A novel dinuclear bismuth(III) coordination compound: bis(μ-pyridine-2,6-di­carboxyl­ato)-κ⁴O²,N,O⁶:O^6′;κ⁴O²:O^2′,N,O⁶-bis­[(azido-κN)(1,10-phenanthroline-κ²N,N′)bismuth(III)] tetra­hydrate

A novel dinuclear bismuth(III) coordination compound, [Bi₂(C₇H₃NO₄)₂(N₃)₂(C₁₂H₈N₂)₂]·4H₂O, has been synthesized by an iono­thermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. The mol­ecular structure consists of one centrosymmetric dinuclear neutral fragment and four water mol­ecules. Within the dinuclear fragment, each Bi^III centre is seven-coordinated by three O atoms and four N atoms. The coordination geometry of each Bi^III atom is distorted penta­gonal–bipy­rami­dal (BiO₃N₄), with one azide N atom and one bridging carboxyl­ate O atom located in axial positions. The carboxyl­ate O atoms and water mol­ecules are assembled via O—H...O hydrogen bonds, resulting in the formation of a three-dimensional supra­molecular structure. Two types of π–π stacking inter­actions are found, with centroid-to-centroid distances of 3.461 (4) and 3.641 (4) Å.

S1. Introduction

In recent years, the design and construction of novel bis­muth(III) metal coordination compounds have developed into an increasingly popular field due to their fascinating structural architectures and potential applications (Villinger & Schulz, 2010; Yang & Sun, 2007; Sun et al., 2004). The large radii, variable coordination numbers and flexible coordination environments of Bi³⁺ cations make it difficult to control the reactions and obtain the desired? final structures of coordination compounds. However, the fascinating coordination chemistry and inter­esting structures, coupled with the functional peculiarities of bis­muth coordination compounds, have attracted increasing inter­est. The judicious choice of organic ligands would be an efficient method for preparing novel bis­muth(III) coordination compounds. For example, the ligand of pyridine-2,6-di­carb­oxy­lic acid has a large variation in coordination behaviour including chelating, bidentate bridging and chelating bridging modes, which allows for the formation of clusters or open frameworks. The linear azide anion N₃^- always exhibits two types of coordination mode, viz. EE (end-to-end) and EO (end-on), which may provide greater opportunities for obtaining bis­muth(III) coordination compounds with higher dimensionalities and new structural features. It is of particular inter­est that the incorporation of the linear azide anion into metal coordination compounds may yield novel magnetic materials (Lyhs et al., 2012; Schulz & Villinger, 2011). While hydro- and solvothermal methods are typical synthetic routes to metal coordination compounds, recent research has revealed that ionothermal synthesis is a promising technique in preparing compounds with new structural architectures, new compositions and inter­esting properties (Cooper et al., 2004; Himeur et al., 2010; Pamham & Morris, 2007). Ionothermal synthesis has received great attention from chemists owing to the different chemistry of the ionic liquid solvent system compared with that of the traditionally used water or alcohols in hydro- and solvothermal methods. Under the above considerations and using three types of ligand, viz. N₃^-, pyridine-2,6-di­carboxyl­ate (pdc^2-) and 1,10-phenanthroline (phen), we have obtained the title novel bis­muth(III) coordination compound, [Bi₂(pdc)₂(N₃)₂(phen)₂].4H₂O, (I), with a three-dimensional supra­molecular structure, under ionothermal conditions using the ionic liquid 1-ethyl-3-methyl­imidazolium ([Emim]Br) as solvent.

S2. Experimental

S2.1. Synthesis and crystallization

All chemicals were of reagent grade quality obtained from commercial sources and were used without further purification. Compound (I) was prepared under ionothermal conditions using the ionic liquid 1-ethyl-3-methyl­imidazolium ([Emim]Br) as solvent. A mixture of Bi(NO₃)₃.5H₂O (0.34 g, 0.70 mmol), NaN₃ (0.29 g, 4.5 mmol), pyridine-2,6-di­carb­oxy­lic acid (0.17 g, 1.0 mmol), 1,10-phenanthroline (0.08 g, 0.40 mmol) and [Emim]Br (1.0 g, 5.23 mmol) was stirred for 30 min, and then transferred to a Teflon-lined stainless steel autoclave (50 ml) and heated at 413 K for 5 d. After the mixture had been cooled slowly [Cooling rate?] to room temperature, colourless rod-shaped crystals of (I) were obtained. The product was filtered off, washed with deionized water, purified ultrasonically and dried in a vacuum desiccator at ambient temperature [yield 43%, based on Bi(NO₃)₃.5H₂O]. Attempts to prepare (I) using H₂O (1.0 g) as solvent were unsuccessful. However, it is worth noting that (I) can be obtained using the ionic liquid 3-butyl-1-methyl­imidazolium bromide ([Bmim]Br) as solvent instead of [Emim]Br. This indicates that the solvent ionic liquid plays a crucial role in the formation of (I).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C). The H atoms bonded to atoms O1W and O2W were located from Fourier difference maps and refined with distance restraints of O1W—H1WA = O1W—H1WB = O2W—H2WB = 0.83 (2) Å, O2W—H2WA = 0.86 (2) Å, H1WA···H1WB = 1.37 Å and H2WA···H2WB = 1.37 Å. Atoms N4 and N5 were refined with the restraint `delu 0.01 0.02 N4 N5' [Please express in non-software-specific terms].

S3. Results and discussion

The molecular structure of (I) (Fig. 1), contains one dimeric neutral [Bi₂(pdc)₂(N₃)₂(phen)₂] fragment which is centrosymmetric. Two [Bi2(pdc)(N₃)(phen)] monomers are connected by two bridging carboxyl­ate O atoms, resulting in the formation of the dimeric fragment, in which each Bi^III centre is seven-coordinated by one tridentate pdc^2- ligand (one N atom and two O atoms), one phen ligand (two N atoms), one linear N₃^- anion (one N atom) and one bridging carboxyl­ate O atom from another carboxyl­ate ligand. The coordination geometry of Bi^III is distorted penta­gonal–bipyramidal [BiO₃N₄], with one N atom and one bridging carboxyl­ate O atom located in axial positions. The Bi1—O and Bi1—N bond lengths vary in the ranges 2.339 (4)–2.905 (4) and 2.209 (5)–2.577 (5) Å, respectively. The dimeric fragment contains one eight-membered ring [atoms Bi1, O1, C1, O2, Bi1ⁱ, O1ⁱ, C1ⁱ and O2ⁱ; symmetry code: (i) -x + 1, -y + 2, -z + 1], which is built up from two Bi^III cations [Bi···Bi = 5.5677 (18) Å] and two carboxyl­ate groups. Inter­estingly, such a long distance has only been observed previously in bis­muth compounds containing eight-membered rings, for example, bis­{[µ₂-1-carb­oxy­methyl-4,7-bis­(1-methyl­imidazol-2-yl­methyl)-1,4,7-tri­aza­cyclo­nonane]chloridobismuth(III)} bis­(tetra­phenyl­borate) (Bi···Bi = 5.350 Å; Vaira et al., 1999), poly[ammonium potassium bis­(µ₄-citrato)dibismuth tetra­hydrate] (Bi···Bi = 5.828 Å; Asato et al., 1993), bis­[trans-tetra­amminedi­nitro­cobalt(III)] bis­(µ₂-ethyl­enedi­amine­tetra­acetato)­bis­[aqua­bis­muth(III)] tetra­hydrate (Bi···Bi = 5.960 Å; Stavila et al., 2003) and bis­(1,10-phenanthrolinium) bis­(µ₂-pyridine-2,6-di­carboxyl­ato-κ⁴O,O',O'',N)bis­[aqua­(pyridine-2,6-di­carboxyl­ato-κ³O,O',N)bis­muth(III)] penta­hydrate (Bi···Bi = 5.997 Å; Sheshmani et al., 2005). Shorter distances (3.650–4.617 Å) are frequently found in bis­muth compounds containing four-membered rings (two Bi^III cations and two O atoms; Yu et al., 2004; Thurston et al., 2002). This is due to the different coordination modes between carboxyl­ate ligands and Bi^III cations.

The three-dimensional supra­molecular structure of (I) is generated by O—H···O hydrogen-bonding inter­actions between the water molecules and carboxyl­ate O atoms (Fig. 2). The hydrogen-bonding parameters are given in Table 2. In addition, there are two types of π–π stacking inter­action (André et al., 1997): (i) the N3/C13/C14/C17–C19 pyridine rings are almost parallel to each other (dihedral angle between the planes = 1°), with a centroid-to-centroid distance of 3.641 (4) Å; (ii) π–π stacking inter­actions are also found between the N3/C13/C14/C17–C19 pyridine rings and the C11–C16 rings of neighbouring molecules (dihedral angle between the planes = 3.6°), with a centroid-to-centroid distance of 3.461 (4) Å.

The energy-dispersive X-ray spectroscopy (EDS) results for a single crystal of (I) indicate the presence of the elements Bi, C, N and O. Elemental analysis (C, H and N) was also performed, using a Perkin–Elmer 240 analyser. Analysis, calculated for (I): C 36.09, H 2.39, N 13.29%; found: C 36.37, H 2.26, N 13.51%. These results are in agreement with the single-crystal X-ray structural analysis.

In the IR spectrum of (I) (Fig. 3), the peaks at 2064 and 1365 cm^-1 can be ascribed to N₃^- anions; both peaks are characteristic asymmetric vibrations resulting from the N₃^- anions (Gao et al., 2003). The peaks at 1639, 1270 and 907 cm^-1 can be attributed to the –COO^- groups, and the peak at 3429 cm^-1 can be assigned to water. In the high-frequency region of the IR spectrum, weak absorption bands observed at 3066 cm^-1 can be attributed to the C—H vibration of the aromatic groups, while in the low-frequency region, a series of absorptions in the range 1516–1064 cm^-1 (1516, 1420, 1270, 1174, 1147, 1099 and 1064 cm^-1) can be assigned to the pdc^2- and phen ligands.

The oxidation state of Bi^III was confirmed further by means of X-ray photoelectron spectroscopy (XPS) measurements. The spin-orbit components (4f 7/2 and 4f 5/2) of the Bi 4f peaks were deconvoluted into two curves at approximately 159.1 and 164.4 eV (Fig. 4), revealing that the oxidation state of Bi is +3 in (I) (Lu et al., 2000).

In summary, the title bis­muth coordination compound, containing three types of ligand, has been obtained by the ionothermal method and enriches the family of reported bis­muth coordination compounds. The successful synthesis of (I) indicates that more bis­muth coordination compounds with novel structures and physical properties may be accessible using a similar method.

Related literature

For related literature, see: André et al. (1997); Asato et al. (1993); Cooper et al. (2004); Gao et al. (2003); Himeur et al. (2010); Lu et al. (2000); Lyhs et al. (2012); Pamham & Morris (2007); Schulz & Villinger (2011); Sheshmani et al. (2005); Stavila et al. (2003); Sun et al. (2004); Thurston et al. (2002); Vaira et al. (1999); Villinger & Schulz (2010); Yang & Sun (2007); Yu et al. (2004).

Computing details

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 (Bruker, 2008); software used to prepare material for publication: SHELXTL (Bruker, 2008).

Figures

Fig. 1. The structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) -x + 1, -y + 2, -z + 1.]

Fig. 2. The three-dimensional supramolecular structure of (I), viewed down the a axis. Dashed lines indicate hydrogen bonds.

Fig. 3. The IR spectrum of (I).

Fig. 4. The XPS spectrum of the oxidation state Bi^III in (I).

Bis(µ-pyridine-2,6-dicarboxylato)-κ⁴O²,N,O⁶:O^6';κ⁴O²:O^2',N,O⁶-bis[(azido-κN)(1,10-phenanthroline-κ²N,N')bismuth(III)] tetrahydrate

Crystal data

[Bi2(C7H3NO4)2(N3)2(C12H8N2)2]·4H2O	F(000) = 2416
Mr = 1264.70	Dx = 2.143 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ac2ab	Cell parameters from 4566 reflections
a = 7.280 (3) Å	θ = 3.1–26.7°
b = 22.171 (10) Å	µ = 9.05 mm^−1
c = 24.289 (11) Å	T = 296 K
V = 3920 (3) Å^3	Rod, colourless
Z = 4	0.18 × 0.16 × 0.14 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	3843 independent reflections
Radiation source: fine-focus sealed tube	2876 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.064
ϕ and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
Tmin = 0.293, Tmax = 0.364	k = −27→25
20096 measured reflections	l = −22→29

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0182P)^2 + 4.6235P] where P = (Fo^2 + 2Fc^2)/3
3843 reflections	(Δ/σ)max = 0.001
301 parameters	Δρmax = 1.07 e Å^−3
7 restraints	Δρmin = −1.05 e Å^−3

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. 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 (Ų)

	x	y	z	Uiso*/Ueq
Bi1	0.58478 (3)	0.927444 (8)	0.409976 (8)	0.02692 (8)
C1	0.6114 (8)	0.9358 (2)	0.5411 (2)	0.0348 (13)
C2	0.5322 (7)	0.8733 (2)	0.5340 (2)	0.0276 (12)
C3	0.4845 (8)	0.8344 (3)	0.5757 (2)	0.0369 (14)
H3	0.5005	0.8454	0.6124	0.044*
C4	0.4128 (9)	0.7790 (3)	0.5623 (2)	0.0451 (15)
H4	0.3842	0.7517	0.5900	0.054*
C5	0.3831 (8)	0.7637 (2)	0.5087 (2)	0.0362 (14)
H5	0.3305	0.7268	0.4995	0.043*
C6	0.4334 (7)	0.8044 (2)	0.4685 (2)	0.0279 (12)
C7	0.4108 (8)	0.7928 (3)	0.4076 (2)	0.0339 (12)
C8	0.8739 (8)	1.0495 (3)	0.4255 (2)	0.0371 (14)
H8	0.8701	1.0371	0.4621	0.045*
C9	0.9543 (9)	1.1047 (3)	0.4129 (3)	0.0444 (16)
H9	1.0046	1.1284	0.4407	0.053*
C10	0.9591 (8)	1.1240 (3)	0.3596 (3)	0.0428 (16)
H10	1.0111	1.1611	0.3509	0.051*
C11	0.8854 (8)	1.0877 (2)	0.3182 (3)	0.0374 (14)
C12	0.8092 (7)	1.0325 (2)	0.3336 (2)	0.0294 (12)
C13	0.7411 (8)	0.9921 (2)	0.2917 (2)	0.0295 (12)
C14	0.7587 (7)	1.0088 (2)	0.2362 (2)	0.0325 (12)
C15	0.8327 (8)	1.0661 (3)	0.2218 (3)	0.0415 (15)
H15	0.8401	1.0775	0.1851	0.050*
C16	0.8920 (8)	1.1039 (3)	0.2615 (3)	0.0446 (16)
H16	0.9384	1.1415	0.2516	0.054*
C17	0.7019 (8)	0.9676 (3)	0.1964 (2)	0.0382 (14)
H17	0.7130	0.9770	0.1593	0.046*
C18	0.6295 (8)	0.9130 (3)	0.2120 (2)	0.0388 (15)
H18	0.5929	0.8849	0.1859	0.047*
C19	0.6121 (8)	0.9010 (3)	0.2682 (2)	0.0359 (13)
H19	0.5612	0.8643	0.2788	0.043*
N1	0.5069 (6)	0.85734 (18)	0.48132 (17)	0.0255 (9)
N2	0.8022 (6)	1.01393 (19)	0.38697 (18)	0.0289 (10)
N3	0.6644 (6)	0.93903 (19)	0.30713 (18)	0.0299 (10)
N4	0.8377 (7)	0.8724 (2)	0.4102 (2)	0.0425 (12)
N5	0.9810 (8)	0.8931 (2)	0.42447 (19)	0.0407 (12)
N6	1.1240 (8)	0.9105 (3)	0.4374 (3)	0.0664 (18)
O1	0.6725 (5)	0.96081 (16)	0.49748 (15)	0.0378 (9)
O2	0.6112 (6)	0.95846 (19)	0.58721 (15)	0.0444 (11)
O3	0.4755 (6)	0.83368 (16)	0.37533 (15)	0.0393 (10)
O4	0.3341 (6)	0.74664 (18)	0.39293 (17)	0.0461 (11)
O2W	0.7224 (9)	0.7537 (3)	0.3031 (2)	0.0845 (17)
O1W	0.9056 (8)	0.2500 (4)	0.1968 (2)	0.0885 (18)
H1WB	0.826 (8)	0.245 (4)	0.173 (2)	0.106*
H1WA	0.860 (9)	0.253 (4)	0.2279 (14)	0.106*
H2WA	0.827 (6)	0.770 (4)	0.298 (4)	0.106*
H2WB	0.664 (9)	0.775 (3)	0.325 (3)	0.106*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.03314 (13)	0.02196 (11)	0.02565 (12)	−0.00099 (9)	−0.00045 (9)	0.00002 (9)
C1	0.033 (3)	0.033 (3)	0.038 (4)	0.002 (3)	−0.006 (3)	−0.002 (3)
C2	0.026 (3)	0.028 (3)	0.029 (3)	0.003 (2)	−0.001 (2)	0.000 (2)
C3	0.040 (3)	0.049 (4)	0.022 (3)	0.004 (3)	0.002 (2)	0.003 (3)
C4	0.057 (4)	0.048 (4)	0.030 (3)	−0.003 (3)	0.008 (3)	0.009 (3)
C5	0.041 (4)	0.024 (3)	0.044 (4)	−0.004 (2)	0.000 (3)	0.005 (2)
C6	0.026 (3)	0.026 (3)	0.032 (3)	0.002 (2)	0.008 (2)	−0.001 (2)
C7	0.032 (3)	0.034 (3)	0.036 (3)	0.003 (3)	0.002 (3)	−0.005 (3)
C8	0.040 (4)	0.032 (3)	0.039 (3)	−0.001 (3)	−0.001 (3)	−0.006 (3)
C9	0.047 (4)	0.033 (3)	0.053 (4)	−0.011 (3)	−0.005 (3)	−0.008 (3)
C10	0.042 (4)	0.026 (3)	0.061 (4)	−0.008 (3)	0.009 (3)	0.001 (3)
C11	0.033 (3)	0.027 (3)	0.052 (4)	−0.002 (2)	0.001 (3)	0.001 (3)
C12	0.030 (3)	0.027 (3)	0.031 (3)	0.001 (2)	0.004 (2)	0.000 (2)
C13	0.030 (3)	0.027 (3)	0.031 (3)	0.005 (3)	0.001 (2)	0.004 (2)
C14	0.023 (3)	0.035 (3)	0.040 (3)	0.006 (2)	0.003 (3)	0.009 (3)
C15	0.042 (4)	0.040 (3)	0.042 (4)	0.007 (3)	0.008 (3)	0.016 (3)
C16	0.038 (4)	0.027 (3)	0.068 (5)	0.003 (3)	0.009 (3)	0.019 (3)
C17	0.040 (4)	0.044 (3)	0.030 (3)	0.007 (3)	0.004 (3)	0.007 (3)
C18	0.044 (4)	0.042 (3)	0.031 (3)	0.003 (3)	−0.003 (3)	−0.005 (3)
C19	0.048 (4)	0.028 (3)	0.032 (3)	−0.001 (3)	−0.003 (3)	0.003 (3)
N1	0.026 (2)	0.024 (2)	0.026 (2)	0.0019 (19)	−0.0021 (18)	−0.0009 (19)
N2	0.030 (3)	0.026 (2)	0.031 (2)	−0.0013 (19)	−0.0007 (19)	−0.003 (2)
N3	0.034 (3)	0.026 (2)	0.030 (2)	−0.001 (2)	0.000 (2)	0.0016 (19)
N4	0.036 (3)	0.024 (2)	0.067 (4)	0.003 (2)	0.003 (3)	0.001 (3)
N5	0.045 (3)	0.048 (3)	0.029 (3)	0.017 (3)	0.003 (2)	0.005 (2)
N6	0.046 (4)	0.079 (4)	0.074 (5)	0.009 (3)	−0.020 (3)	−0.013 (4)
O1	0.050 (3)	0.031 (2)	0.033 (2)	−0.0106 (19)	−0.0015 (18)	−0.0037 (18)
O2	0.063 (3)	0.042 (2)	0.028 (2)	−0.002 (2)	−0.0074 (19)	−0.013 (2)
O3	0.055 (3)	0.033 (2)	0.030 (2)	−0.0165 (19)	0.0005 (18)	−0.0032 (18)
O4	0.061 (3)	0.034 (2)	0.043 (2)	−0.017 (2)	−0.001 (2)	−0.011 (2)
O2W	0.097 (5)	0.097 (4)	0.060 (4)	0.028 (4)	0.012 (3)	−0.006 (3)
O1W	0.072 (4)	0.133 (5)	0.060 (3)	0.012 (4)	−0.004 (3)	0.002 (4)

Geometric parameters (Å, º)

Bi1—N4	2.209 (5)	C9—H9	0.9300
Bi1—O1	2.339 (4)	C10—C11	1.395 (8)
Bi1—O3	2.380 (4)	C10—H10	0.9300
Bi1—N1	2.396 (4)	C11—C12	1.394 (7)
Bi1—N2	2.549 (4)	C11—C16	1.424 (9)
Bi1—N3	2.577 (5)	C12—N2	1.362 (6)
Bi1—O2^i	2.905 (4)	C12—C13	1.443 (7)
C1—O2	1.227 (7)	C13—N3	1.354 (6)
C1—O1	1.277 (7)	C13—C14	1.405 (7)
C1—C2	1.509 (7)	C14—C17	1.392 (8)
C2—N1	1.340 (6)	C14—C15	1.424 (7)
C2—C3	1.376 (7)	C15—C16	1.348 (9)
C3—C4	1.375 (8)	C15—H15	0.9300
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.362 (8)	C17—C18	1.372 (8)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.380 (7)	C18—C19	1.396 (8)
C5—H5	0.9300	C18—H18	0.9300
C6—N1	1.327 (6)	C19—N3	1.324 (7)
C6—C7	1.511 (7)	C19—H19	0.9300
C7—O4	1.219 (6)	N4—N5	1.192 (7)
C7—O3	1.286 (6)	N5—N6	1.154 (7)
C8—N2	1.331 (7)	O2W—H2WA	0.86 (2)
C8—C9	1.391 (9)	O2W—H2WB	0.83 (2)
C8—H8	0.9300	O1W—H1WB	0.83 (2)
C9—C10	1.364 (8)	O1W—H1WA	0.83 (2)
N4—Bi1—O1	86.86 (17)	C11—C10—H10	120.2
N4—Bi1—O3	78.28 (17)	C12—C11—C10	117.8 (5)
O1—Bi1—O3	133.54 (13)	C12—C11—C16	119.5 (5)
N4—Bi1—N1	80.63 (16)	C10—C11—C16	122.6 (5)
O1—Bi1—N1	67.21 (13)	N2—C12—C11	122.3 (5)
O3—Bi1—N1	67.04 (13)	N2—C12—C13	118.0 (4)
N4—Bi1—N2	84.17 (16)	C11—C12—C13	119.6 (5)
O1—Bi1—N2	77.98 (13)	N3—C13—C14	122.2 (5)
O3—Bi1—N2	141.95 (13)	N3—C13—C12	119.1 (4)
N1—Bi1—N2	142.54 (14)	C14—C13—C12	118.7 (5)
N4—Bi1—N3	82.51 (17)	C17—C14—C13	117.7 (5)
O1—Bi1—N3	141.97 (14)	C17—C14—C15	122.0 (5)
O3—Bi1—N3	79.61 (13)	C13—C14—C15	120.3 (5)
N1—Bi1—N3	144.98 (14)	C16—C15—C14	120.1 (6)
N2—Bi1—N3	64.70 (14)	C16—C15—H15	120.0
O2—C1—O1	125.4 (5)	C14—C15—H15	120.0
O2—C1—C2	118.7 (5)	C15—C16—C11	121.6 (5)
O1—C1—C2	115.9 (5)	C15—C16—H16	119.2
N1—C2—C3	120.2 (5)	C11—C16—H16	119.2
N1—C2—C1	113.9 (5)	C18—C17—C14	120.1 (5)
C3—C2—C1	125.9 (5)	C18—C17—H17	119.9
C4—C3—C2	118.7 (5)	C14—C17—H17	119.9
C4—C3—H3	120.6	C17—C18—C19	118.3 (5)
C2—C3—H3	120.6	C17—C18—H18	120.9
C5—C4—C3	120.7 (5)	C19—C18—H18	120.9
C5—C4—H4	119.7	N3—C19—C18	123.4 (5)
C3—C4—H4	119.7	N3—C19—H19	118.3
C4—C5—C6	118.1 (5)	C18—C19—H19	118.3
C4—C5—H5	121.0	C6—N1—C2	120.9 (5)
C6—C5—H5	121.0	C6—N1—Bi1	120.0 (3)
N1—C6—C5	121.3 (5)	C2—N1—Bi1	119.1 (3)
N1—C6—C7	115.1 (4)	C8—N2—C12	118.4 (5)
C5—C6—C7	123.6 (5)	C8—N2—Bi1	122.4 (4)
O4—C7—O3	125.6 (5)	C12—N2—Bi1	117.4 (3)
O4—C7—C6	118.6 (5)	C19—N3—C13	118.3 (5)
O3—C7—C6	115.9 (5)	C19—N3—Bi1	124.3 (4)
N2—C8—C9	122.1 (6)	C13—N3—Bi1	116.6 (3)
N2—C8—H8	118.9	N5—N4—Bi1	121.1 (4)
C9—C8—H8	118.9	N6—N5—N4	176.5 (7)
C10—C9—C8	119.7 (6)	C1—O1—Bi1	121.5 (3)
C10—C9—H9	120.2	C7—O3—Bi1	121.5 (3)
C8—C9—H9	120.2	H2WA—O2W—H2WB	108 (3)
C9—C10—C11	119.6 (5)	H1WB—O1W—H1WA	111 (4)
C9—C10—H10	120.2
O2—C1—C2—N1	168.0 (5)	O3—Bi1—N1—C2	178.4 (4)
O1—C1—C2—N1	−11.4 (7)	N2—Bi1—N1—C2	29.9 (5)
O2—C1—C2—C3	−11.1 (8)	N3—Bi1—N1—C2	159.5 (3)
O1—C1—C2—C3	169.6 (5)	C9—C8—N2—C12	0.3 (8)
N1—C2—C3—C4	0.7 (8)	C9—C8—N2—Bi1	−163.9 (5)
C1—C2—C3—C4	179.7 (6)	C11—C12—N2—C8	−1.2 (8)
C2—C3—C4—C5	−2.4 (9)	C13—C12—N2—C8	176.4 (5)
C3—C4—C5—C6	2.4 (9)	C11—C12—N2—Bi1	163.7 (4)
C4—C5—C6—N1	−0.6 (8)	C13—C12—N2—Bi1	−18.7 (6)
C4—C5—C6—C7	179.1 (5)	N4—Bi1—N2—C8	−93.7 (4)
N1—C6—C7—O4	−175.7 (5)	O1—Bi1—N2—C8	−5.6 (4)
C5—C6—C7—O4	4.6 (8)	O3—Bi1—N2—C8	−156.2 (4)
N1—C6—C7—O3	4.2 (7)	N1—Bi1—N2—C8	−27.4 (5)
C5—C6—C7—O3	−175.6 (5)	N3—Bi1—N2—C8	−178.1 (5)
N2—C8—C9—C10	0.8 (10)	N4—Bi1—N2—C12	102.1 (4)
C8—C9—C10—C11	−0.9 (10)	O1—Bi1—N2—C12	−169.9 (4)
C9—C10—C11—C12	0.0 (9)	O3—Bi1—N2—C12	39.6 (5)
C9—C10—C11—C16	−177.5 (6)	N1—Bi1—N2—C12	168.3 (3)
C10—C11—C12—N2	1.1 (8)	N3—Bi1—N2—C12	17.6 (3)
C16—C11—C12—N2	178.7 (5)	C18—C19—N3—C13	−1.0 (8)
C10—C11—C12—C13	−176.4 (5)	C18—C19—N3—Bi1	168.8 (4)
C16—C11—C12—C13	1.1 (8)	C14—C13—N3—C19	3.0 (8)
N2—C12—C13—N3	3.5 (7)	C12—C13—N3—C19	−176.2 (5)
C11—C12—C13—N3	−178.9 (5)	C14—C13—N3—Bi1	−167.6 (4)
N2—C12—C13—C14	−175.8 (5)	C12—C13—N3—Bi1	13.2 (6)
C11—C12—C13—C14	1.9 (8)	N4—Bi1—N3—C19	87.4 (4)
N3—C13—C14—C17	−2.9 (8)	O1—Bi1—N3—C19	162.5 (4)
C12—C13—C14—C17	176.3 (5)	O3—Bi1—N3—C19	8.0 (4)
N3—C13—C14—C15	177.2 (5)	N1—Bi1—N3—C19	25.7 (6)
C12—C13—C14—C15	−3.6 (8)	N2—Bi1—N3—C19	174.5 (5)
C17—C14—C15—C16	−177.7 (6)	N4—Bi1—N3—C13	−102.7 (4)
C13—C14—C15—C16	2.2 (8)	O1—Bi1—N3—C13	−27.6 (5)
C14—C15—C16—C11	0.9 (9)	O3—Bi1—N3—C13	177.9 (4)
C12—C11—C16—C15	−2.6 (9)	N1—Bi1—N3—C13	−164.4 (3)
C10—C11—C16—C15	174.8 (6)	N2—Bi1—N3—C13	−15.6 (4)
C13—C14—C17—C18	0.8 (8)	O1—Bi1—N4—N5	−45.7 (5)
C15—C14—C17—C18	−179.3 (5)	O3—Bi1—N4—N5	178.6 (5)
C14—C17—C18—C19	1.1 (8)	N1—Bi1—N4—N5	−113.1 (5)
C17—C18—C19—N3	−1.1 (9)	N2—Bi1—N4—N5	32.6 (5)
C5—C6—N1—C2	−1.1 (8)	N3—Bi1—N4—N5	97.7 (5)
C7—C6—N1—C2	179.2 (4)	O2—C1—O1—Bi1	−160.5 (4)
C5—C6—N1—Bi1	−178.5 (4)	C2—C1—O1—Bi1	18.8 (6)
C7—C6—N1—Bi1	1.8 (6)	N4—Bi1—O1—C1	−95.1 (4)
C3—C2—N1—C6	1.0 (8)	O3—Bi1—O1—C1	−24.6 (5)
C1—C2—N1—C6	−178.1 (5)	N1—Bi1—O1—C1	−14.0 (4)
C3—C2—N1—Bi1	178.5 (4)	N2—Bi1—O1—C1	−179.9 (4)
C1—C2—N1—Bi1	−0.6 (6)	N3—Bi1—O1—C1	−168.8 (4)
N4—Bi1—N1—C6	−85.3 (4)	O4—C7—O3—Bi1	171.5 (5)
O1—Bi1—N1—C6	−175.8 (4)	C6—C7—O3—Bi1	−8.3 (6)
O3—Bi1—N1—C6	−4.1 (4)	N4—Bi1—O3—C7	91.4 (4)
N2—Bi1—N1—C6	−152.7 (3)	O1—Bi1—O3—C7	17.4 (5)
N3—Bi1—N1—C6	−23.0 (5)	N1—Bi1—O3—C7	6.8 (4)
N4—Bi1—N1—C2	97.3 (4)	N2—Bi1—O3—C7	155.8 (4)
O1—Bi1—N1—C2	6.7 (3)	N3—Bi1—O3—C7	175.9 (4)

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···O4^ii	0.83 (2)	1.98 (3)	2.793 (7)	167 (8)
O2W—H2WA···O1W^iii	0.86 (2)	2.00 (6)	2.709 (9)	140 (9)
O1W—H1WA···O2W^iv	0.83 (2)	1.92 (2)	2.746 (9)	173 (9)
O2W—H2WB···O3	0.83 (2)	2.25 (2)	3.075 (7)	172 (8)

Symmetry codes: (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, y+1/2, −z+1/2; (iv) −x+3/2, y−1/2, z.