Chlorido­bis­[2-(pyridin-2-yl-κN)benzo[b][1,5]naphthyridine-κN1]copper(II) perchlorate aceto­nitrile disolvate

Ohtsu, H.; Tezuka, Y.; Narita, M.; Tsuge, K.; Tanaka, K.

doi:10.1107/S2414314616015625

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161562

https://doi.org/10.1107/S2414314616015625

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Chloridobis[2-(pyridin-2-yl-κN)benzo[b][1,5]naphthyridine-κN¹]copper(II) perchlorate acetonitrile disolvate

Hideki Ohtsu,^a ^* Yosuke Tezuka,^a Michitari Narita,^a Kiyoshi Tsuge ^a and Koji Tanaka ^b

^aGraduate School of Science and Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan, and ^bInstitute for Integrated Cell-Material Science (iCeMS), Kyoto University, Advanced Chemical Technology Center in Kyoto, 105 Jibu-cho, Fushimi-ku, Kyoto, 612-8374, Japan
^*Correspondence e-mail: ohtsu@sci.u-toyama.ac.jp

Edited by M. Bolte, Goethe-Universität Frankfurt Germany (Received 19 September 2016; accepted 4 October 2016; online 11 October 2016)

The copper(II) ion in the title complex, [CuCl(C₁₇H₁₁N₃)₂]ClO₄·2CH₃CN, is coordinated by four N atoms from two pbn ligands and one Cl⁻ ion in a distorted trigonal–bipyramidal geometry (τ = 0.84). The asymmetric unit comprises half of the cationic complex molecule, and complete molecules are generated by twofold rotation symmetry with the corresponding axis running through the Cu atom and the coordinating Cl atom. The perchlorate anion is also located on a twofold rotation axis (passing through the Cl atom). In the crystal, there are π–π stacking interactions between the benzonaphthyridine rings of the pbn ligand of neighbouring cations.

Keywords: crystal structure; copper(II) complex; NAD⁺/NADH-analogous ligand.

CCDC reference: 1504744

Structure description

Understanding the relationship between coordination geometry and reactivity of complexes containing the NAD⁺/NADH-analogous ligand pbn [pbn = 2-(pyridin-2-yl)benzo[b][1,5]naphthyridine] is of great interest and importance in order to develop a photorenewable hydride reagent. In our previous studies, photocatalytic CO₂ reduction using the pbn complex has proved to be successful (Ohtsu & Tanaka, 2012 ), and control over the reaction rate of the CO₂ hydride reduction using a pbn complex has been accomplished by tuning of the basicity of the bases (Ohtsu et al., 2015 ). As part of our ongoing research on transition-metal complexes containing a pbn ligand, we have synthesized a new copper(II) pbn complex and its structure determination has been undertaken.

The molecular structure of the title complex is shown in Fig. 1. The copper(II) ion of the cation has a pentacoordinate structure formed by four N atoms from two pbn ligands and one Cl ligand. The complex cation exhibits point group symmetry 2, with the twofold rotation axis running through Cu1 and Cl1. The perchlorate anion is also located on a twofold rotation axis (passing through Cl2). The bond lengths from the copper to each of donor N atoms and chloride are Cu1—N1 2.0230 (18) Å, Cu1—N3 2.0778 (19) Å, and Cu1—Cl1 2.2795 (9) Å. The quantitative difference in five-coordinate geometry is indicated by the τ parameter, the value of which can range from τ = 1 for a perfect trigonal–bipyramidal geometry to τ = 0 for a perfect square-pyramidal geometry (Addison et al., 1984 ). The τ value for the copper(II) ion of the cation in the title complex is calculated to be 0.84 using the equation τ = (β − α)/60 (Addison et al., 1984), where α = N3—Cu1—Cl1 [125.66 (5)°] and β = N1—Cu1—N1ⁱ [175.78 (11)°; symmetry code: (i) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ − z). Thus, the coordination environment of the copper(II) ion in [Cu(pbn)₂Cl]⁺ is slightly distorted trigonal–bipyramidal.

Figure 1
The molecular structure of the title complex, with displacement ellipsoids at the 30% probability level [symmetry codes: (i) x, $[{1\over 2}]$ − y, $[{1\over 2}]$ − z; (ii) $[{1\over 2}]$ − x, −y, z]. H atoms have been omitted for clarity.

The crystal packing of the title complex is shown in Fig. 2. The relatively short interplanar distances between the benzonaphthyridine rings of the pbn ligand of neighbouring cations indicate intermolecular π–π stacking interactions [distance between the centroids of the (C8/N2/C9–C12) and (C2/N1/C1/C9/C10/C3)ⁱⁱ rings = 3.6070 (3) Å; symmetry code: (ii) − $[{1\over 2}]$ + x, y, 1 − z].

Figure 2
The crystal packing of the title complex, viewed along the a axis. H atoms have been omitted for clarity.

Synthesis and crystallization

The NAD⁺/NADH-analogous ligand pbn [pbn = 2-(pyridin-2-yl)benzo[b][1,5]naphthyridine] was prepared according to the procedure of Koizumi & Tanaka (2005 ). To a dichloromethane solution (4 ml) of pbn (50.0 mg, 0.19 mmol) was added dropwise a mixture of CuCl₂·2H₂O (8.3 mg, 0.05 mmol) and Cu(ClO₄)₂·6H₂O (19.9 mg, 0.05 mmol) in acetonitrile (4 ml). The resulting pale yellow–green precipitate was filtered and dissolved in hot acetonitrile for recrystallization. After the solution was left to stand for a few weeks at room temperature, pale yellow–green crystals of the title complex, [Cu(pbn)₂Cl]ClO₄·2CH₃CN, were obtained (yield: 33.7 mg, 48.6%). Elemental analysis found: C 53.40, H 3.55, N 10.83%; calculated for C₃₄H₂₈Cl₂CuN₆O₇: C 53.24, H 3.68, N 10.96%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[CuCl(C₁₇H₁₁N₃)₂]ClO₄·2C₂H₃N
M_r	795.14
Crystal system, space group	Orthorhombic, Pnna
Temperature (K)	173
a, b, c (Å)	7.53614 (16), 30.5246 (6), 15.4918 (4)
V (Å³)	3563.71 (13)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.82
Crystal size (mm)	0.25 × 0.23 × 0.02

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995 )
T_min, T_max	0.751, 0.984
No. of measured, independent and observed [F² > 2.0σ(F²)] reflections	32886, 4072, 3235
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.132, 1.06
No. of reflections	4072
No. of parameters	242
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.50
Computer programs: RAPID-AUTO (Rigaku, 2001 ), SIR2011 (Burla et al., 2012 ), SHELXL2016 (Sheldrick, 2015 ), CrystalStructure (Rigaku, 2016 ), Mercury (Macrae et al., 2008 ), CrystalMaker (Palmer, 2007 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1504744

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616015625/bt4028sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616015625/bt4028Isup2.hkl

checkCIF report

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2001); cell refinement: RAPID-AUTO (Rigaku, 2001); data reduction: RAPID-AUTO (Rigaku, 2001); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015); molecular graphics: CrystalStructure (Rigaku, 2016), Mercury (Macrae et al., 2008) and CrystalMaker (Palmer, 2007); software used to prepare material for publication: CrystalStructure (Rigaku, 2016) and publCIF (Westrip, 2010).

Chloridobis[2-(pyridin-2-yl-κN)benzo[b][1,5]naphthyridine-κN¹]copper(II) perchlorate acetonitrile disolvate top

Crystal data top

[CuCl(C₁₇H₁₁N₃)₂]ClO₄·2C₂H₃N	D_x = 1.482 Mg m⁻³
M_r = 795.14	Mo Kα radiation, λ = 0.71075 Å
Orthorhombic, Pnna	Cell parameters from 21593 reflections
a = 7.53614 (16) Å	θ = 3.0–27.5°
b = 30.5246 (6) Å	µ = 0.82 mm⁻¹
c = 15.4918 (4) Å	T = 173 K
V = 3563.71 (13) Å³	Platelet, yellowish green
Z = 4	0.25 × 0.23 × 0.02 mm
F(000) = 1628.00

Data collection top

Rigaku R-AXIS RAPID diffractometer	3235 reflections with F² > 2.0σ(F²)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.043
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −8→9
T_min = 0.751, T_max = 0.984	k = −39→39
32886 measured reflections	l = −20→20
4072 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.132	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0731P)² + 2.7626P] where P = (F_o² + 2F_c²)/3
4072 reflections	(Δ/σ)_max < 0.001
242 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

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 was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
CU1	0.27555 (5)	0.250000	0.250000	0.02241 (13)
CL1	−0.02693 (11)	0.250000	0.250000	0.0367 (2)
CL2	0.750000	0.000000	0.16427 (8)	0.0533 (3)
O1	0.8062 (9)	0.03461 (19)	0.1220 (6)	0.244 (4)
O2	0.6099 (6)	0.01641 (18)	0.2183 (3)	0.1367 (17)
N1	0.2854 (2)	0.23357 (6)	0.37642 (12)	0.0233 (4)
N2	0.1294 (3)	0.15656 (7)	0.54355 (13)	0.0294 (4)
N3	0.4363 (3)	0.30003 (6)	0.29646 (12)	0.0271 (4)
N4	0.1061 (4)	0.13340 (10)	0.12987 (17)	0.0557 (7)
C1	0.3578 (3)	0.26382 (7)	0.42751 (14)	0.0241 (5)
C2	0.3555 (3)	0.26007 (8)	0.51920 (15)	0.0283 (5)
H2	0.407636	0.282244	0.553951	0.034*
C3	0.2785 (3)	0.22473 (8)	0.55655 (14)	0.0282 (5)
H3	0.275313	0.222235	0.617656	0.034*
C4	−0.0133 (3)	0.08709 (8)	0.53424 (18)	0.0357 (6)
H4	−0.017468	0.085455	0.595443	0.043*
C5	−0.0791 (4)	0.05395 (9)	0.48647 (19)	0.0403 (6)
H5	−0.129111	0.029212	0.514602	0.048*
C6	−0.0750 (4)	0.05533 (8)	0.3947 (2)	0.0408 (6)
H6	−0.120543	0.031392	0.362345	0.049*
C7	−0.0063 (4)	0.09064 (8)	0.35284 (17)	0.0353 (6)
H7	−0.005778	0.091390	0.291536	0.042*
C8	0.1360 (3)	0.16370 (7)	0.36126 (15)	0.0268 (5)
H8	0.135199	0.166429	0.300175	0.032*
C9	0.2028 (3)	0.19150 (7)	0.50445 (15)	0.0250 (5)
C10	0.2084 (3)	0.19688 (7)	0.41263 (14)	0.0232 (4)
C11	0.0629 (3)	0.12479 (8)	0.49334 (16)	0.0287 (5)
C12	0.0652 (3)	0.12666 (7)	0.40064 (15)	0.0280 (5)
C13	0.4470 (3)	0.30072 (7)	0.38324 (15)	0.0266 (5)
C14	0.5399 (4)	0.33320 (8)	0.42694 (17)	0.0347 (6)
H14	0.545306	0.333179	0.488203	0.042*
C15	0.6248 (4)	0.36570 (9)	0.37968 (19)	0.0424 (7)
H15	0.688212	0.388422	0.408040	0.051*
C16	0.6153 (4)	0.36437 (9)	0.2907 (2)	0.0414 (6)
H16	0.673472	0.386018	0.256982	0.050*
C17	0.5203 (3)	0.33121 (9)	0.25129 (16)	0.0334 (5)
H17	0.514287	0.330496	0.190050	0.040*
C18	0.2394 (6)	0.05650 (14)	0.1102 (4)	0.0886 (15)
H18A	0.256040	0.050434	0.048564	0.106*
H18B	0.158888	0.034679	0.135016	0.106*
H18C	0.354269	0.055080	0.139691	0.106*
C19	0.1648 (5)	0.09945 (11)	0.1207 (2)	0.0506 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
CU1	0.0261 (2)	0.0236 (2)	0.0175 (2)	0.000	0.000	−0.00087 (14)
CL1	0.0256 (4)	0.0562 (6)	0.0283 (4)	0.000	0.000	0.0163 (4)
CL2	0.0604 (7)	0.0417 (5)	0.0579 (7)	−0.0012 (5)	0.000	0.000
O1	0.189 (6)	0.131 (4)	0.412 (11)	0.034 (4)	0.106 (6)	0.162 (6)
O2	0.118 (3)	0.190 (4)	0.102 (3)	0.080 (3)	0.014 (2)	0.006 (3)
N1	0.0255 (10)	0.0250 (9)	0.0192 (9)	0.0038 (8)	−0.0017 (7)	−0.0003 (7)
N2	0.0269 (10)	0.0343 (11)	0.0269 (10)	0.0065 (8)	0.0020 (8)	0.0043 (8)
N3	0.0275 (10)	0.0282 (9)	0.0257 (10)	−0.0009 (8)	0.0001 (8)	−0.0038 (8)
N4	0.0638 (18)	0.0584 (17)	0.0449 (15)	−0.0029 (14)	−0.0009 (13)	0.0052 (13)
C1	0.0235 (11)	0.0258 (10)	0.0230 (11)	0.0055 (9)	−0.0033 (9)	−0.0024 (8)
C2	0.0256 (12)	0.0351 (12)	0.0243 (11)	0.0042 (9)	−0.0046 (9)	−0.0079 (9)
C3	0.0271 (12)	0.0388 (13)	0.0187 (10)	0.0069 (10)	−0.0013 (9)	−0.0014 (9)
C4	0.0305 (13)	0.0373 (13)	0.0393 (13)	0.0066 (11)	0.0048 (11)	0.0095 (11)
C5	0.0330 (14)	0.0333 (13)	0.0545 (17)	0.0014 (11)	0.0074 (12)	0.0125 (12)
C6	0.0384 (14)	0.0281 (12)	0.0559 (17)	−0.0023 (11)	0.0018 (13)	−0.0029 (12)
C7	0.0365 (14)	0.0319 (12)	0.0375 (13)	−0.0006 (11)	0.0021 (11)	−0.0029 (10)
C8	0.0308 (12)	0.0259 (11)	0.0236 (10)	0.0034 (9)	−0.0018 (9)	−0.0012 (9)
C9	0.0243 (11)	0.0290 (11)	0.0219 (10)	0.0073 (9)	−0.0001 (8)	−0.0001 (9)
C10	0.0228 (11)	0.0246 (10)	0.0223 (10)	0.0054 (9)	−0.0014 (8)	0.0002 (8)
C11	0.0253 (12)	0.0302 (11)	0.0305 (12)	0.0072 (10)	0.0029 (9)	0.0047 (9)
C12	0.0258 (11)	0.0273 (11)	0.0310 (12)	0.0047 (9)	0.0006 (10)	0.0003 (9)
C13	0.0249 (11)	0.0273 (11)	0.0276 (11)	0.0046 (9)	−0.0034 (9)	−0.0040 (9)
C14	0.0391 (14)	0.0323 (12)	0.0327 (13)	−0.0006 (11)	−0.0080 (11)	−0.0057 (10)
C15	0.0439 (16)	0.0360 (14)	0.0472 (16)	−0.0102 (12)	−0.0105 (13)	−0.0064 (12)
C16	0.0385 (15)	0.0383 (14)	0.0473 (16)	−0.0134 (12)	0.0009 (12)	0.0009 (12)
C17	0.0326 (13)	0.0359 (13)	0.0316 (12)	−0.0066 (11)	0.0025 (10)	0.0000 (10)
C18	0.075 (3)	0.058 (2)	0.132 (4)	0.005 (2)	−0.007 (3)	0.001 (3)
C19	0.0528 (18)	0.0517 (18)	0.0473 (17)	−0.0038 (16)	−0.0015 (15)	0.0086 (14)

Geometric parameters (Å, º) top

CU1—N1	2.0230 (18)	C4—H4	0.9500
CU1—N1ⁱ	2.0230 (18)	C5—C6	1.423 (4)
CU1—N3	2.0778 (19)	C5—H5	0.9500
CU1—N3ⁱ	2.0779 (19)	C6—C7	1.360 (4)
CU1—CL1	2.2795 (9)	C6—H6	0.9500
CL2—O1ⁱⁱ	1.313 (5)	C7—C12	1.431 (3)
CL2—O1	1.313 (5)	C7—H7	0.9500
CL2—O2	1.438 (4)	C8—C12	1.391 (3)
CL2—O2ⁱⁱ	1.438 (4)	C8—C10	1.399 (3)
N1—C1	1.333 (3)	C8—H8	0.9500
N1—C10	1.381 (3)	C9—C10	1.433 (3)
N2—C11	1.341 (3)	C11—C12	1.437 (3)
N2—C9	1.345 (3)	C13—C14	1.390 (3)
N3—C17	1.340 (3)	C14—C15	1.389 (4)
N3—C13	1.347 (3)	C14—H14	0.9500
N4—C19	1.136 (4)	C15—C16	1.380 (4)
C1—C2	1.425 (3)	C15—H15	0.9500
C1—C13	1.480 (3)	C16—C17	1.382 (4)
C2—C3	1.355 (4)	C16—H16	0.9500
C2—H2	0.9500	C17—H17	0.9500
C3—C9	1.416 (3)	C18—C19	1.436 (6)
C3—H3	0.9500	C18—H18A	0.9800
C4—C5	1.348 (4)	C18—H18B	0.9800
C4—C11	1.434 (3)	C18—H18C	0.9800

N1—CU1—N1ⁱ	175.78 (11)	C6—C7—C12	120.4 (2)
N1—CU1—N3	79.95 (8)	C6—C7—H7	119.8
N1ⁱ—CU1—N3	97.56 (7)	C12—C7—H7	119.8
N1—CU1—N3ⁱ	97.57 (7)	C12—C8—C10	119.3 (2)
N1ⁱ—CU1—N3ⁱ	79.95 (8)	C12—C8—H8	120.4
N3—CU1—N3ⁱ	108.69 (11)	C10—C8—H8	120.4
N1—CU1—CL1	92.11 (5)	N2—C9—C3	118.5 (2)
N1ⁱ—CU1—CL1	92.11 (5)	N2—C9—C10	123.4 (2)
N3—CU1—CL1	125.66 (5)	C3—C9—C10	118.2 (2)
N3ⁱ—CU1—CL1	125.65 (5)	N1—C10—C8	121.3 (2)
O1ⁱⁱ—CL2—O1	120.2 (9)	N1—C10—C9	120.6 (2)
O1ⁱⁱ—CL2—O2	109.5 (4)	C8—C10—C9	118.1 (2)
O1—CL2—O2	104.3 (4)	N2—C11—C4	118.3 (2)
O1ⁱⁱ—CL2—O2ⁱⁱ	104.3 (4)	N2—C11—C12	123.1 (2)
O1—CL2—O2ⁱⁱ	109.5 (4)	C4—C11—C12	118.6 (2)
O2—CL2—O2ⁱⁱ	108.8 (4)	C8—C12—C7	122.8 (2)
C1—N1—C10	119.52 (19)	C8—C12—C11	118.4 (2)
C1—N1—CU1	114.72 (15)	C7—C12—C11	118.8 (2)
C10—N1—CU1	125.38 (15)	N3—C13—C14	121.8 (2)
C11—N2—C9	117.8 (2)	N3—C13—C1	115.0 (2)
C17—N3—C13	118.8 (2)	C14—C13—C1	123.1 (2)
C17—N3—CU1	128.05 (16)	C15—C14—C13	119.0 (2)
C13—N3—CU1	113.10 (16)	C15—C14—H14	120.5
N1—C1—C2	122.1 (2)	C13—C14—H14	120.5
N1—C1—C13	116.0 (2)	C16—C15—C14	118.8 (2)
C2—C1—C13	121.9 (2)	C16—C15—H15	120.6
C3—C2—C1	119.7 (2)	C14—C15—H15	120.6
C3—C2—H2	120.2	C15—C16—C17	119.3 (3)
C1—C2—H2	120.2	C15—C16—H16	120.3
C2—C3—C9	120.0 (2)	C17—C16—H16	120.3
C2—C3—H3	120.0	N3—C17—C16	122.3 (2)
C9—C3—H3	120.0	N3—C17—H17	118.9
C5—C4—C11	120.5 (2)	C16—C17—H17	118.9
C5—C4—H4	119.8	C19—C18—H18A	109.5
C11—C4—H4	119.8	C19—C18—H18B	109.5
C4—C5—C6	121.2 (2)	H18A—C18—H18B	109.5
C4—C5—H5	119.4	C19—C18—H18C	109.5
C6—C5—H5	119.4	H18A—C18—H18C	109.5
C7—C6—C5	120.5 (3)	H18B—C18—H18C	109.5
C7—C6—H6	119.7	N4—C19—C18	179.3 (4)
C5—C6—H6	119.7

C10—N1—C1—C2	−1.3 (3)	C5—C4—C11—N2	−178.8 (2)
CU1—N1—C1—C2	172.05 (17)	C5—C4—C11—C12	0.9 (4)
C10—N1—C1—C13	176.41 (19)	C10—C8—C12—C7	−178.0 (2)
CU1—N1—C1—C13	−10.3 (2)	C10—C8—C12—C11	2.5 (3)
N1—C1—C2—C3	0.3 (4)	C6—C7—C12—C8	−179.6 (2)
C13—C1—C2—C3	−177.2 (2)	C6—C7—C12—C11	0.0 (4)
C1—C2—C3—C9	0.8 (3)	N2—C11—C12—C8	−1.6 (4)
C11—C4—C5—C6	0.0 (4)	C4—C11—C12—C8	178.7 (2)
C4—C5—C6—C7	−0.9 (4)	N2—C11—C12—C7	178.8 (2)
C5—C6—C7—C12	0.9 (4)	C4—C11—C12—C7	−0.9 (3)
C11—N2—C9—C3	−178.1 (2)	C17—N3—C13—C14	1.1 (4)
C11—N2—C9—C10	1.9 (3)	CU1—N3—C13—C14	−176.30 (18)
C2—C3—C9—N2	179.2 (2)	C17—N3—C13—C1	−177.1 (2)
C2—C3—C9—C10	−0.9 (3)	CU1—N3—C13—C1	5.5 (2)
C1—N1—C10—C8	−177.9 (2)	N1—C1—C13—N3	3.0 (3)
CU1—N1—C10—C8	9.5 (3)	C2—C1—C13—N3	−179.3 (2)
C1—N1—C10—C9	1.1 (3)	N1—C1—C13—C14	−175.2 (2)
CU1—N1—C10—C9	−171.43 (15)	C2—C1—C13—C14	2.5 (4)
C12—C8—C10—N1	177.8 (2)	N3—C13—C14—C15	−0.4 (4)
C12—C8—C10—C9	−1.3 (3)	C1—C13—C14—C15	177.7 (2)
N2—C9—C10—N1	179.9 (2)	C13—C14—C15—C16	−0.6 (4)
C3—C9—C10—N1	−0.1 (3)	C14—C15—C16—C17	0.8 (4)
N2—C9—C10—C8	−1.0 (3)	C13—N3—C17—C16	−1.0 (4)
C3—C9—C10—C8	179.0 (2)	CU1—N3—C17—C16	176.0 (2)
C9—N2—C11—C4	179.1 (2)	C15—C16—C17—N3	0.0 (4)
C9—N2—C11—C12	−0.6 (3)

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

Acknowledgements

This work was supported in part by Grant-in-Aids for Scientific Research B (No. 26288024, to KT) and for Scientific Research C (No. 25410067, to HO) from the Japan Society for the Promotion of Science (JSPS) and the Ministry of Education, Culture, Sports, Science, and Technology of Japan (MEXT).

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