Poly[[{μ(3)-dihydrogen [(pyridin-4-yl-methyl-imino)-bis-(methyl-ene)]diphos-phon-ato-κO:O',N,O'':N'}copper(II)] dihydrate].

In the title polymer, {[Cu(C(8)H(12)N(2)O(6)P(2))]·2H(2)O}(n), the geometry of the five-coordinate Cu(II) ion can best be described as slightly distorted square-pyramidal formed by one N and two O atoms of an N(CH(2)PO(3)H)(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 diphospho-nate ligand. The inter-connection of Cu(2+) ions by the diphospho-nate ligands results in the formation of a double-chain array along the b axis, in which the two sub-chains are inter-locked by pairs of PO(3) groups. The outside of each sub-chain is decorated by other PO(3) groups. These double chains are further assembled into a three-dimensional supra-molecular architecture via a large number of O-H⋯O hydrogen bonds between the phospho-nate groups and lattice water mol-ecules.

Related literature

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

Crystal data

[Cu(C8H12N2O6P2)]·2H2O

M = 393.71

Triclinic,

a = 8.9250 (3) Å

b = 9.0000 (3) Å

c = 10.5066 (3) Å

α = 75.648 (2)°

β = 67.124 (2)°

γ = 67.126 (2)°

V = 711.75 (4) Å3

Z = 2

Mo Kα radiation

μ = 1.80 mm−1

T = 296 K

0.40 × 0.03 × 0.02 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.605, T max = 0.746

7659 measured reflections

3267 independent reflections

2309 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.118

S = 1.03

3267 reflections

202 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.60 e Å−3

Data collection: APEX2 (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, 2010 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052512/fj2483sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052512/fj2483Isup2.hkl

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

[Cu(C8H12N2O6P2)]·2H2O	Z = 2
Mr = 393.71	F(000) = 402
Triclinic, P1	Dx = 1.837 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9250 (3) Å	Cell parameters from 1430 reflections
b = 9.0000 (3) Å	θ = 2.1–27.6°
c = 10.5066 (3) Å	µ = 1.80 mm−1
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

Bruker APEXII CCD diffractometer	3267 independent reflections
Radiation source: fine-focus sealed tube	2309 reflections with I > 2σ(I)
graphite	Rint = 0.043
phi and ω scans	θmax = 27.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→11
Tmin = 0.605, Tmax = 0.746	k = −11→11
7659 measured reflections	l = −13→13

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H 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 parameters	Δρmax = 0.50 e Å−3
6 restraints	Δρmin = −0.60 e Å−3

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
Cu1	0.47006 (6)	0.60143 (5)	0.25556 (5)	0.02485 (17)
P1	0.69833 (14)	0.32696 (12)	0.39341 (11)	0.0237 (2)
P2	0.17163 (14)	0.57368 (13)	0.21239 (12)	0.0265 (3)
N1	0.5076 (4)	−0.1825 (4)	0.2025 (3)	0.0240 (7)
N2	0.4396 (4)	0.3746 (4)	0.2980 (3)	0.0207 (7)
C1	0.3823 (5)	−0.0485 (5)	0.1777 (4)	0.0282 (9)
H1A	0.2869	−0.0590	0.1696	0.034*
C2	0.3912 (5)	0.1042 (5)	0.1641 (4)	0.0293 (10)
H2A	0.3025	0.1945	0.1457	0.035*
C3	0.5301 (5)	0.1261 (4)	0.1773 (4)	0.0233 (9)
C4	0.6596 (6)	−0.0148 (5)	0.1992 (4)	0.0294 (9)
H4A	0.7570	−0.0076	0.2065	0.035*
C5	0.6465 (5)	−0.1652 (5)	0.2102 (4)	0.0273 (9)
H5A	0.7364	−0.2575	0.2233	0.033*
C6	0.5389 (5)	0.2920 (4)	0.1674 (4)	0.0243 (9)
H6A	0.4964	0.3607	0.0933	0.029*
H6B	0.6587	0.2831	0.1412	0.029*
C7	0.5053 (5)	0.2840 (5)	0.4152 (4)	0.0235 (9)
H7A	0.5324	0.1684	0.4164	0.028*
H7B	0.4179	0.3168	0.5029	0.028*
C8	0.2500 (5)	0.4113 (5)	0.3387 (4)	0.0224 (8)
H8A	0.1931	0.4454	0.4312	0.027*
H8B	0.2255	0.3151	0.3391	0.027*
O1	0.8567 (4)	0.1971 (3)	0.3047 (3)	0.0309 (7)
H1B	0.9034	0.2423	0.2302	0.046*
O2	0.6750 (3)	0.4935 (3)	0.3111 (3)	0.0278 (6)
O3	0.7175 (4)	0.3101 (3)	0.5319 (3)	0.0307 (7)
O4	0.2907 (3)	0.6731 (3)	0.1706 (3)	0.0273 (6)
O5	0.1664 (4)	0.5097 (3)	0.0961 (3)	0.0356 (7)
O6	−0.0163 (4)	0.6712 (4)	0.2955 (3)	0.0393 (8)
H6C	−0.0137	0.7334	0.3394	0.059*
O1W	1.0256 (4)	0.3000 (4)	0.0716 (3)	0.0381 (8)
H1WA	1.065 (6)	0.366 (5)	0.078 (5)	0.057*
H1WB	0.964 (6)	0.344 (5)	0.021 (5)	0.057*
O2W	−0.0383 (5)	0.8732 (4)	0.4421 (4)	0.0462 (9)
H2WA	−0.037 (7)	0.965 (4)	0.397 (5)	0.069*
H2WB	0.053 (5)	0.832 (6)	0.464 (6)	0.069*

	U11	U22	U33	U12	U13	U23
Cu1	0.0279 (3)	0.0187 (3)	0.0339 (3)	−0.0064 (2)	−0.0186 (2)	−0.0011 (2)
P1	0.0258 (6)	0.0185 (5)	0.0290 (6)	−0.0027 (4)	−0.0154 (5)	−0.0030 (4)
P2	0.0283 (6)	0.0233 (5)	0.0369 (6)	−0.0077 (5)	−0.0215 (5)	−0.0020 (5)
N1	0.0277 (18)	0.0195 (17)	0.0268 (19)	−0.0072 (14)	−0.0117 (15)	−0.0025 (14)
N2	0.0248 (17)	0.0177 (16)	0.0235 (17)	−0.0068 (14)	−0.0127 (15)	−0.0014 (13)
C1	0.026 (2)	0.023 (2)	0.042 (3)	−0.0039 (17)	−0.018 (2)	−0.0081 (19)
C2	0.030 (2)	0.022 (2)	0.040 (3)	−0.0025 (18)	−0.020 (2)	−0.0054 (18)
C3	0.028 (2)	0.0192 (19)	0.023 (2)	−0.0061 (17)	−0.0087 (18)	−0.0038 (16)
C4	0.031 (2)	0.028 (2)	0.034 (2)	−0.0097 (19)	−0.015 (2)	−0.0042 (19)
C5	0.028 (2)	0.0169 (19)	0.039 (3)	−0.0065 (17)	−0.017 (2)	−0.0003 (18)
C6	0.028 (2)	0.022 (2)	0.027 (2)	−0.0063 (17)	−0.0142 (18)	−0.0024 (17)
C7	0.031 (2)	0.0188 (19)	0.023 (2)	−0.0078 (17)	−0.0125 (18)	0.0005 (16)
C8	0.023 (2)	0.022 (2)	0.026 (2)	−0.0100 (17)	−0.0100 (18)	−0.0025 (17)
O1	0.0302 (16)	0.0228 (15)	0.0335 (17)	−0.0006 (13)	−0.0123 (14)	−0.0028 (13)
O2	0.0279 (16)	0.0194 (14)	0.0395 (17)	−0.0054 (12)	−0.0194 (14)	0.0008 (13)
O3	0.0312 (17)	0.0335 (16)	0.0321 (17)	−0.0054 (13)	−0.0200 (14)	−0.0043 (13)
O4	0.0315 (16)	0.0234 (14)	0.0367 (17)	−0.0100 (12)	−0.0243 (14)	0.0038 (13)
O5	0.049 (2)	0.0308 (16)	0.0431 (19)	−0.0148 (15)	−0.0302 (16)	−0.0026 (14)
O6	0.0290 (17)	0.0360 (18)	0.061 (2)	−0.0048 (14)	−0.0248 (16)	−0.0111 (16)
O1W	0.041 (2)	0.0387 (19)	0.042 (2)	−0.0163 (16)	−0.0204 (16)	0.0014 (15)
O2W	0.048 (2)	0.0337 (19)	0.061 (2)	−0.0053 (17)	−0.030 (2)	−0.0057 (17)

Cu1—O2	1.949 (3)	C2—C3	1.390 (5)
Cu1—O4	1.949 (2)	C2—H2A	0.9300
Cu1—N1i	2.008 (3)	C3—C4	1.385 (5)
Cu1—N2	2.080 (3)	C3—C6	1.501 (5)
Cu1—O3ii	2.315 (3)	C4—C5	1.376 (5)
P1—O3	1.495 (3)	C4—H4A	0.9300
P1—O2	1.514 (3)	C5—H5A	0.9300
P1—O1	1.570 (3)	C6—H6A	0.9700
P1—C7	1.827 (4)	C6—H6B	0.9700
P2—O5	1.497 (3)	C7—H7A	0.9700
P2—O4	1.518 (3)	C7—H7B	0.9700
P2—O6	1.563 (3)	C8—H8A	0.9700
P2—C8	1.831 (4)	C8—H8B	0.9700
N1—C1	1.340 (5)	O1—H1B	0.8200
N1—C5	1.341 (5)	O3—Cu1ii	2.315 (3)
N1—Cu1iii	2.008 (3)	O6—H6C	0.8200
N2—C7	1.489 (5)	O1W—H1WA	0.832 (19)
N2—C8	1.492 (5)	O1W—H1WB	0.836 (19)
N2—C6	1.507 (5)	O2W—H2WA	0.846 (19)
C1—C2	1.376 (6)	O2W—H2WB	0.848 (19)
C1—H1A	0.9300
O2—Cu1—O4	167.12 (11)	C3—C2—H2A	119.4
O2—Cu1—N1i	93.65 (12)	C4—C3—C2	115.6 (3)
O4—Cu1—N1i	92.92 (12)	C4—C3—C6	122.4 (4)
O2—Cu1—N2	86.48 (11)	C2—C3—C6	121.9 (3)
O4—Cu1—N2	86.29 (11)	C5—C4—C3	121.1 (4)
N1i—Cu1—N2	176.50 (13)	C5—C4—H4A	119.4
O2—Cu1—O3ii	96.97 (11)	C3—C4—H4A	119.4
O4—Cu1—O3ii	94.37 (11)	N1—C5—C4	121.9 (4)
N1i—Cu1—O3ii	87.53 (12)	N1—C5—H5A	119.0
N2—Cu1—O3ii	95.93 (11)	C4—C5—H5A	119.0
O3—P1—O2	116.53 (16)	C3—C6—N2	115.5 (3)
O3—P1—O1	108.57 (16)	C3—C6—H6A	108.4
O2—P1—O1	110.13 (17)	N2—C6—H6A	108.4
O3—P1—C7	110.01 (18)	C3—C6—H6B	108.4
O2—P1—C7	103.88 (16)	N2—C6—H6B	108.4
O1—P1—C7	107.31 (17)	H6A—C6—H6B	107.5
O5—P2—O4	115.75 (17)	N2—C7—P1	109.1 (3)
O5—P2—O6	108.56 (17)	N2—C7—H7A	109.9
O4—P2—O6	111.15 (16)	P1—C7—H7A	109.9
O5—P2—C8	112.42 (17)	N2—C7—H7B	109.9
O4—P2—C8	103.00 (16)	P1—C7—H7B	109.9
O6—P2—C8	105.44 (18)	H7A—C7—H7B	108.3
C1—N1—C5	118.3 (3)	N2—C8—P2	108.1 (3)
C1—N1—Cu1iii	120.0 (3)	N2—C8—H8A	110.1
C5—N1—Cu1iii	121.1 (3)	P2—C8—H8A	110.1
C7—N2—C8	111.7 (3)	N2—C8—H8B	110.1
C7—N2—C6	112.3 (3)	P2—C8—H8B	110.1
C8—N2—C6	112.8 (3)	H8A—C8—H8B	108.4
C7—N2—Cu1	107.6 (2)	P1—O1—H1B	109.5
C8—N2—Cu1	104.3 (2)	P1—O2—Cu1	119.08 (16)
C6—N2—Cu1	107.7 (2)	P1—O3—Cu1ii	133.88 (16)
N1—C1—C2	121.7 (4)	P2—O4—Cu1	117.93 (16)
N1—C1—H1A	119.1	P2—O6—H6C	109.5
C2—C1—H1A	119.1	H1WA—O1W—H1WB	109 (4)
C1—C2—C3	121.3 (4)	H2WA—O2W—H2WB	107 (4)
C1—C2—H2A	119.4

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O1W	0.82	1.68	2.494 (4)	169
O6—H6C···O2W	0.82	1.75	2.567 (5)	172
O1W—H1WA···O5iv	0.83 (2)	1.92 (2)	2.746 (4)	177 (5)
O1W—H1WB···O5v	0.84 (2)	1.93 (2)	2.747 (4)	167 (5)
O2W—H2WA···O1vi	0.85 (2)	2.09 (3)	2.882 (4)	155 (5)
O2W—H2WB···O3ii	0.85 (2)	1.96 (3)	2.776 (4)	161 (6)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O1W	0.82	1.68	2.494 (4)	169
O6—H6C⋯O2W	0.82	1.75	2.567 (5)	172
O1W—H1WA⋯O5i	0.83 (2)	1.92 (2)	2.746 (4)	177 (5)
O1W—H1WB⋯O5ii	0.84 (2)	1.93 (2)	2.747 (4)	167 (5)
O2W—H2WA⋯O1iii	0.85 (2)	2.09 (3)	2.882 (4)	155 (5)
O2W—H2WB⋯O3iv	0.85 (2)	1.96 (3)	2.776 (4)	161 (6)

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