Oxonium (dihydrogen 1-amino­ethane-1,1-diyldiphospho­nato-κ2N,O)[hydrogen (1-amino-1-phosphono­ethyl)phospho­nato-κ2N,O]palladium(II) trihydrate

Dudko, A.; Bon, V.; Kozachkova, A.; Tsaryk, N.; Pekhnyo, V.

doi:10.1107/S1600536810000930

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Pages m170-m171

https://doi.org/10.1107/S1600536810000930

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Oxonium (dihydrogen 1-aminoethane-1,1-diyldiphosphonato-κ²N,O)[hydrogen (1-amino-1-phosphonoethyl)phosphonato-κ²N,O]palladium(II) trihydrate

Anatolij Dudko,^a ^* Vladimir Bon,^a Alexandra Kozachkova,^a Natalia Tsaryk ^a and Vasily Pekhnyo ^a

^aInstitute of General and Inorganic Chemistry, National Academy of Science Ukraine, Prospekt Palladina 32/34, Kyiv 03680, Ukraine
^*Correspondence e-mail: dudco_anatolij@ukr.net

(Received 24 December 2009; accepted 7 January 2010; online 16 January 2010)

The title compound, (H₃O)[Pd(C₂H₇NO₆P₂)(C₂H₈NO₆P₂)]·3H₂O, was synthesized by the reaction of [Pd(H₂O)₄](NO₃)₂ with 1-aminoethane-1,1-diyldiphosphonic acid in aqueous solution. The asymmetric unit contains one molecule of the complex existing as an anion, an oxonium counter-ion and three solvent water molecules. The Pd^II ion occupies a position on a pseudo-twofold axis, which is not realized crystallographically. The slightly distorted square-planar coordination environment of the Pd^II ion consists of the O atoms from two phosphonic acid groups and two N atoms of the amino groups in cis positions. The crystal structure displays N—H⋯O and O—H⋯O hydrogen bonding, which creates a wide three-dimensional network.

Related literature

For general background and the medical use of organic diphosphonic acids, see: Matczak-Jon & Videnova-Adrabinska (2005 ); Curic et al. (1996 ); Szabo et al. (2002 ). For related structures, see: Shkol'nikova et al. (1991 ).

Experimental

Crystal data

(H₃O)[Pd(C₂H₇NO₆P₂)(C₂H₈NO₆P₂)]·3H₂O
M_r = 586.53
Orthorhombic, P c a 2₁
a = 9.9412 (2) Å
b = 9.0941 (2) Å
c = 19.9004 (3) Å
V = 1799.12 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.47 mm⁻¹
T = 100 K
0.48 × 0.29 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.536, T_max = 0.823
53680 measured reflections
5568 independent reflections
5545 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.015
wR(F²) = 0.041
S = 1.09
5568 reflections
301 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.61 e Å⁻³
Absolute structure: racemic twin (Flack, 1983 ), 2697 Friedel pairs
Flack parameter: 0.362 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11N⋯O1ⁱ	0.83 (2)	2.28 (2)	3.0527 (16)	154 (2)
N1—H12N⋯O16	0.77 (2)	2.38 (2)	3.0647 (18)	149 (2)
N2—H21N⋯O7ⁱ	0.86 (2)	2.01 (2)	2.8245 (17)	159 (2)
N2—H22N⋯O10	0.80 (2)	2.53 (2)	2.9844 (17)	117.7 (19)
O2—H2O⋯O6ⁱⁱ	0.77 (2)	1.79 (2)	2.5582 (15)	174 (3)
O4—H4O⋯O11ⁱⁱⁱ	0.73 (3)	1.94 (3)	2.6593 (16)	170 (3)
O13—H133⋯O5	1.06 (2)	1.40 (3)	2.4558 (16)	174 (2)
O8—H8O⋯O15	0.81 (2)	1.76 (2)	2.5607 (17)	173 (3)
O10—H10O⋯O16^iv	0.83 (3)	1.80 (3)	2.6298 (17)	172 (3)
O12—H12O⋯O14	0.79 (2)	1.71 (2)	2.4608 (16)	159 (3)
O13—H131⋯O3^v	0.80 (3)	1.79 (3)	2.5728 (16)	165 (2)
O13—H132⋯O9^vi	0.89 (2)	1.62 (2)	2.5044 (16)	174 (2)
O14—H141⋯O3^vii	0.79 (2)	1.96 (2)	2.7220 (16)	162 (2)
O14—H142⋯O11^viii	0.80 (3)	1.90 (3)	2.6911 (17)	171 (3)
O15—H151⋯O4^ix	0.82 (3)	2.18 (3)	2.9904 (18)	169 (3)
O15—H152⋯O6^iv	0.79 (2)	1.97 (2)	2.7504 (17)	176 (3)
O16—H161⋯O14^ix	0.76 (3)	2.19 (3)	2.8534 (16)	147 (3)
O16—H162⋯O8^x	0.87 (3)	2.48 (3)	3.0109 (17)	120 (2)
O16—H162⋯O2	0.87 (3)	2.62 (3)	3.1809 (16)	123 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+1, z]$ ; (ii) $[x-{\script{1\over 2}}, -y, z]$ ; (iii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iv) x, y+1, z; (v) $[x+{\script{1\over 2}}, -y, z]$ ; (vi) $[-x+{\script{1\over 2}}, y-1, z-{\script{1\over 2}}]$ ; (vii) $[-x+1, -y+1, z+{\script{1\over 2}}]$ ; (viii) $[x+{\script{1\over 2}}, -y+2, z]$ ; (ix) $[x-{\script{1\over 2}}, -y+1, z]$ ; (x) x, y-1, z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810000930/hg2625sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000930/hg2625Isup2.hkl

checkCIF report

Comment top

During the last decade, there has been a growing interest in the study of organic diphosphonic acids owing to their potentially very powerful chelating properties used in metal extractions and are tested by the pharmaceutical industry for use as efficient drugs preventing calcification and inhibiting bone resorption (Matczak-Jon & Videnova-Adrabinska, 2005). Diphosphonic acids and their metal complexes are used in the treatment of Pagets disease, osteoporosis and tumoral osteolysis (Szabo et al., 2002). Also in the last years, there has been a surge of interest in palladium complexes as a perspective antitumor preparation (Curic et al., 1996).

The title compound crystallized in non-centrosymmetric space group Pca2₁ with Flack parameter equal 0.362 (11), which indicate the presence of racemic twin in the structure (Flack, 1983). The asymmetric unit of title compound contains one formula unit, which exists as a complex anion and oxonium cation, which are bonding together via strong H-bond (Fig.1, Table 1). The Pd atom occupies a position on the pseudo twofold axis and shows slightly distorted square-planar coordination environment, which consists of O atoms from two phosphonic groups and two N atoms of amino group, located in cis position. The crystal structure displays N—H···O and O—H···O hydrogen bonding, which creates a three-dimensional network (Table 1, Fig.2). Hydrogen bonds often play a dominant role in crystal engineering (Matczak-Jon & Videnova-Adrabinska, 2005) because they combine the desirable attributes of specificity, strength and directionality.

Related literature top

For general background and the medical use of organic diphosphonic acids, see: Matczak-Jon & Videnova-Adrabinska (2005); Curic et al. (1996); Szabo et al. (2002). For related structures, see: Shkol'nikova et al. (1991).

Experimental top

Aqueous solution of AgNO₃ (0,4076 g, 0,24 mmol) was added to the solution of PdCl₂ (0,063 g, 0,6 mmol) in 12 ml of hydrochloric acid. The solution was stirred at 3–4 °C and protected from light for 30 min. The AgCl precipitated and was filtered off. The dark red solution turned yellow and than 1-aminoethane-1,1-diyldiphosphonic acid (0,2459 g, 0,12 mmol) was added in one portion. The solution was stirred for 1 h at 3–4 °C and left staying overnight at room temperature. The solvent was removed under reduced pressure leaving a pale yellow solid, which was washed twice with methanol and diethyl ether and dried under vacuum. Suitable single crystals of title compound were produced by slow evaporation of a water solution at room temperature. A pale yellow rectangular crystal was used for data collection.

Structure description top

For general background and the medical use of organic diphosphonic acids, see: Matczak-Jon & Videnova-Adrabinska (2005); Curic et al. (1996); Szabo et al. (2002). For related structures, see: Shkol'nikova et al. (1991).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 top

	Fig. 1. The title compound showing 50% probability displacement ellipsoids for the non-H atoms. Dashed lines indicate hydrogen bonds.
	Fig. 2. Crystal packing of title compound, projection down the b axis. Dashed lines indicate hydrogen bonds.

Oxonium (dihydrogen 1-aminoethane-1,1-diyldiphosphonato-κ²N,O)[hydrogen (1-amino-1-phosphonoethyl)phosphonato-κ²N,O]palladium(II) trihydrate top

Crystal data top

(H₃O)[Pd(C₂H₇NO₆P₂)(C₂H₈NO₆P₂)]·3H₂O	D_x = 2.165 Mg m⁻³
M_r = 586.53	Melting point: 542 K
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 9199 reflections
a = 9.9412 (2) Å	θ = 3.0–30.7°
b = 9.0941 (2) Å	µ = 1.47 mm⁻¹
c = 19.9004 (3) Å	T = 100 K
V = 1799.12 (6) Å³	Prism, yellow
Z = 4	0.48 × 0.29 × 0.14 mm
F(000) = 1184

Data collection top

Bruker APEXII CCD diffractometer	5568 independent reflections
Radiation source: fine-focus sealed tube	5545 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
Detector resolution: 8.26 pixels mm^-1	θ_max = 30.7°, θ_min = 2.1°
φ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −13→13
T_min = 0.536, T_max = 0.823	l = −28→28
53680 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.015	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.0254P)² + 0.6821P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
5568 reflections	Δρ_max = 0.80 e Å⁻³
301 parameters	Δρ_min = −0.61 e Å⁻³
6 restraints	Absolute structure: racemic twin (Flack, 1983), with how many Friedel pairs?
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.362 (11)

Crystal data top

(H₃O)[Pd(C₂H₇NO₆P₂)(C₂H₈NO₆P₂)]·3H₂O	V = 1799.12 (6) Å³
M_r = 586.53	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 9.9412 (2) Å	µ = 1.47 mm⁻¹
b = 9.0941 (2) Å	T = 100 K
c = 19.9004 (3) Å	0.48 × 0.29 × 0.14 mm

Data collection top

Bruker APEXII CCD diffractometer	5568 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	5545 reflections with I > 2σ(I)
T_min = 0.536, T_max = 0.823	R_int = 0.027
53680 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.015	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.041	Δρ_max = 0.80 e Å⁻³
S = 1.09	Δρ_min = −0.61 e Å⁻³
5568 reflections	Absolute structure: racemic twin (Flack, 1983), with how many Friedel pairs?
301 parameters	Absolute structure parameter: 0.362 (11)
6 restraints

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

	x	y	z	U_iso*/U_eq
Pd1	0.277544 (8)	0.490311 (10)	0.552262 (8)	0.00533 (3)
P1	0.18198 (3)	0.27187 (4)	0.450244 (18)	0.00635 (6)
P2	0.45406 (3)	0.13836 (4)	0.414989 (18)	0.00657 (6)
P3	0.18727 (3)	0.72538 (4)	0.648914 (17)	0.00648 (6)
P4	0.46193 (3)	0.80633 (4)	0.704329 (19)	0.00694 (6)
C1	0.36318 (13)	0.30710 (15)	0.43864 (7)	0.0064 (2)
C2	0.37971 (15)	0.42927 (16)	0.38612 (7)	0.0101 (2)
H2A	0.3247	0.5142	0.3990	0.015*
H2B	0.3506	0.3930	0.3421	0.015*
H2C	0.4744	0.4587	0.3838	0.015*
C3	0.35636 (14)	0.65907 (15)	0.67191 (7)	0.0068 (2)
C4	0.34278 (15)	0.53574 (17)	0.72415 (7)	0.0107 (2)
H4A	0.2757	0.4642	0.7088	0.016*
H4B	0.3142	0.5777	0.7672	0.016*
H4C	0.4298	0.4866	0.7298	0.016*
N1	0.41461 (12)	0.36316 (14)	0.50470 (6)	0.0071 (2)
H11N	0.488 (2)	0.403 (3)	0.4966 (12)	0.009*
H12N	0.429 (2)	0.295 (3)	0.5263 (11)	0.009*
N2	0.41624 (12)	0.59683 (14)	0.60867 (6)	0.0071 (2)
H21N	0.487 (2)	0.545 (3)	0.6173 (12)	0.009*
H22N	0.447 (2)	0.661 (3)	0.5861 (11)	0.009*
O1	0.13407 (10)	0.40368 (12)	0.49205 (5)	0.00857 (18)
O2	0.17592 (11)	0.13034 (12)	0.49408 (6)	0.0109 (2)
H2O	0.121 (2)	0.072 (2)	0.4877 (12)	0.016*
O3	0.11271 (12)	0.25861 (13)	0.38397 (6)	0.0100 (2)
O4	0.59246 (11)	0.19312 (13)	0.38559 (6)	0.0108 (2)
H4O	0.595 (2)	0.180 (3)	0.3495 (13)	0.016*
O5	0.37046 (11)	0.06419 (12)	0.36199 (5)	0.01071 (19)
H133	0.379 (2)	−0.084 (3)	0.3421 (12)	0.016*
O6	0.48312 (10)	0.05260 (13)	0.47795 (6)	0.00955 (19)
O7	0.13394 (10)	0.60237 (12)	0.60317 (5)	0.00854 (19)
O8	0.20867 (11)	0.86805 (13)	0.60679 (6)	0.0109 (2)
H8O	0.238 (2)	0.846 (3)	0.5705 (9)	0.016*
O9	0.10146 (11)	0.75447 (13)	0.70822 (6)	0.0119 (2)
O10	0.50545 (12)	0.90097 (12)	0.64312 (6)	0.01182 (19)
H10O	0.470 (3)	0.982 (3)	0.6345 (16)	0.018*
O11	0.38539 (11)	0.88643 (13)	0.75747 (5)	0.01041 (19)
O12	0.58885 (11)	0.72475 (14)	0.72731 (6)	0.0118 (2)
H12O	0.649 (2)	0.778 (3)	0.7377 (12)	0.018*
O13	0.38258 (11)	−0.19735 (12)	0.33187 (5)	0.00984 (19)
H131	0.447 (3)	−0.227 (3)	0.3520 (13)	0.015*
H132	0.382 (2)	−0.212 (3)	0.2878 (12)	0.015*
O14	0.80746 (11)	0.83022 (13)	0.75959 (5)	0.01002 (18)
H141	0.813 (2)	0.801 (2)	0.7968 (9)	0.015*
H142	0.822 (3)	0.917 (3)	0.7586 (12)	0.015*
O15	0.30815 (12)	0.81984 (13)	0.49016 (6)	0.0136 (2)
H151	0.257 (3)	0.820 (3)	0.4577 (13)	0.020*
H152	0.356 (2)	0.888 (2)	0.4850 (13)	0.020*
O16	0.37176 (13)	0.14546 (13)	0.62029 (6)	0.0138 (2)
H161	0.376 (3)	0.179 (3)	0.6551 (13)	0.021*
H162	0.287 (3)	0.126 (3)	0.6135 (13)	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.00476 (4)	0.00531 (4)	0.00592 (4)	0.00017 (3)	−0.00038 (4)	−0.00138 (4)
P1	0.00546 (15)	0.00627 (15)	0.00734 (15)	0.00002 (11)	−0.00077 (11)	−0.00155 (12)
P2	0.00633 (13)	0.00681 (15)	0.00657 (14)	0.00094 (11)	−0.00007 (11)	−0.00088 (12)
P3	0.00557 (14)	0.00721 (15)	0.00667 (15)	0.00051 (11)	0.00001 (11)	−0.00196 (12)
P4	0.00715 (14)	0.00637 (15)	0.00732 (14)	−0.00025 (11)	−0.00118 (11)	−0.00102 (12)
C1	0.0067 (5)	0.0059 (5)	0.0066 (5)	−0.0002 (4)	−0.0007 (4)	−0.0005 (4)
C2	0.0112 (6)	0.0077 (6)	0.0114 (6)	0.0000 (5)	0.0000 (5)	0.0017 (5)
C3	0.0083 (5)	0.0057 (5)	0.0064 (5)	0.0000 (4)	−0.0004 (4)	−0.0008 (4)
C4	0.0113 (6)	0.0111 (6)	0.0098 (6)	−0.0008 (5)	−0.0014 (5)	0.0030 (5)
N1	0.0056 (5)	0.0080 (5)	0.0078 (5)	0.0005 (4)	−0.0012 (4)	−0.0016 (4)
N2	0.0063 (5)	0.0073 (5)	0.0077 (5)	−0.0007 (4)	0.0001 (4)	−0.0017 (4)
O1	0.0051 (4)	0.0104 (5)	0.0102 (4)	0.0008 (3)	−0.0014 (3)	−0.0049 (4)
O2	0.0090 (4)	0.0095 (5)	0.0141 (5)	−0.0031 (4)	−0.0020 (4)	0.0026 (4)
O3	0.0075 (4)	0.0135 (5)	0.0092 (5)	0.0005 (4)	−0.0027 (3)	−0.0034 (4)
O4	0.0082 (4)	0.0152 (5)	0.0089 (5)	−0.0004 (4)	0.0031 (3)	−0.0006 (4)
O5	0.0125 (5)	0.0090 (5)	0.0106 (5)	0.0019 (4)	−0.0032 (4)	−0.0029 (4)
O6	0.0101 (5)	0.0085 (5)	0.0101 (5)	0.0021 (4)	−0.0002 (3)	0.0009 (4)
O7	0.0063 (4)	0.0100 (5)	0.0093 (5)	0.0008 (3)	−0.0003 (3)	−0.0042 (4)
O8	0.0127 (5)	0.0082 (5)	0.0119 (5)	0.0009 (3)	−0.0006 (4)	0.0011 (4)
O9	0.0088 (4)	0.0175 (5)	0.0094 (5)	0.0016 (4)	0.0021 (4)	−0.0047 (4)
O10	0.0136 (5)	0.0086 (5)	0.0133 (5)	−0.0024 (4)	0.0032 (4)	0.0017 (4)
O11	0.0127 (5)	0.0089 (5)	0.0096 (4)	0.0021 (4)	−0.0006 (4)	−0.0024 (4)
O12	0.0089 (5)	0.0097 (5)	0.0167 (5)	0.0004 (4)	−0.0051 (4)	−0.0018 (4)
O13	0.0093 (4)	0.0108 (5)	0.0094 (5)	0.0009 (4)	−0.0020 (4)	−0.0014 (4)
O14	0.0100 (4)	0.0101 (5)	0.0099 (5)	−0.0014 (4)	−0.0005 (4)	0.0007 (4)
O15	0.0148 (5)	0.0129 (5)	0.0131 (5)	−0.0017 (4)	0.0014 (4)	0.0033 (4)
O16	0.0180 (5)	0.0133 (5)	0.0101 (5)	−0.0017 (4)	−0.0008 (4)	−0.0002 (4)

Geometric parameters (Å, º) top

Pd1—N1	2.0223 (12)	C3—N2	1.5028 (18)
Pd1—O1	2.0226 (10)	C3—C4	1.535 (2)
Pd1—N2	2.0247 (12)	C4—H4A	0.9800
Pd1—O7	2.0256 (10)	C4—H4B	0.9800
P1—O3	1.4926 (12)	C4—H4C	0.9800
P1—O1	1.5349 (11)	N1—H11N	0.83 (2)
P1—O2	1.5560 (12)	N1—H12N	0.77 (2)
P1—C1	1.8442 (14)	N2—H21N	0.86 (2)
P2—O5	1.5027 (11)	N2—H22N	0.80 (2)
P2—O6	1.5039 (12)	O2—H2O	0.774 (16)
P2—O4	1.5759 (11)	O4—H4O	0.73 (3)
P2—C1	1.8418 (14)	O5—H133	1.40 (3)
P3—O9	1.4801 (12)	O8—H8O	0.805 (16)
P3—O7	1.5366 (11)	O10—H10O	0.83 (3)
P3—O8	1.5593 (12)	O12—H12O	0.791 (17)
P3—C3	1.8435 (14)	O13—H133	1.06 (2)
P4—O11	1.4926 (11)	O13—H131	0.80 (3)
P4—O12	1.5335 (12)	O13—H132	0.89 (2)
P4—O10	1.5530 (12)	O14—H141	0.788 (16)
P4—C3	1.8196 (14)	O14—H142	0.80 (3)
C1—N1	1.4998 (18)	O15—H151	0.82 (3)
C1—C2	1.5342 (19)	O15—H152	0.785 (16)
C2—H2A	0.9800	O16—H161	0.76 (3)
C2—H2B	0.9800	O16—H162	0.87 (3)
C2—H2C	0.9800

N1—Pd1—O1	88.58 (5)	H2A—C2—H2C	109.5
N1—Pd1—N2	94.26 (5)	H2B—C2—H2C	109.5
O1—Pd1—N2	174.28 (5)	N2—C3—C4	109.07 (11)
N1—Pd1—O7	175.31 (5)	N2—C3—P4	110.22 (9)
O1—Pd1—O7	89.73 (4)	C4—C3—P4	110.38 (9)
N2—Pd1—O7	87.82 (5)	N2—C3—P3	106.05 (9)
O3—P1—O1	113.50 (6)	C4—C3—P3	109.08 (10)
O3—P1—O2	114.25 (7)	P4—C3—P3	111.91 (7)
O1—P1—O2	109.28 (6)	C3—C4—H4A	109.5
O3—P1—C1	110.74 (6)	C3—C4—H4B	109.5
O1—P1—C1	103.61 (6)	H4A—C4—H4B	109.5
O2—P1—C1	104.58 (6)	C3—C4—H4C	109.5
O5—P2—O6	117.27 (7)	H4A—C4—H4C	109.5
O5—P2—O4	111.35 (7)	H4B—C4—H4C	109.5
O6—P2—O4	107.79 (6)	C1—N1—Pd1	112.02 (8)
O5—P2—C1	106.38 (6)	C1—N1—H11N	106.1 (16)
O6—P2—C1	108.26 (6)	Pd1—N1—H11N	115.9 (16)
O4—P2—C1	105.06 (6)	C1—N1—H12N	106.4 (17)
O9—P3—O7	113.81 (6)	Pd1—N1—H12N	108.9 (17)
O9—P3—O8	111.01 (7)	H11N—N1—H12N	107 (2)
O7—P3—O8	109.53 (6)	C3—N2—Pd1	112.01 (8)
O9—P3—C3	112.71 (6)	C3—N2—H21N	111.1 (16)
O7—P3—C3	102.92 (6)	Pd1—N2—H21N	113.9 (16)
O8—P3—C3	106.34 (6)	C3—N2—H22N	110.5 (16)
O11—P4—O12	116.37 (6)	Pd1—N2—H22N	107.3 (16)
O11—P4—O10	115.30 (7)	H21N—N2—H22N	101 (2)
O12—P4—O10	105.83 (7)	P1—O1—Pd1	113.98 (6)
O11—P4—C3	108.45 (7)	P1—O2—H2O	120.4 (18)
O12—P4—C3	102.96 (7)	P2—O4—H4O	110.0 (19)
O10—P4—C3	106.88 (6)	P2—O5—H133	126.4 (10)
N1—C1—C2	108.33 (11)	P3—O7—Pd1	114.80 (6)
N1—C1—P2	109.88 (9)	P3—O8—H8O	108.8 (17)
C2—C1—P2	112.13 (9)	P4—O10—H10O	122 (2)
N1—C1—P1	106.40 (9)	P4—O12—H12O	113.7 (19)
C2—C1—P1	108.40 (9)	H133—O13—H131	105 (2)
P2—C1—P1	111.49 (7)	H133—O13—H132	110 (2)
C1—C2—H2A	109.5	H131—O13—H132	116 (2)
C1—C2—H2B	109.5	H141—O14—H142	110 (2)
H2A—C2—H2B	109.5	H151—O15—H152	106 (3)
C1—C2—H2C	109.5	H161—O16—H162	106 (3)

O5—P2—C1—N1	162.48 (9)	O7—P3—C3—N2	42.06 (10)
O6—P2—C1—N1	35.62 (11)	O8—P3—C3—N2	−73.07 (10)
O4—P2—C1—N1	−79.34 (10)	O9—P3—C3—C4	47.74 (11)
O5—P2—C1—C2	−76.99 (11)	O7—P3—C3—C4	−75.28 (10)
O6—P2—C1—C2	156.15 (10)	O8—P3—C3—C4	169.59 (9)
O4—P2—C1—C2	41.19 (11)	O9—P3—C3—P4	−74.69 (9)
O5—P2—C1—P1	44.78 (9)	O7—P3—C3—P4	162.28 (7)
O6—P2—C1—P1	−82.09 (8)	O8—P3—C3—P4	47.16 (9)
O4—P2—C1—P1	162.95 (7)	C2—C1—N1—Pd1	80.78 (11)
O3—P1—C1—N1	163.27 (9)	P2—C1—N1—Pd1	−156.42 (6)
O1—P1—C1—N1	41.23 (10)	P1—C1—N1—Pd1	−35.59 (11)
O2—P1—C1—N1	−73.22 (10)	O1—Pd1—N1—C1	17.73 (10)
O3—P1—C1—C2	46.95 (11)	N2—Pd1—N1—C1	−157.30 (10)
O1—P1—C1—C2	−75.08 (10)	C4—C3—N2—Pd1	79.72 (12)
O2—P1—C1—C2	170.47 (9)	P4—C3—N2—Pd1	−158.94 (6)
O3—P1—C1—P2	−76.95 (9)	P3—C3—N2—Pd1	−37.63 (10)
O1—P1—C1—P2	161.02 (7)	N1—Pd1—N2—C3	−156.26 (9)
O2—P1—C1—P2	46.57 (8)	O7—Pd1—N2—C3	19.52 (9)
O11—P4—C3—N2	167.68 (9)	O3—P1—O1—Pd1	−148.99 (7)
O12—P4—C3—N2	−68.45 (10)	O2—P1—O1—Pd1	82.21 (7)
O10—P4—C3—N2	42.79 (11)	C1—P1—O1—Pd1	−28.83 (8)
O11—P4—C3—C4	−71.76 (11)	N1—Pd1—O1—P1	10.10 (7)
O12—P4—C3—C4	52.11 (11)	O7—Pd1—O1—P1	−165.52 (7)
O10—P4—C3—C4	163.35 (10)	O9—P3—O7—Pd1	−150.89 (7)
O11—P4—C3—P3	49.93 (9)	O8—P3—O7—Pd1	84.19 (7)
O12—P4—C3—P3	173.79 (7)	C3—P3—O7—Pd1	−28.61 (8)
O10—P4—C3—P3	−74.96 (9)	O1—Pd1—O7—P3	−165.75 (7)
O9—P3—C3—N2	165.08 (9)	N2—Pd1—O7—P3	9.09 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O1ⁱ	0.83 (2)	2.28 (2)	3.0527 (16)	154 (2)
N1—H12N···O16	0.77 (2)	2.38 (2)	3.0647 (18)	149 (2)
N2—H21N···O7ⁱ	0.86 (2)	2.01 (2)	2.8245 (17)	159 (2)
N2—H22N···O10	0.80 (2)	2.53 (2)	2.9844 (17)	117.7 (19)
O2—H2O···O6ⁱⁱ	0.77 (2)	1.79 (2)	2.5582 (15)	174 (3)
O4—H4O···O11ⁱⁱⁱ	0.73 (3)	1.94 (3)	2.6593 (16)	170 (3)
O13—H133···O5	1.06 (2)	1.40 (3)	2.4558 (16)	174 (2)
O8—H8O···O15	0.81 (2)	1.76 (2)	2.5607 (17)	173 (3)
O10—H10O···O16^iv	0.83 (3)	1.80 (3)	2.6298 (17)	172 (3)
O12—H12O···O14	0.79 (2)	1.71 (2)	2.4608 (16)	159 (3)
O13—H131···O3^v	0.80 (3)	1.79 (3)	2.5728 (16)	165 (2)
O13—H132···O9^vi	0.89 (2)	1.62 (2)	2.5044 (16)	174 (2)
O14—H141···O3^vii	0.79 (2)	1.96 (2)	2.7220 (16)	162 (2)
O14—H142···O11^viii	0.80 (3)	1.90 (3)	2.6911 (17)	171 (3)
O15—H151···O4^ix	0.82 (3)	2.18 (3)	2.9904 (18)	169 (3)
O15—H152···O6^iv	0.79 (2)	1.97 (2)	2.7504 (17)	176 (3)
O16—H161···O14^ix	0.76 (3)	2.19 (3)	2.8534 (16)	147 (3)
O16—H162···O8^x	0.87 (3)	2.48 (3)	3.0109 (17)	120 (2)
O16—H162···O2	0.87 (3)	2.62 (3)	3.1809 (16)	123 (2)

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

Experimental details

Crystal data
Chemical formula	(H₃O)[Pd(C₂H₇NO₆P₂)(C₂H₈NO₆P₂)]·3H₂O
M_r	586.53
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	100
a, b, c (Å)	9.9412 (2), 9.0941 (2), 19.9004 (3)
V (Å³)	1799.12 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.47
Crystal size (mm)	0.48 × 0.29 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.536, 0.823
No. of measured, independent and observed [I > 2σ(I)] reflections	53680, 5568, 5545
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.719

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.015, 0.041, 1.09
No. of reflections	5568
No. of parameters	301
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)	0.80, −0.61
Absolute structure	Racemic twin (Flack, 1983), with how many Friedel pairs?
Absolute structure parameter	0.362 (11)

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11N···O1ⁱ	0.83 (2)	2.28 (2)	3.0527 (16)	154 (2)
N1—H12N···O16	0.77 (2)	2.38 (2)	3.0647 (18)	149 (2)
N2—H21N···O7ⁱ	0.86 (2)	2.01 (2)	2.8245 (17)	159 (2)
N2—H22N···O10	0.80 (2)	2.53 (2)	2.9844 (17)	117.7 (19)
O2—H2O···O6ⁱⁱ	0.774 (16)	1.787 (17)	2.5582 (15)	174 (3)
O4—H4O···O11ⁱⁱⁱ	0.73 (3)	1.94 (3)	2.6593 (16)	170 (3)
O13—H133···O5	1.06 (2)	1.40 (3)	2.4558 (16)	174 (2)
O8—H8O···O15	0.805 (16)	1.760 (16)	2.5607 (17)	173 (3)
O10—H10O···O16^iv	0.83 (3)	1.80 (3)	2.6298 (17)	172 (3)
O12—H12O···O14	0.791 (17)	1.707 (18)	2.4608 (16)	159 (3)
O13—H131···O3^v	0.80 (3)	1.79 (3)	2.5728 (16)	165 (2)
O13—H132···O9^vi	0.89 (2)	1.62 (2)	2.5044 (16)	174 (2)
O14—H141···O3^vii	0.788 (16)	1.961 (17)	2.7220 (16)	162 (2)
O14—H142···O11^viii	0.80 (3)	1.90 (3)	2.6911 (17)	171 (3)
O15—H151···O4^ix	0.82 (3)	2.18 (3)	2.9904 (18)	169 (3)
O15—H152···O6^iv	0.785 (16)	1.967 (17)	2.7504 (17)	176 (3)
O16—H161···O14^ix	0.76 (3)	2.19 (3)	2.8534 (16)	147 (3)
O16—H162···O8^x	0.87 (3)	2.48 (3)	3.0109 (17)	120 (2)
O16—H162···O2	0.87 (3)	2.62 (3)	3.1809 (16)	123 (2)

References

Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Curic, M., Tusek-Bozic, L., Vikic-Topic, D., Scarcia, V., Furlani, A., Balzarini, J. & Clercq, E. (1996). J. Inorg. Biochem. 63, 125–142. CrossRef CAS PubMed Web of Science Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Matczak-Jon, E. & Videnova-Adrabinska, V. (2005). Coord. Chem. Rev. 249, 2458–2488. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shkol'nikova, L. M., Porai-Koshits, M. A., Fundamenskii, V. S., Poznyak, A. L. & Kalugina, E. V. (1991). Koord. Khim. 17, 954–963 CAS Google Scholar
Szabo, Ch. M., Martin, M. B. & Oldfield, E. (2002). J. Med. Chem. 45, 2894–2903. Web of Science CSD CrossRef PubMed CAS Google Scholar
Westrip, S. P. (2010). publCIF. In preparation. Google Scholar

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Volume 66| Part 2| February 2010| Pages m170-m171

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