Crystal structure of {2-methyl-2-[(pyridin-2-yl­meth­yl)amino]­propan-1-ol-κ3N,N′,O}bis­(nitrato-κO)copper(II) from synchrotron data

Shin, J.W.; Kim, D.-W.; Jeon, J.-W.; Moon, D.

doi:10.1107/S2056989018018352

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ISSN: 2056-9890

Volume 75| Part 2| February 2019| Pages 150-153

https://doi.org/10.1107/S2056989018018352

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Crystal structure of {2-methyl-2-[(pyridin-2-ylmethyl)amino]propan-1-ol-κ³N,N′,O}bis(nitrato-κO)copper(II) from synchrotron data

Jong Won Shin,^a Dae-Woong Kim,^b Jae-Woo Jeon ^c,^d and Dohyun Moon ^b ^*

^aDaegu-Gyeongbuk Branch, Korea Institute of Science and Technology Information, 10 Exco-ro, Buk-gu, Daegu 41515, Republic of Korea, ^bBeamline Department, Pohang Accelerator Laboratory, 80 Jigokro-127-beongil, Nam-Gu Pohang, Gyeongbuk 37673, Republic of Korea, ^cDepartment of Electronic Materials Science and Engineering, Kyungpook National University, Daegu 41566, Republic of Korea, and ^dSEGI RETECH, 1-67 Ogyegongdan-gil, Yeongcheon, Gyeongbuk, 38882, Republic of Korea
^*Correspondence e-mail: dmoon@postech.ac.kr

Edited by H. Ishida, Okayama University, Japan (Received 16 November 2018; accepted 27 December 2018; online 4 January 2019)

The title compound, [Cu(NO₃)₂(C₁₀H₁₆N₂O)], has been synthesized and characterized by synchrotron single-crystal diffraction at 100 K. The Cu^II ion has a distorted square-pyramidal coordination geometry with two N and one O atoms of the C₁₀H₁₆N₂O ligand and one nitrate anion in the equatorial plane and another nitrate anion at the axial position. The equatorial Cu—N and Cu—O bond lengths are in the range 1.9608 (14)–2.0861 (15) Å, which are shorter than the axial Cu—O_nitrate bond length [2.1259 (16) Å]. In the crystal, molecules are linked via intermolecular N—H⋯O and O—H⋯O hydrogen bonds, forming a sheet structure parallel to the bc plane. The sheets are further linked through a face-to-face π–π interaction [centroid–centroid distance = 3.994 (1) Å]. Weak intermolecular C—H⋯O interactions are also observed in the sheet and between adjacent sheets.

Keywords: crystal structure; π–π interaction; hydrogen bond; synchrotron data.

CCDC reference: 1887447

1. Chemical context

Transition-metal complexes containing amine or its derivative ligands have attracted considerable attention owing to their diverse coordination geometries and their various applications in catalysis (Ahn et al., 2017 ), as magnetic materials (Liu, Zhou et al., 2017 ) and fluorescent substances (Chia & Tay, 2014 ) as well as sensing materials (Liu, Wang et al., 2017 ). In addition, polyamine ligands containing hydroxyl groups can easily form multinuclear complexes (such as dinuclear or trinuclear) with various transition-metal ions and hydrogen-bonded supramolecular compounds due to the deprotonation of hydroxyl groups by the transition-metal ions and anions (Shin et al., 2014 ). For example, N-(2-pyridylmethyl)iminodiethanol and N-(2-pyridylmethyl)iminodiisopropanol ligands containing amine, pyridine and hydroxyl groups have been used to form trinuclear metal complexes with cobalt and nickel ions, respectively, and these complexes have shown significant olefin epoxidations and magnetic interactions (Shin, Jeong et al., 2016 ). The nitrate anion is a good candidate for the construction of multinuclear complexes or supramolecular compounds by bridging metal ions or hydrogen bonding adjacent molecules (El-Khatib et al., 2018 ). Here, we report the preparation and crystal structure of a copper(II) complex, [Cu(C₁₀H₁₆N₂O)(NO₃)₂], formed with a functional tridentate ligand, 2-methyl-2-[(2-pyridinylmethyl)amino]-1-propanol, and nitrate anions.

2. Structural commentary

A view of the molecular structure of the title compound is shown in Fig. 1. The central Cu^II ion is coordinated by two nitrogen and one oxygen atoms from the C₁₀H₁₆N₂O ligand and by two oxygen atoms from nitrate anions, and adopts a distorted square-pyramidal geometry. The equatorial plane consists of the two nitrogen atoms (N1 and N2) and the oxygen atom (O1) of the hydroxyl group in the C₁₀H₁₆N₂O ligand and one oxygen atom (O5) of the nitrate anion. The coordination geometry is completed by an oxygen atom (O2) from the other nitrate anion in the axial position. The equatorial bond lengths, Cu—N and Cu—O, are in the range 1.9608 (14) to 2.0861 (15) Å. The axial bond length, Cu—O_nitrate, is 2.1259 (16) Å. The average length of the Cu—N and Cu—O bonds between the Cu^II ion and the C₁₀H₁₆N₂O ligand is 2.0081 (8) Å, which is shorter than the average bond length in the reported [Cu(C₁₀H₁₆N₂O)Cl₂] complex possessing the same ligand and metal (Shin, Lee et al., 2016 ). The axial bond length is also shorter than that in [Cu(C₁₀H₁₆N₂O)Cl₂], which can be attributed to the size effect of the coordinated anions. The nitrate anions are coordinated in a cis position to each other and the axial bond is longer than the equatorial bond. The bite angles N1—Cu1—N2 and N2—Cu1—O1 in the five-membered chelate rings are 84.53 (7) and 82.92 (7)°, respectively.

Figure 1
View of the molecular structure of the title compound, showing the atom-labelling scheme, with displacement ellipsoids drawn at the 50% probability.

3. Supramolecular features

In the crystal, two nitrate anions form intermolecular hydrogen bonds (O1—H1O1⋯O3ⁱ, N2—H2⋯O7ⁱⁱ and C8—H8AB⋯O5^iv; symmetry codes as in Table 1) with adjacent C₁₀H₁₆N₂O ligands, generating an undulating sheet structure parallel to the bc plane (Fig. 2). Another C—H⋯O hydrogen bond (C4—H4⋯O2ⁱⁱⁱ; Table 1) links the sheets into a three-dimensional structure (Fig. 3). Moreover, the sheets are linked by a π–π interaction between pyridine rings; the distance between the centroids of the pyridine rings is 3.994 (1) Å and the dihedral angle is 19.317 (1)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O1⋯O3ⁱ	0.83 (1)	1.89 (2)	2.685 (2)	159 (4)
N2—H2⋯O7ⁱⁱ	0.98 (1)	1.97 (2)	2.930 (3)	167 (3)
C4—H4⋯O2ⁱⁱⁱ	0.95	2.31	3.204 (3)	156
C8—H8AB⋯O5^iv	0.99	2.55	3.455 (3)	152
Symmetry codes: (i) x, y, z+1; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
A packing diagram of the title compound viewed along the a axis, showing the N—H⋯O (purple dashed lines) and O—H⋯O (dark green dashed lines) hydrogen bonds.

Figure 3
A packing diagram of the title compound viewed along the b axis, showing the N—H⋯O (purple dashed lines), O—H⋯O (dark green dashed lines) and C—H⋯O (orange dashed lines) hydrogen bonds as well as π–π interactions (violet dashed lines).

4. Database survey

A search of the Cambridge Structural Database (Version 5.39, update of August 2018; Groom et al., 2016 ) shows only one mononuclear copper(II) complex with the same C₁₀H₁₆N₂O ligand, for which the synthesis and crystal structure have been reported (Shin, Lee et al., 2016). A similar copper(II) complex with poly(2,6-dimethyl-1,4-phenylene ether) ligands involving secondary amine, pyridine and hydroxyl groups has been prepared to study its catalytic activities (Guieu et al., 2004 ).

5. Synthesis and crystallization

The C₁₀H₁₆N₂O ligand was prepared according to a slight modification of the previous reported method (Shin, Lee et al., 2016). To a methanol solution (10 mL) of Cu(NO₃)₂·3H₂O (200 mg, 0.823 mmol) was added dropwise a methanol solution (10 mL) of C₁₀H₁₆N₂O (149 mg, 0.823 mmol); the colour became dark blue, and the solution was stirred for 30 min at room temperature. Blue crystals of the title compound were obtained by diffusion of diethyl ether into the dark-blue solution for several days, and collected by filtration and washed with diethyl ether and dried in air (yield: 189 mg, 62%). FT–IR(ATR, cm⁻¹): 3215, 3168, 3071, 2967, 1607, 1506, 1384, 1278, 1065, 1020.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C-bound H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95–0.99 Å, and with U_iso(H) = 1.5 or 1.2U_eq(C). The positions of the O- and N-bound H atoms were assigned based on a difference-Fourier map, and were refined with distance restraints of O—H = 0.84 (1) Å and N—H = 1.00 (1) Å, and with U_iso(H) = 1.5U_eq(O) and 1.2U_eq(N). One reflection with a poor agreement between the measured and calculated intensities was omitted from the final refinement cycles.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₁₀H₁₆N₂O)]
M_r	367.81
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	100
a, b, c (Å)	14.990 (3), 12.520 (3), 7.6290 (15)
V (Å³)	1431.8 (5)
Z	4
Radiation type	Synchrotron, λ = 0.630 Å
μ (mm⁻¹)	1.13
Crystal size (mm)	0.11 × 0.10 × 0.08

Data collection
Diffractometer	ADSC Q210 CCD area detector
Absorption correction	Empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997 )
T_min, T_max	0.912, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	13671, 4431, 4234
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.720

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.066, 1.08
No. of reflections	4431
No. of parameters	208
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.68
Absolute structure	Flack x determined using 1883 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.037 (5)
Computer programs: PAL BL2D-SMDC (Shin, Eom et al., 2016 ), HKL3000sm (Otwinowski & Minor, 1997), SHELXT2014 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Putz & Brandenburg, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1887447

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018018352/is5504sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018018352/is5504Isup3.hkl

checkCIF report

Computing details top

Data collection: PAL BL2D-SMDC (Shin, Eom et al., 2016); cell refinement: HKL3000sm (Otwinowski & Minor, 1997); data reduction: HKL3000sm (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: DIAMOND (Putz & Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

{2-Methyl-2-[(pyridin-2-ylmethyl)amino]propan-1-ol-κ³N,N',O}bis(nitrato-κO)copper(II) top

Crystal data top

[Cu(NO₃)₂(C₁₀H₁₆N₂O)]	D_x = 1.706 Mg m⁻³
M_r = 367.81	Synchrotron radiation, λ = 0.630 Å
Orthorhombic, Pna2₁	Cell parameters from 29915 reflections
a = 14.990 (3) Å	θ = 0.4–33.6°
b = 12.520 (3) Å	µ = 1.13 mm⁻¹
c = 7.6290 (15) Å	T = 100 K
V = 1431.8 (5) Å³	Block, blue
Z = 4	0.11 × 0.10 × 0.08 mm
F(000) = 756

Data collection top

ADSC Q210 CCD area detector diffractometer	4234 reflections with I > 2σ(I)
Radiation source: PLSII 2D bending magnet	R_int = 0.032
ω scan	θ_max = 27.0°, θ_min = 1.9°
Absorption correction: empirical (using intensity measurements) (HKL3000sm SCALEPACK; Otwinowski & Minor, 1997)	h = −21→21
T_min = 0.912, T_max = 1.000	k = −18→18
13671 measured reflections	l = −10→10
4431 independent reflections

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0434P)² + 0.0982P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.025	(Δ/σ)_max = 0.002
wR(F²) = 0.066	Δρ_max = 0.40 e Å⁻³
S = 1.08	Δρ_min = −0.68 e Å⁻³
4431 reflections	Extinction correction: SHELXL2018 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
208 parameters	Extinction coefficient: 0.026 (3)
3 restraints	Absolute structure: Flack x determined using 1883 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Hydrogen site location: mixed	Absolute structure parameter: 0.037 (5)

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.70732 (2)	0.68798 (2)	0.59459 (4)	0.01603 (8)
O1	0.76542 (12)	0.78901 (12)	0.77964 (19)	0.0201 (3)
H1O1	0.773 (2)	0.766 (3)	0.881 (2)	0.030*
O2	0.79419 (10)	0.74637 (16)	0.3963 (2)	0.0245 (3)
O3	0.81254 (12)	0.75969 (13)	0.1158 (2)	0.0264 (3)
O4	0.68899 (14)	0.69393 (15)	0.2203 (3)	0.0301 (4)
O5	0.79776 (9)	0.57547 (12)	0.6143 (3)	0.0201 (3)
O6	0.75455 (11)	0.55182 (13)	0.8859 (2)	0.0256 (3)
O7	0.85090 (12)	0.44393 (14)	0.7666 (2)	0.0291 (3)
N1	0.60049 (10)	0.59461 (12)	0.5810 (3)	0.0173 (3)
N2	0.61927 (12)	0.80764 (12)	0.5732 (3)	0.0188 (3)
H2	0.638 (2)	0.856 (2)	0.479 (3)	0.023*
N3	0.76463 (13)	0.73260 (14)	0.2413 (2)	0.0193 (3)
N4	0.80075 (11)	0.52272 (14)	0.7611 (3)	0.0181 (3)
C1	0.59808 (12)	0.48835 (14)	0.6052 (3)	0.0202 (3)
H1	0.652533	0.451412	0.624769	0.024*
C2	0.51962 (13)	0.43077 (14)	0.6027 (4)	0.0236 (3)
H2A	0.520110	0.355445	0.617692	0.028*
C3	0.43973 (14)	0.48534 (17)	0.5779 (3)	0.0267 (4)
H3	0.384490	0.448145	0.578571	0.032*
C4	0.44214 (14)	0.59522 (18)	0.5522 (3)	0.0251 (4)
H4	0.388472	0.634150	0.534687	0.030*
C5	0.52366 (14)	0.64731 (16)	0.5523 (2)	0.0196 (4)
C6	0.53236 (15)	0.76513 (16)	0.5116 (3)	0.0223 (4)
H6A	0.527092	0.776224	0.383523	0.027*
H6AB	0.483274	0.804667	0.569281	0.027*
C7	0.61826 (15)	0.87026 (16)	0.7416 (3)	0.0213 (4)
C8	0.71738 (16)	0.88814 (17)	0.7830 (3)	0.0241 (4)
H8A	0.743334	0.937761	0.695808	0.029*
H8AB	0.723273	0.921226	0.900327	0.029*
C9	0.57393 (18)	0.97932 (19)	0.7166 (3)	0.0307 (5)
H9A	0.603838	1.017915	0.621562	0.046*
H9AB	0.578676	1.020589	0.825375	0.046*
H9AC	0.510874	0.969297	0.686921	0.046*
C10	0.57262 (18)	0.80604 (18)	0.8857 (3)	0.0278 (5)
H10A	0.511114	0.790176	0.850852	0.042*
H10B	0.572316	0.847605	0.994588	0.042*
H10C	0.605093	0.739069	0.904426	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01865 (12)	0.01345 (11)	0.01599 (12)	−0.00077 (6)	−0.00037 (10)	0.00057 (10)
O1	0.0285 (8)	0.0172 (6)	0.0146 (6)	−0.0006 (6)	−0.0019 (6)	−0.0012 (5)
O2	0.0284 (8)	0.0316 (8)	0.0136 (7)	−0.0090 (6)	−0.0019 (5)	0.0027 (6)
O3	0.0362 (8)	0.0279 (7)	0.0152 (7)	−0.0099 (6)	0.0022 (7)	0.0028 (6)
O4	0.0301 (9)	0.0375 (10)	0.0226 (8)	−0.0144 (7)	−0.0013 (7)	−0.0045 (6)
O5	0.0222 (6)	0.0196 (6)	0.0184 (8)	0.0025 (4)	0.0013 (6)	0.0035 (6)
O6	0.0281 (8)	0.0301 (7)	0.0185 (7)	0.0043 (6)	0.0045 (6)	0.0005 (6)
O7	0.0355 (9)	0.0255 (7)	0.0263 (7)	0.0120 (6)	0.0004 (7)	0.0058 (6)
N1	0.0183 (6)	0.0162 (6)	0.0174 (7)	−0.0012 (5)	−0.0016 (7)	−0.0004 (7)
N2	0.0242 (7)	0.0156 (6)	0.0167 (9)	0.0008 (5)	0.0001 (7)	0.0010 (6)
N3	0.0264 (8)	0.0160 (7)	0.0154 (7)	−0.0037 (6)	−0.0004 (7)	0.0005 (5)
N4	0.0187 (7)	0.0186 (8)	0.0171 (7)	−0.0013 (5)	−0.0021 (6)	0.0006 (6)
C1	0.0208 (7)	0.0161 (7)	0.0238 (8)	−0.0016 (5)	−0.0048 (9)	0.0012 (8)
C2	0.0247 (8)	0.0204 (7)	0.0256 (8)	−0.0056 (6)	−0.0042 (10)	0.0022 (9)
C3	0.0217 (8)	0.0299 (9)	0.0284 (11)	−0.0072 (7)	−0.0047 (9)	0.0051 (9)
C4	0.0176 (8)	0.0298 (9)	0.0279 (11)	0.0003 (7)	−0.0041 (7)	0.0049 (7)
C5	0.0207 (9)	0.0202 (8)	0.0179 (8)	0.0011 (6)	−0.0026 (6)	0.0028 (6)
C6	0.0247 (10)	0.0205 (9)	0.0217 (9)	0.0023 (7)	−0.0043 (7)	0.0040 (7)
C7	0.0296 (10)	0.0179 (8)	0.0165 (8)	0.0038 (7)	0.0034 (8)	−0.0002 (6)
C8	0.0334 (11)	0.0174 (9)	0.0215 (10)	0.0000 (7)	−0.0005 (8)	−0.0042 (7)
C9	0.0414 (13)	0.0215 (9)	0.0292 (10)	0.0091 (9)	0.0044 (10)	−0.0016 (8)
C10	0.0348 (12)	0.0297 (11)	0.0188 (9)	0.0028 (8)	0.0057 (9)	0.0029 (7)

Geometric parameters (Å, º) top

Cu1—O5	1.9608 (14)	C2—C3	1.392 (3)
Cu1—N1	1.9854 (16)	C2—H2A	0.9500
Cu1—N2	2.0033 (17)	C3—C4	1.390 (3)
Cu1—O1	2.0861 (15)	C3—H3	0.9500
Cu1—O2	2.1259 (16)	C4—C5	1.385 (3)
O1—C8	1.435 (3)	C4—H4	0.9500
O1—H1O1	0.834 (13)	C5—C6	1.513 (3)
O2—N3	1.274 (2)	C6—H6A	0.9900
O3—N3	1.244 (2)	C6—H6AB	0.9900
O4—N3	1.243 (3)	C7—C10	1.524 (3)
O5—N4	1.301 (3)	C7—C9	1.531 (3)
O6—N4	1.232 (2)	C7—C8	1.535 (3)
O7—N4	1.241 (2)	C8—H8A	0.9900
N1—C1	1.344 (2)	C8—H8AB	0.9900
N1—C5	1.345 (2)	C9—H9A	0.9800
N2—C6	1.484 (3)	C9—H9AB	0.9800
N2—C7	1.505 (3)	C9—H9AC	0.9800
N2—H2	0.977 (13)	C10—H10A	0.9800
C1—C2	1.380 (2)	C10—H10B	0.9800
C1—H1	0.9500	C10—H10C	0.9800

O5—Cu1—N1	97.97 (6)	C2—C3—H3	120.6
O5—Cu1—N2	177.48 (6)	C5—C4—C3	119.3 (2)
N1—Cu1—N2	84.53 (7)	C5—C4—H4	120.4
O5—Cu1—O1	95.45 (7)	C3—C4—H4	120.4
N1—Cu1—O1	136.81 (7)	N1—C5—C4	121.63 (18)
N2—Cu1—O1	82.92 (7)	N1—C5—C6	115.97 (17)
O5—Cu1—O2	83.01 (7)	C4—C5—C6	122.34 (18)
N1—Cu1—O2	131.25 (7)	N2—C6—C5	111.13 (16)
N2—Cu1—O2	95.08 (8)	N2—C6—H6A	109.4
O1—Cu1—O2	91.00 (6)	C5—C6—H6A	109.4
C8—O1—Cu1	109.09 (13)	N2—C6—H6AB	109.4
C8—O1—H1O1	111 (3)	C5—C6—H6AB	109.4
Cu1—O1—H1O1	118 (3)	H6A—C6—H6AB	108.0
N3—O2—Cu1	113.62 (12)	N2—C7—C10	110.21 (17)
N4—O5—Cu1	117.05 (13)	N2—C7—C9	111.27 (18)
C1—N1—C5	119.01 (16)	C10—C7—C9	111.44 (19)
C1—N1—Cu1	126.70 (13)	N2—C7—C8	104.00 (16)
C5—N1—Cu1	114.22 (13)	C10—C7—C8	111.27 (19)
C6—N2—C7	116.65 (17)	C9—C7—C8	108.41 (19)
C6—N2—Cu1	109.64 (12)	O1—C8—C7	110.84 (17)
C7—N2—Cu1	109.06 (13)	O1—C8—H8A	109.5
C6—N2—H2	103.6 (18)	C7—C8—H8A	109.5
C7—N2—H2	108.1 (19)	O1—C8—H8AB	109.5
Cu1—N2—H2	109.5 (18)	C7—C8—H8AB	109.5
O4—N3—O3	122.21 (18)	H8A—C8—H8AB	108.1
O4—N3—O2	119.33 (18)	C7—C9—H9A	109.5
O3—N3—O2	118.45 (17)	C7—C9—H9AB	109.5
O6—N4—O7	123.36 (19)	H9A—C9—H9AB	109.5
O6—N4—O5	119.70 (17)	C7—C9—H9AC	109.5
O7—N4—O5	116.95 (18)	H9A—C9—H9AC	109.5
N1—C1—C2	122.58 (17)	H9AB—C9—H9AC	109.5
N1—C1—H1	118.7	C7—C10—H10A	109.5
C2—C1—H1	118.7	C7—C10—H10B	109.5
C1—C2—C3	118.62 (17)	H10A—C10—H10B	109.5
C1—C2—H2A	120.7	C7—C10—H10C	109.5
C3—C2—H2A	120.7	H10A—C10—H10C	109.5
C4—C3—C2	118.86 (18)	H10B—C10—H10C	109.5
C4—C3—H3	120.6

Cu1—O2—N3—O4	4.0 (3)	C7—N2—C6—C5	−101.79 (19)
Cu1—O2—N3—O3	−176.76 (14)	Cu1—N2—C6—C5	22.8 (2)
Cu1—O5—N4—O6	−7.5 (2)	N1—C5—C6—N2	−20.6 (2)
Cu1—O5—N4—O7	172.10 (14)	C4—C5—C6—N2	162.32 (19)
C5—N1—C1—C2	−0.4 (4)	C6—N2—C7—C10	52.6 (2)
Cu1—N1—C1—C2	176.29 (18)	Cu1—N2—C7—C10	−72.26 (19)
N1—C1—C2—C3	−1.4 (4)	C6—N2—C7—C9	−71.6 (2)
C1—C2—C3—C4	1.6 (4)	Cu1—N2—C7—C9	163.60 (15)
C2—C3—C4—C5	−0.1 (4)	C6—N2—C7—C8	171.93 (16)
C1—N1—C5—C4	1.9 (3)	Cu1—N2—C7—C8	47.09 (17)
Cu1—N1—C5—C4	−175.13 (15)	Cu1—O1—C8—C7	32.1 (2)
C1—N1—C5—C6	−175.2 (2)	N2—C7—C8—O1	−52.1 (2)
Cu1—N1—C5—C6	7.7 (2)	C10—C7—C8—O1	66.5 (2)
C3—C4—C5—N1	−1.7 (3)	C9—C7—C8—O1	−170.60 (18)
C3—C4—C5—C6	175.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O1···O3ⁱ	0.83 (1)	1.89 (2)	2.685 (2)	159 (4)
N2—H2···O7ⁱⁱ	0.98 (1)	1.97 (2)	2.930 (3)	167 (3)
C4—H4···O2ⁱⁱⁱ	0.95	2.31	3.204 (3)	156
C8—H8AB···O5^iv	0.99	2.55	3.455 (3)	152

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

Funding information

This work was supported by the Basic Science Research Program of the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2017R1C1B2003111). The X-ray crystallography BL2D-SMC beamline and the FT–IR experiment 12D-IRS beamline at the PLS-II were supported in part by MSICT and POSTECH.

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