One- and two-dimensional Cd^II coordination polymers incorporating organophosphinate ligands

Reaction of cadmium nitrate with di­phenyl­phosphinic acid in di­methyl­formamide solvent yielded the one-dimensional coordination polymer catena-poly[[bis­(di­methyl­formamide-κO)cadmium(II)]-bis­(μ-di­phenyl­phosphinato-κ²O:O′)], [Cd(C₁₂H₁₀O₂P)₂(C₃H₇NO)₂]_n, (I). Addition of 4,4′-bi­pyridine to the synthesis afforded a two-dimensional extended structure, poly[[­(μ-4,4′-bi­pyridine-κ²N:N′)bis­(μ-di­phenyl­phos­phinato-κ²O:O′)cadmium(II)] di­methyl­formamide monosolvate], {[Cd(C₁₂H₁₀O₂P)₂(C₁₀H₈N₂)]·C₃H₇NO}_n, (II). In (II), the 4,4′-bi­pyridine mol­ecules link the Cd^II centers in the crystallographic a direction, while the phosphinate ligands link the Cd^II centers in the crystallographic b direction to complete a two-dimensional sheet structure. Consideration of additional π–π inter­actions of the phenyl rings in (II) produces a three-dimensional structure with channels that encapsulate di­methyl­formamide mol­ecules as solvent of crystallization. Both compounds were characterized by single-crystal X-ray diffraction and FT–IR analysis.

S1. Introduction

In the field of hybrid materials, coordination polymers have garnered much inter­est in recent decades. The structural diversity of this class of materials makes them attractive for a variety of potential applications that include small-molecule storage, optics, and separation science (Furukawa et al., 2013, and references therein; Czaja et al., 2009; Dinča & Long, 2008). The seemingly endless combination of metal ions and organic molecules has created a vast array of structural topologies (Li et al., 2014; Stock & Biswas, 2012; Zhao et al., 2011). By far, the most common systems that have been investigated are metal carboxyl­ates (ror selected reviews, see Farha & Hupp, 2010; Horike & Kitagawa, 2011; Tranchemontagne et al., 2009; James, 2003).

In order to recognize the full potential of this exciting field, extensions to other classes of organic molecules have been explored. While such classes have varied, largely speaking, phospho­nates and sulfonates have received the most attention. In general, sulfonates tend to show relatively weak coordination to metals and therefore lead to structures with less than desirable materials applications such as low thermal stability and a lack of porosity (Côte & Shimizu, 2003; Videnova-Adrabinska, 2007). Phospho­nates have been used for robust crystalline materials that are capable of being characterized by single-crystal X-ray diffraction (Liang & Shimizu, 2007; Konar et al., 2007; Clearfield, 2008). Challenges with phospho­nate chemistry historically have included rapid precipitation due to the formation of dense, layered phases which often form intra­cta­ble solids that are difficult to characterize. Furthermore, compared to carboxyl­ates, phospho­nates offer many more bridging modes to metals, making the establishment of structural motifs for the design of specific materials less predi­cta­ble (Shimizu et al., 2009).

Our inter­est lies in exploring phosphinates (R₂PO₂^-) as less conventional organic linker molecules that could be useful in the synthesis of coordination polymers. Relative to the classes of materials discussed previously, less attention has been given to phosphinates in extended materials (Al-Shboul et al., 2012; Rood et al., 2014). Compared to metal phospho­nates, the acid–base chemistry of metal phosphinates may more closely resemble that of metal carboxyl­ates. Such behavior could lead to precipitation rates that are slower than that of metal phospho­nates and off a route to isolating new materials that can be more readily characterized by single-crystal X-ray diffraction. The structures of metal di­phenyl­phosphinate compounds have been well studied for copper (Bino & Sassman, 1987), nickel (Annan et al., 1991), and manganese (Ruettinger et al., 1999; Du et al., 1991). Orlandini and co-workers have expanded the area to include studies on diphosphinates with transition metals (Costantino, Ienco et al., 2008; Bataille et al., 2008; Costantino Midollini & Orlandini, 2008; Midollini & Orlandini, 2006; Ciattini et al., 2005; Midollini et al., 2004; Cecconi et al., 2004; Berti et al., 2002) and p-block metals (Cecconi et al., 2003; Beckman et al., 2004, 2005). As part of our investigations in this area, we isolated one- and two-dimensional cadmium(II) coordination polymers incorporating di­phenyl­phosphinate ligands. We report here on the synthesis and crystal structures of [Cd(O₂PPh₂)(DMF)₂]_n (DMF is di­methyl­formamide), (I), and {[Cd(O₂PPh₂)(bipy)].DMF}_n (bipy is 4,4'-bi­pyridine), (II).

S2. Experimental

Cadmium nitrate tetra­hydrate and di­methyl­formamide were obtained commercially and used as received. Di­phenyl­phosphinic acid (99%) was purchased from Alfa Aesar and used without further purification. IR spectra were obtained on a Nicolet Magna 760 FT–IR spectrometer. Reported yields are based on the first crop of crystals that were isolated from the reaction solution.

S2.1. Synthesis and crystallization

S2.1.1. Preparation [Cd(O₂PPh₂)₂(DMF)₂], (I)

A capped vial containing Cd(NO₃)₂.4H₂O (77 mg, 0.25 mmol) and di­phenyl­phosphinic acid (109 mg, 0.5 mmol) dissolved in DMF (5 ml) was heated without stirring at 333 K for 3 d resulting in a colorless solution. The vial was transferred to a 278 K refrigerator for 2 d, resulting in the formation of colorless crystals (yield 0.043 g, 25% based on Cd). IR (KBr pellet, ν, cm^-1): 3563 (w), 3388 (m), 3047 (w), 2941 (w), 1676 (m), 1604 (s), 1535 (m), 1485 (w), 1436 (m), 1414 (m), 1385 (w), 1345 (w), 1318 (w), 1221 (w), 1180 (s), 1129 (s), 1052 (s), 1024 (w), 991 (w), 942 (w), 910 (m), 867 (w), 809 (m), 754 (m), 721 (s), 698 (s).

S2.1.2. Preparation [Cd(O₂PPh₂)₂(bipy)].DMF, (II)

Cd(NO₃)₂.4H₂O (77 mg, 0.25 mmol), di­phenyl­phosphinic acid (109 mg, 0.5 mmol) and 4,4'-bi­pyridine (40 mg, 0.25 mmol) were added to a vial, along with DMF (10 ml). The vial was capped and heated to 333 K in a silicone oil bath for 7 d, during which time pale-pink crystals deposited on the walls of the vial (yield 0.103 g, 53% yield based on Cd). IR (KBr pellet, ν, cm^-1): 3050 (w), 3006 (w), 2925 (w), 2359 (m), 2343 (m), 2179 (s), 1647 (s), 1485 (w), 1437 (s), 1417 (w), 1391 (s), 1314 (w), 1261 (w), 1192 (s), 1161 (m), 1131 (s), 1052 (s), 1023 (s), 998 (m), 925 (w), 756 (m), 723 (s), 696 (s), 677 (m).

S2.2. Crystallography and refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. Crystals were mounted on MiTeGen loops at 150 K using Paratone-N oil. Data were collected using a combination of ω and ϕ scans. Compound (I) was examined on a Bruker APEXII instrument. A data collection strategy requiring a minimum of fourfold redundancy was employed. Due to the diminutive size of the crystals of compound (II), intensity data were collected at 150 K on a D8 goniostat equipped with a Bruker APEXII CCD detector at Beamline 11.3.1 at the Advanced Light Source (Lawrence Berkeley National Laboratory) using synchrotron radiation tuned to λ = 0.77490 Å. For data collection, frames were measured for a duration of 1 s at 0.3° inter­vals of ω with a maximum 2θ value of ~60°. The data frames were collected using the program APEX2 (Bruker, 2010) and processed using the program SAINT routine within APEX2. The data were corrected for absorption and beam corrections based on the multi-scan technique as implemented in SADABS. For compound (II), anomalous dispersion factors were calculated using the method of Brennan and Cowan in PLATON (Brennan & Cowan, 1992; Spek, 2009).

The structures of (I) and (II) were solved from partial data sets using the Autostructure option in APEX2 (Bruker, 2010). This option employs direct methods, Patterson synthesis and dual space routines of SHELXTL (Sheldrick, 2008a). H atoms were placed at calculated positions with U_iso(H) values set at 1.5U_eq(C) for methyl groups or at 1.2U_eq(C) otherwise. All crystallographic details are available in Table 1.

In the refinement of compound (I), the ratio of maximum to minimum electron density was 5.94. A three-electron peak resides at 1.75 Å from atom O1. Upon examination, there is possible twinning in the crystal that cannot be excised into separate components because the reflections are too close to the primary component. Reintegration of the data did not improve this and the structure solution is reported as such.

Both structures are achiral, however solutions in acentric space-group options yielded chemically reasonable models which fit better to the data. Similarly, an alternative potential space group of Pcca for (II) was abandoned because of poorer fit as opposed to the reported space group. Analysis of intensities of Friedel pairs of reflections through Flack's methodology (Parsons et al., 2013) and Hooft's Bayesian analysis (Hooft et al., 2008) also support the choice of acentric space groups. For (I), the null value with low errors, the Flack x parameter is 0.04 (2) and the Hooft y parameter is 0.04 (2), is indicative of the correct assignment of handedness. For (II), the fractional, but not half, value with low errors, the Flack x parameter = 0.30 (4) and the Hooft y parameter = 0.29 (2), is suggestive of racemic twinning.

S3. Results and discussion

S3.1. Synthesis and spectroscopy

Compounds (I) and (II) were prepared by the reaction of cadmium nitrate and the appropriate organic linker molecules. The compounds were crystallized from DMF solutions. The IR spectrum of each compound is consistent with the proposed formulations provided previously. In both compounds, strong P—O stretches from the phosphinate ligands were evident near 1200 cm^-1. In (I), the C═ O stretch from the DMF ligands was observed at 1604 cm^-1. Compound (II) displayed appropriate aryl stretches near 3000 cm^-1 from 4,4'-bi­pyridine, as well as additional strong stretches at 1647, 1437, and 696 cm^-1 resulting from this ligand.

S3.2. Crystal structure of [Cd(O₂PPh₂)₂(DMF)₂], (I)

As shown in Fig. 1, the structure of (I) revealed a one-dimensional chain motif that runs parallel to the crystallographic c axis. The compound crystallized in the monoclinic space group P2₁. Throughout the structure, the Cd^II centers reside in pseudo-o­cta­hedral geometries and are connected together by a single type of phosphinate bridging mode. A Cd—O—P—O—Cd motif is displayed throughout the chain. The o­cta­hedral geometry results from contacts to four O atoms from four separate phosphinate ligands plus two O atoms from two DMF ligands. The Cd—O bond lengths are in the range 2.236 (6)–2.323 (6) Å. The trans-O—Cd—O bond angles range from 174.3 (3) to 179.2 (3)°, while the cis-O—Cd—O angles range from 84.1 (3) to 95.3 (2)°. A complete list of bond lengths and angles involving the Cd^II centers is given in Table 2.

In an attempt to isolate a higher dimensionality structure using the di­phenyl­phosphinate anion, we employed a similar synthesis as described for (I) and added one equivalent of 4,4'-bi­pyridine. By displacing the DMF molecules from cadmium, the chains could be assembled into two-dimensional structures. Upon standing at 333 K for several days, small crystals suitable for synchrotron X-ray diffraction were obtained. Compound (II) formed a two-dimensional sheet structure where the cadmium(II) phosphinate chains were crosslinked by 4,4'-bi­pyridine. These sheets run along the crystallographic ac plane. Fig. 2 shows the local geometry around the Cd^II center. In (II), the Cd—O distances range from 2.276 (5) to 2.296 (5) Å and the Cd—N distances are 2.349 (4) and 2.402 (4) Å. The cis bond angles around the Cd^II center range from 85.0 (4) to 95.6 (4)°. The trans angles range from 171.03 (11) to 178.1 (8)°, with the N—Cd—N angle being widest. Fig. 3 illustrates portions of three cadmium(II) phosphinate chains running vertically and connected by 4,4'-bi­pyridine in the horizontal direction. A similar approach using 4,4'-bi­pyridine has been noted by Dong and co-workers. In their study, a mixed carboxyl­ate–phosphinate dianionic ligand generated chain structures with cadmium(II). Sheet-like structures similar to (II) were isolated upon addition of 4,4'-bi­pyridine. An inter­esting difference in this case was that each Cd^II center was bis-coordinated to phosphinate moieties, whereas (II) exhibits tetra-coordination to the phosphinates (Dong et al. 2012).

Upon closer inspection of the structure of (II), the two-dimensional sheets assemble into a three-dimensional architecture via parallel displaced π–π inter­actions between the phenyl rings of neighboring di­phenyl­phosphinate ligands on adjacent chains (Hunter & Sanders, 1990). The inter­planar separation of aligning C atoms are as follows: C2 and C16 at a distance of 3.637 (15) Å, C3 and C17 at a distance of 3.477 (9) Å, and C4 and C18 at a distance of 3.565 (15) Å. The periplanar angle formed by these phenyl and pyridyl rings is 9.73 (3)°. While weak, these inter­actions help the structure assemble pores parallel to the crystallographic c axis which encapsulate free DMF molecules as solvents of crystallization. The π–π inter­actions as viewed between C atoms and the expanded framework are illustrated in Fig. 4.

S4. Conclusions

One- and two-dimensional cadmium phosphinate coordination polymers have been synthesized and characterized in the solid state. The two-dimensional structure, (II), takes on a three-dimensional architecture when π–π inter­actions between phenyl rings of the di­phenyl­phoshinate ligands are considered. Both materials exhibit a single type of phosphinate bridging mode. This general M—O—P—O—M motif has been noted for other transition-metal phosphinates, as well as a series of alkaline-earth-metal phosphinates that we recently reported. In general, chains predominant the literature for most metal complexes incorporating di­phenyl­phosphinate ligands. This study has shown that additional neutral organic molecules, such as 4,4'-bi­pyridine, can be used to synthesize higher-dimensional structures beyond that of chains. Such findings prompt future studies aimed at isolating porous materials with potentially useful properties in materials applications.

Related literature

For related literature, see: Al-Shboul, Volland, Görls, Krieck & Westerhausen (2012); Annan et al. (1991); Bataille et al. (2008); Beckman et al. (2004, 2005); Berti et al. (2002); Bino & Sassman (1987); Brennan & Cowan (1992); Bruker (2010); Côte & Shimizu (2003); Cecconi et al. (2003, 2004); Ciattini et al. (2005); Clearfield (2008); Costantino, Ienco, Midollini & Orlandini (2008); Costantino, Midollini & Orlandini (2008); Czaja et al. (2009); Dinča & Long (2008); Dong et al. (2012); Du et al. (1991); Farha & Hupp (2010); Furukawa et al. (2013); Hooft et al. (2008); Horike & Kitagawa (2011); Hunter & Sanders (1990); James (2003); Konar et al. (2007); Li et al. (2014); Liang & Shimizu (2007); Midollini & Orlandini (2006); Midollini et al. (2004); Parsons et al. (2013); Rood et al. (2014); Ruettinger et al. (1999); Sheldrick (2008a); Shimizu et al. (2009); Spek (2009); Stock & Biswas (2012); Tranchemontagne et al. (2009); Videnova-Adrabinska (2007); Zhao et al. (2011).

Computing details

For both compounds, data collection: APEX2 (Bruker, 2010). Cell refinement: APEX2 and SAINT (Bruker, 2010) for CompoundI; SAINT (Bruker, 2010) for CompoundII. Data reduction: SAINT (Bruker, 2010) and XPREP (Sheldrick, 2008a) for CompoundI; SAINT (Bruker, 2010) for CompoundII. For both compounds, program(s) used to solve structure: SHELXTL (Sheldrick, 2008a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008a). Molecular graphics: XP in SHELXTL (Sheldrick, 2008a) and CrystalMaker (Palmer, 2010) for CompoundI; SHELXTL (Sheldrick, 2008a) and CrystalMaker (Palmer, 2010) for CompoundII. Software used to prepare material for publication: XCIF (Bruker, 2010) and enCIFer (CCDC, 2004) for CompoundI; SHELXTL (Sheldrick, 2008a) for CompoundII.

Figures

	Fig. 1. A single chain observed in (I). H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x, -y+1, z, (ii) x, y+1, z].
	Fig. 2. The geometry around a Cd^II center in (II). H atoms have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) x-1/2, -y, z; (ii) -x+1/2, y, z+1/2; (iii) -x+1/2, y, z-1/2.]
	Fig. 3. A portion of a single two-dimensional sheet formed in (II). H atoms have been omitted for clarity.
	Fig. 4. An illustration of the π–π interactions between phenyl rings in (II) and the extended structure showing DMF molecules in the resulting channels. In the figure on the left, only the N atoms of 4,4'-bipyridine have been shown for clarity.

(CompoundI) catena-Poly[[bis(dimethylformamide-κO)cadmium(II)]-bis(µ-diphenylphosphinato-κ²O:O')]

Crystal data

[Cd(C12H10O2P)2(C3H7NO)2]	F(000) = 708
Mr = 692.93	Dx = 1.579 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 15.285 (3) Å	Cell parameters from 2486 reflections
b = 5.7077 (11) Å	θ = 2.4–22.2°
c = 16.907 (3) Å	µ = 0.91 mm^−1
β = 98.912 (5)°	T = 120 K
V = 1457.1 (5) Å^3	Rod, colorless
Z = 2	0.24 × 0.18 × 0.15 mm

Data collection

Bruker X8 APEXII CCD diffractometer	5731 independent reflections
Radiation source: fine-focus sealed tube	4600 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
Detector resolution: 8.33 pixels mm^-1	θmax = 26.5°, θmin = 1.2°
ϕ and ω scans	h = −19→18
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b)	k = −7→6
Tmin = 0.92, Tmax = 0.94	l = −20→21
15833 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0562P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
5731 reflections	Δρmax = 3.18 e Å^−3
374 parameters	Δρmin = −0.54 e Å^−3
1 restraint	Absolute structure: Flack x determined using 1693 quotients [(I^+)-(I&-&)]/[(I^+)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

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.

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

	x	y	z	Uiso*/Ueq
Cd1	0.19261 (4)	0.18695 (14)	0.72123 (3)	0.01222 (16)
O1	0.1296 (4)	0.4926 (12)	0.7730 (4)	0.0175 (16)
O2	0.0870 (4)	0.9237 (11)	0.7429 (4)	0.0165 (15)
O3	0.2691 (4)	−0.1035 (12)	0.6671 (4)	0.0165 (17)
O4	0.3001 (4)	−0.5428 (13)	0.7010 (4)	0.0184 (17)
O5	0.2671 (4)	0.0952 (11)	0.8478 (4)	0.0190 (16)
O6	0.1125 (4)	0.2837 (11)	0.5991 (4)	0.0162 (15)
N1	0.3365 (6)	−0.1926 (17)	0.9255 (6)	0.023 (2)
N2	0.1040 (6)	0.5686 (16)	0.5051 (5)	0.013 (2)
P1	0.07575 (14)	0.7027 (7)	0.78742 (12)	0.0133 (5)
P2	0.32813 (12)	−0.3125 (8)	0.66868 (11)	0.0143 (4)
C1	0.0968 (6)	0.7584 (15)	0.8946 (5)	0.015 (2)
C2	0.0731 (6)	0.9701 (18)	0.9253 (6)	0.019 (2)
H2	0.0463	1.0881	0.8900	0.022*
C3	0.0880 (6)	1.0113 (18)	1.0071 (6)	0.021 (2)
H3	0.0709	1.1564	1.0276	0.025*
C4	0.1278 (7)	0.8421 (19)	1.0587 (6)	0.025 (2)
H4	0.1376	0.8699	1.1148	0.030*
C5	0.1535 (6)	0.6302 (18)	1.0286 (5)	0.024 (3)
H5	0.1821	0.5144	1.0639	0.029*
C6	0.1372 (6)	0.5888 (16)	0.9464 (6)	0.019 (2)
H6	0.1539	0.4435	0.9258	0.023*
C7	−0.0404 (6)	0.6246 (14)	0.7649 (5)	0.014 (2)
C8	−0.0665 (6)	0.4061 (16)	0.7320 (5)	0.015 (2)
H8	−0.0230	0.2925	0.7248	0.018*
C9	−0.1559 (6)	0.3542 (17)	0.7098 (5)	0.019 (2)
H9	−0.1731	0.2061	0.6868	0.023*
C10	−0.2197 (7)	0.5162 (17)	0.7209 (6)	0.021 (2)
H10	−0.2805	0.4796	0.7054	0.025*
C11	−0.1955 (6)	0.7323 (17)	0.7546 (5)	0.020 (3)
H11	−0.2396	0.8435	0.7624	0.024*
C12	−0.1063 (6)	0.7859 (16)	0.7770 (6)	0.019 (2)
H12	−0.0898	0.9334	0.8007	0.022*
C13	0.3520 (6)	−0.3608 (16)	0.5683 (5)	0.017 (3)
C14	0.3256 (6)	−0.5671 (17)	0.5281 (6)	0.020 (2)
H14	0.2962	−0.6851	0.5537	0.024*
C15	0.3424 (6)	−0.6013 (19)	0.4493 (6)	0.025 (2)
H15	0.3237	−0.7419	0.4217	0.030*
C16	0.3858 (7)	−0.431 (2)	0.4120 (6)	0.027 (3)
H16	0.3966	−0.4549	0.3588	0.033*
C17	0.4136 (7)	−0.2266 (19)	0.4524 (6)	0.026 (3)
H17	0.4445	−0.1109	0.4273	0.031*
C18	0.3961 (6)	−0.1909 (18)	0.5303 (6)	0.022 (2)
H18	0.4144	−0.0495	0.5575	0.027*
C19	0.4344 (6)	−0.2360 (15)	0.7290 (5)	0.016 (2)
C20	0.4484 (6)	−0.0156 (17)	0.7645 (5)	0.018 (2)
H20	0.4046	0.1025	0.7525	0.022*
C21	0.5250 (7)	0.0340 (18)	0.8169 (6)	0.025 (2)
H21	0.5328	0.1821	0.8427	0.030*
C22	0.5909 (7)	−0.1376 (19)	0.8313 (6)	0.026 (2)
H22	0.6440	−0.1058	0.8669	0.031*
C23	0.5793 (6)	−0.352 (2)	0.7940 (6)	0.026 (3)
H23	0.6247	−0.4671	0.8036	0.031*
C24	0.5015 (7)	−0.4013 (17)	0.7424 (6)	0.024 (2)
H24	0.4943	−0.5490	0.7163	0.029*
C25	0.2902 (6)	−0.1099 (18)	0.8601 (5)	0.016 (2)
H25	0.2727	−0.2183	0.8180	0.020*
C26	0.3643 (10)	−0.033 (2)	0.9927 (7)	0.058 (4)
H26A	0.4237	0.0268	0.9893	0.087*
H26B	0.3653	−0.1180	1.0432	0.087*
H26C	0.3226	0.0977	0.9903	0.087*
C27	0.3684 (8)	−0.434 (2)	0.9320 (8)	0.035 (3)
H27A	0.3390	−0.5248	0.8864	0.052*
H27B	0.3551	−0.5030	0.9819	0.052*
H27C	0.4326	−0.4357	0.9323	0.052*
C28	0.1175 (6)	0.4939 (17)	0.5806 (5)	0.016 (2)
H28	0.1314	0.6059	0.6222	0.019*
C29	0.1208 (8)	0.815 (2)	0.4874 (7)	0.019 (3)
H29A	0.1254	0.9072	0.5368	0.029*
H29B	0.0719	0.8751	0.4483	0.029*
H29C	0.1763	0.8272	0.4654	0.029*
C30	0.0834 (7)	0.4068 (16)	0.4372 (5)	0.020 (2)
H30A	0.0625	0.2576	0.4560	0.031*
H30B	0.1368	0.3798	0.4130	0.031*
H30C	0.0372	0.4751	0.3972	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.0117 (3)	0.0116 (3)	0.0133 (3)	0.0007 (4)	0.00152 (19)	0.0004 (4)
O1	0.014 (4)	0.020 (4)	0.020 (4)	0.003 (3)	0.006 (3)	−0.006 (3)
O2	0.016 (4)	0.016 (4)	0.018 (4)	−0.006 (3)	0.003 (3)	−0.002 (3)
O3	0.017 (4)	0.014 (4)	0.018 (4)	0.001 (3)	0.002 (3)	−0.001 (3)
O4	0.011 (4)	0.021 (4)	0.025 (4)	−0.002 (3)	0.008 (3)	−0.003 (3)
O5	0.019 (4)	0.020 (4)	0.015 (3)	0.000 (3)	−0.004 (3)	0.002 (3)
O6	0.017 (3)	0.014 (4)	0.016 (3)	0.000 (3)	−0.003 (3)	−0.001 (3)
N1	0.020 (5)	0.018 (5)	0.025 (5)	−0.006 (4)	−0.009 (4)	0.004 (4)
N2	0.017 (5)	0.010 (4)	0.013 (4)	0.004 (4)	0.000 (4)	−0.001 (4)
P1	0.0142 (10)	0.0129 (13)	0.0130 (10)	0.0012 (17)	0.0033 (8)	0.0006 (16)
P2	0.0119 (10)	0.0144 (11)	0.0168 (10)	0.0001 (19)	0.0028 (8)	−0.0014 (19)
C1	0.012 (5)	0.014 (6)	0.019 (5)	−0.002 (3)	0.006 (4)	−0.005 (4)
C2	0.016 (5)	0.022 (6)	0.018 (5)	−0.003 (4)	0.002 (4)	0.001 (4)
C3	0.022 (6)	0.020 (5)	0.022 (5)	−0.003 (4)	0.005 (4)	−0.009 (4)
C4	0.031 (6)	0.031 (7)	0.014 (5)	−0.004 (5)	0.009 (5)	−0.008 (5)
C5	0.025 (5)	0.038 (9)	0.008 (4)	−0.005 (5)	−0.002 (4)	−0.003 (4)
C6	0.018 (5)	0.013 (5)	0.026 (6)	0.002 (4)	0.007 (4)	0.002 (4)
C7	0.022 (5)	0.016 (6)	0.005 (4)	−0.003 (4)	0.003 (3)	0.002 (3)
C8	0.021 (5)	0.014 (5)	0.011 (5)	0.002 (4)	0.004 (4)	0.003 (4)
C9	0.024 (6)	0.016 (5)	0.018 (5)	−0.006 (4)	0.001 (4)	0.000 (4)
C10	0.022 (6)	0.018 (5)	0.021 (5)	−0.010 (4)	0.000 (4)	0.010 (4)
C11	0.021 (5)	0.015 (8)	0.025 (5)	0.005 (4)	0.007 (4)	0.008 (4)
C12	0.017 (5)	0.014 (5)	0.025 (5)	−0.003 (4)	0.004 (4)	−0.003 (4)
C13	0.011 (4)	0.017 (8)	0.024 (5)	0.000 (4)	−0.002 (4)	−0.005 (4)
C14	0.020 (5)	0.017 (6)	0.023 (5)	−0.002 (4)	0.004 (4)	−0.001 (4)
C15	0.021 (6)	0.031 (7)	0.022 (5)	0.004 (5)	0.000 (4)	−0.005 (5)
C16	0.028 (6)	0.036 (7)	0.020 (6)	0.010 (5)	0.007 (5)	0.002 (5)
C17	0.022 (6)	0.037 (7)	0.020 (5)	0.001 (4)	0.009 (5)	0.001 (5)
C18	0.015 (5)	0.024 (6)	0.027 (6)	−0.002 (4)	0.005 (4)	0.001 (5)
C19	0.011 (5)	0.019 (6)	0.018 (5)	0.000 (3)	0.005 (4)	0.004 (4)
C20	0.012 (5)	0.019 (6)	0.023 (5)	0.004 (4)	0.003 (4)	0.001 (4)
C21	0.029 (6)	0.021 (6)	0.024 (6)	−0.005 (5)	0.000 (5)	−0.003 (4)
C22	0.017 (6)	0.038 (7)	0.019 (5)	−0.009 (5)	−0.007 (4)	0.010 (5)
C23	0.008 (4)	0.035 (10)	0.033 (5)	0.003 (5)	−0.003 (4)	0.004 (5)
C24	0.025 (6)	0.027 (6)	0.021 (5)	0.002 (4)	0.009 (4)	0.003 (4)
C25	0.015 (5)	0.023 (6)	0.013 (5)	−0.003 (4)	0.005 (4)	0.001 (4)
C26	0.097 (12)	0.034 (8)	0.030 (7)	−0.008 (8)	−0.031 (8)	0.000 (6)
C27	0.032 (8)	0.031 (7)	0.039 (7)	0.005 (6)	−0.004 (6)	0.009 (6)
C28	0.013 (5)	0.020 (6)	0.016 (5)	−0.001 (4)	0.003 (4)	−0.001 (4)
C29	0.021 (6)	0.014 (6)	0.022 (6)	0.000 (5)	0.000 (5)	0.003 (5)
C30	0.034 (6)	0.012 (5)	0.014 (5)	0.004 (4)	0.001 (4)	0.002 (4)

Geometric parameters (Å, º)

Cd1—O1	2.236 (6)	C17—C18	1.398 (14)
Cd1—O2^i	2.275 (7)	C19—C24	1.386 (12)
Cd1—O3	2.298 (7)	C19—C20	1.396 (13)
Cd1—O6	2.299 (6)	C20—C21	1.383 (13)
Cd1—O4^ii	2.317 (7)	C21—C22	1.399 (14)
Cd1—O5	2.323 (6)	C22—C23	1.375 (16)
O1—P1	1.496 (8)	C23—C24	1.390 (13)
O2—P1	1.493 (8)	C2—H2	0.9500
O2—Cd1^ii	2.276 (6)	C3—H3	0.9500
O3—P2	1.494 (8)	C4—H4	0.9500
O4—P2	1.511 (8)	C5—H5	0.9500
O4—Cd1^i	2.317 (7)	C6—H6	0.9500
O5—C25	1.231 (11)	C8—H8	0.9500
O6—C28	1.245 (11)	C9—H9	0.9500
N1—C25	1.305 (13)	C10—H10	0.9500
N1—C27	1.459 (12)	C11—H11	0.9500
N1—C26	1.465 (14)	C12—H12	0.9500
N2—C28	1.332 (12)	C14—H14	0.9500
N2—C29	1.468 (11)	C15—H15	0.9500
N2—C30	1.469 (12)	C16—H16	0.9500
P1—C7	1.812 (9)	C17—H17	0.9500
P1—C1	1.818 (9)	C18—H18	0.9500
P2—C13	1.811 (9)	C20—H20	0.9500
P2—C19	1.832 (9)	C21—H21	0.9500
C1—C6	1.385 (12)	C22—H22	0.9500
C1—C2	1.386 (13)	C23—H23	0.9500
C2—C3	1.386 (13)	C24—H24	0.9500
C3—C4	1.378 (14)	C25—H25	0.9500
C4—C5	1.392 (14)	C26—H26A	0.9800
C5—C6	1.394 (12)	C26—H26B	0.9800
C7—C8	1.398 (12)	C26—H26C	0.9800
C7—C12	1.403 (12)	C27—H27A	0.9800
C8—C9	1.392 (13)	C27—H27B	0.9800
C9—C10	1.377 (14)	C27—H27C	0.9800
C10—C11	1.385 (14)	C28—H28	0.9500
C11—C12	1.391 (13)	C29—H29A	0.9800
C13—C14	1.388 (13)	C29—H29B	0.9800
C13—C18	1.394 (13)	C29—H29C	0.9800
C14—C15	1.410 (13)	C30—H30A	0.9800
C15—C16	1.380 (15)	C30—H30B	0.9800
C16—C17	1.387 (14)	C30—H30C	0.9800
O1—Cd1—O2^i	95.3 (2)	O5—C25—N1	126.2 (10)
O1—Cd1—O3	174.3 (3)	O6—C28—N2	122.9 (9)
O2^i—Cd1—O3	90.3 (3)	C1—C2—H2	119.7
O1—Cd1—O6	87.9 (2)	C3—C2—H2	119.7
O2^i—Cd1—O6	90.6 (2)	C4—C3—H3	120.0
O3—Cd1—O6	92.8 (2)	C2—C3—H3	120.0
O1—Cd1—O4^ii	84.1 (3)	C3—C4—H4	120.0
O2^i—Cd1—O4^ii	179.2 (3)	C5—C4—H4	120.0
O3—Cd1—O4^ii	90.3 (2)	C4—C5—H5	120.2
O6—Cd1—O4^ii	89.9 (2)	C6—C5—H5	120.2
O1—Cd1—O5	89.7 (2)	C1—C6—H6	119.8
O2^i—Cd1—O5	87.8 (2)	C5—C6—H6	119.8
O3—Cd1—O5	89.8 (2)	C9—C8—H8	119.8
O6—Cd1—O5	177.0 (2)	C7—C8—H8	119.8
O4^ii—Cd1—O5	91.6 (2)	C10—C9—H9	119.8
P1—O1—Cd1	166.1 (4)	C8—C9—H9	119.8
P1—O2—Cd1^ii	141.2 (4)	C9—C10—H10	119.8
P2—O3—Cd1	155.8 (4)	C11—C10—H10	119.8
P2—O4—Cd1^i	151.6 (4)	C10—C11—H11	120.2
C25—O5—Cd1	117.2 (6)	C12—C11—H11	120.2
C28—O6—Cd1	114.3 (6)	C11—C12—H12	119.6
C25—N1—C27	122.4 (10)	C7—C12—H12	119.6
C25—N1—C26	119.1 (10)	C13—C14—H14	120.0
C27—N1—C26	118.2 (10)	C15—C14—H14	120.0
C28—N2—C29	119.7 (9)	C16—C15—H15	119.8
C28—N2—C30	122.1 (9)	C14—C15—H15	119.8
C29—N2—C30	117.8 (9)	C15—C16—H16	120.0
O2—P1—O1	119.1 (4)	C17—C16—H16	120.0
O2—P1—C7	106.7 (4)	C16—C17—H17	120.1
O1—P1—C7	108.3 (4)	C18—C17—H17	120.1
O2—P1—C1	109.8 (4)	C13—C18—H18	119.7
O1—P1—C1	106.6 (4)	C17—C18—H18	119.7
C7—P1—C1	105.6 (4)	C21—C20—H20	119.4
O3—P2—O4	119.8 (3)	C19—C20—H20	119.4
O3—P2—C13	108.3 (4)	C20—C21—H21	120.6
O4—P2—C13	108.4 (5)	C22—C21—H21	120.6
O3—P2—C19	107.5 (4)	C23—C22—H22	119.8
O4—P2—C19	106.4 (4)	C21—C22—H22	119.8
C13—P2—C19	105.5 (4)	C22—C23—H23	119.9
C6—C1—C2	119.3 (8)	C24—C23—H23	119.9
C6—C1—P1	120.1 (7)	C19—C24—C23	120.3 (10)
C2—C1—P1	120.7 (7)	C19—C24—H24	119.8
C1—C2—C3	120.7 (9)	C23—C24—H24	119.8
C4—C3—C2	120.0 (9)	O5—C25—H25	116.9
C3—C4—C5	120.0 (8)	N1—C25—H25	116.9
C4—C5—C6	119.6 (9)	N1—C26—H26A	109.5
C1—C6—C5	120.4 (9)	N1—C26—H26B	109.5
C8—C7—C12	118.4 (8)	H26A—C26—H26B	109.5
C8—C7—P1	120.9 (7)	N1—C26—H26C	109.5
C12—C7—P1	120.7 (7)	H26A—C26—H26C	109.5
C9—C8—C7	120.3 (9)	H26B—C26—H26C	109.5
C10—C9—C8	120.4 (9)	N1—C27—H27A	109.5
C9—C10—C11	120.3 (9)	N1—C27—H27B	109.5
C10—C11—C12	119.7 (9)	H27A—C27—H27B	109.5
C11—C12—C7	120.8 (9)	N1—C27—H27C	109.5
C14—C13—C18	119.3 (9)	H27A—C27—H27C	109.5
C14—C13—P2	120.2 (8)	H27B—C27—H27C	109.5
C18—C13—P2	120.6 (7)	O6—C28—H28	118.6
C13—C14—C15	119.9 (9)	N2—C28—H28	118.6
C16—C15—C14	120.3 (10)	N2—C29—H29A	109.5
C15—C16—C17	120.0 (10)	N2—C29—H29B	109.5
C16—C17—C18	119.8 (10)	H29A—C29—H29B	109.5
C13—C18—C17	120.7 (10)	N2—C29—H29C	109.5
C24—C19—C20	118.8 (9)	H29A—C29—H29C	109.5
C24—C19—P2	119.9 (7)	H29B—C29—H29C	109.5
C20—C19—P2	121.2 (7)	N2—C30—H30A	109.5
C21—C20—C19	121.2 (9)	N2—C30—H30B	109.5
C20—C21—C22	118.9 (10)	H30A—C30—H30B	109.5
C23—C22—C21	120.4 (9)	N2—C30—H30C	109.5
C22—C23—C24	120.3 (10)	H30A—C30—H30C	109.5
C19—C24—C23	120.3 (10)	H30B—C30—H30C	109.5

Symmetry codes: (i) x, y−1, z; (ii) x, y+1, z.

(CompoundII) Poly[[(µ-4,4'-bipyridine-κ²N:N')bis(µ-diphenylphosphinato-κ²O:O')cadmium(II)] dimethylformamide monosolvate]

Crystal data

[Cd(C12H10O2P)2(C10H8N2)]·C3H7NO	Dx = 1.513 Mg m^−3
Mr = 776.02	Synchrotron radiation, λ = 0.77490 Å
Orthorhombic, Pca21	Cell parameters from 9937 reflections
a = 23.695 (2) Å	θ = 2.6–28.9°
b = 12.8861 (12) Å	µ = 0.97 mm^−1
c = 11.1594 (10) Å	T = 150 K
V = 3407.3 (5) Å^3	Blade, pink–cyan
Z = 4	0.08 × 0.03 × 0.01 mm
F(000) = 1584

Data collection

Bruker APEXII diffractometer	6924 independent reflections
Radiation source: synchrotron	6231 reflections with I > 2σ(I)
Si-<111> channel cut crystal monochromator	Rint = 0.081
Detector resolution: 8.33 pixels mm^-1	θmax = 28.9°, θmin = 2.0°
phi and ω scans	h = −29→29
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b)	k = −16→16
Tmin = 0.93, Tmax = 0.96	l = −13→13
36812 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.106	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 5.2727P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.009
6924 reflections	Δρmax = 1.15 e Å^−3
411 parameters	Δρmin = −0.58 e Å^−3
1 restraint	Absolute structure: Refined as an inversion twin.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.30 (4)

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. Refined as a two-component inversion twin.

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

	x	y	z	Uiso*/Ueq
Cd1	0.26337 (2)	0.00576 (3)	0.49304 (17)	0.01693 (12)
P1	0.2550 (2)	−0.17052 (11)	0.2486 (2)	0.0181 (5)
P2	0.2541 (2)	0.18215 (11)	0.7376 (2)	0.0177 (5)
O1	0.25947 (19)	−0.1405 (3)	0.3791 (5)	0.0214 (10)
O2	0.22963 (18)	−0.0952 (3)	0.1619 (5)	0.0227 (10)
O3	0.2575 (2)	0.1516 (3)	0.6086 (5)	0.0226 (10)
O4	0.22853 (18)	0.1077 (3)	0.8258 (5)	0.0207 (9)
N1	0.36474 (17)	0.0043 (4)	0.4958 (18)	0.0202 (9)
N2	0.66424 (18)	−0.0064 (3)	0.4971 (17)	0.0198 (10)
C1	0.2154 (3)	−0.2908 (5)	0.2380 (7)	0.0252 (15)
C2	0.2171 (3)	−0.3654 (5)	0.3261 (8)	0.0352 (18)
H2	0.2385	−0.3530	0.3966	0.042*
C3	0.1880 (4)	−0.4586 (6)	0.3138 (9)	0.048 (2)
H3	0.1893	−0.5087	0.3761	0.057*
C4	0.1580 (6)	−0.4778 (9)	0.2137 (16)	0.058 (4)
H4	0.1390	−0.5422	0.2044	0.069*
C5	0.1548 (4)	−0.4021 (7)	0.1228 (10)	0.053 (3)
H5	0.1321	−0.4143	0.0542	0.063*
C6	0.1845 (3)	−0.3106 (6)	0.1328 (8)	0.0351 (18)
H6	0.1840	−0.2614	0.0694	0.042*
C7	0.3249 (3)	−0.2063 (4)	0.1974 (6)	0.0196 (13)
C8	0.3342 (3)	−0.2304 (5)	0.0780 (7)	0.0249 (14)
H8	0.3032	−0.2290	0.0239	0.030*
C9	0.3869 (3)	−0.2565 (5)	0.0351 (7)	0.0317 (16)
H9	0.3924	−0.2738	−0.0468	0.038*
C10	0.4316 (3)	−0.2566 (6)	0.1146 (8)	0.0356 (18)
H10	0.4684	−0.2730	0.0864	0.043*
C11	0.4235 (3)	−0.2330 (6)	0.2368 (8)	0.039 (2)
H11	0.4545	−0.2331	0.2910	0.047*
C12	0.3706 (3)	−0.2099 (5)	0.2756 (7)	0.0263 (15)
H12	0.3646	−0.1959	0.3582	0.032*
C13	0.2143 (3)	0.3022 (5)	0.7493 (7)	0.0219 (14)
C14	0.1823 (3)	0.3216 (6)	0.8499 (8)	0.0374 (19)
H14	0.1803	0.2712	0.9118	0.045*
C15	0.1528 (4)	0.4153 (7)	0.8613 (11)	0.060 (3)
H15	0.1317	0.4286	0.9321	0.072*
C16	0.1540 (6)	0.4878 (7)	0.7721 (17)	0.054 (4)
H16	0.1325	0.5496	0.7787	0.065*
C17	0.1872 (4)	0.4699 (7)	0.6714 (8)	0.046 (2)
H17	0.1898	0.5214	0.6107	0.055*
C18	0.2165 (3)	0.3777 (5)	0.6591 (7)	0.0309 (16)
H18	0.2382	0.3654	0.5890	0.037*
C19	0.3241 (3)	0.2182 (5)	0.7866 (7)	0.0225 (13)
C20	0.3331 (3)	0.2423 (5)	0.9074 (7)	0.0257 (15)
H20	0.3027	0.2403	0.9627	0.031*
C21	0.3870 (3)	0.2694 (5)	0.9457 (8)	0.0322 (16)
H21	0.3931	0.2864	1.0275	0.039*
C22	0.4316 (3)	0.2719 (6)	0.8670 (9)	0.043 (2)
H22	0.4683	0.2903	0.8941	0.051*
C23	0.4227 (3)	0.2479 (6)	0.7496 (9)	0.041 (2)
H23	0.4537	0.2487	0.6957	0.050*
C24	0.3684 (3)	0.2218 (5)	0.7062 (7)	0.0291 (16)
H24	0.3626	0.2071	0.6237	0.035*
C25	0.3948 (3)	0.0662 (5)	0.4213 (6)	0.0210 (13)
H25	0.3751	0.1102	0.3673	0.025*
C26	0.4535 (3)	0.0679 (5)	0.4209 (6)	0.0220 (14)
H26	0.4728	0.1173	0.3729	0.026*
C27	0.48342 (19)	0.0002 (4)	0.488 (3)	0.0172 (15)
C29	0.3936 (3)	−0.0595 (5)	0.5653 (7)	0.0235 (15)
H29	0.3729	−0.1044	0.6166	0.028*
C30	0.5460 (2)	−0.0025 (4)	0.490 (2)	0.0190 (12)
C31	0.5763 (5)	−0.0213 (7)	0.5960 (10)	0.0221 (17)
H31	0.5566	−0.0338	0.6688	0.027*
C32	0.6352 (4)	−0.0214 (6)	0.5945 (9)	0.0208 (17)
H32	0.6548	−0.0329	0.6675	0.025*
C33	0.6347 (5)	0.0126 (6)	0.3927 (11)	0.023 (2)
H33	0.6556	0.0260	0.3216	0.028*
C34	0.5772 (5)	0.0132 (5)	0.3863 (10)	0.0200 (19)
H34	0.5588	0.0243	0.3118	0.024*
C38	0.4519 (3)	−0.0654 (5)	0.5683 (6)	0.0213 (14)
H38	0.4705	−0.1113	0.6218	0.026*
O1S	0.5225 (3)	0.2435 (6)	0.2704 (7)	0.077 (2)*
N1S	0.5041 (4)	0.4099 (6)	0.2251 (8)	0.060 (2)*
C1S	0.5092 (5)	0.3119 (9)	0.1916 (11)	0.083 (3)*
H1S	0.5032	0.2924	0.1105	0.099*
C2S	0.4943 (7)	0.4802 (13)	0.1267 (19)	0.108 (5)*
H2SA	0.4809	0.4410	0.0570	0.162*
H2SB	0.5295	0.5159	0.1063	0.162*
H2SC	0.4657	0.5314	0.1499	0.162*
C3S	0.5063 (6)	0.4500 (15)	0.3392 (16)	0.105 (5)*
H3SA	0.4889	0.4011	0.3953	0.157*
H3SB	0.4860	0.5161	0.3416	0.157*
H3SC	0.5458	0.4613	0.3620	0.157*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cd1	0.01206 (19)	0.02235 (19)	0.01637 (19)	−0.00014 (14)	0.0000 (5)	−0.0014 (3)
P1	0.0174 (15)	0.0206 (6)	0.0162 (9)	0.0023 (9)	0.0008 (8)	−0.0032 (9)
P2	0.0170 (13)	0.0199 (6)	0.0161 (9)	−0.0007 (10)	0.0012 (8)	−0.0005 (9)
O1	0.023 (3)	0.024 (2)	0.017 (3)	0.0028 (17)	−0.001 (2)	−0.0011 (18)
O2	0.021 (2)	0.026 (2)	0.021 (3)	0.0031 (18)	−0.001 (2)	−0.0018 (19)
O3	0.027 (3)	0.023 (2)	0.018 (3)	−0.0004 (18)	0.000 (2)	−0.0008 (18)
O4	0.018 (2)	0.026 (2)	0.019 (2)	−0.0019 (17)	0.000 (2)	0.0010 (18)
N1	0.0146 (18)	0.027 (2)	0.019 (2)	0.0004 (17)	0.004 (7)	−0.006 (2)
N2	0.0146 (19)	0.024 (2)	0.021 (3)	0.0000 (17)	−0.010 (6)	0.005 (2)
C1	0.024 (4)	0.024 (3)	0.028 (4)	0.001 (3)	0.003 (3)	−0.006 (3)
C2	0.039 (4)	0.028 (3)	0.039 (5)	−0.001 (3)	0.010 (4)	−0.006 (3)
C3	0.056 (5)	0.025 (4)	0.063 (6)	−0.003 (4)	0.029 (5)	0.000 (4)
C4	0.043 (7)	0.040 (5)	0.091 (10)	−0.024 (6)	0.013 (7)	−0.023 (7)
C5	0.043 (5)	0.044 (5)	0.071 (7)	−0.005 (4)	−0.016 (5)	−0.019 (5)
C6	0.028 (4)	0.033 (4)	0.044 (5)	0.003 (3)	−0.013 (4)	−0.013 (3)
C7	0.016 (3)	0.020 (3)	0.023 (3)	0.001 (2)	−0.005 (3)	0.002 (2)
C8	0.022 (3)	0.028 (3)	0.025 (4)	0.001 (2)	−0.002 (3)	−0.006 (3)
C9	0.028 (4)	0.042 (4)	0.025 (4)	0.005 (3)	−0.001 (3)	−0.006 (3)
C10	0.014 (3)	0.051 (4)	0.041 (5)	0.007 (3)	0.007 (3)	−0.008 (3)
C11	0.020 (4)	0.062 (5)	0.036 (5)	0.008 (3)	−0.008 (3)	−0.002 (4)
C12	0.026 (4)	0.035 (4)	0.018 (4)	0.002 (3)	−0.004 (3)	−0.005 (3)
C13	0.015 (3)	0.021 (3)	0.029 (4)	−0.003 (2)	−0.007 (3)	−0.009 (2)
C14	0.034 (4)	0.033 (4)	0.044 (5)	−0.003 (3)	0.005 (4)	−0.008 (3)
C15	0.044 (5)	0.045 (5)	0.090 (9)	0.006 (4)	0.021 (6)	−0.028 (5)
C16	0.035 (7)	0.035 (5)	0.091 (10)	0.010 (4)	−0.006 (6)	−0.015 (6)
C17	0.055 (6)	0.028 (4)	0.053 (6)	0.009 (4)	−0.025 (5)	−0.006 (4)
C18	0.042 (4)	0.026 (3)	0.025 (4)	0.003 (3)	−0.013 (4)	−0.001 (3)
C19	0.021 (3)	0.023 (3)	0.024 (4)	0.001 (2)	−0.007 (3)	0.000 (2)
C20	0.025 (4)	0.028 (3)	0.024 (4)	−0.003 (3)	−0.001 (3)	−0.003 (3)
C21	0.028 (4)	0.039 (4)	0.029 (4)	−0.001 (3)	−0.009 (3)	−0.008 (3)
C22	0.029 (4)	0.049 (4)	0.051 (6)	−0.009 (3)	0.001 (4)	−0.010 (4)
C23	0.020 (4)	0.062 (5)	0.043 (5)	−0.006 (3)	0.010 (4)	−0.011 (4)
C24	0.025 (4)	0.034 (4)	0.028 (4)	0.000 (3)	0.005 (3)	0.000 (3)
C25	0.019 (3)	0.029 (3)	0.015 (3)	0.002 (2)	0.002 (3)	0.002 (2)
C26	0.017 (3)	0.027 (3)	0.022 (4)	0.000 (2)	0.002 (3)	0.005 (2)
C27	0.014 (2)	0.023 (2)	0.014 (4)	−0.0016 (17)	0.006 (6)	−0.003 (2)
C29	0.017 (3)	0.027 (3)	0.026 (4)	−0.003 (2)	0.003 (3)	0.000 (3)
C30	0.016 (2)	0.022 (2)	0.020 (3)	−0.0003 (19)	−0.012 (7)	−0.002 (2)
C31	0.016 (4)	0.031 (3)	0.019 (4)	−0.004 (4)	0.002 (3)	−0.001 (4)
C32	0.018 (4)	0.027 (3)	0.017 (4)	0.005 (4)	−0.001 (3)	0.005 (4)
C33	0.019 (4)	0.032 (4)	0.019 (4)	0.001 (3)	0.000 (3)	−0.001 (3)
C34	0.019 (4)	0.029 (3)	0.012 (4)	−0.002 (3)	0.000 (3)	0.004 (3)
C38	0.016 (3)	0.026 (3)	0.022 (4)	−0.001 (2)	0.001 (3)	0.000 (3)

Geometric parameters (Å, º)

Cd1—O1	2.276 (5)	C27—C38	1.441 (19)
Cd1—O3	2.283 (5)	C27—C30	1.483 (7)
Cd1—O4^i	2.291 (5)	C29—C38	1.384 (9)
Cd1—O2^ii	2.296 (5)	C30—C34	1.39 (2)
Cd1—N2^iii	2.349 (4)	C30—C31	1.41 (2)
Cd1—N1	2.402 (4)	C31—C32	1.395 (16)
P1—O2	1.497 (6)	C33—C34	1.365 (18)
P1—O1	1.511 (6)	O1S—C1S	1.285 (13)
P1—C7	1.811 (8)	N1S—C1S	1.322 (13)
P1—C1	1.816 (7)	N1S—C3S	1.375 (19)
P2—O3	1.495 (6)	N1S—C2S	1.44 (2)
P2—O4	1.502 (5)	C2—H2	0.9500
P2—C19	1.807 (8)	C3—H3	0.9500
P2—C13	1.818 (7)	C4—H4	0.9500
O2—Cd1^i	2.296 (5)	C5—H5	0.9500
O4—Cd1^ii	2.291 (5)	C6—H6	0.9500
N1—C29	1.321 (15)	C8—H8	0.9500
N1—C25	1.355 (14)	C9—H9	0.9500
N2—C32	1.30 (2)	C10—H10	0.9500
N2—C33	1.38 (2)	C11—H11	0.9500
N2—Cd1^iv	2.349 (4)	C12—H12	0.9500
C1—C2	1.375 (11)	C14—H14	0.9500
C1—C6	1.408 (11)	C15—H15	0.9500
C2—C3	1.392 (10)	C16—H16	0.9500
C3—C4	1.347 (19)	C17—H17	0.9500
C4—C5	1.409 (19)	C18—H18	0.9500
C5—C6	1.376 (11)	C20—H20	0.9500
C7—C8	1.386 (10)	C21—H21	0.9500
C7—C12	1.391 (9)	C22—H22	0.9500
C8—C9	1.380 (9)	C23—H23	0.9500
C9—C10	1.381 (11)	C24—H24	0.9500
C10—C11	1.411 (12)	C25—H25	0.9500
C11—C12	1.360 (10)	C26—H26	0.9500
C13—C14	1.376 (11)	C29—H29	0.9500
C13—C18	1.400 (10)	C31—H31	0.9500
C14—C15	1.401 (11)	C32—H32	0.9500
C15—C16	1.37 (2)	C33—H33	0.9500
C16—C17	1.39 (2)	C34—H34	0.9500
C17—C18	1.383 (10)	C38—H38	0.9500
C19—C24	1.381 (9)	C1S—H1S	0.9500
C19—C20	1.400 (10)	C2S—H2SA	0.9800
C20—C21	1.392 (9)	C2S—H2SB	0.9800
C21—C22	1.373 (11)	C2S—H2SC	0.9800
C22—C23	1.362 (13)	C3S—H3SA	0.9800
C23—C24	1.415 (10)	C3S—H3SB	0.9800
C25—C26	1.391 (9)	C3S—H3SC	0.9800
C26—C27	1.350 (18)
O1—Cd1—O3	174.16 (12)	N2—C32—C31	122.6 (10)
O1—Cd1—O4^i	91.34 (19)	C33—C34—C30	119.3 (11)
O3—Cd1—O4^i	89.60 (18)	C29—C38—C27	118.1 (7)
O1—Cd1—O2^ii	89.56 (18)	C1S—N1S—C3S	128.1 (13)
O3—Cd1—O2^ii	90.41 (19)	C1S—N1S—C2S	113.6 (12)
O4^i—Cd1—O2^ii	171.03 (11)	C3S—N1S—C2S	118.4 (10)
O1—Cd1—N2^iii	88.5 (3)	C1—C2—H2	119.4
O3—Cd1—N2^iii	85.7 (3)	C3—C2—H2	119.4
O4^i—Cd1—N2^iii	95.6 (4)	C4—C3—H3	119.9
O2^ii—Cd1—N2^iii	93.4 (4)	C2—C3—H3	119.9
O1—Cd1—N1	92.4 (3)	C3—C4—H4	120.1
O3—Cd1—N1	93.5 (3)	C5—C4—H4	120.1
O4^i—Cd1—N1	86.0 (4)	C6—C5—H5	119.8
O2^ii—Cd1—N1	85.0 (4)	C4—C5—H5	119.7
N2^iii—Cd1—N1	178.1 (8)	C5—C6—H6	120.4
O2—P1—O1	119.0 (3)	C1—C6—H6	120.4
O2—P1—C7	109.2 (4)	C9—C8—H8	119.0
O1—P1—C7	107.8 (4)	C7—C8—H8	119.0
O2—P1—C1	107.7 (4)	C8—C9—H9	120.9
O1—P1—C1	108.5 (4)	C10—C9—H9	120.9
C7—P1—C1	103.6 (3)	C9—C10—H10	119.4
O3—P2—O4	119.0 (3)	C11—C10—H10	119.4
O3—P2—C19	108.1 (4)	C12—C11—H11	120.7
O4—P2—C19	109.7 (4)	C10—C11—H11	120.7
O3—P2—C13	108.7 (4)	C11—C12—H12	119.2
O4—P2—C13	106.6 (4)	C7—C12—H12	119.2
C19—P2—C13	103.7 (3)	C13—C14—H14	119.8
P1—O1—Cd1	138.9 (3)	C15—C14—H14	119.8
P1—O2—Cd1^i	150.3 (3)	C16—C15—H15	119.6
P2—O3—Cd1	139.8 (3)	C14—C15—H15	119.6
P2—O4—Cd1^ii	150.0 (3)	C15—C16—H16	120.4
C29—N1—C25	117.1 (4)	C17—C16—H16	120.4
C29—N1—Cd1	122.0 (7)	C18—C17—H17	119.8
C25—N1—Cd1	120.9 (8)	C16—C17—H17	119.8
C32—N2—C33	117.6 (4)	C17—C18—H18	119.8
C32—N2—Cd1^iv	123.1 (10)	C13—C18—H18	119.8
C33—N2—Cd1^iv	119.3 (10)	C21—C20—H20	120.3
C2—C1—C6	119.0 (7)	C19—C20—H20	120.3
C2—C1—P1	122.4 (6)	C22—C21—H21	119.5
C6—C1—P1	118.6 (6)	C20—C21—H21	119.5
C1—C2—C3	121.2 (8)	C23—C22—H22	120.3
C4—C3—C2	120.1 (10)	C21—C22—H22	120.3
C3—C4—C5	119.8 (9)	C22—C23—H23	119.2
C6—C5—C4	120.5 (10)	C24—C23—H23	119.2
C5—C6—C1	119.2 (8)	C19—C24—H24	120.8
C8—C7—C12	118.2 (6)	C23—C24—H24	120.8
C8—C7—P1	120.3 (5)	N1—C25—H25	118.8
C12—C7—P1	121.5 (5)	C26—C25—H25	118.8
C9—C8—C7	122.0 (7)	C27—C26—H26	119.6
C8—C9—C10	118.2 (7)	C25—C26—H26	119.6
C9—C10—C11	121.1 (7)	N1—C29—H29	117.8
C12—C11—C10	118.7 (7)	C38—C29—H29	117.8
C11—C12—C7	121.7 (7)	C32—C31—H31	120.0
C14—C13—C18	118.7 (6)	C30—C31—H31	120.0
C14—C13—P2	119.9 (6)	N2—C32—H32	118.7
C18—C13—P2	121.3 (6)	C31—C32—H32	118.7
C13—C14—C15	120.4 (9)	C34—C33—N2	123.4 (11)
C16—C15—C14	120.8 (11)	C34—C33—H33	118.3
C15—C16—C17	119.2 (9)	N2—C33—H33	118.3
C18—C17—C16	120.4 (9)	C33—C34—H34	120.4
C17—C18—C13	120.5 (8)	C30—C34—H34	120.4
C24—C19—C20	120.2 (6)	C29—C38—H38	120.9
C24—C19—P2	120.6 (5)	C27—C38—H38	120.9
C20—C19—P2	119.2 (6)	O1S—C1S—N1S	119.0 (11)
C21—C20—C19	119.4 (7)	O1S—C1S—H1S	120.5
C22—C21—C20	121.0 (7)	N1S—C1S—H1S	120.5
C23—C22—C21	119.4 (8)	N1S—C2S—H2SA	109.5
C22—C23—C24	121.6 (8)	N1S—C2S—H2SB	109.5
C19—C24—C23	118.4 (7)	H2SA—C2S—H2SB	109.5
N1—C25—C26	122.5 (7)	N1S—C2S—H2SC	109.5
C27—C26—C25	120.9 (7)	H2SA—C2S—H2SC	109.5
C26—C27—C38	116.8 (4)	H2SB—C2S—H2SC	109.5
C26—C27—C30	123.2 (12)	N1S—C3S—H3SA	109.5
C38—C27—C30	119.8 (12)	N1S—C3S—H3SB	109.5
N1—C29—C38	124.3 (7)	H3SA—C3S—H3SB	109.5
C34—C30—C31	117.0 (4)	N1S—C3S—H3SC	109.5
C34—C30—C27	121.2 (14)	H3SA—C3S—H3SC	109.5
C31—C30—C27	121.7 (15)	H3SB—C3S—H3SC	109.5
C32—C31—C30	120.1 (10)
O2—P1—O1—Cd1	−24.0 (7)	P2—C13—C14—C15	178.0 (7)
C7—P1—O1—Cd1	101.0 (5)	C13—C14—C15—C16	1.7 (14)
C1—P1—O1—Cd1	−147.4 (4)	C14—C15—C16—C17	−3.1 (18)
O1—P1—O2—Cd1^i	120.6 (6)	C15—C16—C17—C18	3.1 (18)
C7—P1—O2—Cd1^i	−3.7 (7)	C16—C17—C18—C13	−1.7 (13)
C1—P1—O2—Cd1^i	−115.6 (6)	C14—C13—C18—C17	0.2 (10)
O4—P2—O3—Cd1	−27.4 (8)	P2—C13—C18—C17	−178.0 (6)
C19—P2—O3—Cd1	98.4 (5)	O3—P2—C19—C24	4.8 (6)
C13—P2—O3—Cd1	−149.7 (4)	O4—P2—C19—C24	135.9 (6)
O3—P2—O4—Cd1^ii	118.7 (6)	C13—P2—C19—C24	−110.5 (6)
C19—P2—O4—Cd1^ii	−6.4 (7)	O3—P2—C19—C20	−175.1 (5)
C13—P2—O4—Cd1^ii	−118.0 (6)	O4—P2—C19—C20	−44.0 (6)
O2—P1—C1—C2	−161.7 (6)	C13—P2—C19—C20	69.6 (6)
O1—P1—C1—C2	−31.6 (7)	C24—C19—C20—C21	−0.3 (10)
C7—P1—C1—C2	82.7 (7)	P2—C19—C20—C21	179.6 (5)
O2—P1—C1—C6	21.9 (7)	C19—C20—C21—C22	−0.6 (11)
O1—P1—C1—C6	152.0 (5)	C20—C21—C22—C23	0.2 (12)
C7—P1—C1—C6	−93.7 (6)	C21—C22—C23—C24	1.0 (13)
C6—C1—C2—C3	−1.2 (11)	C20—C19—C24—C23	1.5 (10)
P1—C1—C2—C3	−177.6 (6)	P2—C19—C24—C23	−178.4 (6)
C1—C2—C3—C4	0.8 (14)	C22—C23—C24—C19	−1.8 (12)
C2—C3—C4—C5	−1.8 (18)	C29—N1—C25—C26	−3.3 (16)
C3—C4—C5—C6	3.3 (18)	Cd1—N1—C25—C26	179.6 (6)
C4—C5—C6—C1	−3.7 (14)	N1—C25—C26—C27	6.1 (16)
C2—C1—C6—C5	2.6 (11)	C25—C26—C27—C38	−6 (2)
P1—C1—C6—C5	179.2 (6)	C25—C26—C27—C30	179.1 (11)
O2—P1—C7—C8	−44.8 (6)	C25—N1—C29—C38	1.3 (17)
O1—P1—C7—C8	−175.4 (5)	Cd1—N1—C29—C38	178.4 (6)
C1—P1—C7—C8	69.7 (6)	C26—C27—C30—C34	−38.5 (18)
O2—P1—C7—C12	134.9 (5)	C38—C27—C30—C34	147.1 (13)
O1—P1—C7—C12	4.2 (6)	C26—C27—C30—C31	141.6 (16)
C1—P1—C7—C12	−110.6 (6)	C38—C27—C30—C31	−32.8 (15)
C12—C7—C8—C9	−0.7 (10)	C34—C30—C31—C32	1.2 (13)
P1—C7—C8—C9	179.0 (5)	C27—C30—C31—C32	−178.8 (7)
C7—C8—C9—C10	−1.0 (10)	C33—N2—C32—C31	1.5 (14)
C8—C9—C10—C11	1.3 (12)	Cd1^iv—N2—C32—C31	179.7 (6)
C9—C10—C11—C12	0.1 (13)	C30—C31—C32—N2	−1.2 (13)
C10—C11—C12—C7	−1.9 (12)	C32—N2—C33—C34	−2.1 (13)
C8—C7—C12—C11	2.2 (10)	Cd1^iv—N2—C33—C34	179.6 (6)
P1—C7—C12—C11	−177.5 (6)	N2—C33—C34—C30	2.2 (12)
O3—P2—C13—C14	148.8 (6)	C31—C30—C34—C33	−1.7 (12)
O4—P2—C13—C14	19.4 (7)	C27—C30—C34—C33	178.3 (6)
C19—P2—C13—C14	−96.4 (6)	N1—C29—C38—C27	−1.9 (14)
O3—P2—C13—C18	−33.0 (7)	C26—C27—C38—C29	4 (2)
O4—P2—C13—C18	−162.4 (5)	C30—C27—C38—C29	179.1 (10)
C19—P2—C13—C18	81.8 (6)	C3S—N1S—C1S—O1S	−6.3 (19)
C18—C13—C14—C15	−0.2 (11)	C2S—N1S—C1S—O1S	174.6 (11)

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