supplementary materials


fj2483 scheme

Acta Cryst. (2012). E68, m38-m39    [ doi:10.1107/S1600536811052512 ]

Poly[[{[mu]3-dihydrogen [(pyridin-4-ylmethylimino)bis(methylene)]diphosphonato-[kappa]5O:O',N,O'':N'}copper(II)] dihydrate]

S.-Y. Zhang, Z.-G. Zhou and K.-J. Wang

Abstract top

In the title polymer, {[Cu(C8H12N2O6P2)]·2H2O}n, the geometry of the five-coordinate CuII ion can best be described as slightly distorted square-pyramidal formed by one N and two O atoms of an N(CH2PO3H)2 group and one N atom from a pyridine ring. The elongated apex of the pyramid is occupied by one O atom from a third diphosphonate ligand. The interconnection of Cu2+ ions by the diphosphonate ligands results in the formation of a double-chain array along the b axis, in which the two sub-chains are interlocked by pairs of PO3 groups. The outside of each sub-chain is decorated by other PO3 groups. These double chains are further assembled into a three-dimensional supramolecular architecture via a large number of O-H...O hydrogen bonds between the phosphonate groups and lattice water molecules.

Comment top

During the past few decades, the syntheses of metal phosphonates with various structures has attracted much attention, owing to their potential applications in areas such as catalysis, ion exchange, intercalation chemistry, and material chemistry (Maeda, 2004; Mao, 2007; Shimizu et al., 2009). The strategy of attaching functional groups such as amine, hydroxyl, carboxylate, sulfonate, and sulfone groups to the phosphonic acid has proven to be an effective method for the isolation of a variety of metal phosphonates with new structures (Drumel et al., 1995; Mao et al., 2002; Liang & Shimizu, 2007; Du et al. 2006, 2010b). Recently, we are interested in the combination of multiple functional groups to phosphonic acid as a more complex ligand. Herein, we report a copper(II) phosphonate based on an amino-bis(methyl-phosphonic acid) ligand, which contains pyridyl group as an additional functional group. As far as we are aware, only one layered cobalt(II) phosphonate has been reported based on the same ligand (Song & Mao, 2005).

The title compound (I) features a one-dimensional double-chain structure. The formula of it contains one Cu2+ ion, one H2L2- anion and two lattice water molecules. Cu(1) ion is five-coordinate and its coordination geometry can be described as a slightly distorted square-pyramid (Fig. 1): the square plane is formed by one N and two O atoms of a N(CH2PO3H)2 group as well as one N atom of a pyridyl group from two H2L2- ligand, and the prolonged apex of the pyramid is occupied by one O atom from a third H2L2- ligand. The H2L2- ligand in compound (I) acts as a pentadentate chelating and bridging ligand. It chelates one Cu2+ ion by its N(CH2PO3H)2 group in a tridentate fashion (2O and 1 N), and also bridges with other two Cu2+ ions via its pyridyl group and a third O atom (Scheme 1). The two phosphonate groups of the H2L2- ligand both are 1H-protonated as the requirement for charge balance and also as indicated by two much longer P—O bonds. It is worthy of note that the strongly basic N atom in the H2L2- ligand is not protonated but bonded to a Cu2+ ion, which is rarely observed for phosphonic acid ligands containing a tertiary amine group (Yang et al., 2008; Du et al., 2009, 2010a).

The interconnection of the Cu2+ ions by the HL2- anions results in the formation of a one-dimensional double-chain array along the b-axis, in which the two sub-chains are inter-locked by pairs of P(1)O3 groups and the outside of each sub-chain is decorated by P(2)O3 groups. It is worthy of note that such two sub-chains are related by inversion centers, and the shortest Cd···Cd distance between them is 5.170 (4) Å while that in each sub-chain is 9.000 (1) Å. These double-chains are further assembled into a three-dimensional supramolecular architecture via a large number of hydrogen bonds between the phosphonate groups and lattice water molecules (Fig. 3 and Table 1).

Related literature top

For background to metal phosphonate chemistry, see: Maeda (2004); Mao (2007); Shimizu et al. (2009). For the synthetic strategy of attaching functional groups to a phosphonic acid ligand, see: Drumel et al. (1995); Mao et al. (2002); Liang & Shimizu (2007); Du et al. (2006, 2010b). For a structurally related complex, see: Song & Mao (2005). For the zwitterionic behavior of aminophosphonic acid, see: Yang et al. (2008); Du et al. (2009, 2010a).

Experimental top

4-Pyridyl-CH2N(CH2PO3H2)2 (0.2 mmol) was dissolved in 4 ml H2O and poured into a test tube, then CuCl2.2H2O (0.15 mmol) dissolved in 8 ml EtOH was carefully layered onto it and left to stand at room temperature. Blue column-shaped crystals of (I) were obtained after about two weeks later. IR data for (I) (KBr, cm-1): 3477(s), 3228(s), 3141(m), 3079(m), 2975(m), 2913(m), 2376(m), 1846(m), 1624(s), 1502(m), 1448(m), 1433(m), 1350(m), 1266(s), 1221(m), 1173(s), 1140(versus), 1065(s), 1051(s), 1032(s), 945(s), 929(m), 906(m), 866(m), 844(m), 795(m), 742(m), 648(m), 588(s), 524(m), 482(m), 453(m).

Refinement top

C-bound H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 or 0.97 Å, and with Uiso(H) = 1.2Ueq(C). H atoms of –PO3H- groups were also placed in idealized positions and constrained to ride on their parent atoms, with O—H distances of 0.82 Å, and with Uiso(H) = 1.2Ueq(O). Water H atoms were located in a difference map and refined with Uiso(H) values set at 1.5Ueq(O). The O—H distances of water were restrained to be 0.85 (1) Å.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the selected unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) x, y + 1, z; (ii) -x + 1, -y + 1, -z + 1; (iii) x, y - 1, z.]
[Figure 2] Fig. 2. View of the double-chain structure of (I) along the b-axis. The CPO3 tetrahedra are shaded in purple. Cu, N and C atoms are drawn as cyan, blue and black circles, respectively.
[Figure 3] Fig. 3. View of the structure of (I) down the b-axis. For display details, see the caption for Fig. 2. Hydrogen bonds are represented by dashed lines.
Poly[[{µ3-dihydrogen [(pyridin-4-ylmethylimino)bis(methylene)]diphosphonato- κ5O:O',N,O'':N'}copper(II)] dihydrate] top
Crystal data top
[Cu(C8H12N2O6P2)]·2H2OZ = 2
Mr = 393.71F(000) = 402
Triclinic, P1Dx = 1.837 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.9250 (3) ÅCell parameters from 1430 reflections
b = 9.0000 (3) Åθ = 2.1–27.6°
c = 10.5066 (3) ŵ = 1.80 mm1
α = 75.648 (2)°T = 296 K
β = 67.124 (2)°Needle, blue
γ = 67.126 (2)°0.40 × 0.03 × 0.02 mm
V = 711.75 (4) Å3
Data collection top
Bruker APEXII CCD
diffractometer
3267 independent reflections
Radiation source: fine-focus sealed tube2309 reflections with I > 2σ(I)
graphiteRint = 0.043
phi and ω scansθmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 1011
Tmin = 0.605, Tmax = 0.746k = 1111
7659 measured reflectionsl = 1313
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.055P)2 + 0.1702P]
where P = (Fo2 + 2Fc2)/3
3267 reflections(Δ/σ)max < 0.001
202 parametersΔρmax = 0.50 e Å3
6 restraintsΔρmin = 0.60 e Å3
Crystal data top
[Cu(C8H12N2O6P2)]·2H2Oγ = 67.126 (2)°
Mr = 393.71V = 711.75 (4) Å3
Triclinic, P1Z = 2
a = 8.9250 (3) ÅMo Kα radiation
b = 9.0000 (3) ŵ = 1.80 mm1
c = 10.5066 (3) ÅT = 296 K
α = 75.648 (2)°0.40 × 0.03 × 0.02 mm
β = 67.124 (2)°
Data collection top
Bruker APEXII CCD
diffractometer
3267 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
2309 reflections with I > 2σ(I)
Tmin = 0.605, Tmax = 0.746Rint = 0.043
7659 measured reflectionsθmax = 27.6°
Refinement top
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.118Δρmax = 0.50 e Å3
S = 1.03Δρmin = 0.60 e Å3
3267 reflectionsAbsolute structure: ?
202 parametersFlack parameter: ?
6 restraintsRogers parameter: ?
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.

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 (Å2) top
xyzUiso*/Ueq
Cu10.47006 (6)0.60143 (5)0.25556 (5)0.02485 (17)
P10.69833 (14)0.32696 (12)0.39341 (11)0.0237 (2)
P20.17163 (14)0.57368 (13)0.21239 (12)0.0265 (3)
N10.5076 (4)0.1825 (4)0.2025 (3)0.0240 (7)
N20.4396 (4)0.3746 (4)0.2980 (3)0.0207 (7)
C10.3823 (5)0.0485 (5)0.1777 (4)0.0282 (9)
H1A0.28690.05900.16960.034*
C20.3912 (5)0.1042 (5)0.1641 (4)0.0293 (10)
H2A0.30250.19450.14570.035*
C30.5301 (5)0.1261 (4)0.1773 (4)0.0233 (9)
C40.6596 (6)0.0148 (5)0.1992 (4)0.0294 (9)
H4A0.75700.00760.20650.035*
C50.6465 (5)0.1652 (5)0.2102 (4)0.0273 (9)
H5A0.73640.25750.22330.033*
C60.5389 (5)0.2920 (4)0.1674 (4)0.0243 (9)
H6A0.49640.36070.09330.029*
H6B0.65870.28310.14120.029*
C70.5053 (5)0.2840 (5)0.4152 (4)0.0235 (9)
H7A0.53240.16840.41640.028*
H7B0.41790.31680.50290.028*
C80.2500 (5)0.4113 (5)0.3387 (4)0.0224 (8)
H8A0.19310.44540.43120.027*
H8B0.22550.31510.33910.027*
O10.8567 (4)0.1971 (3)0.3047 (3)0.0309 (7)
H1B0.90340.24230.23020.046*
O20.6750 (3)0.4935 (3)0.3111 (3)0.0278 (6)
O30.7175 (4)0.3101 (3)0.5319 (3)0.0307 (7)
O40.2907 (3)0.6731 (3)0.1706 (3)0.0273 (6)
O50.1664 (4)0.5097 (3)0.0961 (3)0.0356 (7)
O60.0163 (4)0.6712 (4)0.2955 (3)0.0393 (8)
H6C0.01370.73340.33940.059*
O1W1.0256 (4)0.3000 (4)0.0716 (3)0.0381 (8)
H1WA1.065 (6)0.366 (5)0.078 (5)0.057*
H1WB0.964 (6)0.344 (5)0.021 (5)0.057*
O2W0.0383 (5)0.8732 (4)0.4421 (4)0.0462 (9)
H2WA0.037 (7)0.965 (4)0.397 (5)0.069*
H2WB0.053 (5)0.832 (6)0.464 (6)0.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0279 (3)0.0187 (3)0.0339 (3)0.0064 (2)0.0186 (2)0.0011 (2)
P10.0258 (6)0.0185 (5)0.0290 (6)0.0027 (4)0.0154 (5)0.0030 (4)
P20.0283 (6)0.0233 (5)0.0369 (6)0.0077 (5)0.0215 (5)0.0020 (5)
N10.0277 (18)0.0195 (17)0.0268 (19)0.0072 (14)0.0117 (15)0.0025 (14)
N20.0248 (17)0.0177 (16)0.0235 (17)0.0068 (14)0.0127 (15)0.0014 (13)
C10.026 (2)0.023 (2)0.042 (3)0.0039 (17)0.018 (2)0.0081 (19)
C20.030 (2)0.022 (2)0.040 (3)0.0025 (18)0.020 (2)0.0054 (18)
C30.028 (2)0.0192 (19)0.023 (2)0.0061 (17)0.0087 (18)0.0038 (16)
C40.031 (2)0.028 (2)0.034 (2)0.0097 (19)0.015 (2)0.0042 (19)
C50.028 (2)0.0169 (19)0.039 (3)0.0065 (17)0.017 (2)0.0003 (18)
C60.028 (2)0.022 (2)0.027 (2)0.0063 (17)0.0142 (18)0.0024 (17)
C70.031 (2)0.0188 (19)0.023 (2)0.0078 (17)0.0125 (18)0.0005 (16)
C80.023 (2)0.022 (2)0.026 (2)0.0100 (17)0.0100 (18)0.0025 (17)
O10.0302 (16)0.0228 (15)0.0335 (17)0.0006 (13)0.0123 (14)0.0028 (13)
O20.0279 (16)0.0194 (14)0.0395 (17)0.0054 (12)0.0194 (14)0.0008 (13)
O30.0312 (17)0.0335 (16)0.0321 (17)0.0054 (13)0.0200 (14)0.0043 (13)
O40.0315 (16)0.0234 (14)0.0367 (17)0.0100 (12)0.0243 (14)0.0038 (13)
O50.049 (2)0.0308 (16)0.0431 (19)0.0148 (15)0.0302 (16)0.0026 (14)
O60.0290 (17)0.0360 (18)0.061 (2)0.0048 (14)0.0248 (16)0.0111 (16)
O1W0.041 (2)0.0387 (19)0.042 (2)0.0163 (16)0.0204 (16)0.0014 (15)
O2W0.048 (2)0.0337 (19)0.061 (2)0.0053 (17)0.030 (2)0.0057 (17)
Geometric parameters (Å, °) top
Cu1—O21.949 (3)C2—C31.390 (5)
Cu1—O41.949 (2)C2—H2A0.9300
Cu1—N1i2.008 (3)C3—C41.385 (5)
Cu1—N22.080 (3)C3—C61.501 (5)
Cu1—O3ii2.315 (3)C4—C51.376 (5)
P1—O31.495 (3)C4—H4A0.9300
P1—O21.514 (3)C5—H5A0.9300
P1—O11.570 (3)C6—H6A0.9700
P1—C71.827 (4)C6—H6B0.9700
P2—O51.497 (3)C7—H7A0.9700
P2—O41.518 (3)C7—H7B0.9700
P2—O61.563 (3)C8—H8A0.9700
P2—C81.831 (4)C8—H8B0.9700
N1—C11.340 (5)O1—H1B0.8200
N1—C51.341 (5)O3—Cu1ii2.315 (3)
N1—Cu1iii2.008 (3)O6—H6C0.8200
N2—C71.489 (5)O1W—H1WA0.832 (19)
N2—C81.492 (5)O1W—H1WB0.836 (19)
N2—C61.507 (5)O2W—H2WA0.846 (19)
C1—C21.376 (6)O2W—H2WB0.848 (19)
C1—H1A0.9300
O2—Cu1—O4167.12 (11)C3—C2—H2A119.4
O2—Cu1—N1i93.65 (12)C4—C3—C2115.6 (3)
O4—Cu1—N1i92.92 (12)C4—C3—C6122.4 (4)
O2—Cu1—N286.48 (11)C2—C3—C6121.9 (3)
O4—Cu1—N286.29 (11)C5—C4—C3121.1 (4)
N1i—Cu1—N2176.50 (13)C5—C4—H4A119.4
O2—Cu1—O3ii96.97 (11)C3—C4—H4A119.4
O4—Cu1—O3ii94.37 (11)N1—C5—C4121.9 (4)
N1i—Cu1—O3ii87.53 (12)N1—C5—H5A119.0
N2—Cu1—O3ii95.93 (11)C4—C5—H5A119.0
O3—P1—O2116.53 (16)C3—C6—N2115.5 (3)
O3—P1—O1108.57 (16)C3—C6—H6A108.4
O2—P1—O1110.13 (17)N2—C6—H6A108.4
O3—P1—C7110.01 (18)C3—C6—H6B108.4
O2—P1—C7103.88 (16)N2—C6—H6B108.4
O1—P1—C7107.31 (17)H6A—C6—H6B107.5
O5—P2—O4115.75 (17)N2—C7—P1109.1 (3)
O5—P2—O6108.56 (17)N2—C7—H7A109.9
O4—P2—O6111.15 (16)P1—C7—H7A109.9
O5—P2—C8112.42 (17)N2—C7—H7B109.9
O4—P2—C8103.00 (16)P1—C7—H7B109.9
O6—P2—C8105.44 (18)H7A—C7—H7B108.3
C1—N1—C5118.3 (3)N2—C8—P2108.1 (3)
C1—N1—Cu1iii120.0 (3)N2—C8—H8A110.1
C5—N1—Cu1iii121.1 (3)P2—C8—H8A110.1
C7—N2—C8111.7 (3)N2—C8—H8B110.1
C7—N2—C6112.3 (3)P2—C8—H8B110.1
C8—N2—C6112.8 (3)H8A—C8—H8B108.4
C7—N2—Cu1107.6 (2)P1—O1—H1B109.5
C8—N2—Cu1104.3 (2)P1—O2—Cu1119.08 (16)
C6—N2—Cu1107.7 (2)P1—O3—Cu1ii133.88 (16)
N1—C1—C2121.7 (4)P2—O4—Cu1117.93 (16)
N1—C1—H1A119.1P2—O6—H6C109.5
C2—C1—H1A119.1H1WA—O1W—H1WB109 (4)
C1—C2—C3121.3 (4)H2WA—O2W—H2WB107 (4)
C1—C2—H2A119.4
Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O1W0.821.682.494 (4)169
O6—H6C···O2W0.821.752.567 (5)172
O1W—H1WA···O5iv0.83 (2)1.92 (2)2.746 (4)177 (5)
O1W—H1WB···O5v0.84 (2)1.93 (2)2.747 (4)167 (5)
O2W—H2WA···O1vi0.85 (2)2.09 (3)2.882 (4)155 (5)
O2W—H2WB···O3ii0.85 (2)1.96 (3)2.776 (4)161 (6)
Symmetry codes: (iv) x+1, y, z; (v) −x+1, −y+1, −z; (vi) x−1, y+1, z; (ii) −x+1, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °)
top
D—H···AD—HH···AD···AD—H···A
O1—H1B···O1W0.821.682.494 (4)169
O6—H6C···O2W0.821.752.567 (5)172
O1W—H1WA···O5i0.83 (2)1.92 (2)2.746 (4)177 (5)
O1W—H1WB···O5ii0.84 (2)1.93 (2)2.747 (4)167 (5)
O2W—H2WA···O1iii0.85 (2)2.09 (3)2.882 (4)155 (5)
O2W—H2WB···O3iv0.85 (2)1.96 (3)2.776 (4)161 (6)
Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z; (iii) x−1, y+1, z; (iv) −x+1, −y+1, −z+1.
Acknowledgements top

This work was supported by the NSF of Jiangxi Provincial Education Department (grant No. GJJ10714).

references
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