O7  -NA1    52.90  0.60   1.555   1.555   1.555   1.555
PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd) .       1.22 Ratio
PLAT793_ALERT_4_G The Model has Chirality at P1      (Verify) ....          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         10
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          3
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  10 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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S1. Comment

Organophosphates have been widely used in medicinal chemistry and life science. They play an important role in life processes of substance transportation and energy transformation, and are also important for biological substances, such as ATP, DNA, RNA, etc. Bisphosphonates (BPs) are metabolically stable analogues of pyrophosphates. They have a very high affinity to calcium ions and therefore show a very strong inhibitory effect on osteoclastic resorption. They are used as therapeutic agents for several bone-related diseases. Foscarnet and phosphonoacetic acid are known to inhibit viral DNA polymerase, inhibit the replication of herpes viruses, and also inhibit retroviruses (Mesri et al., 1996). Recently, several bifunctional metal-phosphonate complexes have been explored (Galanski et al., 2003; Margiotta et al., 2007; Xue et al., 2010; Torres Martin de Rosales et al., 2009).

The molecular structure of the title compound is shown in Fig. 1. Each Co(II) ion is in an octahedral environment coordinated by two O atoms (O1, O4) from a chelating phosphonoformate ligand, two O atoms (O6, O7) from two bridging water molecules and two O atoms (O2A, O3B) from two other phosphonoformates. Similarly, the Na(I) ion is coordinated by four O atoms (O6, O7, O8, O9) from four bridging water molecules and two O atoms (O9C, O10) from two terminal water ligands. The complex is linked to 3-D structure by phosphonoformate ligands bridging cobalt atoms and water molecules establishing cobalt sodium bridges (Fig. 2).

Related literature

For biological applications of organophosphorus complexes, see: Xue et al. (2010); Torres Martin de Rosales et al. (2009); Galanski et al. (2003); Margiotta et al. (2007); Mesri et al. (1996).

S2. Experimental

An aqueous solution (15 ml) of Co(NO₃)₂ × 6 H₂O (0.145 g, 0.5 mmol) was added dropwisely to an aqueous solution (15 ml) of sodium phosphonoformate (0.180 g, 0.6 mmol) at 323 K. The resulting mixture was refluxed for 3 h, and then the aqueous solution was allowed to cool down to room temperature. Pink block shaped crystals suitable for X-ray single diffraction analysis were harvested by slow evaporation (yield, 65%).

S3. Refinement

H atoms of the water molecules were located in a difference Fourier map and refined, with O—H distances restrained to 0.82 Å.

Computing details

Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear (Rigaku, 1999); data reduction: CrystalStructure (Rigaku/MSC & Rigaku, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Molecular structure of one repeating unit of the coordination polymer with the atom-numbering scheme displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. Packing diagram of the title compound viewed along c axis.

Poly[tri-µ-aqua-diaqua-µ-phosphonoformato-cobalt(II)sodium]

Crystal data

[CoNa(CO5P)(H2O)5]	F(000) = 596
Mr = 294.98	Dx = 2.135 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybc	Cell parameters from 3028 reflections
a = 8.299 (2) Å	θ = 3.1–27.5°
b = 11.785 (3) Å	µ = 2.13 mm^−1
c = 9.769 (3) Å	T = 223 K
β = 106.204 (4)°	Block, pink
V = 917.5 (4) Å^3	0.30 × 0.14 × 0.05 mm
Z = 4

Data collection

Rigaku Saturn diffractometer	1691 independent reflections
Radiation source: fine-focus sealed tube	1539 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 14.63 pixels mm^-1	θmax = 25.5°, θmin = 3.1°
ω scans	h = −8→10
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −12→14
Tmin = 0.636, Tmax = 0.899	l = −11→7
3715 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	All H-atom parameters refined
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0277P)^2] where P = (Fo^2 + 2Fc^2)/3
1691 reflections	(Δ/σ)max = 0.001
168 parameters	Δρmax = 0.37 e Å^−3
10 restraints	Δρmin = −0.45 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Co1	0.08112 (5)	0.64526 (3)	0.69444 (4)	0.01133 (13)
P1	−0.00606 (10)	0.38705 (6)	0.65570 (8)	0.01079 (19)
Na1	0.49306 (16)	0.63218 (10)	0.95685 (13)	0.0201 (3)
O1	0.1359 (3)	0.47211 (16)	0.6737 (2)	0.0137 (5)
O2	0.0139 (3)	0.30646 (17)	0.7807 (2)	0.0146 (5)
O3	−0.0498 (3)	0.32183 (16)	0.5160 (2)	0.0147 (5)
O4	−0.1606 (3)	0.58356 (16)	0.6816 (2)	0.0158 (5)
O5	−0.3256 (3)	0.43235 (17)	0.6558 (2)	0.0189 (5)
O6	0.1718 (3)	0.62170 (19)	0.9232 (2)	0.0179 (5)
H6A	0.139 (5)	0.668 (3)	0.971 (4)	0.047 (14)*
H6B	0.164 (4)	0.5600 (16)	0.960 (3)	0.024 (10)*
O7	0.3298 (3)	0.71602 (19)	0.7377 (3)	0.0171 (5)
H7A	0.313 (6)	0.777 (2)	0.770 (5)	0.088 (19)*
H7B	0.388 (4)	0.706 (3)	0.683 (3)	0.029 (11)*
O8	0.7866 (3)	0.6010 (2)	0.9711 (3)	0.0226 (6)
H8A	0.850 (4)	0.636 (3)	1.038 (3)	0.048 (14)*
H8B	0.816 (4)	0.619 (3)	0.901 (2)	0.027 (11)*
O9	0.5412 (3)	0.5383 (2)	1.1731 (3)	0.0189 (5)
H9A	0.473 (3)	0.540 (3)	1.220 (3)	0.031 (12)*
H9B	0.639 (2)	0.537 (3)	1.221 (4)	0.040 (13)*
O10	0.5291 (3)	0.8103 (2)	1.0633 (3)	0.0219 (6)
H10A	0.484 (7)	0.866 (3)	1.017 (5)	0.12 (2)*
H10B	0.620 (3)	0.839 (3)	1.104 (4)	0.043 (13)*
C1	−0.1872 (4)	0.4775 (2)	0.6624 (3)	0.0133 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0135 (2)	0.0099 (2)	0.0113 (2)	−0.00024 (18)	0.00465 (17)	0.00001 (17)
P1	0.0130 (4)	0.0095 (4)	0.0109 (4)	0.0001 (3)	0.0048 (3)	0.0003 (3)
Na1	0.0223 (7)	0.0168 (6)	0.0199 (7)	0.0021 (6)	0.0037 (6)	−0.0001 (5)
O1	0.0123 (11)	0.0095 (10)	0.0190 (12)	−0.0013 (9)	0.0040 (9)	0.0003 (9)
O2	0.0205 (12)	0.0125 (10)	0.0101 (11)	−0.0016 (9)	0.0030 (9)	0.0013 (9)
O3	0.0230 (13)	0.0117 (10)	0.0101 (11)	−0.0018 (9)	0.0055 (10)	−0.0005 (9)
O4	0.0170 (12)	0.0103 (10)	0.0222 (12)	−0.0006 (9)	0.0090 (10)	−0.0009 (9)
O5	0.0135 (12)	0.0158 (11)	0.0286 (14)	−0.0032 (10)	0.0078 (10)	0.0000 (10)
O6	0.0261 (14)	0.0141 (12)	0.0152 (12)	0.0033 (11)	0.0085 (11)	0.0011 (11)
O7	0.0197 (14)	0.0171 (12)	0.0173 (13)	0.0003 (11)	0.0096 (11)	−0.0026 (10)
O8	0.0244 (14)	0.0275 (13)	0.0157 (14)	−0.0062 (11)	0.0054 (12)	−0.0047 (12)
O9	0.0153 (14)	0.0238 (13)	0.0187 (14)	0.0017 (11)	0.0065 (12)	0.0003 (10)
O10	0.0221 (15)	0.0181 (12)	0.0250 (15)	−0.0031 (11)	0.0059 (12)	−0.0010 (11)
C1	0.0145 (17)	0.0158 (16)	0.0098 (17)	0.0013 (14)	0.0038 (14)	−0.0018 (13)

Geometric parameters (Å, º)

Co1—O3^i	2.036 (2)	Na1—H7A	2.64 (4)
Co1—O2^ii	2.097 (2)	O2—Co1^iv	2.097 (2)
Co1—O4	2.104 (2)	O3—Co1^i	2.036 (2)
Co1—O1	2.113 (2)	O4—C1	1.274 (3)
Co1—O7	2.156 (3)	O5—C1	1.251 (4)
Co1—O6	2.168 (2)	O6—H6A	0.819 (10)
P1—O1	1.519 (2)	O6—H6B	0.820 (10)
P1—O2	1.519 (2)	O7—H7A	0.817 (10)
P1—O3	1.520 (2)	O7—H7B	0.820 (10)
P1—C1	1.859 (3)	O8—H8A	0.821 (10)
Na1—O9	2.319 (3)	O8—H8B	0.817 (10)
Na1—O10	2.325 (3)	O9—Na1^iii	2.351 (3)
Na1—O9^iii	2.351 (3)	O9—H9A	0.822 (10)
Na1—O7	2.404 (3)	O9—H9B	0.818 (10)
Na1—O8	2.429 (3)	O10—H10A	0.822 (10)
Na1—O6	2.596 (3)	O10—H10B	0.818 (10)
Na1—Na1^iii	3.221 (2)
O3^i—Co1—O2^ii	89.89 (8)	O8—Na1—Na1^iii	82.90 (8)
O3^i—Co1—O4	98.89 (9)	O6—Na1—Na1^iii	87.00 (7)
O2^ii—Co1—O4	86.39 (8)	O9—Na1—H7A	149.2 (10)
O3^i—Co1—O1	93.29 (8)	O10—Na1—H7A	72.6 (5)
O2^ii—Co1—O1	169.80 (9)	O9^iii—Na1—H7A	102.7 (5)
O4—Co1—O1	83.54 (8)	O7—Na1—H7A	17.9 (5)
O3^i—Co1—O7	88.26 (9)	O8—Na1—H7A	120.2 (11)
O2^ii—Co1—O7	89.84 (9)	O6—Na1—H7A	65.1 (11)
O4—Co1—O7	171.90 (9)	Na1^iii—Na1—H7A	141.2 (8)
O1—Co1—O7	99.94 (9)	P1—O1—Co1	117.89 (13)
O3^i—Co1—O6	167.17 (9)	P1—O2—Co1^iv	134.36 (12)
O2^ii—Co1—O6	91.74 (8)	P1—O3—Co1^i	137.88 (13)
O4—Co1—O6	93.92 (9)	C1—O4—Co1	118.1 (2)
O1—Co1—O6	87.32 (8)	Co1—O6—Na1	99.98 (10)
O7—Co1—O6	79.02 (9)	Co1—O6—H6A	116 (3)
O1—P1—O2	114.36 (12)	Na1—O6—H6A	113 (3)
O1—P1—O3	114.88 (13)	Co1—O6—H6B	121 (2)
O2—P1—O3	110.56 (12)	Na1—O6—H6B	101 (2)
O1—P1—C1	103.06 (13)	H6A—O6—H6B	105 (4)
O2—P1—C1	103.76 (14)	Co1—O7—Na1	106.63 (11)
O3—P1—C1	109.21 (12)	Co1—O7—H7A	99 (4)
O9—Na1—O10	93.19 (10)	Na1—O7—H7A	98 (3)
O9—Na1—O9^iii	92.76 (10)	Co1—O7—H7B	121 (3)
O10—Na1—O9^iii	173.87 (11)	Na1—O7—H7B	103 (2)
O9—Na1—O7	156.76 (11)	H7A—O7—H7B	125 (4)
O10—Na1—O7	89.86 (9)	Na1—O8—H8A	112 (3)
O9^iii—Na1—O7	85.24 (9)	Na1—O8—H8B	116 (3)
O9—Na1—O8	87.73 (10)	H8A—O8—H8B	105 (4)
O10—Na1—O8	96.27 (10)	Na1—O9—Na1^iii	87.24 (10)
O9^iii—Na1—O8	82.52 (10)	Na1—O9—H9A	122 (3)
O7—Na1—O8	114.84 (10)	Na1^iii—O9—H9A	109 (3)
O9—Na1—O6	90.14 (9)	Na1—O9—H9B	115 (3)
O10—Na1—O6	95.69 (9)	Na1^iii—O9—H9B	104 (3)
O9^iii—Na1—O6	85.74 (9)	H9A—O9—H9B	114 (4)
O7—Na1—O6	66.63 (9)	Na1—O10—H10A	119 (4)
O8—Na1—O6	167.95 (9)	Na1—O10—H10B	125 (3)
O9—Na1—Na1^iii	46.79 (7)	H10A—O10—H10B	99 (4)
O10—Na1—Na1^iii	139.96 (10)	O5—C1—O4	123.0 (3)
O9^iii—Na1—Na1^iii	45.97 (7)	O5—C1—P1	119.6 (2)
O7—Na1—Na1^iii	126.93 (8)	O4—C1—P1	117.3 (2)
O2—P1—O1—Co1	−112.78 (14)	O7—Na1—O6—Co1	20.00 (8)
O3—P1—O1—Co1	117.81 (14)	O8—Na1—O6—Co1	−79.7 (5)
C1—P1—O1—Co1	−0.87 (16)	Na1^iii—Na1—O6—Co1	−112.70 (8)
O3^i—Co1—O1—P1	−96.88 (14)	O3^i—Co1—O7—Na1	−154.99 (11)
O2^ii—Co1—O1—P1	11.0 (5)	O2^ii—Co1—O7—Na1	115.12 (11)
O4—Co1—O1—P1	1.70 (13)	O4—Co1—O7—Na1	52.9 (6)
O7—Co1—O1—P1	174.31 (13)	O1—Co1—O7—Na1	−61.95 (11)
O6—Co1—O1—P1	95.95 (14)	O6—Co1—O7—Na1	23.32 (10)
O1—P1—O2—Co1^iv	−157.24 (16)	O9—Na1—O7—Co1	−19.2 (3)
O3—P1—O2—Co1^iv	−25.7 (2)	O10—Na1—O7—Co1	−116.96 (11)
C1—P1—O2—Co1^iv	91.3 (2)	O9^iii—Na1—O7—Co1	66.71 (11)
O1—P1—O3—Co1^i	−43.0 (2)	O8—Na1—O7—Co1	146.19 (10)
O2—P1—O3—Co1^i	−174.31 (17)	O6—Na1—O7—Co1	−20.70 (9)
C1—P1—O3—Co1^i	72.1 (2)	Na1^iii—Na1—O7—Co1	45.96 (16)
O3^i—Co1—O4—C1	89.9 (2)	O10—Na1—O9—Na1^iii	−178.55 (11)
O2^ii—Co1—O4—C1	179.2 (2)	O9^iii—Na1—O9—Na1^iii	0.0
O1—Co1—O4—C1	−2.5 (2)	O7—Na1—O9—Na1^iii	84.4 (2)
O7—Co1—O4—C1	−118.4 (6)	O8—Na1—O9—Na1^iii	−82.39 (9)
O6—Co1—O4—C1	−89.3 (2)	O6—Na1—O9—Na1^iii	85.74 (9)
O3^i—Co1—O6—Na1	−13.2 (4)	Co1—O4—C1—O5	178.7 (2)
O2^ii—Co1—O6—Na1	−110.39 (9)	Co1—O4—C1—P1	2.6 (3)
O4—Co1—O6—Na1	163.11 (8)	O1—P1—C1—O5	−177.4 (2)
O1—Co1—O6—Na1	79.78 (9)	O2—P1—C1—O5	−57.9 (3)
O7—Co1—O6—Na1	−20.89 (9)	O3—P1—C1—O5	60.1 (3)
O9—Na1—O6—Co1	−159.41 (9)	O1—P1—C1—O4	−1.1 (3)
O10—Na1—O6—Co1	107.37 (10)	O2—P1—C1—O4	118.4 (2)
O9^iii—Na1—O6—Co1	−66.65 (10)	O3—P1—C1—O4	−123.7 (2)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, y+1/2, −z+3/2; (iii) −x+1, −y+1, −z+2; (iv) −x, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10B···O4^v	0.82 (1)	1.99 (1)	2.805 (3)	173 (4)
O10—H10A···O5^ii	0.82 (1)	1.99 (3)	2.736 (3)	151 (5)
O9—H9B···O1^iii	0.82 (1)	1.87 (1)	2.683 (3)	178 (4)
O9—H9A···O5^vi	0.82 (1)	1.98 (1)	2.790 (4)	171 (4)
O8—H8B···O4^vii	0.82 (1)	2.24 (2)	2.988 (4)	152 (3)
O8—H8A···O2^iii	0.82 (1)	1.94 (1)	2.751 (3)	168 (4)
O7—H7B···O10^viii	0.82 (1)	1.88 (1)	2.703 (4)	177 (4)
O7—H7A···O5^ii	0.82 (1)	1.96 (2)	2.757 (3)	166 (5)
O6—H6B···O8^iii	0.82 (1)	2.02 (2)	2.806 (3)	161 (4)
O6—H6A···O3^ii	0.82 (1)	1.97 (2)	2.698 (3)	148 (4)

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