A new one-dimensional cadmium(II) coordination polymer incorporating 4-[4-(1H-imidazol-1-yl)phen­yl]pyridine and 5-hy­droxy­benzene-1,3-di­carboxyl­ate ligands

The design and synthesis of new organic lgands is important to the rapid development of coordination polymers (CPs). However, CPs based on asym­metric ligands are still rare, mainly because such ligands are usually expensive and more difficult to synthesize. The new asymmetric ligand 4-[4-(1H-imidazol-1-yl)phen­yl]pyridine (IPP) has been used to construct the title one-dimensional coordination polymer, catena-poly[[[aqua­{4-[4-(1H-imidazol-1-yl-κN³)phen­yl]pyridine}­cadmium(II)]-μ-5-hy­droxy­benzene-1,3-di­carboxyl­ato-κ³O¹,O^1′:O³] monohydrate], {[Cd(C₈H₄O₅)(C₁₄H₁₁N₃)₂(H₂O)]·H₂O}_n, under hydro­thermal reaction of IPP with Cd^II in the presence of 5-hy­droxy­isophthalic acid (5-OH-H₂bdc). The Cd^II cation is coordinated by two N atoms from two distinct IPP ligands, three carboxyl­ate O atoms from two different 5-OH-bdc²⁻ dianionic ligands and one water O atom in a distorted octa­hedral geometry. The cationic [Cd(IPP)₂]²⁺ nodes are linked by 5-OH-bdc²⁻ ligands to generate a one-dimensional chain. These chains are extended into a two-dimensional layer structure via O—H...O and O—H...N hydrogen bonds and π–π inter­actions.

S1. Introduction

The design and synthesis of new organic lgands is extremely important to the rapid development of coordination polymers (CPs) (Almeida Paz et al., 2012). In recent decades, numerous symmetric organic ligands have been synthesized and employed to construct CPs with different structures and potential applications. Among them, two structurally similar ligands 1,4-bis­(imidazol-1-yl)benzene (bimb) and 1,4-bis­(4-pyridyl)­benzene (bpbenz) have been used widely in the synthesis of CPs as linear ditopic ligands. It has been reported that bimb reacts with Cd(BF₄)₂·6H₂O (Li et al., 2010) to generate a double inter­penetrating α-Po network, while bpbenz reacts with Cd(NO₃)₂·6H₂O to generate a three-dimensional pillar–layer framework (Guo et al., 2012). However, CPs based on asymmetric ligands are still rare. This is mainly because such ligands are usually expensive and more difficult to synthesize. As far as we know, there is some probability that the noncentrosymmetry of the asymmetric organic ligands could be transferred into the framework of the CPs and some symmetry-dependent properties such as piezoelectricity, pyroelectricity, ferroelectricity and second-order nonlinear optics (Zhang & Xiong, 2012) may thus occur in these noncentrosymmetric CPs. Therefore, we designed and synthesized a new asymmetric heterobifunctional organic ligand, 4-[4-(1H-imidazol-1-yl)phenyl]­pyridine (IPP), containing both pyridine and imidazole rings. Reacting IPP, we successfully obtained a new cadmium coordination polymer, {[Cd(5—OH-bdc)(IPP)₂(H₂O)]·H₂O}_n (I), the crystal structure of (I) we now report.

S2. Experimental

S2.1. Synthesis and crystallization

For the synthesis of IPP, a mixture of tetra­kis(tri­phenyl­phosphane)palladium (0.08 g, 0.05 mmol), 1,4-di­bromo­benzene (2.36 g, 10 mmol), (pyridin-4-yl)boronic acid (1.00 g, 7.5 mmol) and K₂CO₃ (5.52 g, 4.0 mmol) in anhydrous N,N-di­methyl­formamide (DMF, 30 ml) in a 100 ml two-necked round-bottomed flask under N₂ was stirred at 363 K for 48 h. The reaction mixture was filtered and the collected solid was purified on a silica-gel column using petroleum ether and ethyl acetate (3:1 v/v) as eluent to afford the 4-pyridyl bromo­benzene [ambiguous, please clarify ]. A mixture of CuI (0.09 g, 0.5 mmol), 4-pyridyl bromo­benzene (2.46 g, 10 mmol), imidazole (1.36 g, 2.0 mmol) and K₂CO₃ (2.76 g, 2.0 mmol) in DMF (30 ml) in a 100 ml two-necked round-bottomed flask under a nitro­gen atmosphere was stirred at 423 K for 48 h. The reaction mixture was filtered and the filtrate was added to H₂O (200 ml). The precipitate was filtered off and washed with water and dried in a vacuum to afford the product in 80% yield. ¹H NMR (CDCl₃, 400 Hz): δ 8.70 (d, J = 4.8 Hz, 2H), 7.76 (d, J = 7.2 Hz, 2H), 7.51–7.54 (m, 4H), 7.35 (s, 1H), 7.25–7.26 (m, 2H). Analysis calculated for C₁₄H₁₁N₃: C 75.31, H 5.87, N 18.82%; found: C 75.48, H 5.94, N 18.72%.

For the synthesis of (I), a mixture of Cd(NO₃)₂.6H₂O (172 mg, 0.5 mmol), 5-hy­droxy benzene-1,3-di­carb­oxy­lic acid (5-OH—H₂bdc) (80 mg, 0.5 mmol), IPP (110 mg, 0.5 mmol), water (6 ml) and DMF (1 ml) was placed in a Teflon reactor (25 ml). The mixture was heated at 373 K for 3 d and then allowed to cool to room temperature. Colourless block-shaped crystals of (I) were obtained (yield 42%, based on Cd). Analysis calculated for C₃₆H₃₀CdN₆O₇: C 56.08, H 3.92, N 10.90%; found: C 55.99, H 3.97, N 10.92%. IR (KBr pellet, cm^-1): 3414 (s), 3129 (s), 1606 (m), 1550 (m), 1396 (m),1303 (w), 1267 (w), 1124 (w), 1061 (m), 814 (m), 729 (m), 646 (w), 559 (w), 499 (w), 459 (w).

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The water H atoms were located in a difference Fourier map and included as riding atoms, with O—H = 0.85 and U_iso(H) = 1.5U_eq(O). The C-bound H atoms were placed in calculated positions and treated as riding, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The title compound, (I), crystallizes in the centrosymmetric triclinic space group P1 with an asymmetric unit comprised of a bivalent Cd^II ion, two IPP ligands, one dianionic 5-OH-bdc^2- ligand, one coordinated water molecule and one lattice water molecule (Fig. 1). The coordination environment of the Cd^II atom is best considered as a slightly distorted o­cta­hedral geometry. The equatorial plane is defined by three carboxyl­ate O atoms from two different 5-OH-bdc^2- ligands and one O atom from a coordinated water molecule, while the apical positions are occupied by two N atoms from two different IPP ligands. The Cd—N bond lengths are 2.2626 (19) and 2.315 (2) Å, while the Cd—O bond lengths vary greatly, from 2.2330 (16) to 2.5081 (16) Å. The average Cd—O and Cd—N distances in (I) are comparable with those reported for other Cd^II compounds (Zhang et al., 2015; Yin et al., 2012). Each Cd^II cation is linked to a terminal water molecular and two IPP ligands to form a [Cd(IPP)₂(H₂O)]²⁺ unit. These units are then inter­connected by bridging 5-OH-bdc^2- ligands in a κ²,κ¹-µ₂ coordination mode to generate a one-dimensional [Cd(5—OH-bdc)(IPP)₂(H₂O)]_n chain along the b axis, with a Cd···Cd separation of 10.3722 (5) Å (Fig. 2). Only the imidazole ring of the IPP ligand coordinates to the Cd^II ion. As shown in Fig. 3, neighbouring chains in (I) are linked by π–π stacking inter­actions, leading to the formation of a two-dimensional layer structure. Moreover, there are five inter­molecular O—H···O and O—H···N hydrogen bonds (Table 2) involved in this two-dimensional layer structure, which further enchance the stability of the two-dimensional network. The first hydrogen bond is between the lattice water molecule and the carboxyl­ate O atom of the 5-OH-bdc^2- ligand, the second is between the lattice water and the uncoordinated pyridine N atom of the IPP ligand, the third is between the hy­droxy group of 5-OH-bdc^2- and the uncoordinated pyridine N atom of the IPP ligand, the fourth is between the coordinated water molecule and the carboxyl­ate O atoms of the 5-OH-bdc^2- ligands, and the last is between the coordinated water molecular and the lattice water molecule. Thus, the combination of π–π inter­actions and extensive hydrogen bonds results in the formation of a two-dimensional network (Fig. 4).

In summary, a new asymmetric ditopic ligand, namely 4-[4-(1H-imidazol-1-yl)phenyl]­pyridine (IPP), has been synthesized and used to construct a one-dimensional cadmium(II) coordination polymer. The IPP ligand is coordinated to the Cd^II ion by an imidazole-ring N atom only, while the pyridine N atom remains uncoordinated and acts as a hydrogen-bond acceptor. Even though the IPP ligand does not expand the structure, the uncoordinated pyridine ring still plays an important role in the stabilization of the structure.

Structure description

The design and synthesis of new organic lgands is extremely important to the rapid development of coordination polymers (CPs) (Almeida Paz et al., 2012). In recent decades, numerous symmetric organic ligands have been synthesized and employed to construct CPs with different structures and potential applications. Among them, two structurally similar ligands 1,4-bis­(imidazol-1-yl)benzene (bimb) and 1,4-bis­(4-pyridyl)­benzene (bpbenz) have been used widely in the synthesis of CPs as linear ditopic ligands. It has been reported that bimb reacts with Cd(BF₄)₂·6H₂O (Li et al., 2010) to generate a double inter­penetrating α-Po network, while bpbenz reacts with Cd(NO₃)₂·6H₂O to generate a three-dimensional pillar–layer framework (Guo et al., 2012). However, CPs based on asymmetric ligands are still rare. This is mainly because such ligands are usually expensive and more difficult to synthesize. As far as we know, there is some probability that the noncentrosymmetry of the asymmetric organic ligands could be transferred into the framework of the CPs and some symmetry-dependent properties such as piezoelectricity, pyroelectricity, ferroelectricity and second-order nonlinear optics (Zhang & Xiong, 2012) may thus occur in these noncentrosymmetric CPs. Therefore, we designed and synthesized a new asymmetric heterobifunctional organic ligand, 4-[4-(1H-imidazol-1-yl)phenyl]­pyridine (IPP), containing both pyridine and imidazole rings. Reacting IPP, we successfully obtained a new cadmium coordination polymer, {[Cd(5—OH-bdc)(IPP)₂(H₂O)]·H₂O}_n (I), the crystal structure of (I) we now report.

The title compound, (I), crystallizes in the centrosymmetric triclinic space group P1 with an asymmetric unit comprised of a bivalent Cd^II ion, two IPP ligands, one dianionic 5-OH-bdc^2- ligand, one coordinated water molecule and one lattice water molecule (Fig. 1). The coordination environment of the Cd^II atom is best considered as a slightly distorted o­cta­hedral geometry. The equatorial plane is defined by three carboxyl­ate O atoms from two different 5-OH-bdc^2- ligands and one O atom from a coordinated water molecule, while the apical positions are occupied by two N atoms from two different IPP ligands. The Cd—N bond lengths are 2.2626 (19) and 2.315 (2) Å, while the Cd—O bond lengths vary greatly, from 2.2330 (16) to 2.5081 (16) Å. The average Cd—O and Cd—N distances in (I) are comparable with those reported for other Cd^II compounds (Zhang et al., 2015; Yin et al., 2012). Each Cd^II cation is linked to a terminal water molecular and two IPP ligands to form a [Cd(IPP)₂(H₂O)]²⁺ unit. These units are then inter­connected by bridging 5-OH-bdc^2- ligands in a κ²,κ¹-µ₂ coordination mode to generate a one-dimensional [Cd(5—OH-bdc)(IPP)₂(H₂O)]_n chain along the b axis, with a Cd···Cd separation of 10.3722 (5) Å (Fig. 2). Only the imidazole ring of the IPP ligand coordinates to the Cd^II ion. As shown in Fig. 3, neighbouring chains in (I) are linked by π–π stacking inter­actions, leading to the formation of a two-dimensional layer structure. Moreover, there are five inter­molecular O—H···O and O—H···N hydrogen bonds (Table 2) involved in this two-dimensional layer structure, which further enchance the stability of the two-dimensional network. The first hydrogen bond is between the lattice water molecule and the carboxyl­ate O atom of the 5-OH-bdc^2- ligand, the second is between the lattice water and the uncoordinated pyridine N atom of the IPP ligand, the third is between the hy­droxy group of 5-OH-bdc^2- and the uncoordinated pyridine N atom of the IPP ligand, the fourth is between the coordinated water molecule and the carboxyl­ate O atoms of the 5-OH-bdc^2- ligands, and the last is between the coordinated water molecular and the lattice water molecule. Thus, the combination of π–π inter­actions and extensive hydrogen bonds results in the formation of a two-dimensional network (Fig. 4).

In summary, a new asymmetric ditopic ligand, namely 4-[4-(1H-imidazol-1-yl)phenyl]­pyridine (IPP), has been synthesized and used to construct a one-dimensional cadmium(II) coordination polymer. The IPP ligand is coordinated to the Cd^II ion by an imidazole-ring N atom only, while the pyridine N atom remains uncoordinated and acts as a hydrogen-bond acceptor. Even though the IPP ligand does not expand the structure, the uncoordinated pyridine ring still plays an important role in the stabilization of the structure.

Synthesis and crystallization

For the synthesis of IPP, a mixture of tetra­kis(tri­phenyl­phosphane)palladium (0.08 g, 0.05 mmol), 1,4-di­bromo­benzene (2.36 g, 10 mmol), (pyridin-4-yl)boronic acid (1.00 g, 7.5 mmol) and K₂CO₃ (5.52 g, 4.0 mmol) in anhydrous N,N-di­methyl­formamide (DMF, 30 ml) in a 100 ml two-necked round-bottomed flask under N₂ was stirred at 363 K for 48 h. The reaction mixture was filtered and the collected solid was purified on a silica-gel column using petroleum ether and ethyl acetate (3:1 v/v) as eluent to afford the 4-pyridyl bromo­benzene [ambiguous, please clarify ]. A mixture of CuI (0.09 g, 0.5 mmol), 4-pyridyl bromo­benzene (2.46 g, 10 mmol), imidazole (1.36 g, 2.0 mmol) and K₂CO₃ (2.76 g, 2.0 mmol) in DMF (30 ml) in a 100 ml two-necked round-bottomed flask under a nitro­gen atmosphere was stirred at 423 K for 48 h. The reaction mixture was filtered and the filtrate was added to H₂O (200 ml). The precipitate was filtered off and washed with water and dried in a vacuum to afford the product in 80% yield. ¹H NMR (CDCl₃, 400 Hz): δ 8.70 (d, J = 4.8 Hz, 2H), 7.76 (d, J = 7.2 Hz, 2H), 7.51–7.54 (m, 4H), 7.35 (s, 1H), 7.25–7.26 (m, 2H). Analysis calculated for C₁₄H₁₁N₃: C 75.31, H 5.87, N 18.82%; found: C 75.48, H 5.94, N 18.72%.

For the synthesis of (I), a mixture of Cd(NO₃)₂.6H₂O (172 mg, 0.5 mmol), 5-hy­droxy benzene-1,3-di­carb­oxy­lic acid (5-OH—H₂bdc) (80 mg, 0.5 mmol), IPP (110 mg, 0.5 mmol), water (6 ml) and DMF (1 ml) was placed in a Teflon reactor (25 ml). The mixture was heated at 373 K for 3 d and then allowed to cool to room temperature. Colourless block-shaped crystals of (I) were obtained (yield 42%, based on Cd). Analysis calculated for C₃₆H₃₀CdN₆O₇: C 56.08, H 3.92, N 10.90%; found: C 55.99, H 3.97, N 10.92%. IR (KBr pellet, cm^-1): 3414 (s), 3129 (s), 1606 (m), 1550 (m), 1396 (m),1303 (w), 1267 (w), 1124 (w), 1061 (m), 814 (m), 729 (m), 646 (w), 559 (w), 499 (w), 459 (w).

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. The water H atoms were located in a difference Fourier map and included as riding atoms, with O—H = 0.85 and U_iso(H) = 1.5U_eq(O). The C-bound H atoms were placed in calculated positions and treated as riding, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The coordination environment of the Cd^II atom in (I), shwon with 30% probability displacement ellipsoids. [Symmetry codes: (i) x, y - 1, z; (ii) x, y + 1, z.] [Please provide a fully labelled plot]
	Fig. 2. A view of the one-dimensional [Cd(5—OH-bdc)(IPP)2(H2O)]n chain of (I).
	Fig. 3. The π–π stacking interactions of (I).
	Fig. 4. The two-dimensional layer structure generated by hydrogen bonds and π–π stacking interactions.

catena-Poly[[[aqua{4-[4-(1H-imidazol-1-yl-κN³)phenyl]pyridine}cadmium(II)]-µ-5-hydroxybenzene-1,3-dicarboxylato-κ³O¹,O^1':O³] monohydrate]

Crystal data

[Cd(C8H4O5)(C14H12N3)2(H2O)]·H2O	Z = 2
Mr = 771.06	F(000) = 784
Triclinic, P1	Dx = 1.597 Mg m^−3
a = 9.9863 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3722 (5) Å	Cell parameters from 7368 reflections
c = 15.7502 (7) Å	θ = 3.1–28.5°
α = 91.755 (4)°	µ = 0.74 mm^−1
β = 99.029 (5)°	T = 293 K
γ = 95.042 (3)°	Block, clear light colourless
V = 1603.32 (13) Å^3	0.37 × 0.35 × 0.32 mm

Data collection

Agilent SuperNova Dual Source diffractometer with an Eos detector	6291 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	5707 reflections with I > 2σ(I)
Detector resolution: 16.0733 pixels mm^-1	Rint = 0.031
ω scans	θmax = 26.0°, θmin = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.771, Tmax = 0.797	k = −12→12
11317 measured reflections	l = −19→18

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)] = 0.029	Hydrogen site location: mixed
wR(F^2) = 0.071	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0318P)^2 + 0.3064P] where P = (Fo^2 + 2Fc^2)/3
6291 reflections	(Δ/σ)max = 0.001
455 parameters	Δρmax = 0.40 e Å^−3
1 restraint	Δρmin = −0.68 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.8071 (2)	0.2728 (2)	0.90705 (15)	0.0330 (5)
H1	0.8086	0.3253	0.8603	0.040*
C2	0.9156 (2)	0.2549 (2)	0.96616 (15)	0.0322 (5)
H2	1.0047	0.2907	0.9676	0.039*
C3	0.7338 (2)	0.1437 (2)	0.99689 (15)	0.0295 (5)
H3	0.6774	0.0895	1.0248	0.035*
C4	0.1449 (3)	0.2412 (2)	0.78415 (16)	0.0370 (6)
H4	0.1174	0.2261	0.8370	0.044*
C5	0.0615 (2)	0.2658 (3)	0.71204 (16)	0.0368 (6)
H5	−0.0320	0.2710	0.7059	0.044*
C6	0.2706 (3)	0.2665 (3)	0.68687 (16)	0.0377 (6)
H6	0.3458	0.2728	0.6586	0.045*
C7	1.2812 (3)	−0.0029 (3)	1.47052 (16)	0.0406 (6)
H7	1.2855	0.0332	1.5258	0.049*
C8	1.1981 (3)	0.0484 (3)	1.40408 (16)	0.0384 (6)
H8	1.1471	0.1161	1.4151	0.046*
C9	1.1913 (2)	−0.0019 (2)	1.32065 (15)	0.0299 (5)
C10	1.2711 (2)	−0.1024 (3)	1.30983 (15)	0.0343 (6)
H10	1.2718	−0.1384	1.2551	0.041*
C11	1.3484 (2)	−0.1481 (3)	1.37969 (15)	0.0364 (6)
H11	1.3995	−0.2166	1.3706	0.044*
C12	0.0179 (3)	0.4426 (2)	0.15817 (16)	0.0364 (6)
H12	0.0807	0.4500	0.1204	0.044*
C13	0.0637 (2)	0.4141 (2)	0.24226 (16)	0.0340 (6)
H13	0.1555	0.4048	0.2602	0.041*
C14	−0.0281 (2)	0.3993 (2)	0.29992 (15)	0.0294 (5)
C15	−0.1633 (2)	0.4139 (2)	0.26798 (15)	0.0330 (5)
H15	−0.2294	0.4029	0.3034	0.040*
C16	−0.1992 (2)	0.4447 (2)	0.18335 (15)	0.0350 (6)
H16	−0.2901	0.4556	0.1636	0.042*
C17	0.0161 (2)	0.3685 (2)	0.39079 (15)	0.0307 (5)
C18	0.1464 (2)	0.4107 (3)	0.43354 (16)	0.0383 (6)
H18	0.2065	0.4581	0.4042	0.046*
C19	0.1882 (2)	0.3836 (3)	0.51815 (16)	0.0398 (6)
H19	0.2751	0.4139	0.5457	0.048*
C20	0.1009 (2)	0.3116 (2)	0.56174 (15)	0.0320 (5)
C21	−0.0285 (2)	0.2682 (3)	0.52087 (16)	0.0369 (6)
H21	−0.0876	0.2193	0.5502	0.044*
C22	−0.0699 (2)	0.2973 (3)	0.43654 (16)	0.0356 (6)
H22	−0.1576	0.2685	0.4098	0.043*
C23	0.9476 (2)	0.1282 (2)	1.09904 (14)	0.0276 (5)
C24	1.0810 (2)	0.1036 (3)	1.09647 (15)	0.0339 (6)
H24	1.1180	0.1146	1.0462	0.041*
C25	1.1582 (2)	0.0629 (3)	1.16904 (15)	0.0352 (6)
H25	1.2477	0.0460	1.1673	0.042*
C26	1.1055 (2)	0.0462 (2)	1.24510 (15)	0.0303 (5)
C27	0.9714 (2)	0.0714 (2)	1.24604 (15)	0.0310 (5)
H27	0.9344	0.0614	1.2964	0.037*
C28	0.8922 (2)	0.1110 (2)	1.17361 (15)	0.0312 (5)
H28	0.8021	0.1260	1.1748	0.037*
C29	0.5459 (2)	0.4491 (2)	0.79281 (15)	0.0267 (5)
C30	0.5340 (2)	0.5771 (2)	0.75120 (13)	0.0233 (5)
C31	0.5242 (2)	0.5830 (2)	0.66271 (14)	0.0272 (5)
H31	0.5343	0.5097	0.6297	0.033*
C32	0.4995 (2)	0.6981 (2)	0.62325 (14)	0.0286 (5)
C33	0.4868 (2)	−0.0752 (2)	0.81420 (14)	0.0256 (5)
C34	0.4870 (2)	−0.1921 (2)	0.67279 (14)	0.0277 (5)
H34	0.4707	−0.1149	0.6463	0.033*
C35	0.4984 (2)	−0.1965 (2)	0.76162 (13)	0.0227 (4)
C36	0.5216 (2)	−0.3125 (2)	0.80058 (14)	0.0239 (5)
H36	0.5289	−0.3164	0.8600	0.029*
Cd1	0.47879 (2)	0.20674 (2)	0.85471 (2)	0.02486 (6)
N1	0.69323 (19)	0.20182 (19)	0.92609 (12)	0.0304 (4)
N2	0.86848 (18)	0.17278 (19)	1.02407 (12)	0.0278 (4)
N3	1.3554 (2)	−0.1008 (2)	1.46020 (13)	0.0354 (5)
N4	0.2763 (2)	0.2415 (2)	0.76850 (13)	0.0358 (5)
N5	0.14254 (19)	0.2819 (2)	0.64895 (12)	0.0323 (5)
N6	−0.1111 (2)	0.4599 (2)	0.12818 (13)	0.0354 (5)
O1	0.56899 (17)	0.35329 (15)	0.74880 (10)	0.0349 (4)
O2	0.52448 (17)	0.44150 (16)	0.86949 (10)	0.0350 (4)
O3	0.46282 (18)	0.02488 (16)	0.77267 (11)	0.0382 (4)
O4	0.50274 (17)	−0.07717 (16)	0.89424 (10)	0.0353 (4)
O5	0.36295 (17)	0.19246 (17)	0.96874 (10)	0.0377 (4)
H5A	0.3412	0.2660	0.9833	0.056*
H5B	0.4042	0.1636	1.0154	0.056*
O44	0.4871 (2)	0.69915 (18)	0.53596 (10)	0.0465 (5)
H44	0.4564	0.7664	0.5193	0.070*
O1W	0.25935 (19)	0.41602 (18)	0.01315 (12)	0.0424 (4)
H1WA	0.3283	0.4623	0.0401	0.064*
H1WB	0.2151	0.4611	−0.0237	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0399 (13)	0.0305 (14)	0.0279 (12)	−0.0008 (11)	0.0047 (10)	0.0051 (10)
C2	0.0307 (12)	0.0345 (14)	0.0309 (13)	−0.0021 (10)	0.0051 (10)	0.0056 (10)
C3	0.0273 (11)	0.0307 (13)	0.0298 (12)	0.0026 (10)	0.0013 (9)	0.0069 (10)
C4	0.0414 (14)	0.0338 (15)	0.0352 (14)	0.0001 (11)	0.0060 (11)	0.0013 (11)
C5	0.0318 (13)	0.0402 (16)	0.0374 (14)	−0.0007 (11)	0.0038 (11)	0.0033 (11)
C6	0.0344 (13)	0.0488 (17)	0.0295 (14)	0.0124 (12)	−0.0003 (10)	−0.0012 (11)
C7	0.0556 (16)	0.0394 (16)	0.0250 (13)	0.0099 (13)	−0.0014 (11)	−0.0031 (11)
C8	0.0473 (15)	0.0323 (14)	0.0344 (14)	0.0133 (12)	−0.0010 (11)	−0.0041 (11)
C9	0.0284 (12)	0.0306 (13)	0.0292 (12)	0.0013 (10)	0.0005 (9)	0.0028 (10)
C10	0.0341 (13)	0.0420 (15)	0.0273 (13)	0.0091 (11)	0.0038 (10)	−0.0006 (10)
C11	0.0357 (13)	0.0402 (15)	0.0340 (14)	0.0117 (11)	0.0037 (10)	0.0029 (11)
C12	0.0398 (14)	0.0333 (14)	0.0376 (14)	−0.0003 (11)	0.0129 (11)	−0.0007 (11)
C13	0.0263 (12)	0.0356 (14)	0.0396 (14)	0.0014 (10)	0.0044 (10)	0.0012 (11)
C14	0.0276 (11)	0.0278 (13)	0.0318 (13)	0.0036 (10)	0.0020 (9)	−0.0005 (10)
C15	0.0300 (12)	0.0338 (14)	0.0358 (14)	0.0044 (10)	0.0063 (10)	0.0029 (10)
C16	0.0322 (12)	0.0366 (15)	0.0354 (14)	0.0051 (11)	0.0017 (10)	0.0026 (11)
C17	0.0272 (12)	0.0325 (14)	0.0320 (13)	0.0053 (10)	0.0024 (10)	0.0015 (10)
C18	0.0313 (13)	0.0439 (16)	0.0383 (14)	−0.0028 (11)	0.0044 (11)	0.0041 (11)
C19	0.0255 (12)	0.0526 (17)	0.0370 (14)	−0.0039 (11)	−0.0034 (10)	−0.0005 (12)
C20	0.0307 (12)	0.0337 (14)	0.0306 (13)	0.0085 (10)	−0.0007 (10)	−0.0002 (10)
C21	0.0306 (12)	0.0393 (15)	0.0387 (14)	−0.0020 (11)	0.0011 (11)	0.0063 (11)
C22	0.0249 (12)	0.0442 (16)	0.0350 (14)	−0.0011 (11)	−0.0016 (10)	0.0045 (11)
C23	0.0266 (11)	0.0282 (13)	0.0259 (12)	0.0010 (9)	−0.0021 (9)	0.0027 (9)
C24	0.0294 (12)	0.0456 (16)	0.0276 (13)	0.0066 (11)	0.0044 (10)	0.0045 (11)
C25	0.0250 (12)	0.0453 (16)	0.0355 (14)	0.0068 (11)	0.0032 (10)	0.0046 (11)
C26	0.0309 (12)	0.0282 (13)	0.0301 (13)	0.0027 (10)	0.0001 (10)	0.0000 (9)
C27	0.0341 (12)	0.0322 (14)	0.0276 (12)	0.0050 (10)	0.0063 (10)	0.0040 (10)
C28	0.0263 (11)	0.0317 (14)	0.0364 (14)	0.0064 (10)	0.0051 (10)	0.0033 (10)
C29	0.0272 (11)	0.0190 (12)	0.0324 (13)	0.0053 (9)	−0.0021 (9)	0.0017 (9)
C30	0.0233 (10)	0.0183 (11)	0.0277 (12)	0.0035 (8)	0.0010 (9)	0.0030 (9)
C31	0.0307 (12)	0.0221 (12)	0.0290 (12)	0.0069 (9)	0.0033 (9)	−0.0024 (9)
C32	0.0350 (12)	0.0295 (13)	0.0223 (12)	0.0085 (10)	0.0035 (9)	0.0043 (9)
C33	0.0221 (11)	0.0219 (12)	0.0329 (13)	0.0020 (9)	0.0052 (9)	0.0008 (9)
C34	0.0328 (12)	0.0201 (12)	0.0305 (12)	0.0053 (9)	0.0037 (10)	0.0064 (9)
C35	0.0217 (10)	0.0197 (11)	0.0265 (11)	0.0023 (8)	0.0030 (8)	0.0014 (8)
C36	0.0274 (11)	0.0204 (11)	0.0227 (11)	0.0013 (9)	0.0012 (9)	0.0006 (8)
Cd1	0.03083 (10)	0.02039 (10)	0.02260 (10)	0.00547 (7)	−0.00001 (7)	0.00232 (6)
N1	0.0310 (10)	0.0277 (11)	0.0311 (11)	0.0024 (8)	−0.0003 (8)	0.0061 (8)
N2	0.0263 (9)	0.0292 (11)	0.0270 (10)	0.0036 (8)	0.0006 (8)	0.0043 (8)
N3	0.0390 (11)	0.0370 (12)	0.0292 (11)	0.0073 (9)	0.0001 (9)	0.0036 (9)
N4	0.0385 (11)	0.0370 (13)	0.0304 (11)	0.0111 (9)	−0.0027 (9)	−0.0029 (9)
N5	0.0292 (10)	0.0365 (12)	0.0287 (11)	0.0045 (9)	−0.0028 (8)	−0.0016 (8)
N6	0.0440 (12)	0.0303 (12)	0.0314 (11)	0.0041 (9)	0.0047 (9)	0.0018 (9)
O1	0.0518 (10)	0.0207 (9)	0.0334 (9)	0.0111 (7)	0.0055 (7)	0.0029 (6)
O2	0.0538 (10)	0.0235 (9)	0.0278 (9)	0.0068 (8)	0.0046 (8)	0.0067 (7)
O3	0.0580 (11)	0.0206 (9)	0.0353 (10)	0.0121 (8)	0.0009 (8)	0.0007 (7)
O4	0.0489 (10)	0.0309 (10)	0.0277 (9)	0.0067 (8)	0.0097 (8)	−0.0005 (7)
O5	0.0512 (10)	0.0377 (10)	0.0268 (9)	0.0137 (8)	0.0090 (8)	0.0032 (7)
O44	0.0800 (14)	0.0374 (11)	0.0247 (9)	0.0226 (10)	0.0058 (9)	0.0052 (8)
O1W	0.0483 (11)	0.0400 (11)	0.0375 (11)	0.0079 (9)	−0.0002 (8)	0.0041 (8)

Geometric parameters (Å, º)

C1—C2	1.344 (3)	C20—N5	1.423 (3)
C1—N1	1.378 (3)	C21—C22	1.379 (3)
C1—H1	0.9300	C21—H21	0.9300
C2—N2	1.375 (3)	C22—H22	0.9300
C2—H2	0.9300	C23—C24	1.385 (3)
C3—N1	1.309 (3)	C23—C28	1.384 (3)
C3—N2	1.350 (3)	C23—N2	1.427 (3)
C3—H3	0.9300	C24—C25	1.375 (3)
C4—C5	1.344 (3)	C24—H24	0.9300
C4—N4	1.373 (3)	C25—C26	1.391 (3)
C4—H4	0.9300	C25—H25	0.9300
C5—N5	1.382 (3)	C26—C27	1.390 (3)
C5—H5	0.9300	C27—C28	1.377 (3)
C6—N4	1.313 (3)	C27—H27	0.9300
C6—N5	1.349 (3)	C28—H28	0.9300
C6—H6	0.9300	C29—O1	1.252 (3)
C7—N3	1.329 (3)	C29—O2	1.263 (3)
C7—C8	1.381 (4)	C29—C30	1.504 (3)
C7—H7	0.9300	C30—C31	1.386 (3)
C8—C9	1.389 (3)	C30—C36^i	1.390 (3)
C8—H8	0.9300	C31—C32	1.385 (3)
C9—C10	1.388 (3)	C31—H31	0.9300
C9—C26	1.480 (3)	C32—O44	1.361 (3)
C10—C11	1.364 (3)	C32—C34^i	1.387 (3)
C10—H10	0.9300	C33—O4	1.247 (3)
C11—N3	1.335 (3)	C33—O3	1.264 (3)
C11—H11	0.9300	C33—C35	1.508 (3)
C12—N6	1.330 (3)	C34—C32^ii	1.387 (3)
C12—C13	1.381 (3)	C34—C35	1.388 (3)
C12—H12	0.9300	C34—H34	0.9300
C13—C14	1.391 (3)	C35—C36	1.389 (3)
C13—H13	0.9300	C36—C30^ii	1.390 (3)
C14—C15	1.388 (3)	C36—H36	0.9300
C14—C17	1.483 (3)	Cd1—O3	2.2330 (16)
C15—C16	1.380 (3)	Cd1—N1	2.2626 (19)
C15—H15	0.9300	Cd1—O5	2.2857 (15)
C16—N6	1.333 (3)	Cd1—N4	2.315 (2)
C16—H16	0.9300	Cd1—O2	2.4348 (16)
C17—C22	1.385 (3)	Cd1—O1	2.5081 (16)
C17—C18	1.394 (3)	O5—H5A	0.8458
C18—C19	1.377 (3)	O5—H5B	0.8601
C18—H18	0.9300	O44—H44	0.8200
C19—C20	1.377 (3)	O1W—H1WA	0.8500
C19—H19	0.9300	O1W—H1WB	0.8500
C20—C21	1.380 (3)
C2—C1—N1	109.8 (2)	C24—C25—H25	119.2
C2—C1—H1	125.1	C26—C25—H25	119.2
N1—C1—H1	125.1	C27—C26—C25	118.2 (2)
C1—C2—N2	106.2 (2)	C27—C26—C9	122.3 (2)
C1—C2—H2	126.9	C25—C26—C9	119.4 (2)
N2—C2—H2	126.9	C28—C27—C26	121.0 (2)
N1—C3—N2	111.1 (2)	C28—C27—H27	119.5
N1—C3—H3	124.4	C26—C27—H27	119.5
N2—C3—H3	124.4	C27—C28—C23	119.7 (2)
C5—C4—N4	110.2 (2)	C27—C28—H28	120.2
C5—C4—H4	124.9	C23—C28—H28	120.2
N4—C4—H4	124.9	O1—C29—O2	122.8 (2)
C4—C5—N5	106.3 (2)	O1—C29—C30	118.9 (2)
C4—C5—H5	126.9	O2—C29—C30	118.1 (2)
N5—C5—H5	126.9	C31—C30—C36^i	119.8 (2)
N4—C6—N5	111.9 (2)	C31—C30—C29	120.0 (2)
N4—C6—H6	124.0	C36^i—C30—C29	119.98 (19)
N5—C6—H6	124.0	C30—C31—C32	120.2 (2)
N3—C7—C8	123.9 (2)	C30—C31—H31	119.9
N3—C7—H7	118.0	C32—C31—H31	119.9
C8—C7—H7	118.0	O44—C32—C31	118.4 (2)
C7—C8—C9	119.4 (2)	O44—C32—C34^i	121.8 (2)
C7—C8—H8	120.3	C31—C32—C34^i	119.8 (2)
C9—C8—H8	120.3	O4—C33—O3	123.8 (2)
C10—C9—C8	116.6 (2)	O4—C33—C35	119.8 (2)
C10—C9—C26	119.9 (2)	O3—C33—C35	116.4 (2)
C8—C9—C26	123.5 (2)	C32^ii—C34—C35	120.6 (2)
C11—C10—C9	119.8 (2)	C32^ii—C34—H34	119.7
C11—C10—H10	120.1	C35—C34—H34	119.7
C9—C10—H10	120.1	C34—C35—C36	119.3 (2)
N3—C11—C10	124.1 (2)	C34—C35—C33	119.6 (2)
N3—C11—H11	117.9	C36—C35—C33	121.15 (19)
C10—C11—H11	117.9	C30^ii—C36—C35	120.3 (2)
N6—C12—C13	123.7 (2)	C30^ii—C36—H36	119.8
N6—C12—H12	118.2	C35—C36—H36	119.8
C13—C12—H12	118.2	O3—Cd1—N1	99.32 (7)
C12—C13—C14	119.7 (2)	O3—Cd1—O5	114.82 (6)
C12—C13—H13	120.2	N1—Cd1—O5	99.12 (6)
C14—C13—H13	120.2	O3—Cd1—N4	83.79 (7)
C15—C14—C13	116.6 (2)	N1—Cd1—N4	169.72 (7)
C15—C14—C17	121.7 (2)	O5—Cd1—N4	88.32 (7)
C13—C14—C17	121.7 (2)	O3—Cd1—O2	148.76 (6)
C16—C15—C14	119.6 (2)	N1—Cd1—O2	85.67 (6)
C16—C15—H15	120.2	O5—Cd1—O2	94.49 (6)
C14—C15—H15	120.2	N4—Cd1—O2	86.68 (7)
N6—C16—C15	123.8 (2)	O3—Cd1—O1	95.95 (6)
N6—C16—H16	118.1	N1—Cd1—O1	89.59 (6)
C15—C16—H16	118.1	O5—Cd1—O1	145.86 (6)
C22—C17—C18	117.4 (2)	N4—Cd1—O1	80.32 (7)
C22—C17—C14	121.6 (2)	O2—Cd1—O1	53.05 (5)
C18—C17—C14	121.1 (2)	C3—N1—C1	105.88 (19)
C19—C18—C17	121.6 (2)	C3—N1—Cd1	128.52 (15)
C19—C18—H18	119.2	C1—N1—Cd1	125.30 (16)
C17—C18—H18	119.2	C3—N2—C2	107.05 (19)
C20—C19—C18	119.7 (2)	C3—N2—C23	126.84 (19)
C20—C19—H19	120.1	C2—N2—C23	126.11 (19)
C18—C19—H19	120.1	C7—N3—C11	116.2 (2)
C19—C20—C21	119.9 (2)	C6—N4—C4	105.4 (2)
C19—C20—N5	120.5 (2)	C6—N4—Cd1	121.94 (16)
C21—C20—N5	119.6 (2)	C4—N4—Cd1	132.70 (17)
C22—C21—C20	119.9 (2)	C6—N5—C5	106.3 (2)
C22—C21—H21	120.1	C6—N5—C20	126.5 (2)
C20—C21—H21	120.1	C5—N5—C20	127.2 (2)
C21—C22—C17	121.5 (2)	C12—N6—C16	116.6 (2)
C21—C22—H22	119.2	C29—O1—Cd1	89.25 (13)
C17—C22—H22	119.2	C29—O2—Cd1	92.37 (13)
C24—C23—C28	120.4 (2)	C33—O3—Cd1	114.28 (15)
C24—C23—N2	119.1 (2)	Cd1—O5—H5A	110.8
C28—C23—N2	120.5 (2)	Cd1—O5—H5B	117.3
C25—C24—C23	119.2 (2)	H5A—O5—H5B	104.9
C25—C24—H24	120.4	C32—O44—H44	109.5
C23—C24—H24	120.4	H1WA—O1W—H1WB	109.5
C24—C25—C26	121.5 (2)
N1—C1—C2—N2	−1.0 (3)	C36^i—C30—C31—C32	−1.3 (3)
N4—C4—C5—N5	0.1 (3)	C29—C30—C31—C32	173.5 (2)
N3—C7—C8—C9	−1.1 (4)	C30—C31—C32—O44	−178.3 (2)
C7—C8—C9—C10	−0.3 (4)	C30—C31—C32—C34^i	1.2 (3)
C7—C8—C9—C26	180.0 (2)	C32^ii—C34—C35—C36	−0.5 (3)
C8—C9—C10—C11	1.3 (4)	C32^ii—C34—C35—C33	178.96 (19)
C26—C9—C10—C11	−178.9 (2)	O4—C33—C35—C34	−176.96 (19)
C9—C10—C11—N3	−1.2 (4)	O3—C33—C35—C34	2.0 (3)
N6—C12—C13—C14	1.5 (4)	O4—C33—C35—C36	2.5 (3)
C12—C13—C14—C15	0.4 (4)	O3—C33—C35—C36	−178.58 (19)
C12—C13—C14—C17	179.9 (2)	C34—C35—C36—C30^ii	0.4 (3)
C13—C14—C15—C16	−1.6 (3)	C33—C35—C36—C30^ii	−179.08 (18)
C17—C14—C15—C16	178.9 (2)	N2—C3—N1—C1	−0.5 (3)
C14—C15—C16—N6	1.2 (4)	N2—C3—N1—Cd1	−174.36 (15)
C15—C14—C17—C22	29.9 (4)	C2—C1—N1—C3	0.9 (3)
C13—C14—C17—C22	−149.6 (3)	C2—C1—N1—Cd1	175.03 (16)
C15—C14—C17—C18	−150.0 (2)	N1—C3—N2—C2	−0.1 (3)
C13—C14—C17—C18	30.5 (4)	N1—C3—N2—C23	179.4 (2)
C22—C17—C18—C19	−0.5 (4)	C1—C2—N2—C3	0.6 (3)
C14—C17—C18—C19	179.4 (2)	C1—C2—N2—C23	−178.8 (2)
C17—C18—C19—C20	1.1 (4)	C24—C23—N2—C3	144.9 (2)
C18—C19—C20—C21	−0.8 (4)	C28—C23—N2—C3	−35.7 (4)
C18—C19—C20—N5	179.5 (2)	C24—C23—N2—C2	−35.7 (3)
C19—C20—C21—C22	−0.1 (4)	C28—C23—N2—C2	143.7 (2)
N5—C20—C21—C22	179.6 (2)	C8—C7—N3—C11	1.3 (4)
C20—C21—C22—C17	0.8 (4)	C10—C11—N3—C7	−0.1 (4)
C18—C17—C22—C21	−0.5 (4)	N5—C6—N4—C4	−0.2 (3)
C14—C17—C22—C21	179.7 (2)	N5—C6—N4—Cd1	179.33 (16)
C28—C23—C24—C25	−0.5 (4)	C5—C4—N4—C6	0.0 (3)
N2—C23—C24—C25	178.9 (2)	C5—C4—N4—Cd1	−179.41 (18)
C23—C24—C25—C26	−0.2 (4)	N4—C6—N5—C5	0.3 (3)
C24—C25—C26—C27	0.3 (4)	N4—C6—N5—C20	179.1 (2)
C24—C25—C26—C9	178.0 (2)	C4—C5—N5—C6	−0.2 (3)
C10—C9—C26—C27	135.3 (3)	C4—C5—N5—C20	−179.0 (2)
C8—C9—C26—C27	−45.0 (3)	C19—C20—N5—C6	−30.1 (4)
C10—C9—C26—C25	−42.3 (3)	C21—C20—N5—C6	150.2 (3)
C8—C9—C26—C25	137.4 (3)	C19—C20—N5—C5	148.5 (3)
C25—C26—C27—C28	0.4 (4)	C21—C20—N5—C5	−31.2 (4)
C9—C26—C27—C28	−177.2 (2)	C13—C12—N6—C16	−2.0 (4)
C26—C27—C28—C23	−1.2 (4)	C15—C16—N6—C12	0.6 (4)
C24—C23—C28—C27	1.2 (4)	O2—C29—O1—Cd1	16.1 (2)
N2—C23—C28—C27	−178.2 (2)	C30—C29—O1—Cd1	−159.74 (17)
O1—C29—C30—C31	11.5 (3)	O1—C29—O2—Cd1	−16.7 (2)
O2—C29—C30—C31	−164.6 (2)	C30—C29—O2—Cd1	159.25 (17)
O1—C29—C30—C36^i	−173.8 (2)	O4—C33—O3—Cd1	7.9 (3)
O2—C29—C30—C36^i	10.2 (3)	C35—C33—O3—Cd1	−171.02 (13)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···N6^iii	0.85	2.04	2.877 (3)	169
O1W—H1WA···O2^iv	0.85	2.05	2.878 (2)	166
O44—H44···N3^v	0.82	1.95	2.757 (3)	167
O5—H5B···O4^vi	0.86	1.87	2.724 (2)	171
O5—H5A···O1W^vii	0.85	1.90	2.736 (3)	170
C16—H16···O2^viii	0.93	2.64	3.539 (3)	162
C11—H11···O1^ix	0.93	2.40	3.142 (3)	137
C6—H6···O1	0.93	2.51	3.034 (3)	116
C3—H3···O4^vi	0.93	2.36	3.171 (3)	146
C3—H3···O4^vi	0.93	2.36	3.171 (3)	146
C6—H6···O1	0.93	2.51	3.034 (3)	116
C11—H11···O1^ix	0.93	2.40	3.142 (3)	137
C16—H16···O2^viii	0.93	2.64	3.539 (3)	162
O5—H5A···O1W^vii	0.85	1.90	2.736 (3)	170
O5—H5B···O4^vi	0.86	1.87	2.724 (2)	171
O44—H44···N3^v	0.82	1.95	2.757 (3)	167

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