Poly[[tri-μ-aqua-do-deca-aqua-tris-(μ3-1-hy-droxy-ethyl-idene-1,1-di-phospho-nato)tricalcium(II)tripalladium(II)] penta-hydrate].

The asymmetric unit of the title compound, {[CaPd{CH3OHC(PO3)2}(H2O)5]·5/3H2O} n , consists of one half of the complex [Pd{CH3OHC(PO3)2}](2-) anion (point group symmetry m..), one Ca(2+) cation [site symmetry (.2.)] that is surrounded by three water mol-ecules (one of which is on the same rotation axis) and by three disordered lattice water mol-ecules. The anions form a trinuclear metallocycle around a crystallographic threefold rotation axis. The cations are related by a twofold rotation axis to form a [Ca2(H2O)10](2+) dimer. The slightly distorted square-planar coordination environment of the Pd(II) atoms in the complex anions is formed by O atoms of the bidentate chelating phospho-nate groups of the 1-hy-droxy-ethyl-idene-1,1-di-phospho-nate ligands. In the crystal, cations are bound to anions through -Ca-O-P-O- bonds, as well as through O-H⋯O hydrogen bonds, resulting in a three-dimensional polymer. The structure is completed by five disordered solvent mol-ecules localized in cavities within the framework.

Related literature

For background to di­phospho­nic acids see: Zhang et al. (2007 ▶); Szabo et al. (2002 ▶); Matczak-Jon & Videnova-Adrabinska (2005 ▶). For background to the anti­tumor activity of pan class="Chemical">palladium(II) complexes, see: Juribašiċ et al. (2011 ▶); Curic et al. (1996 ▶); Abu-Surrah et al. (2008 ▶); Ruiz et al. (2005 ▶, 2006 ▶); Tušek-Božiċ et al. (2008 ▶). For the structures of related complexes, see: Babaryk et al. (2012 ▶); Hammerl et al. (2002 ▶); Müller (1972 ▶).

Experimental

Crystal data

[CaPd(C2H4O7P2)(n>an class="Chemical">H2O)5]·1.67H2O

M = 468.58

Hexagonal,

a = 15.9731 (3) Å

c = 18.4149 (4) Å

V = 4068.91 (14) Å3

Z = 12

Mo Kα radiation

μ = 2.05 mm−1

T = 296 K

0.39 × 0.07 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2009 ▶) T min = 0.502, T max = 0.887

37638 measured reflections

1774 independent reflections

1410 reflections with I > 2σ(I)

R int = 0.082

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.071

S = 1.08

1774 reflections

116 parameters

28 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.56 e Å−3

Δρmin = −0.57 e Å−3

Data collection: pan class="Gene">APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814015189/br2239sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015189/br2239Isup2.hkl

CCDC reference: 1010912

Additional supporting information: crystallographic information; 3D view; checkCIF report

[CaPd(C2H4O7P2)(H2O)5]·1.67H2O	F(000) = 2816
Mr = 468.58	Dx = 2.295 Mg m−3
Hexagonal, P6/mcc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 6 2c	µ = 2.05 mm−1
a = 15.9731 (3) Å	T = 296 K
c = 18.4149 (4) Å	Rectangular, yellow
V = 4068.91 (14) Å3	0.39 × 0.07 × 0.06 mm
Z = 12

Bruker APEXII CCD area-detector diffractometer	1774 independent reflections
Radiation source: fine-focus sealed tube	1410 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
phi and ω scans	θmax = 28.4°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2009)	h = −21→21
Tmin = 0.502, Tmax = 0.887	k = −21→18
37638 measured reflections	l = −22→24

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0249P)2 + 11.4857P] where P = (Fo2 + 2Fc2)/3
1774 reflections	(Δ/σ)max = 0.013
116 parameters	Δρmax = 0.56 e Å−3
28 restraints	Δρmin = −0.57 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	Occ. (<1)
Pd1	0.63688 (3)	0.44960 (3)	0.0000	0.01659 (11)
Ca1	0.37002 (6)	0.37002 (6)	0.2500	0.0182 (2)
P1	0.45030 (6)	0.28992 (6)	0.08236 (4)	0.01779 (18)
O1	0.48149 (18)	0.21370 (18)	0.08028 (12)	0.0246 (5)
O2	0.53726 (17)	0.39316 (17)	0.07897 (12)	0.0223 (5)
O3	0.38931 (18)	0.27739 (18)	0.14777 (12)	0.0218 (5)
O5	0.33373 (19)	0.50409 (19)	0.22123 (13)	0.0243 (5)
H1	0.327 (3)	0.507 (3)	0.1764 (6)	0.037*
H2	0.367 (2)	0.5554 (18)	0.2384 (19)	0.037*
O6	0.5000	0.5000	0.17187 (18)	0.0221 (7)
H3	0.484 (3)	0.526 (3)	0.1407 (15)	0.033*
O7	0.2157 (2)	0.2933 (2)	0.18857 (17)	0.0395 (7)
H4	0.182 (3)	0.318 (3)	0.184 (2)	0.059*
H5	0.238 (3)	0.291 (4)	0.1493 (16)	0.059*
C1	0.3787 (3)	0.2740 (3)	0.0000	0.0224 (10)
O4A	0.2883 (5)	0.1836 (5)	0.0000	0.0311 (19)*	0.50
H4A	0.253 (4)	0.185 (4)	−0.031 (6)	0.047*	0.25
C2A	0.3627 (7)	0.3633 (5)	0.0000	0.023 (2)*	0.50
H21	0.3251	0.3600	−0.0416	0.034*	0.25
H22	0.4242	0.4218	−0.0018	0.034*	0.50
H23	0.3291	0.3626	0.0434	0.034*	0.25
C2B	0.3085 (7)	0.1626 (5)	0.0000	0.019 (2)*	0.50
H24	0.2910	0.1403	0.0491	0.029*	0.25
H25	0.3399	0.1310	−0.0219	0.029*	0.25
H26	0.2515	0.1478	−0.0271	0.029*	0.25
O4B	0.3386 (6)	0.3370 (6)	0.0000	0.029*	0.50
H4B	0.298 (7)	0.321 (6)	−0.033 (5)	0.029*	0.25
O8	0.1458 (11)	0.1163 (12)	−0.1026 (9)	0.169 (6)*	0.50
O9	0.0000	0.0000	0.0000	0.40 (3)*
O10	0.108 (2)	0.079 (3)	−0.2084 (13)	0.184 (14)*	0.25

	U11	U22	U33	U12	U13	U23
Pd1	0.01985 (19)	0.0223 (2)	0.00785 (16)	0.01075 (16)	0.000	0.000
Ca1	0.0199 (3)	0.0199 (3)	0.0176 (4)	0.0119 (4)	−0.00021 (18)	0.00021 (18)
P1	0.0220 (4)	0.0215 (4)	0.0089 (4)	0.0101 (4)	0.0018 (3)	−0.0004 (3)
O1	0.0386 (15)	0.0328 (14)	0.0105 (11)	0.0240 (12)	0.0048 (10)	0.0016 (10)
O2	0.0237 (12)	0.0255 (12)	0.0119 (11)	0.0080 (10)	0.0043 (10)	−0.0021 (9)
O3	0.0261 (13)	0.0265 (13)	0.0106 (11)	0.0116 (11)	0.0045 (9)	−0.0005 (10)
O5	0.0261 (14)	0.0318 (14)	0.0165 (12)	0.0155 (12)	−0.0011 (10)	0.0024 (10)
O6	0.0280 (19)	0.0228 (18)	0.0194 (17)	0.0156 (15)	0.000	0.000
O7	0.0380 (17)	0.0476 (18)	0.0439 (18)	0.0297 (15)	−0.0130 (14)	−0.0102 (15)
C1	0.021 (2)	0.025 (3)	0.016 (2)	0.007 (2)	0.000	0.000

Pd1—O2i	2.006 (2)	Ca1—O5iv	2.538 (3)
Pd1—O2	2.006 (2)	Ca1—Ca1vi	4.1524 (18)
Pd1—O1ii	2.010 (2)	P1—O3	1.498 (2)
Pd1—O1iii	2.010 (2)	P1—O1	1.529 (2)
Ca1—O7	2.416 (3)	P1—O2	1.537 (2)
Ca1—O7iv	2.416 (3)	P1—C1	1.839 (3)
Ca1—O3	2.507 (2)	C1—O4B	1.438 (6)
Ca1—O3iv	2.507 (2)	C1—O4A	1.444 (6)
Ca1—O6v	2.526 (2)	C1—C2B	1.559 (6)
Ca1—O6	2.526 (2)	C1—C2A	1.569 (6)
Ca1—O5	2.538 (3)	C1—P1i	1.839 (3)
O2i—Pd1—O2	92.91 (13)	O6v—Ca1—O5iv	68.18 (6)
O2i—Pd1—O1ii	85.78 (9)	O6—Ca1—O5iv	82.30 (7)
O2—Pd1—O1ii	173.09 (10)	O5—Ca1—O5iv	144.16 (13)
O2i—Pd1—O1iii	173.09 (10)	O7—Ca1—Ca1vi	139.79 (8)
O2—Pd1—O1iii	85.78 (9)	O7iv—Ca1—Ca1vi	139.79 (8)
O1ii—Pd1—O1iii	94.70 (14)	O3—Ca1—Ca1vi	103.51 (6)
O7—Ca1—O7iv	80.42 (16)	O3iv—Ca1—Ca1vi	103.51 (6)
O7—Ca1—O3	75.19 (9)	O3—P1—O1	111.26 (14)
O7iv—Ca1—O3	84.19 (10)	O3—P1—O2	110.76 (13)
O7—Ca1—O3iv	84.19 (10)	O1—P1—O2	111.95 (14)
O7iv—Ca1—O3iv	75.19 (9)	O3—P1—C1	109.08 (15)
O3—Ca1—O3iv	152.97 (12)	O1—P1—C1	107.27 (16)
O7—Ca1—O6v	153.43 (7)	O2—P1—C1	106.30 (16)
O7iv—Ca1—O6v	111.16 (10)	P1—O1—Pd1vii	128.04 (14)
O3—Ca1—O6v	128.30 (7)	P1—O2—Pd1	126.86 (14)
O3iv—Ca1—O6v	76.37 (7)	P1—O3—Ca1	142.04 (15)
O7—Ca1—O6	111.16 (10)	Ca1vi—O6—Ca1	110.56 (13)
O7iv—Ca1—O6	153.43 (7)	O4B—C1—O4A	97.3 (6)
O3—Ca1—O6	76.37 (7)	O4B—C1—C2B	118.7 (6)
O3iv—Ca1—O6	128.30 (7)	O4A—C1—C2A	111.9 (6)
O6v—Ca1—O6	69.44 (13)	C2B—C1—C2A	133.4 (6)
O7—Ca1—O5	74.02 (9)	O4B—C1—P1i	111.5 (2)
O7iv—Ca1—O5	138.18 (9)	O4A—C1—P1i	112.3 (2)
O3—Ca1—O5	119.24 (8)	C2B—C1—P1i	101.6 (3)
O3iv—Ca1—O5	69.84 (8)	C2A—C1—P1i	104.3 (2)
O6v—Ca1—O5	82.30 (7)	O4B—C1—P1	111.5 (2)
O6—Ca1—O5	68.18 (6)	O4A—C1—P1	112.3 (2)
O7—Ca1—O5iv	138.18 (9)	C2B—C1—P1	101.6 (3)
O7iv—Ca1—O5iv	74.02 (9)	C2A—C1—P1	104.3 (2)
O3—Ca1—O5iv	69.84 (8)	P1i—C1—P1	111.1 (2)
O3iv—Ca1—O5iv	119.24 (8)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1···O1viii	0.84 (1)	1.95 (2)	2.756 (3)	160 (4)
O5—H2···O5v	0.79 (2)	2.07 (2)	2.799 (5)	155 (4)
O6—H3···O2vi	0.82 (2)	1.87 (2)	2.685 (3)	170 (4)
O7—H4···O3viii	0.82 (2)	2.07 (2)	2.865 (4)	166 (4)
O4A—H4A···O8	0.82	1.99	2.731 (16)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H1⋯O1i	0.84 (1)	1.95 (2)	2.756 (3)	160 (4)
O5—H2⋯O5ii	0.79 (2)	2.07 (2)	2.799 (5)	155 (4)
O6—H3⋯O2iii	0.82 (2)	1.87 (2)	2.685 (3)	170 (4)
O7—H4⋯O3i	0.82 (2)	2.07 (2)	2.865 (4)	166 (4)
O4A—H4A⋯O8	0.82	1.99	2.731 (16)	150

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