A linear heterometallic bismuth-copper coordination polymer containing two types of organic ligands

In the linear coordination polymer catena-poly[[[aqua­(1,10-phenanthroline-[kappa]²N,N')copper(II)]-[mu]-pyridine-2,6-dicarboxyl­ato-[kappa]⁴O²:O^2',N,O⁶-[(nitrato-[kappa]²O,O')bismuth(III)]-[mu]-pyridine-2,6-di­carboxyl­ato-[kappa]⁴O²,N,O⁶:O^6'] dihydrate], {[Bi^IIICu^II(C₇H₃NO₄)₂(NO₃)(C₁₂H₈N₂)(H₂O)]·2H₂O}_n, the Bi^III cation is O,N,O'-chelated by the two pyridine-2,6-di­carboxyl­ate ligands and O,O'-chelated by the nitrate anion, the nine coordinating atoms conferring a tricapped trigonal prismatic environment on the metal centre. Each pyridine-2,6-di­carboxyl­ate ligand uses one of its carboxyl­ate O atoms to bind to an aqua­(1,10-phenanthroline)copper(II) unit, the Cu-O dative bonds giving rise to the formation of a ribbon motif. The Cu^II cation exhibits a square-pyramidal geometry. The ribbon motif propagates along the shortest axis of the triclinic unit cell and the solvent water mol­ecules are hydrogen bonded to the same ribbon.

S1. Introduction

For bis­muth derivatives of pyridine-2,6-di­carb­oxy­lic acid, the anion, in addition to engaging in N,O,O'-chelation, can also serve as a bridge between adjacent metal centres. Because the metal is trivalent and the carb­oxy­lic acid diprotic, some compounds exist as salts; in these bis­muthates, the negative charge is balanced by an ammonium counter-ion. Neutral compounds have also been isolated (Aghabozorg, Nemati et al., 2008; Aghabozorg, Ramezanipour et al., 2008; Aghabozorg et al., 2011; Anjaneyulu et al., 2010; Anjaneyulu & Kumara Swamy, 2011; Jeon et al., 2012; Ranjbar et al., 2003; Sharif et al., 2007; Sheshmani et al., 2005; Soleimannejad & Gholizadeh, 2012; Sushrutha & Natarajan, 2013; Stavila et al., 2009; Thirumurugan et al., 2012; Zevaco et al., 1992, 2009; Zhang, Tian et al., 2013; Zhang, Wang et al., 2013).

Charge balance in other bis­muthate salts is maintained by suitable metal cations. In the cobalt and nickel salts, the hexa­aqua­metallate(II) cation inter­acts with the dibismuthate anion through hydrogen-bonding inter­actions involving coordinated water molecules (Stavila et al., 2011). In the lithium derivative, the pyridine-2,6-di­carboxyl­ate unit uses a carboxyl­ate arm to bind to the metal centre (Thirumurugan et al., 2012).

An attempt to synthesize a heterometallic bis­muth pyridine-2,6-di­carboxyl­ate (pydc) complex using a hydro­thermal method instead of a conventional solution method yielded the hydrated bis­(2,2'-bi­pyridine)­chloridocopper(II) hemi[aqua­chloridobis(pyridine-2,6-di­carboxyl­ato)bis­muthate(III)] salt (Wang et al., 2011). Inter­estingly, replacing copper chloride with copper nitrate [as well as changing the ligand from 2,2'-bi­pyridine to 1,10-phenanthroline (phen)] yielded the title heterometallic compound, {[Bi^IIICu^II(pydc)₂(NO₃)(phen)(H₂O)].2H₂O}_n, (I), the structure of which is reported here.

S2. Experimental

S2.1. Synthesis and crystallization

Bismuth nitrate penta­hydrate (0.49 g, 1 mmol), copper chloride dihydrate (0.26 g, 1.5 mmol), pyridine-2,6-di­carb­oxy­lic acid (0.25 g, 1.5 mmol), 1,10-phenanthroline (0.09 g, 0.5 mmol), ethyl­ene glycol (6 ml) and water (2 ml) were placed in a 50 ml Teflon-lined Parr bomb. The Parr bomb was maintained at 433 K for 7 d and then cooled to room temperature at a rate of 10 K h^-1. The solution was filtered and slow evaporation over a period of 5 d yielded blue prismatic crystals in 40% yield (based on bis­muth nitrate). These were collected and washed with water. Elemental analysis, calculated: C 34.74, H 2.24, N 7.79%; found: C 35.11, H 1.90, N 8.07%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were placed in calculated positions, with C—H = 0.93 Å, and were included in the refinement in the riding-model approximation, with U_iso(H) = 1.2–1.5U_eq(C). The water H atoms were placed in chemically sensible positions on the basis of hydrogen-bonding inter­actions, with O—H = 0.84 Å and U_iso(H) = 1.5U_eq(O). The final difference Fourier map had a peak 0.90 Å from atom Bi1 and a hole 0.92 Å from the same atom.

S3. Results and discussion

The Bi^III cation in (I) is N,O,O'-chelated by the pydc ligands and O,O'-chelated by the nitrate anion, the nine coordinating atoms leading to a tricapped trigonal prismatic environment at the metal centre. The two chelating pydc ligands are approximately perpendicular; their planes are aligned at an angle of 83.3 (1)°. The triangles of the trigonal prism are nearly parallel, these being aligned at an angle of 16.1 (3)°. The Bi^III cation lies 0.357 (3) Å out of the plane that is made up of the atoms that cap the squares; this large deviation arises from the somewhat anisobidendate chelating nature of the nitrate ion (Fig. 2).

Each pydc ligand uses one of its carboxyl­ate O atoms to bind to a water-coordinated phen-chelated Cu^II cation. The two chelating ligands are nearly coplanar, aligned at an angle of 3.2 (2)°. This coplanarity allows for the formation of a water–carboxyl­ate O—H···O hydrogen bond that stabilizes the ribbon motif. The Cu^II cation shows a square-pyramidal geometry (Fig. 3). The ribbon motif propagates along the shortest axis of the triclinic unit cell, and the solvent water molecules are hydrogen-bonded to the same ribbon (Fig. 4, Table 2).

The title compound is the first heterometallic system having a bis­muth carboxyl­ate unit connected to a Cu^II cation whose structure has been determined by X-ray crystallography. There is only one other example of a copper carboxyl­ate that is connected to a Bi^III cation; this system is a mixed-metal metal–organic framework (MOF) displaying a two-dimensional network that possesses catalytic activity (Shi et al., 2013).

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x, -y + 2, -z; (ii) x + 1, y, z.]
	Fig. 2. The nine-coordinate geometry of the Bi^III cation in (I).
	Fig. 3. The five-coordinate geometry of the Cu^II cation in (I).
	Fig. 4. The linear ribbon motif in (I).

catena-Poly[[[aqua(1,10-phenanthroline-κ²N,N')copper(II)]-µ-pyridine-2,6-dicarboxylato-κ⁴O²:O^2',N,O⁶-[(nitrato-κ²O,O')bismuth(III)]-µ-pyridine-2,6-dicarboxylato-κ⁴<O²,N,O⁶:O^6']] dihydrate]

Crystal data

[BiCu(C7H3NO4)2(NO3)(C12H8N2)(H2O)]·2H2O	Z = 2
Mr = 898.99	F(000) = 870
Triclinic, P1	Dx = 2.136 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1376 (8) Å	Cell parameters from 3108 reflections
b = 12.1229 (11) Å	θ = 2.4–26.5°
c = 13.4135 (12) Å	µ = 7.13 mm^−1
α = 86.649 (2)°	T = 296 K
β = 87.233 (2)°	Prism, blue
γ = 70.502 (1)°	0.26 × 0.22 × 0.18 mm
V = 1397.6 (2) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	5656 independent reflections
Radiation source: fine-focus sealed tube	4523 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 26.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.259, Tmax = 0.360	k = −14→15
7803 measured reflections	l = −12→16

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.119	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0611P)^2] where P = (Fo^2 + 2Fc^2)/3
5656 reflections	(Δ/σ)max = 0.001
424 parameters	Δρmax = 3.53 e Å^−3
0 restraints	Δρmin = −2.65 e Å^−3

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

	x	y	z	Uiso*/Ueq
Bi1	−0.02065 (3)	0.85438 (3)	0.09838 (2)	0.02660 (12)
Cu1	0.52249 (12)	0.60313 (9)	0.35139 (8)	0.0333 (3)
O1	0.4276 (6)	0.5682 (5)	0.2330 (5)	0.0326 (14)
O2	0.2141 (7)	0.7270 (6)	0.2166 (5)	0.0421 (16)
O3	−0.1075 (7)	0.8068 (5)	−0.0390 (5)	0.0378 (14)
O4	−0.1050 (8)	0.6804 (7)	−0.1528 (6)	0.0534 (19)
O5	−0.3263 (7)	0.6866 (6)	0.2597 (5)	0.0459 (17)
O6	−0.1276 (6)	0.7210 (5)	0.1796 (5)	0.0350 (15)
O7	−0.1487 (6)	1.0661 (5)	0.0272 (5)	0.0375 (15)
O8	−0.3633 (8)	1.2232 (6)	0.0187 (8)	0.079 (3)
O9	−0.1198 (11)	0.9311 (10)	0.2849 (8)	0.090 (3)
O10	0.0815 (14)	0.9761 (9)	0.2612 (9)	0.104 (4)
O11	−0.0129 (14)	0.9629 (9)	0.4110 (9)	0.106 (4)
O1W	0.3405 (7)	0.7382 (6)	0.3830 (5)	0.0435 (16)
H11	0.2814	0.7490	0.3347	0.065*
H12	0.3613	0.8003	0.3866	0.065*
O2W	0.3191 (12)	0.9533 (9)	0.4277 (9)	0.105 (4)
H21	0.3448	0.9559	0.4866	0.158*
H22	0.3768	0.9764	0.3871	0.158*
O3W	0.3984 (18)	0.9817 (17)	0.6101 (12)	0.191 (9)
H31	0.3147	1.0094	0.6430	0.286*
H32	0.4512	0.9167	0.6362	0.286*
N1	0.1397 (7)	0.6530 (5)	0.0496 (5)	0.0259 (15)
N2	−0.3049 (7)	0.9379 (6)	0.1230 (5)	0.0301 (16)
N3	0.6818 (8)	0.4442 (7)	0.3510 (6)	0.0365 (18)
N4	0.6224 (10)	0.6074 (7)	0.4842 (6)	0.043 (2)
N5	−0.0189 (12)	0.9561 (7)	0.3127 (8)	0.052 (2)
C1	0.3048 (9)	0.6303 (7)	0.1887 (7)	0.0317 (19)
C2	0.2644 (9)	0.5831 (7)	0.0960 (6)	0.0278 (18)
C3	0.3495 (10)	0.4738 (7)	0.0625 (7)	0.038 (2)
H3	0.4351	0.4253	0.0968	0.046*
C4	0.3037 (10)	0.4387 (8)	−0.0237 (7)	0.039 (2)
H4	0.3607	0.3664	−0.0488	0.047*
C5	0.1731 (11)	0.5106 (8)	−0.0730 (8)	0.040 (2)
H5	0.1402	0.4873	−0.1303	0.047*
C6	0.0933 (9)	0.6189 (7)	−0.0332 (7)	0.0294 (19)
C7	−0.0498 (10)	0.7049 (8)	−0.0805 (7)	0.034 (2)
C8	−0.2708 (10)	0.7488 (7)	0.2063 (6)	0.0293 (19)
C9	−0.3752 (9)	0.8694 (7)	0.1709 (6)	0.0286 (18)
C10	−0.5334 (10)	0.9061 (8)	0.1866 (8)	0.043 (2)
H10	−0.5825	0.8555	0.2149	0.052*
C11	−0.6183 (10)	1.0219 (8)	0.1586 (8)	0.045 (2)
H11A	−0.7254	1.0498	0.1700	0.054*
C12	−0.5427 (10)	1.0959 (8)	0.1137 (7)	0.039 (2)
H12A	−0.5968	1.1741	0.0974	0.047*
C13	−0.3843 (9)	1.0483 (7)	0.0941 (7)	0.0320 (19)
C14	−0.2916 (10)	1.1200 (8)	0.0438 (8)	0.042 (2)
C15	0.7806 (10)	0.4208 (8)	0.4282 (7)	0.039 (2)
C16	0.7088 (11)	0.3632 (8)	0.2819 (8)	0.043 (2)
H16	0.6435	0.3774	0.2281	0.052*
C17	0.8334 (13)	0.2577 (9)	0.2892 (10)	0.059 (3)
H17	0.8496	0.2030	0.2404	0.070*
C18	0.9311 (13)	0.2345 (10)	0.3673 (10)	0.065 (3)
H18	1.0129	0.1639	0.3713	0.078*
C19	0.9094 (11)	0.3160 (8)	0.4419 (8)	0.047 (3)
C20	0.9999 (14)	0.3015 (12)	0.5285 (11)	0.071 (4)
H20	1.0836	0.2329	0.5380	0.085*
C21	0.9679 (13)	0.3845 (11)	0.5974 (9)	0.060 (3)
H21A	1.0304	0.3729	0.6524	0.071*
C22	0.8377 (13)	0.4900 (11)	0.5857 (8)	0.053 (3)
C23	0.7957 (15)	0.5801 (13)	0.6539 (9)	0.067 (4)
H23	0.8531	0.5725	0.7108	0.080*
C24	0.6716 (16)	0.6783 (12)	0.6369 (10)	0.068 (4)
H24	0.6435	0.7379	0.6820	0.082*
C25	0.5843 (13)	0.6891 (10)	0.5484 (8)	0.053 (3)
H25	0.4988	0.7559	0.5369	0.064*
C26	0.7464 (11)	0.5079 (9)	0.5014 (7)	0.042 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.02385 (16)	0.02133 (16)	0.0358 (2)	−0.00949 (11)	−0.00466 (12)	0.00475 (12)
Cu1	0.0334 (5)	0.0340 (6)	0.0361 (7)	−0.0163 (5)	−0.0091 (4)	0.0052 (5)
O1	0.027 (3)	0.029 (3)	0.042 (4)	−0.007 (2)	−0.016 (3)	−0.001 (3)
O2	0.042 (4)	0.036 (4)	0.044 (4)	−0.006 (3)	−0.011 (3)	−0.003 (3)
O3	0.035 (3)	0.037 (4)	0.039 (4)	−0.009 (3)	−0.014 (3)	0.000 (3)
O4	0.047 (4)	0.060 (5)	0.053 (5)	−0.014 (3)	−0.023 (3)	−0.013 (4)
O5	0.042 (4)	0.038 (4)	0.060 (5)	−0.021 (3)	0.002 (3)	0.017 (3)
O6	0.030 (3)	0.023 (3)	0.050 (4)	−0.010 (2)	0.005 (3)	0.016 (3)
O7	0.025 (3)	0.030 (3)	0.055 (4)	−0.008 (2)	0.003 (3)	0.013 (3)
O8	0.038 (4)	0.027 (4)	0.155 (9)	0.001 (3)	0.024 (5)	0.032 (4)
O9	0.070 (6)	0.110 (8)	0.094 (8)	−0.031 (6)	−0.002 (5)	−0.021 (6)
O10	0.121 (9)	0.082 (7)	0.119 (10)	−0.047 (7)	0.027 (7)	−0.036 (7)
O11	0.153 (11)	0.098 (8)	0.091 (9)	−0.071 (8)	−0.026 (7)	−0.006 (6)
O1W	0.040 (4)	0.045 (4)	0.048 (4)	−0.016 (3)	−0.006 (3)	−0.008 (3)
O2W	0.120 (9)	0.078 (7)	0.121 (9)	−0.031 (6)	−0.033 (7)	−0.027 (6)
O3W	0.157 (13)	0.28 (2)	0.187 (15)	−0.129 (14)	0.037 (11)	−0.155 (15)
N1	0.026 (3)	0.021 (3)	0.033 (4)	−0.011 (3)	−0.007 (3)	0.006 (3)
N2	0.025 (3)	0.020 (3)	0.041 (5)	−0.004 (3)	−0.002 (3)	0.007 (3)
N3	0.034 (4)	0.037 (4)	0.042 (5)	−0.018 (3)	−0.014 (3)	0.013 (4)
N4	0.061 (5)	0.054 (5)	0.027 (5)	−0.035 (4)	−0.006 (4)	0.002 (4)
N5	0.056 (6)	0.037 (5)	0.065 (7)	−0.019 (4)	0.008 (5)	−0.006 (4)
C1	0.029 (4)	0.030 (5)	0.039 (5)	−0.015 (4)	−0.004 (4)	0.005 (4)
C2	0.022 (4)	0.023 (4)	0.037 (5)	−0.007 (3)	−0.002 (3)	0.008 (3)
C3	0.033 (5)	0.026 (5)	0.055 (7)	−0.009 (4)	−0.010 (4)	0.011 (4)
C4	0.041 (5)	0.026 (4)	0.046 (6)	−0.005 (4)	−0.006 (4)	−0.005 (4)
C5	0.044 (5)	0.030 (5)	0.046 (6)	−0.014 (4)	0.001 (4)	−0.003 (4)
C6	0.021 (4)	0.030 (4)	0.036 (5)	−0.008 (3)	0.001 (3)	0.002 (4)
C7	0.030 (4)	0.038 (5)	0.035 (6)	−0.012 (4)	−0.001 (4)	0.004 (4)
C8	0.038 (5)	0.028 (4)	0.028 (5)	−0.020 (4)	−0.002 (4)	0.005 (3)
C9	0.028 (4)	0.030 (4)	0.028 (5)	−0.011 (3)	0.001 (3)	−0.001 (3)
C10	0.028 (4)	0.044 (6)	0.060 (7)	−0.016 (4)	−0.006 (4)	0.018 (5)
C11	0.022 (4)	0.044 (6)	0.064 (7)	−0.008 (4)	−0.002 (4)	0.017 (5)
C12	0.026 (4)	0.032 (5)	0.055 (6)	−0.005 (4)	0.000 (4)	0.008 (4)
C13	0.025 (4)	0.025 (4)	0.047 (6)	−0.010 (3)	−0.007 (4)	0.010 (4)
C14	0.031 (5)	0.026 (5)	0.066 (7)	−0.007 (4)	−0.005 (4)	0.015 (4)
C15	0.036 (5)	0.042 (5)	0.047 (6)	−0.025 (4)	−0.008 (4)	0.013 (4)
C16	0.049 (6)	0.036 (5)	0.044 (6)	−0.013 (4)	−0.010 (5)	0.005 (4)
C17	0.057 (7)	0.038 (6)	0.078 (9)	−0.010 (5)	−0.013 (6)	0.000 (6)
C18	0.052 (6)	0.038 (6)	0.101 (10)	−0.010 (5)	−0.024 (6)	0.022 (6)
C19	0.047 (6)	0.036 (5)	0.063 (7)	−0.023 (4)	−0.013 (5)	0.019 (5)
C20	0.056 (7)	0.076 (9)	0.089 (10)	−0.037 (6)	−0.045 (7)	0.053 (8)
C21	0.061 (7)	0.071 (8)	0.061 (8)	−0.045 (7)	−0.039 (6)	0.037 (7)
C22	0.065 (7)	0.073 (8)	0.039 (7)	−0.048 (6)	−0.003 (5)	0.010 (6)
C23	0.074 (8)	0.101 (11)	0.046 (8)	−0.059 (8)	−0.020 (6)	0.022 (7)
C24	0.083 (9)	0.079 (9)	0.062 (9)	−0.052 (8)	0.001 (7)	−0.014 (7)
C25	0.062 (7)	0.052 (7)	0.049 (7)	−0.023 (5)	−0.007 (5)	−0.003 (5)
C26	0.043 (5)	0.055 (6)	0.038 (6)	−0.031 (5)	−0.014 (4)	0.024 (5)

Geometric parameters (Å, º)

Bi1—O2	2.708 (6)	N4—C26	1.369 (13)
Bi1—O3	2.220 (6)	C1—C2	1.510 (13)
Bi1—O6	2.346 (5)	C2—C3	1.382 (12)
Bi1—O9	2.727 (10)	C3—C4	1.384 (14)
Bi1—O7	2.586 (6)	C3—H3	0.9300
Bi1—O7^i	2.591 (5)	C4—C5	1.392 (13)
Bi1—O10	3.052 (11)	C4—H4	0.9300
Bi1—N1	2.498 (6)	C5—C6	1.395 (12)
Bi1—N2	2.466 (6)	C5—H5	0.9300
Cu1—O1	1.977 (6)	C6—C7	1.514 (12)
Cu1—O5^ii	2.251 (6)	C8—C9	1.518 (12)
Cu1—O1W	1.955 (6)	C9—C10	1.372 (11)
Cu1—N3	1.990 (8)	C10—C11	1.397 (13)
Cu1—N4	2.051 (8)	C10—H10	0.9300
O1—C1	1.276 (10)	C11—C12	1.398 (12)
O2—C1	1.254 (10)	C11—H11A	0.9300
O3—C7	1.315 (11)	C12—C13	1.386 (11)
O4—C7	1.210 (11)	C12—H12A	0.9300
O5—C8	1.223 (9)	C13—C14	1.515 (11)
O5—Cu1^iii	2.251 (6)	C15—C19	1.425 (13)
O6—C8	1.277 (9)	C15—C26	1.432 (15)
O7—C14	1.265 (10)	C16—C17	1.402 (14)
O7—Bi1^i	2.591 (5)	C16—H16	0.9300
O8—C14	1.239 (11)	C17—C18	1.364 (16)
O9—N5	1.146 (12)	C17—H17	0.9300
O10—N5	1.202 (13)	C18—C19	1.408 (17)
O11—N5	1.331 (13)	C18—H18	0.9300
O1W—H11	0.8400	C19—C20	1.426 (16)
O1W—H12	0.8400	C20—C21	1.356 (19)
O2W—H21	0.8400	C20—H20	0.9300
O2W—H22	0.8399	C21—C22	1.433 (16)
O3W—H31	0.8400	C21—H21A	0.9300
O3W—H32	0.8400	C22—C26	1.401 (14)
N1—C2	1.328 (10)	C22—C23	1.407 (18)
N1—C6	1.342 (11)	C23—C24	1.359 (18)
N2—C9	1.329 (10)	C23—H23	0.9300
N2—C13	1.337 (10)	C24—C25	1.438 (17)
N3—C16	1.344 (13)	C24—H24	0.9300
N3—C15	1.361 (12)	C25—H25	0.9300
N4—C25	1.298 (13)
O3—Bi1—O6	84.5 (2)	O2—C1—C2	117.4 (7)
O3—Bi1—N2	77.4 (2)	O1—C1—C2	117.4 (7)
O6—Bi1—N2	67.5 (2)	N1—C2—C3	122.2 (8)
O3—Bi1—N1	68.9 (2)	N1—C2—C1	115.4 (7)
O6—Bi1—N1	71.9 (2)	C3—C2—C1	122.4 (8)
N2—Bi1—N1	128.8 (2)	C2—C3—C4	118.0 (8)
O3—Bi1—O7	83.5 (2)	C2—C3—H3	121.0
O6—Bi1—O7	131.46 (17)	C4—C3—H3	121.0
N2—Bi1—O7	64.00 (19)	C3—C4—C5	120.5 (8)
N1—Bi1—O7	142.7 (2)	C3—C4—H4	119.7
O3—Bi1—O7^i	83.5 (2)	C5—C4—H4	119.7
O6—Bi1—O7^i	159.0 (2)	C4—C5—C6	117.5 (9)
N2—Bi1—O7^i	126.0 (2)	C4—C5—H5	121.3
N1—Bi1—O7^i	87.68 (19)	C6—C5—H5	121.3
O7—Bi1—O7^i	64.0 (2)	N1—C6—C5	121.6 (8)
O3—Bi1—O2	130.1 (2)	N1—C6—C7	116.0 (7)
O6—Bi1—O2	78.5 (2)	C5—C6—C7	122.4 (8)
N2—Bi1—O2	134.1 (2)	O4—C7—O3	123.0 (8)
N1—Bi1—O2	61.3 (2)	O4—C7—C6	121.1 (8)
O7—Bi1—O2	140.6 (2)	O3—C7—C6	116.0 (8)
O7^i—Bi1—O2	96.25 (19)	O5—C8—O6	124.4 (8)
O3—Bi1—O9	140.9 (3)	O5—C8—C9	119.2 (7)
O6—Bi1—O9	72.3 (3)	O6—C8—C9	116.3 (6)
N2—Bi1—O9	65.0 (3)	N2—C9—C10	121.5 (8)
N1—Bi1—O9	128.4 (3)	N2—C9—C8	116.2 (7)
O7—Bi1—O9	88.8 (3)	C10—C9—C8	122.2 (7)
O7^i—Bi1—O9	126.7 (3)	C9—C10—C11	118.1 (8)
O2—Bi1—O9	76.1 (3)	C9—C10—H10	121.0
O3—Bi1—O10	166.4 (3)	C11—C10—H10	121.0
O6—Bi1—O10	106.8 (3)	C10—C11—C12	120.1 (8)
N2—Bi1—O10	99.8 (3)	C10—C11—H11A	119.9
N1—Bi1—O10	121.2 (3)	C12—C11—H11A	119.9
O7—Bi1—O10	83.4 (3)	C13—C12—C11	117.6 (8)
O7^i—Bi1—O10	87.7 (3)	C13—C12—H12A	121.2
O2—Bi1—O10	61.1 (3)	C11—C12—H12A	121.2
O9—Bi1—O10	42.0 (3)	N2—C13—C12	121.2 (7)
O1W—Cu1—O1	93.2 (3)	N2—C13—C14	116.8 (7)
O1W—Cu1—N3	163.6 (3)	C12—C13—C14	121.9 (7)
O1—Cu1—N3	90.3 (3)	O8—C14—O7	126.3 (8)
O1W—Cu1—N4	92.3 (3)	O8—C14—C13	117.4 (8)
O1—Cu1—N4	168.9 (3)	O7—C14—C13	116.2 (7)
N3—Cu1—N4	81.8 (3)	N3—C15—C19	124.8 (10)
O1W—Cu1—O5^ii	102.3 (3)	N3—C15—C26	116.1 (9)
O1—Cu1—O5^ii	93.6 (3)	C19—C15—C26	119.0 (9)
N3—Cu1—O5^ii	93.5 (3)	N3—C16—C17	121.3 (10)
N4—Cu1—O5^ii	94.7 (3)	N3—C16—H16	119.3
C1—O1—Cu1	129.2 (6)	C17—C16—H16	119.3
C1—O2—Bi1	119.6 (6)	C18—C17—C16	120.6 (12)
C7—O3—Bi1	124.9 (5)	C18—C17—H17	119.7
C8—O5—Cu1^iii	167.6 (6)	C16—C17—H17	119.7
C8—O6—Bi1	122.8 (5)	C17—C18—C19	120.8 (10)
C14—O7—Bi1	120.5 (5)	C17—C18—H18	119.6
C14—O7—Bi1^i	122.8 (5)	C19—C18—H18	119.6
Bi1—O7—Bi1^i	116.0 (2)	C18—C19—C15	114.8 (9)
N5—O9—Bi1	103.6 (8)	C18—C19—C20	126.5 (11)
N5—O10—Bi1	85.7 (8)	C15—C19—C20	118.7 (11)
Cu1—O1W—H11	106.0	C21—C20—C19	122.1 (12)
Cu1—O1W—H12	113.1	C21—C20—H20	118.9
H11—O1W—H12	106.3	C19—C20—H20	118.9
H21—O2W—H22	110.3	C20—C21—C22	120.1 (10)
H31—O3W—H32	109.9	C20—C21—H21A	120.0
C2—N1—C6	120.1 (7)	C22—C21—H21A	120.0
C2—N1—Bi1	125.8 (6)	C26—C22—C23	116.6 (11)
C6—N1—Bi1	114.0 (5)	C26—C22—C21	119.5 (11)
C9—N2—C13	121.2 (7)	C23—C22—C21	123.8 (11)
C9—N2—Bi1	116.7 (5)	C24—C23—C22	120.3 (11)
C13—N2—Bi1	122.0 (5)	C24—C23—H23	119.8
C16—N3—C15	117.7 (8)	C22—C23—H23	119.8
C16—N3—Cu1	128.4 (6)	C23—C24—C25	119.2 (12)
C15—N3—Cu1	113.8 (7)	C23—C24—H24	120.4
C25—N4—C26	119.6 (9)	C25—C24—H24	120.4
C25—N4—Cu1	129.1 (8)	N4—C25—C24	121.4 (11)
C26—N4—Cu1	111.3 (7)	N4—C25—H25	119.3
O9—N5—O10	126.0 (13)	C24—C25—H25	119.3
O9—N5—O11	116.6 (10)	N4—C26—C22	122.9 (10)
O10—N5—O11	117.5 (12)	N4—C26—C15	116.7 (8)
O2—C1—O1	125.2 (8)	C22—C26—C15	120.5 (10)
O1W—Cu1—O1—C1	11.6 (7)	O1W—Cu1—N4—C26	168.0 (6)
N3—Cu1—O1—C1	175.5 (7)	O1—Cu1—N4—C26	48.5 (18)
N4—Cu1—O1—C1	131.0 (15)	N3—Cu1—N4—C26	3.4 (6)
O5^ii—Cu1—O1—C1	−90.9 (7)	O5^ii—Cu1—N4—C26	−89.5 (6)
O3—Bi1—O2—C1	9.5 (7)	Bi1—O9—N5—O10	19.3 (14)
O6—Bi1—O2—C1	82.1 (6)	Bi1—O9—N5—O11	−160.3 (8)
N2—Bi1—O2—C1	124.3 (6)	Bi1—O10—N5—O9	−16.8 (13)
N1—Bi1—O2—C1	6.6 (6)	Bi1—O10—N5—O11	162.8 (9)
O7—Bi1—O2—C1	−133.0 (6)	Bi1—O2—C1—O1	172.9 (6)
O7^i—Bi1—O2—C1	−77.3 (6)	Bi1—O2—C1—C2	−7.9 (10)
O9—Bi1—O2—C1	156.4 (7)	Cu1—O1—C1—O2	−3.8 (12)
O10—Bi1—O2—C1	−161.1 (7)	Cu1—O1—C1—C2	177.1 (5)
O6—Bi1—O3—C7	−70.2 (7)	C6—N1—C2—C3	−0.6 (11)
N2—Bi1—O3—C7	−138.3 (7)	Bi1—N1—C2—C3	−178.1 (6)
N1—Bi1—O3—C7	2.5 (6)	C6—N1—C2—C1	−179.6 (7)
O7—Bi1—O3—C7	156.9 (7)	Bi1—N1—C2—C1	2.9 (9)
O7^i—Bi1—O3—C7	92.5 (7)	O2—C1—C2—N1	3.8 (11)
O2—Bi1—O3—C7	−0.2 (8)	O1—C1—C2—N1	−177.0 (7)
O9—Bi1—O3—C7	−123.0 (7)	O2—C1—C2—C3	−175.2 (8)
O10—Bi1—O3—C7	142.6 (11)	O1—C1—C2—C3	4.0 (12)
O3—Bi1—O6—C8	−83.9 (7)	N1—C2—C3—C4	1.5 (12)
N2—Bi1—O6—C8	−5.3 (6)	C1—C2—C3—C4	−179.6 (8)
N1—Bi1—O6—C8	−153.5 (7)	C2—C3—C4—C5	−1.7 (13)
O7—Bi1—O6—C8	−7.6 (8)	C3—C4—C5—C6	1.1 (13)
O7^i—Bi1—O6—C8	−139.4 (7)	C2—N1—C6—C5	0.0 (12)
O2—Bi1—O6—C8	143.2 (7)	Bi1—N1—C6—C5	177.7 (6)
O9—Bi1—O6—C8	64.3 (7)	C2—N1—C6—C7	−179.9 (7)
O10—Bi1—O6—C8	88.5 (7)	Bi1—N1—C6—C7	−2.1 (9)
O3—Bi1—O7—C14	85.3 (8)	C4—C5—C6—N1	−0.2 (12)
O6—Bi1—O7—C14	8.6 (9)	C4—C5—C6—C7	179.7 (8)
N2—Bi1—O7—C14	6.3 (7)	Bi1—O3—C7—O4	176.4 (7)
N1—Bi1—O7—C14	127.0 (7)	Bi1—O3—C7—C6	−4.5 (10)
O7^i—Bi1—O7—C14	171.3 (9)	N1—C6—C7—O4	−176.7 (8)
O2—Bi1—O7—C14	−122.5 (7)	C5—C6—C7—O4	3.4 (13)
O9—Bi1—O7—C14	−56.3 (8)	N1—C6—C7—O3	4.2 (11)
O10—Bi1—O7—C14	−98.0 (8)	C5—C6—C7—O3	−175.7 (8)
O3—Bi1—O7—Bi1^i	−86.0 (3)	Cu1^iii—O5—C8—O6	−176 (3)
O6—Bi1—O7—Bi1^i	−162.7 (2)	Cu1^iii—O5—C8—C9	6 (4)
N2—Bi1—O7—Bi1^i	−165.0 (4)	Bi1—O6—C8—O5	−170.2 (7)
N1—Bi1—O7—Bi1^i	−44.3 (5)	Bi1—O6—C8—C9	7.8 (10)
O7^i—Bi1—O7—Bi1^i	0.0	C13—N2—C9—C10	4.7 (14)
O2—Bi1—O7—Bi1^i	66.2 (4)	Bi1—N2—C9—C10	−178.4 (7)
O9—Bi1—O7—Bi1^i	132.4 (3)	C13—N2—C9—C8	−175.8 (8)
O10—Bi1—O7—Bi1^i	90.7 (3)	Bi1—N2—C9—C8	1.1 (10)
O3—Bi1—O9—N5	−168.6 (7)	O5—C8—C9—N2	172.4 (8)
O6—Bi1—O9—N5	135.0 (9)	O6—C8—C9—N2	−5.6 (12)
N2—Bi1—O9—N5	−152.1 (9)	O5—C8—C9—C10	−8.0 (14)
N1—Bi1—O9—N5	87.1 (9)	O6—C8—C9—C10	173.9 (9)
O7—Bi1—O9—N5	−90.4 (8)	N2—C9—C10—C11	−5.7 (15)
O7^i—Bi1—O9—N5	−34.6 (10)	C8—C9—C10—C11	174.8 (9)
O2—Bi1—O9—N5	52.8 (8)	C9—C10—C11—C12	1.7 (16)
O10—Bi1—O9—N5	−9.1 (7)	C10—C11—C12—C13	3.0 (16)
O3—Bi1—O10—N5	118.5 (11)	C9—N2—C13—C12	0.4 (14)
O6—Bi1—O10—N5	−27.3 (8)	Bi1—N2—C13—C12	−176.3 (7)
N2—Bi1—O10—N5	42.0 (8)	C9—N2—C13—C14	177.6 (8)
N1—Bi1—O10—N5	−105.9 (7)	Bi1—N2—C13—C14	0.9 (11)
O7—Bi1—O10—N5	104.1 (8)	C11—C12—C13—N2	−4.2 (15)
O7^i—Bi1—O10—N5	168.2 (8)	C11—C12—C13—C14	178.8 (9)
O2—Bi1—O10—N5	−93.4 (8)	Bi1—O7—C14—O8	175.5 (10)
O9—Bi1—O10—N5	8.4 (7)	Bi1^i—O7—C14—O8	−13.8 (16)
O3—Bi1—N1—C2	177.7 (7)	Bi1—O7—C14—C13	−8.1 (12)
O6—Bi1—N1—C2	−91.3 (6)	Bi1^i—O7—C14—C13	162.5 (6)
N2—Bi1—N1—C2	−130.0 (6)	N2—C13—C14—O8	−178.4 (10)
O7—Bi1—N1—C2	132.7 (6)	C12—C13—C14—O8	−1.3 (16)
O7^i—Bi1—N1—C2	93.7 (6)	N2—C13—C14—O7	4.9 (14)
O2—Bi1—N1—C2	−4.7 (6)	C12—C13—C14—O7	−177.9 (9)
O9—Bi1—N1—C2	−43.2 (7)	C16—N3—C15—C19	−1.0 (13)
O10—Bi1—N1—C2	7.8 (7)	Cu1—N3—C15—C19	−176.6 (7)
O3—Bi1—N1—C6	0.1 (5)	C16—N3—C15—C26	−178.7 (8)
O6—Bi1—N1—C6	91.1 (5)	Cu1—N3—C15—C26	5.6 (10)
N2—Bi1—N1—C6	52.4 (6)	C15—N3—C16—C17	0.6 (14)
O7—Bi1—N1—C6	−44.9 (7)	Cu1—N3—C16—C17	175.5 (7)
O7^i—Bi1—N1—C6	−83.9 (5)	N3—C16—C17—C18	0.0 (17)
O2—Bi1—N1—C6	177.7 (6)	C16—C17—C18—C19	−0.3 (18)
O9—Bi1—N1—C6	139.2 (5)	C17—C18—C19—C15	−0.1 (16)
O10—Bi1—N1—C6	−169.8 (5)	C17—C18—C19—C20	178.2 (11)
O3—Bi1—N2—C9	91.0 (6)	N3—C15—C19—C18	0.7 (14)
O6—Bi1—N2—C9	1.8 (6)	C26—C15—C19—C18	178.4 (9)
N1—Bi1—N2—C9	41.8 (7)	N3—C15—C19—C20	−177.7 (9)
O7—Bi1—N2—C9	179.9 (7)	C26—C15—C19—C20	0.0 (13)
O7^i—Bi1—N2—C9	163.2 (6)	C18—C19—C20—C21	−178.6 (11)
O2—Bi1—N2—C9	−43.7 (7)	C15—C19—C20—C21	−0.5 (16)
O9—Bi1—N2—C9	−78.4 (7)	C19—C20—C21—C22	1.3 (17)
O10—Bi1—N2—C9	−102.5 (6)	C20—C21—C22—C26	−1.6 (15)
O3—Bi1—N2—C13	−92.2 (7)	C20—C21—C22—C23	179.6 (10)
O6—Bi1—N2—C13	178.6 (7)	C26—C22—C23—C24	0.4 (15)
N1—Bi1—N2—C13	−141.4 (6)	C21—C22—C23—C24	179.2 (10)
O7—Bi1—N2—C13	−3.3 (6)	C22—C23—C24—C25	−0.2 (17)
O7^i—Bi1—N2—C13	−20.0 (8)	C26—N4—C25—C24	1.2 (15)
O2—Bi1—N2—C13	133.2 (7)	Cu1—N4—C25—C24	−178.0 (8)
O9—Bi1—N2—C13	98.4 (7)	C23—C24—C25—N4	−0.6 (17)
O10—Bi1—N2—C13	74.3 (7)	C25—N4—C26—C22	−1.0 (14)
O1W—Cu1—N3—C16	110.1 (12)	Cu1—N4—C26—C22	178.3 (7)
O1—Cu1—N3—C16	7.8 (8)	C25—N4—C26—C15	179.2 (9)
N4—Cu1—N3—C16	179.9 (8)	Cu1—N4—C26—C15	−1.5 (10)
O5^ii—Cu1—N3—C16	−85.8 (8)	C23—C22—C26—N4	0.3 (14)
O1W—Cu1—N3—C15	−74.7 (12)	C21—C22—C26—N4	−178.6 (8)
O1—Cu1—N3—C15	−177.1 (6)	C23—C22—C26—C15	180.0 (9)
N4—Cu1—N3—C15	−4.9 (6)	C21—C22—C26—C15	1.1 (13)
O5^ii—Cu1—N3—C15	89.3 (6)	N3—C15—C26—N4	−2.7 (12)
O1W—Cu1—N4—C25	−12.7 (9)	C19—C15—C26—N4	179.4 (8)
O1—Cu1—N4—C25	−132.2 (14)	N3—C15—C26—C22	177.5 (8)
N3—Cu1—N4—C25	−177.3 (9)	C19—C15—C26—C22	−0.3 (13)
O5^ii—Cu1—N4—C25	89.8 (9)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O2	0.84	1.79	2.59 (1)	159
O1W—H12···O2W	0.84	1.87	2.65 (1)	153
O2W—H21···O3W	0.84	1.82	2.66 (2)	172
O2W—H22···O3W^iv	0.84	2.28	2.95 (2)	138
O3W—H31···O9^v	0.84	1.92	2.76 (2)	178

Symmetry codes: (iv) −x+1, −y+2, −z+1; (v) −x, −y+2, −z+1.