Synthesis, structural and electrochemical properties of a new family of amino-acid-based coordination complexes

Rey, J.M.; Movilla, F.; Suárez, S.A.; Di Salvo, F.

doi:10.1107/S2052520622003912

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Synthesis, structural and electrochemical properties of a new family of amino-acid-based coordination complexes

J. M. Rey, F. Movilla, S. A. Suárez and F. Di Salvo

Metalloproteins involved in oxidation–reduction processes in metabolism are fundamental for the wellbeing of every organism. The use of amino-acid-based compounds as ligands for the construction of biomimetic coordination systems represents a promising alternative for the development of new catalysts. Herein is presented a new family of copper, zinc and nickel coordination compounds, which show four-, five- and six- coordination geometries, synthesized using Schiff base ligands obtained from the amino acids L-alanine and L-phenylalanine. Structural analysis and property studies were performed using single-crystal X-ray diffraction data, spectroscopic and electrochemical experiments and DFT calculations. The analysis of the molecular and supramolecular architectures showed that the non-covalent interactions developed in the systems, together with the identity of the metal and the amino acid backbone, are determinants for the formation of the complexes and the stabilization of the resultant geometries. The Cu^II complexes were tested as candidates for the electrochemical conversion reduction of nitrite to NO, finding that the five-coordinate L-phenylalanine complex is the most suitable. Finally, some insights into the rational design of ligands for the construction of biomimetic complexes are suggested.

Keywords: amino acids; copper complex; crystal engineering; zinc complex.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520622003912/lo5107sup1.cif Contains datablocks zn_phepip, exp_5058_sq, exp_4899_p1, cu_phepip, exp_4793_sq
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520622003912/lo5107zn_phepipsup2.hkl Contains datablock zn_phepip
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520622003912/lo5107exp_5058_sqsup3.hkl Contains datablock exp_5058_sq
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520622003912/lo5107exp_4899_p1sup4.hkl Contains datablock exp_4899_p1
	Structure factor file (CIF format) https://doi.org/10.1107/S2052520622003912/lo5107cu_phepipsup5.hkl Contains datablock cu_phepip
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520622003912/lo5107sup6.pdf Additional information, figures and tables

CCDC references: 2104068; 2104082; 2104083; 2104084; 2104085

Computing details top

Data collection: MXCuBE (Gabadinho et al., 2010) for zn_phepip, cu_phepip; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for exp_5058_sq, exp_4899_p1, exp_4793_sq. Cell refinement: XDS (Kabsch, 2010) for zn_phepip, cu_phepip; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for exp_5058_sq, exp_4899_p1, exp_4793_sq. Data reduction: XDS (Kabsch, 2010) for zn_phepip, cu_phepip; CrysAlis PRO 1.171.38.43 (Rigaku OD, 2015) for exp_5058_sq, exp_4899_p1, exp_4793_sq. Program(s) used to solve structure: ShelXT (Sheldrick, 2015) for zn_phepip, exp_4899_p1; SHELXT 2018/2 (Sheldrick, 2018) for exp_5058_sq; XT (Sheldrick, 2015) for cu_phepip; SHELXT 2014/5 (Sheldrick, 2014) for exp_4793_sq. Program(s) used to refine structure: SHELXL 2018/3 (Sheldrick, 2015) for zn_phepip, exp_4899_p1, cu_phepip; SHELXL (Sheldrick, 2015) for exp_5058_sq, exp_4793_sq. Molecular graphics: Olex2 1.3 (Dolomanov et al., 2009) for zn_phepip, exp_4899_p1, cu_phepip; Olex2 (Dolomanov et al., 2009) for exp_5058_sq, exp_4793_sq. Software used to prepare material for publication: Olex2 1.3 (Dolomanov et al., 2009) for zn_phepip, exp_4899_p1, cu_phepip; Olex2 (Dolomanov et al., 2009) for exp_5058_sq, exp_4793_sq.

(zn_phepip) top

Crystal data top

C₃₄H₃₃N₂O₉Zn·C₃₄H₃₄N₂O₉Zn	F(000) = 1414
M_r = 1358.99	D_x = 1.469 Mg m⁻³
Monoclinic, C2	Synchrotron radiation, λ = 0.82612 Å
a = 12.050 (8) Å	Cell parameters from 5621 reflections
b = 8.110 (3) Å	θ = 0.8–1°
c = 31.470 (18) Å	µ = 1.29 mm⁻¹
β = 92.48 (3)°	T = 100 K
V = 3073 (3) Å³	Prism, colorless
Z = 2	0.08 × 0.04 × 0.04 mm

Data collection top

Custom air-bearing with MK3 mini-kappa diffractometer	4431 independent reflections
Radiation source: LNLS-MX2	3886 reflections with I > 2σ(I)
Detector resolution: 5.814 pixels mm^-1	R_int = 0.089
shuterless φ scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: empirical (using intensity measurements) XDS (Kabsch, 2010)	h = −12→13
T_min = 0.832, T_max = 1	k = −9→9
56923 measured reflections	l = −35→35

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.091	w = 1/[σ²(F_o²) + (0.134P)² + 32.8019P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.247	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 1.60 e Å⁻³
4431 reflections	Δρ_min = −2.11 e Å⁻³
423 parameters	Absolute structure: Flack x determined using 1605 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
31 restraints	Absolute structure parameter: 0.034 (6)
Primary atom site location: iterative

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	Occ. (<1)
Zn1	0.500000	0.2914 (3)	0.500000	0.0468 (8)
O4	0.6652 (9)	0.2644 (15)	0.5191 (3)	0.049 (3)
O8	0.8312 (9)	0.2290 (13)	0.4942 (4)	0.057 (3)
O12	0.6653 (9)	−0.2236 (15)	0.2841 (3)	0.050 (3)
O16	0.7833 (9)	−0.2700 (14)	0.3423 (3)	0.054 (3)
O24	0.504 (4)	0.529 (2)	0.5130 (11)	0.076 (16)	0.5
H24	0.426655	0.567732	0.513500	0.113*	0.5
N4	0.5584 (10)	0.1839 (13)	0.4448 (4)	0.042 (3)
H4	0.520077	0.238476	0.419709	0.051*
C4	0.4906 (12)	−0.0483 (16)	0.3648 (5)	0.045 (3)
H4A	0.421270	0.004430	0.368490	0.053*
C8	0.7631 (14)	−0.313 (2)	0.2990 (5)	0.054 (4)
H8A	0.750885	−0.432919	0.296087	0.065*
H8B	0.827474	−0.281682	0.282137	0.065*
C12	0.5106 (14)	0.4274 (19)	0.3205 (5)	0.054 (4)
H12	0.441893	0.479647	0.313067	0.064*
C16	0.6799 (10)	0.2229 (18)	0.4439 (5)	0.041 (3)
H16	0.718354	0.128733	0.430184	0.049*
C20	0.6629 (12)	−0.1486 (17)	0.3955 (4)	0.043 (3)
H20	0.713410	−0.166700	0.419050	0.052*
C24	0.7270 (12)	0.2410 (16)	0.4899 (5)	0.042 (3)
C28	0.5570 (11)	−0.0712 (16)	0.4000 (4)	0.041 (3)
C32	0.5641 (16)	0.3309 (19)	0.2904 (5)	0.059 (5)
H32	0.533294	0.319067	0.262312	0.071*
C36	0.5328 (12)	0.000 (2)	0.4424 (4)	0.048 (4)
H36A	0.577738	−0.057815	0.464845	0.057*
H36B	0.453449	−0.017257	0.448027	0.057*
C40	0.6159 (14)	−0.1694 (18)	0.3204 (5)	0.049 (4)
C44	0.5140 (12)	−0.094 (2)	0.3243 (5)	0.051 (4)
H44	0.463904	−0.075610	0.300649	0.061*
C48	0.6542 (13)	0.366 (2)	0.3736 (5)	0.053 (4)
C52	0.7094 (15)	0.267 (2)	0.3438 (5)	0.054 (4)
H52	0.776539	0.211891	0.351879	0.065*
C56	0.6865 (12)	−0.1946 (18)	0.3550 (5)	0.039 (3)
C60	0.7018 (14)	0.379 (2)	0.4188 (5)	0.053 (4)
H60A	0.668001	0.474297	0.433027	0.063*
H60B	0.782908	0.398142	0.418388	0.063*
C64	0.6635 (14)	0.2529 (19)	0.3028 (5)	0.056 (4)
H64	0.700685	0.188324	0.282610	0.068*
C68	0.5582 (14)	0.446 (2)	0.3606 (5)	0.056 (4)
H68	0.523457	0.516154	0.380133	0.067*
Zn2	0.500000	0.5814 (2)	1.000000	0.0399 (7)
O17	0.8328 (7)	0.5250 (11)	0.9904 (4)	0.048 (3)
O18	0.500000	0.8239 (16)	1.000000	0.099 (9)
H18A	0.444469	0.905653	0.985141	0.149*	0.5
H18B	0.555541	0.905653	1.014839	0.149*	0.5
O19	0.7839 (8)	0.0153 (13)	0.8438 (4)	0.047 (3)
O20	0.6604 (9)	0.0488 (14)	0.7858 (4)	0.055 (3)
O21	0.6638 (8)	0.5553 (12)	1.0180 (4)	0.042 (3)
N5	0.5541 (8)	0.4717 (11)	0.9453 (4)	0.037 (3)
H5	0.513462	0.523248	0.920300	0.044*
C69	0.6690 (16)	0.5365 (16)	0.8011 (7)	0.069 (6)
H69	0.708584	0.470399	0.781988	0.083*
C70	0.7635 (12)	−0.0264 (17)	0.8008 (6)	0.050 (4)
H70A	0.758568	−0.147665	0.797681	0.061*
H70B	0.825149	0.013445	0.783676	0.061*
C71	0.5325 (11)	0.2897 (16)	0.9441 (5)	0.038 (3)
H71A	0.453214	0.269343	0.949335	0.045*
H71B	0.577581	0.235583	0.967125	0.045*
C72	0.5735 (16)	0.620 (2)	0.7871 (6)	0.067 (5)
H72	0.547589	0.607563	0.758321	0.081*
C73	0.6758 (11)	0.5115 (16)	0.9427 (5)	0.041 (3)
H73	0.713686	0.418874	0.928142	0.049*
C74	0.7265 (13)	0.5309 (15)	0.9873 (5)	0.043 (4)
C75	0.7067 (14)	0.5510 (18)	0.8439 (6)	0.054 (4)
H75	0.769738	0.490778	0.854314	0.065*
C76	0.6880 (12)	0.6719 (17)	0.9163 (5)	0.049 (4)
H76A	0.645519	0.760920	0.929714	0.059*
H76B	0.767136	0.704853	0.917411	0.059*
C77	0.5159 (16)	0.718 (2)	0.8134 (7)	0.069 (5)
H77	0.451543	0.775366	0.803178	0.083*
C78	0.6635 (11)	0.1377 (15)	0.8967 (5)	0.042 (3)
H78	0.715124	0.121812	0.920012	0.050*
C79	0.6148 (11)	0.1055 (16)	0.8230 (5)	0.043 (4)
C80	0.5602 (11)	0.2126 (16)	0.9014 (4)	0.042 (3)
C81	0.4860 (11)	0.2279 (19)	0.8669 (5)	0.049 (4)
H81	0.415299	0.275448	0.871171	0.058*
C82	0.6846 (11)	0.091 (2)	0.8577 (5)	0.046 (4)
C83	0.6490 (12)	0.6568 (18)	0.8711 (5)	0.045 (3)
C84	0.5537 (13)	0.7323 (19)	0.8561 (5)	0.053 (4)
H84	0.512029	0.796147	0.875101	0.063*
C85	0.5108 (11)	0.1763 (16)	0.8263 (5)	0.042 (3)
H85	0.460151	0.188700	0.802542	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0463 (17)	0.0452 (16)	0.0484 (15)	0.000	−0.0051 (12)	0.000
O4	0.048 (6)	0.064 (7)	0.034 (5)	−0.009 (5)	−0.001 (5)	−0.003 (5)
O8	0.049 (8)	0.042 (6)	0.077 (7)	0.003 (5)	−0.019 (5)	−0.013 (5)
O12	0.048 (6)	0.058 (7)	0.043 (5)	−0.004 (5)	−0.005 (4)	0.000 (5)
O16	0.051 (7)	0.057 (7)	0.053 (6)	−0.002 (5)	−0.007 (5)	−0.005 (5)
O24	0.043 (13)	0.023 (10)	0.16 (5)	−0.026 (12)	−0.01 (3)	0.017 (13)
N4	0.047 (7)	0.024 (6)	0.054 (7)	−0.010 (5)	−0.013 (5)	0.002 (5)
C4	0.050 (9)	0.025 (7)	0.059 (9)	0.003 (6)	0.005 (7)	0.000 (6)
C8	0.061 (10)	0.050 (10)	0.051 (9)	0.007 (8)	−0.002 (7)	−0.006 (7)
C12	0.054 (10)	0.051 (10)	0.054 (10)	−0.004 (7)	−0.012 (7)	0.009 (7)
C16	0.022 (7)	0.045 (8)	0.055 (8)	0.005 (6)	−0.009 (6)	−0.011 (7)
C20	0.043 (8)	0.041 (8)	0.045 (8)	−0.004 (7)	−0.012 (6)	0.001 (6)
C24	0.036 (9)	0.025 (7)	0.062 (10)	−0.003 (6)	−0.018 (7)	0.000 (6)
C28	0.039 (8)	0.039 (8)	0.044 (8)	−0.023 (6)	−0.004 (6)	−0.006 (6)
C32	0.081 (13)	0.044 (10)	0.051 (9)	−0.017 (9)	−0.003 (8)	0.009 (7)
C36	0.035 (8)	0.065 (10)	0.042 (8)	0.000 (7)	−0.008 (6)	0.006 (7)
C40	0.059 (10)	0.044 (9)	0.042 (8)	−0.007 (7)	−0.009 (7)	0.002 (6)
C44	0.038 (9)	0.068 (11)	0.044 (8)	−0.004 (7)	−0.009 (6)	0.005 (7)
C48	0.053 (10)	0.050 (9)	0.056 (9)	−0.007 (8)	−0.011 (8)	0.007 (8)
C52	0.063 (11)	0.053 (10)	0.047 (8)	0.009 (8)	−0.006 (7)	−0.001 (7)
C56	0.027 (7)	0.038 (7)	0.051 (7)	0.003 (6)	−0.008 (6)	0.000 (6)
C60	0.057 (10)	0.044 (8)	0.056 (9)	−0.012 (8)	−0.009 (7)	0.000 (7)
C64	0.061 (11)	0.041 (9)	0.068 (11)	−0.014 (8)	0.011 (8)	−0.014 (8)
C68	0.056 (10)	0.069 (11)	0.043 (8)	−0.013 (8)	0.005 (7)	0.000 (7)
Zn2	0.0211 (12)	0.0266 (12)	0.0707 (18)	0.000	−0.0125 (11)	0.000
O17	0.007 (5)	0.032 (5)	0.104 (8)	−0.003 (3)	−0.016 (4)	0.001 (5)
O18	0.022 (8)	0.007 (6)	0.26 (3)	0.000	−0.051 (12)	0.000
O19	0.024 (5)	0.041 (5)	0.077 (7)	0.007 (4)	−0.005 (5)	−0.006 (5)
O20	0.044 (6)	0.048 (7)	0.070 (8)	−0.003 (5)	−0.005 (5)	−0.003 (5)
O21	0.024 (5)	0.030 (6)	0.073 (7)	−0.010 (4)	−0.010 (5)	0.008 (4)
N5	0.013 (5)	0.010 (5)	0.086 (8)	0.005 (4)	−0.016 (5)	−0.011 (5)
C69	0.077 (13)	0.014 (8)	0.116 (17)	−0.024 (7)	0.000 (11)	0.003 (8)
C70	0.029 (8)	0.026 (8)	0.097 (13)	0.007 (6)	0.005 (7)	0.003 (7)
C71	0.024 (7)	0.030 (7)	0.058 (8)	−0.010 (5)	−0.006 (6)	0.003 (6)
C72	0.077 (13)	0.060 (13)	0.063 (11)	−0.023 (10)	−0.023 (10)	0.000 (9)
C73	0.021 (7)	0.017 (6)	0.084 (10)	−0.005 (5)	−0.009 (6)	0.000 (7)
C74	0.050 (11)	0.010 (6)	0.069 (10)	−0.002 (5)	−0.013 (8)	0.002 (6)
C75	0.047 (9)	0.032 (9)	0.082 (12)	−0.022 (7)	−0.003 (8)	−0.004 (7)
C76	0.034 (8)	0.025 (7)	0.088 (12)	−0.012 (6)	−0.006 (7)	0.006 (7)
C77	0.060 (11)	0.042 (10)	0.105 (15)	−0.030 (9)	−0.014 (10)	0.004 (10)
C78	0.023 (7)	0.021 (6)	0.079 (11)	−0.001 (5)	−0.012 (7)	0.004 (6)
C79	0.031 (8)	0.029 (8)	0.067 (10)	−0.010 (6)	−0.005 (7)	0.006 (6)
C80	0.037 (8)	0.036 (8)	0.052 (8)	−0.003 (6)	0.001 (6)	−0.005 (6)
C81	0.023 (7)	0.043 (8)	0.079 (11)	−0.011 (6)	−0.013 (7)	0.006 (8)
C82	0.030 (8)	0.035 (8)	0.073 (11)	0.001 (7)	−0.004 (7)	0.010 (8)
C83	0.040 (8)	0.034 (7)	0.061 (9)	−0.021 (7)	−0.005 (7)	−0.002 (7)
C84	0.052 (10)	0.038 (8)	0.068 (10)	−0.031 (7)	−0.007 (8)	0.010 (7)
C85	0.037 (8)	0.033 (8)	0.054 (9)	−0.012 (6)	−0.009 (6)	0.009 (6)

Geometric parameters (Å, º) top

Zn1—O4	2.066 (11)	Zn2—O18	1.967 (13)
Zn1—O4ⁱ	2.066 (11)	Zn2—O21	2.041 (9)
Zn1—O24ⁱ	1.97 (2)	Zn2—O21ⁱⁱ	2.041 (9)
Zn1—O24	1.97 (2)	Zn2—N5ⁱⁱ	2.069 (12)
Zn1—N4	2.094 (12)	Zn2—N5	2.069 (12)
Zn1—N4ⁱ	2.094 (12)	O17—C74	1.280 (18)
O4—C24	1.222 (18)	O18—H18A	1.0386
O8—C24	1.261 (17)	O18—H18B	1.0385
O12—C8	1.443 (19)	O19—C70	1.41 (2)
O12—C40	1.382 (19)	O19—C82	1.428 (18)
O16—C8	1.417 (18)	O20—C70	1.444 (18)
O16—C56	1.392 (18)	O20—C79	1.394 (19)
O24—O24ⁱ	0.82 (7)	O21—C74	1.267 (19)
O24—H24	0.9829	N5—H5	1.0000
N4—H4	1.0000	N5—C71	1.499 (15)
N4—C16	1.499 (17)	N5—C73	1.507 (17)
N4—C36	1.52 (2)	C69—H69	0.9500
C4—H4A	0.9500	C69—C72	1.39 (3)
C4—C28	1.35 (2)	C69—C75	1.41 (3)
C4—C44	1.37 (2)	C70—H70A	0.9900
C8—H8A	0.9900	C70—H70B	0.9900
C8—H8B	0.9900	C71—H71A	0.9900
C12—H12	0.9500	C71—H71B	0.9900
C12—C32	1.41 (2)	C71—C80	1.53 (2)
C12—C68	1.37 (2)	C72—H72	0.9500
C16—H16	1.0000	C72—C77	1.36 (3)
C16—C24	1.541 (19)	C73—H73	1.0000
C16—C60	1.52 (2)	C73—C74	1.52 (2)
C20—H20	0.9500	C73—C76	1.554 (19)
C20—C28	1.44 (2)	C75—H75	0.9500
C20—C56	1.37 (2)	C75—C83	1.42 (2)
C28—C36	1.50 (2)	C76—H76A	0.9900
C32—H32	0.9500	C76—H76B	0.9900
C32—C64	1.39 (3)	C76—C83	1.48 (2)
C36—H36A	0.9900	C77—H77	0.9500
C36—H36B	0.9900	C77—C84	1.41 (2)
C40—C44	1.38 (2)	C78—H78	0.9500
C40—C56	1.37 (2)	C78—C80	1.40 (2)
C44—H44	0.9500	C78—C82	1.32 (2)
C48—C52	1.42 (2)	C79—C82	1.35 (2)
C48—C60	1.52 (2)	C79—C85	1.39 (2)
C48—C68	1.37 (2)	C80—C81	1.38 (2)
C52—H52	0.9500	C81—H81	0.9500
C52—C64	1.39 (2)	C81—C85	1.39 (2)
C60—H60A	0.9900	C83—C84	1.37 (2)
C60—H60B	0.9900	C84—H84	0.9500
C64—H64	0.9500	C85—H85	0.9500
C68—H68	0.9500

O4ⁱ—Zn1—O4	167.8 (7)	C48—C68—C12	122.5 (17)
O4—Zn1—N4ⁱ	93.9 (4)	C48—C68—H68	118.8
O4ⁱ—Zn1—N4ⁱ	81.0 (4)	O18—Zn2—O21	96.0 (3)
O4ⁱ—Zn1—N4	93.9 (4)	O18—Zn2—O21ⁱⁱ	96.0 (3)
O4—Zn1—N4	81.0 (4)	O18—Zn2—N5	115.5 (3)
O24ⁱ—Zn1—O4	100.3 (14)	O18—Zn2—N5ⁱⁱ	115.5 (3)
O24—Zn1—O4ⁱ	100.3 (13)	O21—Zn2—O21ⁱⁱ	168.1 (5)
O24ⁱ—Zn1—O4ⁱ	91.7 (13)	O21ⁱⁱ—Zn2—N5ⁱⁱ	81.4 (4)
O24—Zn1—O4	91.7 (13)	O21—Zn2—N5	81.4 (4)
O24—Zn1—O24ⁱ	24.0 (19)	O21—Zn2—N5ⁱⁱ	93.5 (4)
O24—Zn1—N4	125.0 (12)	O21ⁱⁱ—Zn2—N5	93.5 (4)
O24ⁱ—Zn1—N4ⁱ	125.0 (12)	N5ⁱⁱ—Zn2—N5	129.1 (6)
O24—Zn1—N4ⁱ	103.9 (12)	Zn2—O18—H18A	129.7
O24ⁱ—Zn1—N4	103.9 (12)	Zn2—O18—H18B	129.7
N4ⁱ—Zn1—N4	130.7 (6)	H18A—O18—H18B	100.7
C24—O4—Zn1	114.2 (9)	C70—O19—C82	106.4 (11)
C40—O12—C8	105.4 (11)	C79—O20—C70	103.3 (12)
C56—O16—C8	105.9 (11)	C74—O21—Zn2	114.0 (9)
Zn1—O24—H24	107.4	Zn2—N5—H5	108.2
O24ⁱ—O24—Zn1	78.0 (9)	C71—N5—Zn2	112.6 (9)
O24ⁱ—O24—H24	86.9	C71—N5—H5	108.2
Zn1—N4—H4	108.0	C71—N5—C73	112.2 (9)
C16—N4—Zn1	107.0 (8)	C73—N5—Zn2	107.2 (8)
C16—N4—H4	108.0	C73—N5—H5	108.2
C16—N4—C36	113.7 (11)	C72—C69—H69	120.3
C36—N4—Zn1	111.9 (8)	C72—C69—C75	119.5 (18)
C36—N4—H4	108.0	C75—C69—H69	120.3
C28—C4—H4A	117.0	O19—C70—O20	109.0 (11)
C28—C4—C44	126.0 (15)	O19—C70—H70A	109.9
C44—C4—H4A	117.0	O19—C70—H70B	109.9
O12—C8—H8A	110.3	O20—C70—H70A	109.9
O12—C8—H8B	110.3	O20—C70—H70B	109.9
O16—C8—O12	107.1 (12)	H70A—C70—H70B	108.3
O16—C8—H8A	110.3	N5—C71—H71A	109.1
O16—C8—H8B	110.3	N5—C71—H71B	109.1
H8A—C8—H8B	108.6	N5—C71—C80	112.3 (11)
C32—C12—H12	120.2	H71A—C71—H71B	107.9
C68—C12—H12	120.2	C80—C71—H71A	109.1
C68—C12—C32	119.5 (16)	C80—C71—H71B	109.1
N4—C16—H16	108.6	C69—C72—H72	119.1
N4—C16—C24	108.8 (12)	C77—C72—C69	121.8 (18)
N4—C16—C60	112.2 (11)	C77—C72—H72	119.1
C24—C16—H16	108.6	N5—C73—H73	109.2
C60—C16—H16	108.6	N5—C73—C74	109.1 (13)
C60—C16—C24	110.1 (11)	N5—C73—C76	108.8 (11)
C28—C20—H20	122.2	C74—C73—H73	109.2
C56—C20—H20	122.2	C74—C73—C76	111.4 (11)
C56—C20—C28	115.6 (12)	C76—C73—H73	109.2
O4—C24—O8	124.6 (13)	O17—C74—C73	115.4 (14)
O4—C24—C16	120.6 (12)	O21—C74—O17	125.0 (14)
O8—C24—C16	114.8 (14)	O21—C74—C73	119.5 (13)
C4—C28—C20	118.5 (13)	C69—C75—H75	120.6
C4—C28—C36	123.2 (14)	C69—C75—C83	118.9 (17)
C20—C28—C36	117.8 (12)	C83—C75—H75	120.6
C12—C32—H32	120.7	C73—C76—H76A	108.7
C64—C32—C12	118.6 (15)	C73—C76—H76B	108.7
C64—C32—H32	120.7	H76A—C76—H76B	107.6
N4—C36—H36A	109.2	C83—C76—C73	114.2 (12)
N4—C36—H36B	109.2	C83—C76—H76A	108.7
C28—C36—N4	112.0 (11)	C83—C76—H76B	108.7
C28—C36—H36A	109.2	C72—C77—H77	120.7
C28—C36—H36B	109.2	C72—C77—C84	118.6 (19)
H36A—C36—H36B	107.9	C84—C77—H77	120.7
C44—C40—O12	129.1 (14)	C80—C78—H78	122.2
C56—C40—O12	109.6 (14)	C82—C78—H78	122.2
C56—C40—C44	121.2 (15)	C82—C78—C80	115.6 (13)
C4—C44—C40	115.0 (14)	C82—C79—O20	113.2 (13)
C4—C44—H44	122.5	C82—C79—C85	120.6 (15)
C40—C44—H44	122.5	C85—C79—O20	126.2 (13)
C52—C48—C60	119.3 (15)	C78—C80—C71	120.0 (13)
C68—C48—C52	118.9 (14)	C81—C80—C71	119.6 (13)
C68—C48—C60	121.8 (16)	C81—C80—C78	120.3 (14)
C48—C52—H52	120.6	C80—C81—H81	118.7
C64—C52—C48	118.8 (15)	C80—C81—C85	122.6 (14)
C64—C52—H52	120.6	C85—C81—H81	118.7
C20—C56—O16	126.8 (12)	C78—C82—O19	127.2 (13)
C20—C56—C40	123.6 (14)	C78—C82—C79	125.8 (14)
C40—C56—O16	109.6 (13)	C79—C82—O19	107.0 (14)
C16—C60—H60A	109.4	C75—C83—C76	119.1 (15)
C16—C60—H60B	109.4	C84—C83—C75	119.4 (15)
C48—C60—C16	111.2 (13)	C84—C83—C76	121.3 (15)
C48—C60—H60A	109.4	C77—C84—H84	119.2
C48—C60—H60B	109.4	C83—C84—C77	121.6 (18)
H60A—C60—H60B	108.0	C83—C84—H84	119.2
C32—C64—H64	119.2	C79—C85—C81	115.1 (13)
C52—C64—C32	121.6 (16)	C79—C85—H85	122.5
C52—C64—H64	119.2	C81—C85—H85	122.5
C12—C68—H68	118.8

Zn1—O4—C24—O8	176.5 (11)	Zn2—O21—C74—O17	173.7 (10)
Zn1—O4—C24—C16	−3.8 (17)	Zn2—O21—C74—C73	−4.3 (14)
Zn1—N4—C16—C24	29.1 (12)	Zn2—N5—C71—C80	173.4 (8)
Zn1—N4—C16—C60	−92.9 (12)	Zn2—N5—C73—C74	29.8 (11)
Zn1—N4—C36—C28	170.4 (9)	Zn2—N5—C73—C76	−91.9 (12)
O12—C40—C44—C4	−177.2 (14)	O20—C79—C82—O19	−1.4 (16)
O12—C40—C56—O16	−1.4 (17)	O20—C79—C82—C78	178.5 (13)
O12—C40—C56—C20	177.7 (13)	O20—C79—C85—C81	−178.0 (12)
N4—C16—C24—O4	−18.2 (18)	N5—C71—C80—C78	96.1 (14)
N4—C16—C24—O8	161.5 (12)	N5—C71—C80—C81	−79.3 (14)
N4—C16—C60—C48	−57.5 (17)	N5—C73—C74—O17	163.7 (10)
C4—C28—C36—N4	−75.9 (15)	N5—C73—C74—O21	−18.0 (16)
C8—O12—C40—C44	−172.1 (16)	N5—C73—C76—C83	−64.9 (16)
C8—O12—C40—C56	10.4 (16)	C69—C72—C77—C84	−1 (2)
C8—O16—C56—C20	172.6 (15)	C69—C75—C83—C76	179.6 (12)
C8—O16—C56—C40	−8.4 (17)	C69—C75—C83—C84	4.9 (18)
C12—C32—C64—C52	1 (2)	C70—O19—C82—C78	174.5 (14)
C16—N4—C36—C28	−68.3 (15)	C70—O19—C82—C79	−5.5 (15)
C20—C28—C36—N4	95.5 (14)	C70—O20—C79—C82	7.5 (15)
C24—C16—C60—C48	−178.8 (13)	C70—O20—C79—C85	−174.6 (13)
C28—C4—C44—C40	0 (2)	C71—N5—C73—C74	−94.3 (13)
C28—C20—C56—O16	179.4 (13)	C71—N5—C73—C76	144.0 (12)
C28—C20—C56—C40	0 (2)	C71—C80—C81—C85	173.1 (12)
C32—C12—C68—C48	−4 (2)	C72—C69—C75—C83	−3.1 (16)
C36—N4—C16—C24	−94.9 (13)	C72—C77—C84—C83	3 (2)
C36—N4—C16—C60	143.0 (12)	C73—N5—C71—C80	−65.6 (15)
C40—O12—C8—O16	−15.4 (16)	C73—C76—C83—C75	−66.0 (17)
C44—C4—C28—C20	0.8 (18)	C73—C76—C83—C84	108.6 (16)
C44—C4—C28—C36	172.1 (14)	C74—C73—C76—C83	174.9 (13)
C44—C40—C56—O16	−179.2 (14)	C75—C69—C72—C77	1.3 (18)
C44—C40—C56—C20	0 (2)	C75—C83—C84—C77	−5 (2)
C48—C52—C64—C32	−1 (2)	C76—C73—C74—O17	−76.1 (15)
C52—C48—C60—C16	−75.1 (18)	C76—C73—C74—O21	102.1 (15)
C52—C48—C68—C12	3 (2)	C76—C83—C84—C77	−179.6 (13)
C56—O16—C8—O12	14.6 (16)	C78—C80—C81—C85	−2.3 (19)
C56—C20—C28—C4	−0.7 (15)	C79—O20—C70—O19	−10.8 (14)
C56—C20—C28—C36	−172.6 (13)	C80—C78—C82—O19	178.4 (13)
C56—C40—C44—C4	0 (2)	C80—C78—C82—C79	−2 (2)
C60—C16—C24—O4	105.1 (16)	C80—C81—C85—C79	1.2 (19)
C60—C16—C24—O8	−75.2 (15)	C82—O19—C70—O20	10.3 (15)
C60—C48—C52—C64	178.4 (15)	C82—C78—C80—C71	−173.0 (13)
C60—C48—C68—C12	−176.1 (14)	C82—C78—C80—C81	2.4 (17)
C68—C12—C32—C64	1.5 (18)	C82—C79—C85—C81	−0.2 (18)
C68—C48—C52—C64	−1 (2)	C85—C79—C82—O19	−179.4 (12)
C68—C48—C60—C16	104.1 (17)	C85—C79—C82—C78	0 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O24—H24···O8ⁱⁱⁱ	0.98	1.83	2.68 (4)	144
O18—H18A···O17ⁱⁱⁱ	1.04	1.67	2.600 (12)	146
O18—H18B···O17^iv	1.04	1.67	2.600 (12)	146

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

(exp_5058_sq) top

Crystal data top

C₂₂H₂₄CuN₂O₈·4(H₂O)	F(000) = 606
M_r = 580.03	D_x = 1.478 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 13.9887 (7) Å	Cell parameters from 3907 reflections
b = 6.8910 (2) Å	θ = 4.2–26.6°
c = 14.3405 (7) Å	µ = 0.90 mm⁻¹
β = 109.510 (5)°	T = 298 K
V = 1303.00 (11) Å³	Needle, blue
Z = 2	0.7 × 0.2 × 0.2 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	4711 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	4234 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 16.1158 pixels mm^-1	θ_max = 25.5°, θ_min = 3.8°
ω scans	h = −16→16
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −8→8
T_min = 0.775, T_max = 1.000	l = −17→17
9459 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0502P)² + 0.087P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max = 0.001
S = 1.05	Δρ_max = 0.38 e Å⁻³
4711 reflections	Δρ_min = −0.19 e Å⁻³
361 parameters	Absolute structure: Flack x determined using 1656 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
1 restraint	Absolute structure parameter: −0.011 (9)

Special details top

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.71215 (4)	0.49708 (8)	0.57571 (3)	0.04638 (17)
O1	0.9010 (4)	0.7215 (8)	1.1817 (3)	0.0910 (14)
O2	0.8207 (4)	0.9495 (6)	1.0638 (3)	0.0939 (15)
O3	0.5941 (4)	0.0477 (6)	0.6654 (3)	0.1028 (19)
O4	0.6338 (3)	0.2628 (5)	0.5724 (2)	0.0535 (8)
O5	0.7872 (3)	0.7338 (5)	0.5779 (2)	0.0532 (8)
O6	0.8291 (3)	0.9510 (4)	0.4849 (3)	0.0645 (10)
O7	0.4074 (3)	0.3247 (8)	0.0608 (3)	0.0829 (12)
O8	0.5116 (3)	0.3374 (7)	−0.0336 (3)	0.0758 (11)
O10	0.5595 (3)	0.6972 (7)	0.5713 (4)	0.0815 (12)
H10D	0.506379	0.700596	0.520477	0.122*
H10E	0.545204	0.618212	0.610219	0.122*
N1	0.7375 (2)	0.4907 (8)	0.7226 (2)	0.0450 (7)
H1	0.693215	0.589540	0.735659	0.054*
N2	0.6729 (3)	0.5179 (6)	0.4272 (2)	0.0415 (8)
H2	0.599655	0.541717	0.401490	0.050*
C1	0.8651 (6)	0.9172 (12)	1.1660 (5)	0.096 (2)
H1A	0.815413	0.938952	1.198624	0.115*
H1B	0.920996	1.006503	1.193671	0.115*
C2	0.9058 (4)	0.4488 (8)	0.9634 (4)	0.0605 (14)
H2A	0.927544	0.332650	0.944115	0.073*
C3	0.9233 (4)	0.4813 (12)	1.0644 (4)	0.0684 (14)
H3	0.954983	0.389311	1.112194	0.082*
C4	0.8915 (4)	0.6535 (9)	1.0885 (4)	0.0564 (13)
C5	0.8440 (4)	0.7878 (8)	1.0191 (4)	0.0587 (13)
C6	0.8265 (4)	0.7578 (8)	0.9206 (4)	0.0616 (13)
H6	0.794565	0.851638	0.873995	0.074*
C7	0.8579 (3)	0.5824 (7)	0.8922 (4)	0.0516 (12)
C8	0.8432 (4)	0.5422 (9)	0.7851 (3)	0.0611 (15)
H8A	0.863920	0.656087	0.757032	0.073*
H8B	0.887791	0.436560	0.781854	0.073*
C9	0.7030 (4)	0.3017 (8)	0.7489 (4)	0.0554 (12)
H9	0.763442	0.222852	0.780715	0.066*
C10	0.6452 (6)	0.3208 (13)	0.8216 (5)	0.097 (2)
H10A	0.586671	0.401266	0.793286	0.146*
H10B	0.688456	0.378516	0.881873	0.146*
H10C	0.624187	0.194600	0.835479	0.146*
C11	0.6389 (4)	0.1947 (8)	0.6558 (4)	0.0555 (12)
C12	0.7839 (4)	0.8020 (6)	0.4949 (4)	0.0470 (11)
C13	0.6464 (6)	0.8229 (8)	0.3289 (4)	0.087 (2)
H13A	0.615067	0.755268	0.267781	0.131*
H13B	0.680758	0.935833	0.317001	0.131*
H13C	0.595302	0.861571	0.356267	0.131*
C14	0.7224 (4)	0.6897 (7)	0.4015 (4)	0.0512 (13)
H14	0.769890	0.643425	0.369393	0.061*
C15	0.6917 (4)	0.3353 (7)	0.3796 (4)	0.0504 (12)
H15A	0.662444	0.227127	0.403964	0.060*
H15B	0.764216	0.313766	0.399151	0.060*
C16	0.6479 (3)	0.3384 (6)	0.2679 (3)	0.0444 (10)
C17	0.5422 (4)	0.3310 (7)	0.2217 (4)	0.0530 (11)
H17	0.498654	0.324314	0.258386	0.064*
C18	0.5063 (3)	0.3341 (7)	0.1212 (4)	0.0506 (11)
C19	0.5691 (4)	0.3400 (7)	0.0653 (3)	0.0490 (11)
C20	0.6712 (4)	0.3456 (8)	0.1077 (4)	0.0554 (12)
H20	0.713585	0.349929	0.069712	0.066*
C21	0.7101 (4)	0.3445 (7)	0.2111 (4)	0.0490 (11)
H21	0.780029	0.347908	0.242444	0.059*
C22	0.4088 (4)	0.3413 (9)	−0.0372 (4)	0.0668 (14)
H22A	0.377077	0.461911	−0.066586	0.080*
H22B	0.371689	0.234538	−0.077244	0.080*
O9	0.8628 (3)	0.2934 (6)	0.6044 (3)	0.0717 (11)
H9A	0.919412	0.335714	0.603030	0.108*
H9B	0.851330	0.182206	0.577279	0.108*
O11	1.0265 (6)	0.5188 (11)	0.6002 (6)	0.144 (2)
H11A	1.033161	0.635479	0.620589	0.216*
H11B	0.993853	0.527415	0.538620	0.216*
O12	0.9961 (14)	0.863 (3)	0.6893 (10)	0.091 (6)	0.50 (4)
H12A	1.028043	0.761378	0.715747	0.137*	0.50 (4)
H12B	0.933884	0.831942	0.673000	0.137*	0.50 (4)
O13	1.040 (2)	0.928 (4)	0.646 (3)	0.18 (2)	0.50 (4)
H13D	1.069501	0.997838	0.614870	0.267*	0.50 (4)
H13E	0.979368	0.970687	0.627297	0.267*	0.50 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0560 (3)	0.0449 (3)	0.0390 (3)	−0.0119 (3)	0.0170 (2)	−0.0022 (2)
O1	0.100 (3)	0.118 (4)	0.048 (2)	−0.003 (3)	0.015 (2)	−0.015 (2)
O2	0.100 (3)	0.083 (4)	0.086 (3)	0.015 (2)	0.015 (2)	−0.027 (2)
O3	0.171 (5)	0.083 (4)	0.079 (3)	−0.072 (3)	0.075 (3)	−0.024 (2)
O4	0.060 (2)	0.0556 (19)	0.0488 (19)	−0.0175 (17)	0.0239 (15)	−0.0062 (16)
O5	0.061 (2)	0.0476 (19)	0.0479 (19)	−0.0127 (16)	0.0140 (15)	−0.0030 (15)
O6	0.079 (2)	0.046 (2)	0.077 (2)	−0.0156 (17)	0.0372 (19)	−0.0035 (16)
O7	0.050 (2)	0.125 (4)	0.070 (3)	−0.001 (2)	0.0155 (18)	−0.016 (3)
O8	0.080 (3)	0.102 (3)	0.043 (2)	0.000 (2)	0.0175 (18)	−0.002 (2)
O10	0.061 (2)	0.069 (3)	0.101 (3)	0.014 (2)	0.010 (2)	−0.012 (2)
N1	0.0420 (16)	0.0535 (19)	0.0415 (17)	−0.001 (2)	0.0164 (13)	0.004 (2)
N2	0.0525 (18)	0.0310 (19)	0.0427 (17)	0.0007 (19)	0.0183 (14)	−0.0050 (19)
C1	0.080 (4)	0.118 (6)	0.078 (5)	0.011 (4)	0.010 (3)	−0.039 (4)
C2	0.054 (3)	0.065 (4)	0.057 (3)	0.012 (2)	0.011 (2)	−0.002 (2)
C3	0.066 (3)	0.077 (4)	0.052 (3)	0.015 (4)	0.006 (2)	0.007 (3)
C4	0.049 (3)	0.072 (3)	0.046 (3)	−0.002 (3)	0.012 (2)	−0.004 (3)
C5	0.048 (3)	0.058 (3)	0.063 (3)	−0.003 (2)	0.010 (2)	−0.011 (3)
C6	0.063 (3)	0.060 (3)	0.050 (3)	−0.009 (3)	0.004 (2)	0.004 (2)
C7	0.041 (2)	0.063 (3)	0.048 (3)	−0.010 (2)	0.011 (2)	−0.005 (2)
C8	0.049 (2)	0.088 (5)	0.047 (3)	−0.017 (3)	0.018 (2)	−0.009 (3)
C9	0.059 (3)	0.062 (3)	0.050 (3)	−0.012 (3)	0.025 (2)	0.001 (2)
C10	0.116 (5)	0.130 (6)	0.066 (4)	−0.066 (5)	0.056 (4)	−0.033 (4)
C11	0.069 (3)	0.052 (3)	0.057 (3)	−0.013 (3)	0.038 (3)	−0.009 (2)
C12	0.052 (3)	0.036 (2)	0.058 (3)	−0.001 (2)	0.026 (2)	−0.003 (2)
C13	0.133 (6)	0.049 (3)	0.055 (3)	−0.008 (3)	−0.001 (3)	0.007 (3)
C14	0.081 (4)	0.034 (2)	0.047 (3)	−0.003 (2)	0.033 (3)	0.002 (2)
C15	0.071 (3)	0.033 (2)	0.048 (3)	0.000 (2)	0.023 (2)	−0.002 (2)
C16	0.058 (3)	0.031 (2)	0.047 (2)	0.000 (2)	0.021 (2)	−0.0043 (19)
C17	0.055 (3)	0.056 (3)	0.059 (3)	−0.004 (2)	0.034 (2)	−0.009 (2)
C18	0.046 (2)	0.047 (3)	0.057 (3)	0.000 (2)	0.016 (2)	−0.009 (2)
C19	0.062 (3)	0.043 (2)	0.045 (3)	0.002 (2)	0.022 (2)	−0.003 (2)
C20	0.061 (3)	0.063 (3)	0.052 (3)	−0.005 (2)	0.032 (2)	−0.008 (2)
C21	0.047 (2)	0.047 (2)	0.056 (3)	0.000 (2)	0.021 (2)	−0.009 (2)
C22	0.066 (3)	0.058 (3)	0.064 (3)	−0.001 (3)	0.005 (3)	−0.003 (3)
O9	0.065 (2)	0.069 (3)	0.082 (3)	0.001 (2)	0.027 (2)	−0.019 (2)
O11	0.145 (5)	0.109 (4)	0.227 (7)	−0.020 (5)	0.128 (5)	−0.024 (6)
O12	0.074 (8)	0.096 (9)	0.081 (8)	−0.005 (7)	−0.003 (6)	0.004 (6)
O13	0.110 (16)	0.122 (15)	0.23 (3)	0.019 (12)	−0.04 (2)	−0.011 (16)

Geometric parameters (Å, º) top

Cu1—O4	1.943 (3)	C8—H8A	0.9700
Cu1—O5	1.935 (3)	C8—H8B	0.9700
Cu1—N1	2.017 (3)	C9—H9	0.9800
Cu1—N2	2.020 (3)	C9—C10	1.523 (7)
O1—C1	1.431 (9)	C9—C11	1.528 (7)
O1—C4	1.381 (6)	C10—H10A	0.9600
O2—C1	1.405 (8)	C10—H10B	0.9600
O2—C5	1.377 (7)	C10—H10C	0.9600
O3—C11	1.223 (6)	C12—C14	1.537 (7)
O4—C11	1.265 (6)	C13—H13A	0.9600
O5—C12	1.266 (6)	C13—H13B	0.9600
O6—C12	1.239 (5)	C13—H13C	0.9600
O7—C18	1.366 (6)	C13—C14	1.522 (8)
O7—C22	1.418 (7)	C14—H14	0.9800
O8—C19	1.377 (6)	C15—H15A	0.9700
O8—C22	1.420 (7)	C15—H15B	0.9700
O10—H10D	0.8501	C15—C16	1.512 (6)
O10—H10E	0.8495	C16—C17	1.405 (7)
N1—H1	0.9800	C16—C21	1.376 (6)
N1—C8	1.493 (6)	C17—H17	0.9300
N1—C9	1.481 (8)	C17—C18	1.359 (7)
N2—H2	0.9800	C18—C19	1.373 (7)
N2—C14	1.479 (7)	C19—C20	1.353 (7)
N2—C15	1.496 (6)	C20—H20	0.9300
C1—H1A	0.9700	C20—C21	1.400 (7)
C1—H1B	0.9700	C21—H21	0.9300
C2—H2A	0.9300	C22—H22A	0.9700
C2—C3	1.404 (7)	C22—H22B	0.9700
C2—C7	1.373 (7)	O9—H9A	0.8501
C3—H3	0.9300	O9—H9B	0.8499
C3—C4	1.352 (9)	O11—H11A	0.8499
C4—C5	1.359 (8)	O11—H11B	0.8500
C5—C6	1.366 (7)	O12—H12A	0.8501
C6—H6	0.9300	O12—H12B	0.8503
C6—C7	1.393 (7)	O13—H13D	0.8500
C7—C8	1.505 (7)	O13—H13E	0.8503

O4—Cu1—N1	84.75 (18)	C11—C9—H9	107.6
O4—Cu1—N2	94.62 (15)	C9—C10—H10A	109.5
O5—Cu1—O4	178.62 (16)	C9—C10—H10B	109.5
O5—Cu1—N1	95.54 (17)	C9—C10—H10C	109.5
O5—Cu1—N2	84.95 (16)	H10A—C10—H10B	109.5
N1—Cu1—N2	173.97 (16)	H10A—C10—H10C	109.5
C4—O1—C1	104.6 (5)	H10B—C10—H10C	109.5
C5—O2—C1	105.5 (5)	O3—C11—O4	123.0 (5)
C11—O4—Cu1	115.6 (3)	O3—C11—C9	118.3 (5)
C12—O5—Cu1	116.6 (3)	O4—C11—C9	118.6 (5)
C18—O7—C22	106.1 (4)	O5—C12—C14	117.8 (4)
C19—O8—C22	105.9 (4)	O6—C12—O5	123.8 (5)
H10D—O10—H10E	104.5	O6—C12—C14	118.4 (4)
Cu1—N1—H1	106.4	H13A—C13—H13B	109.5
C8—N1—Cu1	114.5 (3)	H13A—C13—H13C	109.5
C8—N1—H1	106.4	H13B—C13—H13C	109.5
C9—N1—Cu1	109.1 (3)	C14—C13—H13A	109.5
C9—N1—H1	106.4	C14—C13—H13B	109.5
C9—N1—C8	113.4 (4)	C14—C13—H13C	109.5
Cu1—N2—H2	106.9	N2—C14—C12	111.0 (4)
C14—N2—Cu1	109.5 (3)	N2—C14—C13	112.0 (5)
C14—N2—H2	106.9	N2—C14—H14	107.7
C14—N2—C15	113.1 (3)	C12—C14—H14	107.7
C15—N2—Cu1	113.2 (3)	C13—C14—C12	110.6 (4)
C15—N2—H2	106.9	C13—C14—H14	107.7
O1—C1—H1A	109.9	N2—C15—H15A	108.8
O1—C1—H1B	109.9	N2—C15—H15B	108.8
O2—C1—O1	108.8 (5)	N2—C15—C16	113.7 (4)
O2—C1—H1A	109.9	H15A—C15—H15B	107.7
O2—C1—H1B	109.9	C16—C15—H15A	108.8
H1A—C1—H1B	108.3	C16—C15—H15B	108.8
C3—C2—H2A	118.9	C17—C16—C15	119.2 (4)
C7—C2—H2A	118.9	C21—C16—C15	121.0 (4)
C7—C2—C3	122.3 (5)	C21—C16—C17	119.8 (4)
C2—C3—H3	121.8	C16—C17—H17	121.4
C4—C3—C2	116.4 (5)	C18—C17—C16	117.3 (4)
C4—C3—H3	121.8	C18—C17—H17	121.4
C3—C4—O1	127.7 (5)	O7—C18—C19	110.0 (4)
C3—C4—C5	122.2 (5)	C17—C18—O7	127.5 (4)
C5—C4—O1	110.1 (5)	C17—C18—C19	122.5 (4)
C4—C5—O2	110.1 (5)	C18—C19—O8	109.4 (4)
C4—C5—C6	121.9 (5)	C20—C19—O8	129.0 (4)
C6—C5—O2	127.9 (5)	C20—C19—C18	121.6 (4)
C5—C6—H6	121.0	C19—C20—H20	121.5
C5—C6—C7	118.0 (5)	C19—C20—C21	117.0 (4)
C7—C6—H6	121.0	C21—C20—H20	121.5
C2—C7—C6	119.2 (4)	C16—C21—C20	121.9 (4)
C2—C7—C8	120.1 (5)	C16—C21—H21	119.1
C6—C7—C8	120.6 (5)	C20—C21—H21	119.1
N1—C8—C7	115.3 (4)	O7—C22—O8	108.1 (4)
N1—C8—H8A	108.5	O7—C22—H22A	110.1
N1—C8—H8B	108.5	O7—C22—H22B	110.1
C7—C8—H8A	108.5	O8—C22—H22A	110.1
C7—C8—H8B	108.5	O8—C22—H22B	110.1
H8A—C8—H8B	107.5	H22A—C22—H22B	108.4
N1—C9—H9	107.6	H9A—O9—H9B	109.5
N1—C9—C10	113.0 (5)	H11A—O11—H11B	104.5
N1—C9—C11	110.4 (4)	H12A—O12—H12B	104.5
C10—C9—H9	107.6	H13D—O13—H13E	104.5
C10—C9—C11	110.4 (4)

Cu1—O4—C11—O3	−179.7 (5)	C3—C4—C5—O2	−179.5 (5)
Cu1—O4—C11—C9	1.0 (6)	C3—C4—C5—C6	−0.8 (9)
Cu1—O5—C12—O6	−179.1 (4)	C4—O1—C1—O2	9.2 (7)
Cu1—O5—C12—C14	−0.8 (6)	C4—C5—C6—C7	0.7 (8)
Cu1—N1—C8—C7	166.7 (4)	C5—O2—C1—O1	−9.1 (7)
Cu1—N1—C9—C10	−137.1 (4)	C5—C6—C7—C2	−0.8 (7)
Cu1—N1—C9—C11	−12.8 (5)	C5—C6—C7—C8	−178.5 (4)
Cu1—N2—C14—C12	−2.4 (5)	C6—C7—C8—N1	−76.5 (6)
Cu1—N2—C14—C13	−126.6 (4)	C7—C2—C3—C4	−0.9 (8)
Cu1—N2—C15—C16	171.1 (3)	C8—N1—C9—C10	94.0 (6)
O1—C4—C5—O2	0.2 (6)	C8—N1—C9—C11	−141.8 (4)
O1—C4—C5—C6	178.9 (5)	C9—N1—C8—C7	−67.1 (6)
O2—C5—C6—C7	179.2 (5)	C10—C9—C11—O3	−45.2 (8)
O5—C12—C14—N2	2.2 (6)	C10—C9—C11—O4	134.1 (6)
O5—C12—C14—C13	127.2 (5)	C14—N2—C15—C16	−63.6 (5)
O6—C12—C14—N2	−179.4 (4)	C15—N2—C14—C12	−129.7 (4)
O6—C12—C14—C13	−54.4 (6)	C15—N2—C14—C13	106.1 (5)
O7—C18—C19—O8	0.9 (6)	C15—C16—C17—C18	180.0 (4)
O7—C18—C19—C20	−178.6 (5)	C15—C16—C21—C20	179.4 (4)
O8—C19—C20—C21	−179.2 (5)	C16—C17—C18—O7	178.6 (5)
N1—C9—C11—O3	−170.9 (5)	C16—C17—C18—C19	1.4 (7)
N1—C9—C11—O4	8.4 (7)	C17—C16—C21—C20	0.7 (7)
N2—C15—C16—C17	−70.4 (6)	C17—C18—C19—O8	178.6 (4)
N2—C15—C16—C21	110.9 (5)	C17—C18—C19—C20	−0.8 (8)
C1—O1—C4—C3	173.9 (6)	C18—O7—C22—O8	6.8 (6)
C1—O1—C4—C5	−5.7 (6)	C18—C19—C20—C21	0.2 (8)
C1—O2—C5—C4	5.6 (7)	C19—O8—C22—O7	−6.3 (6)
C1—O2—C5—C6	−173.1 (6)	C19—C20—C21—C16	−0.1 (7)
C2—C3—C4—O1	−178.8 (5)	C21—C16—C17—C18	−1.3 (7)
C2—C3—C4—C5	0.8 (8)	C22—O7—C18—C17	177.6 (5)
C2—C7—C8—N1	105.8 (6)	C22—O7—C18—C19	−4.8 (6)
C3—C2—C7—C6	0.9 (8)	C22—O8—C19—C18	3.4 (6)
C3—C2—C7—C8	178.6 (5)	C22—O8—C19—C20	−177.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10D···O4ⁱ	0.85	2.01	2.835 (5)	162
O9—H9A···O11	0.85	1.97	2.785 (8)	160
O9—H9B···O6ⁱⁱ	0.85	2.03	2.861 (5)	166
O11—H11A···O12	0.85	2.01	2.795 (17)	153
O11—H11A···O13	0.85	2.04	2.89 (2)	171

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

(exp_4899_p1) top

Crystal data top

C₂₂H₂₄CuN₂O₈	F(000) = 526
M_r = 507.97	D_x = 1.562 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.279 (3) Å	Cell parameters from 1968 reflections
b = 5.5252 (9) Å	θ = 4.1–24.2°
c = 17.450 (3) Å	µ = 1.07 mm⁻¹
β = 96.84 (2)°	T = 299 K
V = 1079.7 (4) Å³	Needle, violet
Z = 2	0.1 × 0.05 × 0.05 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	1577 reflections with I > 2σ(I)
Detector resolution: 16.1158 pixels mm^-1	R_int = 0.094
ω scans	θ_max = 29.3°, θ_min = 3.6°
Absorption correction: analytical CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Spherical absorption correction using equivalent radius and absorption coefficient. Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −13→15
T_min = 0.724, T_max = 0.732	k = −7→6
10344 measured reflections	l = −23→20
2576 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.0626P)² + 0.0382P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2576 reflections	Δρ_max = 0.44 e Å⁻³
152 parameters	Δρ_min = −0.56 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.000000	0.500000	0.500000	0.0347 (2)
O2	0.0693 (2)	0.7466 (4)	0.44201 (14)	0.0415 (6)
O4	0.2156 (3)	0.8080 (5)	0.36986 (16)	0.0582 (8)
O6	0.4256 (3)	0.9605 (6)	0.69985 (19)	0.0657 (9)
O8	0.5029 (3)	0.8655 (8)	0.58716 (19)	0.0880 (12)
N2	0.1148 (3)	0.2740 (5)	0.45769 (16)	0.0357 (7)
H2	0.071253	0.128869	0.438190	0.043*
C12	0.1520 (4)	0.6720 (7)	0.4022 (2)	0.0412 (9)
C13	0.2642 (3)	0.4075 (7)	0.5686 (2)	0.0416 (9)
C14	0.1619 (4)	0.3969 (7)	0.3924 (2)	0.0406 (9)
H14	0.245716	0.352087	0.391346	0.049*
C15	0.3617 (4)	0.7724 (8)	0.6626 (2)	0.0481 (10)
C16	0.2126 (3)	0.1995 (7)	0.5200 (2)	0.0462 (10)
H16A	0.180874	0.081140	0.553163	0.055*
H16B	0.276084	0.122183	0.496009	0.055*
C17	0.4078 (4)	0.7172 (9)	0.5951 (2)	0.0517 (11)
C18	0.2662 (4)	0.6512 (9)	0.6839 (2)	0.0533 (12)
H18	0.233866	0.690350	0.728952	0.064*
C19	0.2191 (4)	0.4679 (7)	0.6362 (2)	0.0458 (10)
H19	0.154272	0.381171	0.650156	0.055*
C20	0.3615 (4)	0.5354 (8)	0.5471 (2)	0.0540 (12)
H20	0.393737	0.498932	0.501823	0.065*
C21	0.0900 (4)	0.3265 (8)	0.3164 (2)	0.0607 (12)
H21A	0.102418	0.158129	0.306287	0.091*
H21B	0.115511	0.422029	0.275386	0.091*
H21C	0.006727	0.354857	0.319395	0.091*
C22	0.5229 (5)	0.9991 (10)	0.6572 (3)	0.0767 (16)
H22A	0.596446	0.946214	0.686954	0.092*
H22B	0.530018	1.170069	0.646022	0.092*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0454 (4)	0.0239 (3)	0.0363 (4)	0.0004 (3)	0.0102 (3)	−0.0008 (3)
O2	0.0565 (16)	0.0236 (13)	0.0481 (16)	0.0024 (12)	0.0214 (13)	−0.0008 (11)
O4	0.083 (2)	0.0349 (16)	0.0642 (19)	−0.0049 (15)	0.0400 (16)	0.0010 (14)
O6	0.065 (2)	0.075 (2)	0.0557 (19)	−0.0087 (17)	0.0024 (16)	−0.0216 (16)
O8	0.088 (3)	0.116 (3)	0.062 (2)	−0.046 (2)	0.0168 (19)	−0.024 (2)
N2	0.0483 (18)	0.0248 (15)	0.0347 (16)	0.0023 (13)	0.0083 (14)	−0.0004 (13)
C12	0.058 (3)	0.035 (2)	0.0320 (19)	−0.0032 (19)	0.0111 (18)	0.0010 (17)
C13	0.041 (2)	0.042 (2)	0.041 (2)	0.0082 (18)	0.0021 (18)	−0.0014 (19)
C14	0.048 (2)	0.035 (2)	0.040 (2)	0.0025 (18)	0.0123 (18)	−0.0089 (18)
C15	0.048 (2)	0.055 (3)	0.040 (2)	0.006 (2)	−0.0006 (19)	−0.005 (2)
C16	0.055 (2)	0.037 (2)	0.046 (2)	0.0125 (19)	0.0038 (19)	0.0031 (18)
C17	0.043 (2)	0.065 (3)	0.048 (2)	−0.006 (2)	0.0076 (19)	−0.003 (2)
C18	0.057 (3)	0.070 (3)	0.034 (2)	0.004 (2)	0.0091 (19)	−0.009 (2)
C19	0.046 (2)	0.056 (3)	0.036 (2)	0.000 (2)	0.0095 (18)	0.0022 (19)
C20	0.045 (2)	0.077 (3)	0.041 (2)	0.000 (2)	0.0105 (19)	−0.014 (2)
C21	0.090 (3)	0.048 (3)	0.044 (2)	0.003 (2)	0.006 (2)	−0.006 (2)
C22	0.075 (3)	0.083 (4)	0.072 (4)	−0.022 (3)	0.005 (3)	−0.020 (3)

Geometric parameters (Å, º) top

Cu1—O2	1.918 (2)	C14—H14	0.9800
Cu1—O2ⁱ	1.918 (2)	C14—C21	1.520 (5)
Cu1—N2ⁱ	2.002 (3)	C15—C17	1.376 (5)
Cu1—N2	2.002 (3)	C15—C18	1.358 (6)
O2—C12	1.296 (4)	C16—H16A	0.9700
O4—C12	1.222 (4)	C16—H16B	0.9700
O6—C15	1.382 (5)	C17—C20	1.371 (6)
O6—C22	1.414 (6)	C18—H18	0.9300
O8—C17	1.370 (5)	C18—C19	1.376 (6)
O8—C22	1.423 (6)	C19—H19	0.9300
N2—H2	0.9800	C20—H20	0.9300
N2—C14	1.478 (5)	C21—H21A	0.9600
N2—C16	1.511 (4)	C21—H21B	0.9600
C12—C14	1.535 (5)	C21—H21C	0.9600
C13—C16	1.504 (5)	C22—H22A	0.9700
C13—C19	1.381 (5)	C22—H22B	0.9700
C13—C20	1.394 (6)

O2—Cu1—O2ⁱ	180.0	N2—C16—H16A	108.9
O2—Cu1—N2ⁱ	94.22 (11)	N2—C16—H16B	108.9
O2ⁱ—Cu1—N2ⁱ	85.78 (11)	C13—C16—N2	113.4 (3)
O2—Cu1—N2	85.78 (11)	C13—C16—H16A	108.9
O2ⁱ—Cu1—N2	94.22 (11)	C13—C16—H16B	108.9
N2—Cu1—N2ⁱ	180.0	H16A—C16—H16B	107.7
C12—O2—Cu1	114.9 (2)	O8—C17—C15	109.6 (4)
C15—O6—C22	105.1 (3)	O8—C17—C20	128.4 (4)
C17—O8—C22	105.6 (4)	C20—C17—C15	122.0 (4)
Cu1—N2—H2	108.6	C15—C18—H18	121.3
C14—N2—Cu1	107.8 (2)	C15—C18—C19	117.3 (4)
C14—N2—H2	108.6	C19—C18—H18	121.3
C14—N2—C16	112.4 (3)	C13—C19—H19	118.7
C16—N2—Cu1	110.7 (2)	C18—C19—C13	122.7 (4)
C16—N2—H2	108.6	C18—C19—H19	118.7
O2—C12—C14	116.2 (3)	C13—C20—H20	121.3
O4—C12—O2	123.5 (4)	C17—C20—C13	117.5 (4)
O4—C12—C14	120.3 (3)	C17—C20—H20	121.3
C19—C13—C16	120.6 (4)	C14—C21—H21A	109.5
C19—C13—C20	119.3 (4)	C14—C21—H21B	109.5
C20—C13—C16	120.0 (4)	C14—C21—H21C	109.5
N2—C14—C12	109.4 (3)	H21A—C21—H21B	109.5
N2—C14—H14	109.5	H21A—C21—H21C	109.5
N2—C14—C21	110.6 (3)	H21B—C21—H21C	109.5
C12—C14—H14	109.5	O6—C22—O8	108.7 (4)
C21—C14—C12	108.2 (3)	O6—C22—H22A	109.9
C21—C14—H14	109.5	O6—C22—H22B	109.9
C17—C15—O6	109.9 (4)	O8—C22—H22A	109.9
C18—C15—O6	128.9 (4)	O8—C22—H22B	109.9
C18—C15—C17	121.2 (4)	H22A—C22—H22B	108.3

Cu1—O2—C12—O4	−170.5 (3)	C16—N2—C14—C12	−97.9 (4)
Cu1—O2—C12—C14	13.5 (4)	C16—N2—C14—C21	143.0 (3)
Cu1—N2—C14—C12	24.4 (3)	C16—C13—C19—C18	177.6 (4)
Cu1—N2—C14—C21	−94.7 (3)	C16—C13—C20—C17	−177.5 (4)
Cu1—N2—C16—C13	−45.5 (4)	C17—O8—C22—O6	−10.8 (6)
O2—C12—C14—N2	−25.9 (4)	C17—C15—C18—C19	1.3 (6)
O2—C12—C14—C21	94.6 (4)	C18—C15—C17—O8	179.8 (4)
O4—C12—C14—N2	158.0 (3)	C18—C15—C17—C20	−1.2 (7)
O4—C12—C14—C21	−81.5 (5)	C19—C13—C16—N2	92.5 (4)
O6—C15—C17—O8	0.5 (5)	C19—C13—C20—C17	0.0 (6)
O6—C15—C17—C20	179.5 (4)	C20—C13—C16—N2	−90.0 (4)
O6—C15—C18—C19	−179.5 (4)	C20—C13—C19—C18	0.2 (6)
O8—C17—C20—C13	179.2 (4)	C22—O6—C15—C17	−7.1 (5)
C14—N2—C16—C13	75.1 (4)	C22—O6—C15—C18	173.6 (5)
C15—O6—C22—O8	11.0 (5)	C22—O8—C17—C15	6.3 (6)
C15—C17—C20—C13	0.5 (7)	C22—O8—C17—C20	−172.6 (5)
C15—C18—C19—C13	−0.8 (6)

Symmetry code: (i) −x, −y+1, −z+1.

(cu_phepip) top

Crystal data top

C₃₄H₃₄CuN₂O₉	Z = 1
M_r = 678.17	F(000) = 353
Triclinic, P1	D_x = 1.471 Mg m⁻³
a = 7.2450 (17) Å	Synchrotron radiation, λ = 0.79986 Å
b = 7.2510 (12) Å	Cell parameters from 9181 reflections
c = 16.014 (3) Å	θ = 2.9–27.5°
α = 91.685 (11)°	µ = 1.06 mm⁻¹
β = 97.664 (7)°	T = 100 K
γ = 112.798 (8)°	Plate, blue
V = 765.6 (3) Å³	0.2 × 0.1 × 0.05 mm

Data collection top

Mx2_info_2019 diffractometer	4427 independent reflections
Radiation source: LNLS-MX2	4293 reflections with I > 2σ(I)
Detector resolution: 5.814 pixels mm^-1	R_int = 0.035
shuterless φ scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: empirical (using intensity measurements) XDS (Kabsch, 2010)	h = −7→7
T_min = 0.780, T_max = 1	k = −8→8
7949 measured reflections	l = −18→18

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.060	w = 1/[σ²(F_o²) + (0.1244P)² + 0.2776P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.159	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 2.33 e Å⁻³
4427 reflections	Δρ_min = −0.82 e Å⁻³
416 parameters	Absolute structure: Flack x determined using 1962 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
165 restraints	Absolute structure parameter: 0.012 (7)

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.71337 (6)	0.79100 (6)	0.50246 (5)	0.0234 (3)
O1	0.3780 (11)	1.1063 (10)	0.5126 (4)	0.0304 (16)
O2	0.9811 (12)	1.0550 (12)	0.5051 (7)	0.071 (3)
H2A	1.104073	1.074290	0.497562	0.106*
H2B	0.963625	1.160322	0.487158	0.106*
O3	1.0106 (10)	0.4404 (9)	0.4921 (4)	0.0306 (16)
O4	0.5429 (11)	0.9293 (10)	0.4651 (4)	0.0283 (15)
O5	0.2836 (12)	0.0242 (11)	0.0668 (4)	0.0391 (18)
O6	−0.0122 (11)	0.6492 (11)	0.8142 (4)	0.0362 (17)
O7	0.3907 (11)	−0.1032 (10)	0.1855 (4)	0.0333 (16)
O8	0.1781 (12)	0.5892 (11)	0.9314 (4)	0.0365 (17)
O9	0.8674 (11)	0.6337 (9)	0.5397 (4)	0.0273 (14)
N1	0.6595 (10)	0.6313 (10)	0.3894 (4)	0.0220 (14)
H1	0.665087	0.720644	0.342532	0.026*
N2	0.6137 (10)	0.7985 (9)	0.6136 (4)	0.0218 (14)
H2	0.727302	0.825565	0.661377	0.026*
C1	0.1475 (14)	0.6120 (13)	0.7896 (5)	0.0287 (19)
C2	0.974 (2)	1.0962 (16)	0.8755 (8)	0.065 (4)
H2C	1.100823	1.092218	0.897410	0.078*
C3	0.8035 (14)	0.8651 (16)	0.1417 (6)	0.039 (2)
H3	0.787875	0.982766	0.123944	0.047*
C4	0.2611 (14)	0.5772 (11)	0.8598 (5)	0.029 (2)
C5	0.4785 (14)	1.0024 (12)	0.5241 (6)	0.025 (2)
C6	0.5395 (13)	0.9636 (12)	0.6150 (5)	0.0239 (18)
H6	0.417944	0.921580	0.644362	0.029*
C7	0.7716 (18)	0.5265 (19)	0.1121 (7)	0.046 (3)
H7	0.732562	0.411427	0.073262	0.056*
C8	0.3864 (12)	0.3462 (12)	0.2959 (5)	0.0247 (17)
C9	0.9905 (13)	0.6875 (14)	0.3446 (5)	0.0304 (19)
H9A	1.048965	0.825478	0.372898	0.036*
H9B	1.099112	0.635799	0.348471	0.036*
C10	0.3060 (13)	0.1479 (13)	0.1375 (5)	0.0295 (19)
C11	0.4282 (14)	0.5370 (12)	0.8537 (5)	0.031 (2)
H11	0.503173	0.509187	0.901430	0.038*
C12	0.3184 (13)	0.4208 (12)	0.2245 (6)	0.0288 (18)
H12	0.299690	0.542711	0.230976	0.035*
C13	−0.0078 (15)	0.6086 (14)	0.9010 (6)	0.035 (2)
H13A	−0.124102	0.482968	0.906788	0.043*
H13B	−0.018558	0.719489	0.934827	0.043*
C14	0.7471 (15)	1.1270 (11)	0.7573 (5)	0.034 (2)
C15	0.8524 (17)	0.5235 (19)	0.1948 (7)	0.045 (3)
H15	0.867914	0.405804	0.212603	0.055*
C16	0.1962 (13)	0.6115 (11)	0.7100 (5)	0.0248 (17)
H16	0.115905	0.633114	0.662447	0.030*
C17	0.8180 (13)	0.5526 (12)	0.3893 (5)	0.0233 (18)
H17	0.756751	0.415301	0.358635	0.028*
C18	0.4510 (13)	0.4697 (12)	0.3820 (5)	0.0257 (17)
H18A	0.353296	0.531366	0.389581	0.031*
H18B	0.447971	0.379615	0.427581	0.031*
C19	0.4826 (14)	0.5394 (12)	0.7722 (5)	0.0279 (18)
H19	0.598997	0.514190	0.764966	0.033*
C20	0.3714 (12)	0.5772 (11)	0.7024 (5)	0.0224 (17)
C21	0.596 (2)	1.0998 (14)	0.8082 (7)	0.042 (3)
H21	0.467947	1.099634	0.785492	0.051*
C22	0.2770 (14)	0.3229 (13)	0.1442 (5)	0.033 (2)
H22	0.230592	0.375297	0.095873	0.039*
C23	0.7467 (15)	0.6984 (17)	0.0851 (6)	0.043 (2)
H23	0.691146	0.700362	0.028095	0.051*
C24	0.7048 (14)	1.1556 (12)	0.6629 (5)	0.0279 (18)
H24A	0.660719	1.268448	0.656748	0.034*
H24B	0.830898	1.189732	0.638146	0.034*
C25	0.643 (2)	1.0726 (16)	0.8947 (8)	0.057 (4)
H25	0.543341	1.052609	0.930565	0.068*
C26	0.9116 (14)	0.6917 (15)	0.2525 (6)	0.035 (2)
C27	0.3023 (15)	−0.1524 (14)	0.0979 (6)	0.035 (2)
H27A	0.389831	−0.193363	0.065760	0.042*
H27B	0.167335	−0.264534	0.091680	0.042*
C28	0.3705 (13)	0.0705 (13)	0.2091 (5)	0.0279 (18)
C29	0.4492 (12)	0.5967 (11)	0.6182 (5)	0.0220 (16)
H29A	0.501752	0.491451	0.609365	0.026*
H29B	0.335187	0.574017	0.572020	0.026*
C30	0.9072 (14)	0.5375 (13)	0.4809 (6)	0.027 (2)
C31	0.9305 (17)	1.1235 (13)	0.7909 (7)	0.043 (2)
H31	1.029713	1.140212	0.755267	0.051*
C32	0.8837 (13)	0.8595 (15)	0.2250 (6)	0.036 (2)
H32	0.920219	0.973783	0.264029	0.043*
C33	0.830 (2)	1.0748 (15)	0.9277 (7)	0.066 (4)
H33	0.859599	1.061574	0.986272	0.079*
C34	0.4104 (12)	0.1636 (12)	0.2887 (5)	0.0251 (17)
H34	0.452370	0.107556	0.336817	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0239 (5)	0.0216 (4)	0.0277 (4)	0.0124 (3)	0.0033 (3)	0.0028 (3)
O1	0.032 (4)	0.026 (3)	0.042 (4)	0.020 (3)	0.010 (3)	0.009 (3)
O2	0.028 (4)	0.037 (4)	0.158 (8)	0.020 (3)	0.021 (5)	0.029 (5)
O3	0.032 (4)	0.025 (3)	0.042 (4)	0.023 (3)	−0.004 (3)	−0.001 (3)
O4	0.030 (4)	0.030 (3)	0.028 (4)	0.017 (3)	0.004 (3)	0.007 (3)
O5	0.051 (5)	0.037 (4)	0.029 (4)	0.020 (3)	0.000 (3)	−0.004 (3)
O6	0.033 (4)	0.042 (4)	0.037 (4)	0.017 (3)	0.009 (3)	0.006 (3)
O7	0.040 (4)	0.030 (3)	0.036 (4)	0.022 (3)	0.003 (3)	0.000 (3)
O8	0.037 (4)	0.047 (4)	0.029 (4)	0.018 (3)	0.010 (3)	0.003 (3)
O9	0.031 (4)	0.029 (3)	0.028 (4)	0.019 (3)	0.000 (3)	−0.002 (3)
N1	0.018 (4)	0.022 (3)	0.029 (3)	0.010 (3)	0.007 (3)	0.000 (2)
N2	0.025 (4)	0.016 (3)	0.025 (3)	0.009 (3)	0.002 (3)	0.002 (2)
C1	0.024 (5)	0.028 (4)	0.035 (5)	0.011 (4)	0.004 (3)	0.003 (3)
C2	0.088 (10)	0.029 (5)	0.059 (7)	0.016 (6)	−0.027 (7)	0.002 (5)
C3	0.028 (5)	0.044 (5)	0.038 (5)	0.006 (4)	0.008 (4)	0.009 (4)
C4	0.034 (5)	0.021 (4)	0.029 (4)	0.007 (4)	0.009 (3)	0.000 (3)
C5	0.027 (5)	0.019 (4)	0.028 (5)	0.007 (4)	0.004 (4)	0.004 (3)
C6	0.022 (4)	0.017 (4)	0.032 (4)	0.007 (3)	0.006 (3)	0.001 (3)
C7	0.045 (7)	0.048 (6)	0.041 (6)	0.010 (5)	0.017 (5)	−0.002 (5)
C8	0.015 (4)	0.022 (4)	0.034 (4)	0.004 (3)	0.004 (3)	−0.001 (3)
C9	0.019 (4)	0.037 (4)	0.035 (5)	0.011 (4)	0.004 (3)	0.002 (4)
C10	0.027 (5)	0.028 (4)	0.029 (4)	0.008 (4)	−0.001 (3)	0.003 (3)
C11	0.031 (5)	0.026 (4)	0.034 (4)	0.009 (4)	0.000 (4)	0.004 (3)
C12	0.028 (5)	0.021 (4)	0.040 (5)	0.012 (3)	0.004 (3)	0.003 (3)
C13	0.035 (5)	0.034 (5)	0.040 (5)	0.014 (4)	0.016 (4)	0.005 (4)
C14	0.050 (6)	0.015 (4)	0.034 (5)	0.012 (4)	0.000 (4)	−0.001 (3)
C15	0.045 (6)	0.059 (7)	0.038 (6)	0.026 (6)	0.008 (5)	0.007 (5)
C16	0.020 (4)	0.019 (4)	0.035 (4)	0.008 (3)	0.004 (3)	0.002 (3)
C17	0.025 (5)	0.024 (4)	0.025 (4)	0.014 (4)	0.006 (3)	0.003 (3)
C18	0.020 (4)	0.023 (4)	0.034 (4)	0.006 (3)	0.011 (3)	0.006 (3)
C19	0.028 (5)	0.022 (4)	0.031 (4)	0.008 (3)	0.001 (3)	0.002 (3)
C20	0.015 (4)	0.015 (3)	0.034 (4)	0.003 (3)	0.005 (3)	0.003 (3)
C21	0.058 (7)	0.030 (5)	0.034 (5)	0.011 (5)	0.013 (5)	0.002 (4)
C22	0.033 (5)	0.035 (5)	0.030 (4)	0.015 (4)	0.003 (4)	0.007 (3)
C23	0.035 (5)	0.059 (6)	0.032 (5)	0.015 (5)	0.008 (4)	0.007 (4)
C24	0.034 (5)	0.017 (4)	0.029 (4)	0.006 (3)	0.003 (3)	−0.001 (3)
C25	0.089 (10)	0.023 (5)	0.042 (7)	0.003 (6)	0.013 (6)	−0.007 (4)
C26	0.025 (5)	0.044 (5)	0.036 (5)	0.012 (4)	0.014 (4)	0.008 (4)
C27	0.033 (5)	0.032 (5)	0.038 (5)	0.013 (4)	0.000 (4)	−0.006 (4)
C28	0.024 (5)	0.026 (4)	0.035 (4)	0.012 (4)	0.003 (3)	0.003 (3)
C29	0.023 (4)	0.014 (3)	0.026 (4)	0.004 (3)	0.003 (3)	0.003 (3)
C30	0.025 (5)	0.019 (4)	0.029 (5)	0.002 (4)	−0.002 (3)	0.002 (3)
C31	0.050 (6)	0.022 (4)	0.052 (6)	0.016 (4)	−0.006 (5)	0.000 (4)
C32	0.020 (4)	0.051 (5)	0.035 (5)	0.011 (4)	0.010 (3)	0.005 (4)
C33	0.107 (11)	0.026 (5)	0.036 (6)	0.004 (6)	−0.018 (7)	0.004 (4)
C34	0.020 (4)	0.026 (4)	0.034 (4)	0.013 (3)	0.002 (3)	0.004 (3)

Geometric parameters (Å, º) top

Cu1—O2	2.127 (8)	C9—H9B	0.9900
Cu1—O4	1.920 (7)	C9—C17	1.538 (12)
Cu1—O9	1.937 (7)	C9—C26	1.514 (13)
Cu1—N1	2.027 (6)	C10—C22	1.368 (13)
Cu1—N2	2.014 (7)	C10—C28	1.395 (12)
O1—C5	1.236 (13)	C11—H11	0.9500
O2—H2A	0.8723	C11—C19	1.412 (13)
O2—H2B	0.8720	C12—H12	0.9500
O3—C30	1.212 (13)	C12—C22	1.389 (13)
O4—C5	1.292 (12)	C13—H13A	0.9900
O5—C10	1.375 (11)	C13—H13B	0.9900
O5—C27	1.435 (12)	C14—C21	1.407 (16)
O6—C1	1.388 (13)	C14—C24	1.539 (12)
O6—C13	1.428 (12)	C14—C31	1.375 (15)
O7—C27	1.436 (11)	C15—H15	0.9500
O7—C28	1.371 (11)	C15—C26	1.396 (16)
O8—C4	1.379 (11)	C16—H16	0.9500
O8—C13	1.430 (13)	C16—C20	1.404 (13)
O9—C30	1.283 (12)	C17—H17	1.0000
N1—H1	1.0000	C17—C30	1.547 (12)
N1—C17	1.467 (12)	C18—H18A	0.9900
N1—C18	1.497 (10)	C18—H18B	0.9900
N2—H2	1.0000	C19—H19	0.9500
N2—C6	1.491 (10)	C19—C20	1.387 (12)
N2—C29	1.499 (9)	C20—C29	1.519 (11)
C1—C4	1.391 (12)	C21—H21	0.9500
C1—C16	1.367 (12)	C21—C25	1.420 (17)
C2—H2C	0.9500	C22—H22	0.9500
C2—C31	1.387 (16)	C23—H23	0.9500
C2—C33	1.39 (2)	C24—H24A	0.9900
C3—H3	0.9500	C24—H24B	0.9900
C3—C23	1.380 (15)	C25—H25	0.9500
C3—C32	1.390 (14)	C25—C33	1.38 (2)
C4—C11	1.365 (14)	C26—C32	1.383 (15)
C5—C6	1.531 (12)	C27—H27A	0.9900
C6—H6	1.0000	C27—H27B	0.9900
C6—C24	1.537 (11)	C28—C34	1.366 (12)
C7—H7	0.9500	C29—H29A	0.9900
C7—C15	1.379 (17)	C29—H29B	0.9900
C7—C23	1.399 (17)	C31—H31	0.9500
C8—C12	1.391 (12)	C32—H32	0.9500
C8—C18	1.534 (11)	C33—H33	0.9500
C8—C34	1.404 (12)	C34—H34	0.9500
C9—H9A	0.9900

O4—Cu1—O2	92.0 (3)	C21—C14—C24	119.7 (9)
O4—Cu1—O9	175.8 (3)	C31—C14—C21	120.5 (10)
O4—Cu1—N1	94.3 (3)	C31—C14—C24	119.7 (9)
O4—Cu1—N2	84.5 (3)	C7—C15—H15	119.7
O9—Cu1—O2	92.2 (3)	C7—C15—C26	120.6 (12)
O9—Cu1—N1	84.3 (3)	C26—C15—H15	119.7
O9—Cu1—N2	94.4 (3)	C1—C16—H16	121.8
N1—Cu1—O2	107.8 (4)	C1—C16—C20	116.3 (8)
N2—Cu1—O2	107.4 (4)	C20—C16—H16	121.8
N2—Cu1—N1	144.8 (3)	N1—C17—C9	111.2 (7)
Cu1—O2—H2A	132.7	N1—C17—H17	108.7
Cu1—O2—H2B	116.0	N1—C17—C30	110.5 (7)
H2A—O2—H2B	104.6	C9—C17—H17	108.7
C5—O4—Cu1	115.7 (6)	C9—C17—C30	108.9 (7)
C10—O5—C27	105.6 (7)	C30—C17—H17	108.7
C1—O6—C13	104.7 (7)	N1—C18—C8	111.6 (6)
C28—O7—C27	105.6 (7)	N1—C18—H18A	109.3
C4—O8—C13	104.9 (7)	N1—C18—H18B	109.3
C30—O9—Cu1	115.8 (6)	C8—C18—H18A	109.3
Cu1—N1—H1	109.9	C8—C18—H18B	109.3
C17—N1—Cu1	107.4 (5)	H18A—C18—H18B	108.0
C17—N1—H1	109.9	C11—C19—H19	119.0
C17—N1—C18	113.1 (6)	C20—C19—C11	122.1 (9)
C18—N1—Cu1	106.6 (5)	C20—C19—H19	119.0
C18—N1—H1	109.9	C16—C20—C29	119.7 (7)
Cu1—N2—H2	109.8	C19—C20—C16	120.8 (8)
C6—N2—Cu1	107.6 (5)	C19—C20—C29	119.3 (8)
C6—N2—H2	109.8	C14—C21—H21	121.3
C6—N2—C29	112.5 (6)	C14—C21—C25	117.4 (12)
C29—N2—Cu1	107.2 (5)	C25—C21—H21	121.3
C29—N2—H2	109.8	C10—C22—C12	117.2 (8)
O6—C1—C4	109.7 (8)	C10—C22—H22	121.4
C16—C1—O6	127.5 (8)	C12—C22—H22	121.4
C16—C1—C4	122.7 (9)	C3—C23—C7	119.6 (9)
C31—C2—H2C	120.5	C3—C23—H23	120.2
C31—C2—C33	119.1 (13)	C7—C23—H23	120.2
C33—C2—H2C	120.5	C6—C24—C14	110.8 (7)
C23—C3—H3	120.3	C6—C24—H24A	109.5
C23—C3—C32	119.5 (10)	C6—C24—H24B	109.5
C32—C3—H3	120.3	C14—C24—H24A	109.5
O8—C4—C1	110.0 (9)	C14—C24—H24B	109.5
C11—C4—O8	127.9 (8)	H24A—C24—H24B	108.1
C11—C4—C1	122.1 (8)	C21—C25—H25	119.4
O1—C5—O4	124.9 (9)	C33—C25—C21	121.2 (13)
O1—C5—C6	118.0 (8)	C33—C25—H25	119.4
O4—C5—C6	117.0 (8)	C15—C26—C9	121.3 (9)
N2—C6—C5	109.2 (7)	C32—C26—C9	120.2 (9)
N2—C6—H6	109.0	C32—C26—C15	118.3 (9)
N2—C6—C24	110.4 (7)	O5—C27—O7	107.2 (7)
C5—C6—H6	109.0	O5—C27—H27A	110.3
C5—C6—C24	110.3 (7)	O5—C27—H27B	110.3
C24—C6—H6	109.0	O7—C27—H27A	110.3
C15—C7—H7	119.9	O7—C27—H27B	110.3
C15—C7—C23	120.3 (11)	H27A—C27—H27B	108.5
C23—C7—H7	119.9	O7—C28—C10	109.6 (8)
C12—C8—C18	120.4 (7)	C34—C28—O7	127.5 (8)
C12—C8—C34	120.2 (8)	C34—C28—C10	122.9 (8)
C34—C8—C18	119.3 (7)	N2—C29—C20	112.5 (6)
H9A—C9—H9B	108.1	N2—C29—H29A	109.1
C17—C9—H9A	109.6	N2—C29—H29B	109.1
C17—C9—H9B	109.6	C20—C29—H29A	109.1
C26—C9—H9A	109.6	C20—C29—H29B	109.1
C26—C9—H9B	109.6	H29A—C29—H29B	107.8
C26—C9—C17	110.3 (7)	O3—C30—O9	125.0 (9)
O5—C10—C28	109.4 (8)	O3—C30—C17	118.7 (8)
C22—C10—O5	129.8 (8)	O9—C30—C17	116.3 (9)
C22—C10—C28	120.8 (8)	C2—C31—H31	119.2
C4—C11—H11	122.1	C14—C31—C2	121.6 (12)
C4—C11—C19	115.8 (8)	C14—C31—H31	119.2
C19—C11—H11	122.1	C3—C32—H32	119.2
C8—C12—H12	118.9	C26—C32—C3	121.7 (9)
C22—C12—C8	122.2 (8)	C26—C32—H32	119.2
C22—C12—H12	118.9	C2—C33—H33	119.9
O6—C13—O8	109.3 (7)	C25—C33—C2	120.2 (11)
O6—C13—H13A	109.8	C25—C33—H33	119.9
O6—C13—H13B	109.8	C8—C34—H34	121.7
O8—C13—H13A	109.8	C28—C34—C8	116.7 (7)
O8—C13—H13B	109.8	C28—C34—H34	121.7
H13A—C13—H13B	108.3

Cu1—O4—C5—O1	175.4 (7)	C12—C8—C34—C28	2.1 (11)
Cu1—O4—C5—C6	−2.1 (10)	C13—O6—C1—C4	−7.7 (9)
Cu1—O9—C30—O3	175.9 (7)	C13—O6—C1—C16	173.6 (9)
Cu1—O9—C30—C17	−2.8 (10)	C13—O8—C4—C1	6.9 (9)
Cu1—N1—C17—C9	−97.0 (7)	C13—O8—C4—C11	−172.7 (8)
Cu1—N1—C17—C30	24.0 (7)	C14—C21—C25—C33	0.6 (14)
Cu1—N1—C18—C8	176.2 (5)	C15—C7—C23—C3	0.0 (15)
Cu1—N2—C6—C5	24.6 (7)	C15—C26—C32—C3	−1.5 (14)
Cu1—N2—C6—C24	−96.8 (6)	C16—C1—C4—O8	179.3 (8)
Cu1—N2—C29—C20	175.7 (6)	C16—C1—C4—C11	−1.0 (12)
O1—C5—C6—N2	166.4 (7)	C16—C20—C29—N2	96.5 (8)
O1—C5—C6—C24	−72.1 (10)	C17—N1—C18—C8	−65.9 (8)
O4—C5—C6—N2	−16.0 (10)	C17—C9—C26—C15	−70.1 (11)
O4—C5—C6—C24	105.5 (9)	C17—C9—C26—C32	105.5 (10)
O5—C10—C22—C12	−177.8 (9)	C18—N1—C17—C9	145.6 (7)
O5—C10—C28—O7	0.1 (10)	C18—N1—C17—C30	−93.4 (8)
O5—C10—C28—C34	178.5 (8)	C18—C8—C12—C22	173.7 (8)
O6—C1—C4—O8	0.5 (9)	C18—C8—C34—C28	−173.3 (7)
O6—C1—C4—C11	−179.8 (8)	C19—C20—C29—N2	−79.1 (9)
O6—C1—C16—C20	177.5 (8)	C21—C14—C24—C6	−66.3 (10)
O7—C28—C34—C8	177.2 (8)	C21—C14—C31—C2	−0.9 (13)
O8—C4—C11—C19	−178.4 (8)	C21—C25—C33—C2	−2.5 (16)
N1—C17—C30—O3	165.9 (7)	C22—C10—C28—O7	−179.2 (8)
N1—C17—C30—O9	−15.2 (10)	C22—C10—C28—C34	−0.8 (14)
N2—C6—C24—C14	−66.8 (9)	C23—C3—C32—C26	1.1 (14)
C1—O6—C13—O8	12.1 (10)	C23—C7—C15—C26	−0.4 (15)
C1—C4—C11—C19	2.0 (11)	C24—C14—C21—C25	179.6 (8)
C1—C16—C20—C19	2.2 (11)	C24—C14—C31—C2	−179.4 (8)
C1—C16—C20—C29	−173.4 (7)	C26—C9—C17—N1	−62.7 (10)
C4—O8—C13—O6	−11.8 (10)	C26—C9—C17—C30	175.3 (8)
C4—C1—C16—C20	−1.1 (12)	C27—O5—C10—C22	−171.0 (9)
C4—C11—C19—C20	−0.9 (11)	C27—O5—C10—C28	9.8 (10)
C5—C6—C24—C14	172.4 (8)	C27—O7—C28—C10	−9.9 (10)
C6—N2—C29—C20	−66.2 (8)	C27—O7—C28—C34	171.8 (9)
C7—C15—C26—C9	176.8 (9)	C28—O7—C27—O5	15.8 (10)
C7—C15—C26—C32	1.1 (14)	C28—C10—C22—C12	1.3 (13)
C8—C12—C22—C10	0.0 (12)	C29—N2—C6—C5	−93.3 (7)
C9—C17—C30—O3	−71.6 (10)	C29—N2—C6—C24	145.3 (7)
C9—C17—C30—O9	107.2 (9)	C31—C2—C33—C25	2.6 (15)
C9—C26—C32—C3	−177.3 (8)	C31—C14—C21—C25	1.1 (12)
C10—O5—C27—O7	−15.8 (11)	C31—C14—C24—C6	112.2 (9)
C10—C28—C34—C8	−0.9 (13)	C32—C3—C23—C7	−0.3 (15)
C11—C19—C20—C16	−1.2 (12)	C33—C2—C31—C14	−0.9 (14)
C11—C19—C20—C29	174.4 (7)	C34—C8—C12—C22	−1.7 (12)
C12—C8—C18—N1	−78.7 (9)	C34—C8—C18—N1	96.7 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱ	0.87	1.89	2.738 (11)	165
O2—H2B···O3ⁱⁱ	0.87	1.92	2.736 (10)	155

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

(exp_4793_sq) top

Crystal data top

C₂₂H₃₀CuN₄O₈·H₂O	F(000) = 586
M_r = 560.05	D_x = 1.430 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 13.9687 (7) Å	Cell parameters from 3515 reflections
b = 6.8845 (3) Å	θ = 4.2–25.8°
c = 14.3443 (7) Å	µ = 0.90 mm⁻¹
β = 109.401 (5)°	T = 298 K
V = 1301.13 (11) Å³	Needle, blue
Z = 2	1 × 0.1 × 0.1 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	4538 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	3848 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.081
Detector resolution: 16.1158 pixels mm^-1	θ_max = 25.0°, θ_min = 3.8°
ω scans	h = −16→16
Absorption correction: multi-scan CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	k = −8→8
T_min = 0.643, T_max = 1.000	l = −17→17
11362 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.078	w = 1/[σ²(F_o²) + (0.1376P)² + 0.5885P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.231	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 1.77 e Å⁻³
4538 reflections	Δρ_min = −0.37 e Å⁻³
332 parameters	Absolute structure: Flack x determined using 1312 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
1 restraint	Absolute structure parameter: 0.01 (3)

Special details top

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

	x	y	z	U_iso*/U_eq
Cu1	0.71116 (9)	0.50126 (18)	0.57494 (8)	0.0489 (4)
O1	0.6335 (6)	0.2644 (11)	0.5726 (6)	0.0579 (18)
O2	0.8284 (6)	0.9549 (10)	0.4845 (6)	0.063 (2)
O3	0.7866 (6)	0.7404 (11)	0.5772 (6)	0.0566 (18)
O4	0.9020 (9)	0.7240 (18)	1.1817 (7)	0.092 (3)
O5	0.5118 (7)	0.3419 (17)	−0.0336 (6)	0.080 (3)
O6	0.4069 (7)	0.3277 (18)	0.0604 (7)	0.084 (3)
O7	0.5929 (9)	0.0481 (14)	0.6645 (7)	0.095 (4)
O8	0.8201 (9)	0.9528 (16)	1.0627 (9)	0.103 (4)
N1	0.7369 (5)	0.4937 (19)	0.7216 (5)	0.0467 (17)
H1	0.692285	0.592286	0.734588	0.056*
N2	0.6729 (6)	0.5219 (15)	0.4258 (5)	0.0441 (17)
H2	0.599693	0.546773	0.400193	0.053*
N3	0.5622 (7)	0.6939 (15)	0.5720 (8)	0.066 (3)
H3A	0.531537	0.738731	0.511182	0.079*
H3B	0.581867	0.793256	0.613740	0.079*
H3C	0.519292	0.619548	0.590090	0.079*
N4	0.8614 (7)	0.2983 (14)	0.6037 (7)	0.057 (2)
H4A	0.844081	0.188150	0.569758	0.068*
H4B	0.887932	0.271421	0.667884	0.068*
H4C	0.906953	0.361145	0.584003	0.068*
C1	0.6478 (8)	0.3432 (13)	0.2664 (7)	0.045 (2)
C2	0.6898 (9)	0.3414 (15)	0.3802 (8)	0.051 (3)
H2A	0.658306	0.235561	0.403978	0.062*
H2B	0.762161	0.315996	0.401134	0.062*
C3	0.8919 (8)	0.656 (2)	1.0877 (9)	0.062 (3)
C4	0.5697 (9)	0.3431 (15)	0.0661 (7)	0.051 (2)
C5	0.8592 (8)	0.5813 (16)	0.8931 (9)	0.055 (3)
C6	0.5411 (8)	0.3334 (16)	0.2218 (8)	0.055 (3)
H6	0.497485	0.326020	0.258503	0.066*
C7	0.6712 (9)	0.3478 (18)	0.1062 (9)	0.058 (3)
H7	0.713108	0.349369	0.067591	0.070*
C8	0.7104 (8)	0.3504 (15)	0.2095 (8)	0.051 (2)
H8	0.780317	0.357009	0.240647	0.062*
C9	0.6376 (9)	0.1957 (17)	0.6534 (8)	0.057 (3)
C10	0.7025 (9)	0.3066 (18)	0.7480 (8)	0.058 (3)
H10	0.763150	0.228085	0.779824	0.069*
C11	0.5068 (8)	0.3356 (17)	0.1205 (8)	0.055 (2)
C12	0.8446 (8)	0.7911 (18)	1.0162 (9)	0.061 (3)
C13	0.7845 (8)	0.8052 (15)	0.4952 (9)	0.053 (2)
C14	0.9048 (8)	0.4484 (18)	0.9606 (10)	0.065 (3)
H14	0.925318	0.331580	0.940643	0.078*
C15	0.8424 (8)	0.546 (2)	0.7856 (8)	0.066 (4)
H15A	0.862545	0.661922	0.758537	0.080*
H15B	0.887471	0.442045	0.780746	0.080*
C16	0.7229 (9)	0.6948 (15)	0.4000 (9)	0.052 (3)
H16	0.770817	0.648334	0.368267	0.063*
C17	0.9227 (9)	0.483 (2)	1.0627 (8)	0.069 (3)
H17	0.954128	0.390366	1.110376	0.083*
C18	0.8280 (10)	0.7591 (18)	0.9205 (10)	0.067 (3)
H18	0.796613	0.852323	0.873355	0.081*
C19	0.4068 (9)	0.3467 (19)	−0.0386 (10)	0.070 (3)
H19A	0.375464	0.468354	−0.066995	0.084*
H19B	0.369349	0.240733	−0.079043	0.084*
C20	0.6500 (14)	0.826 (2)	0.3298 (11)	0.094 (5)
H20A	0.617299	0.758309	0.269026	0.141*
H20B	0.685534	0.936895	0.316972	0.141*
H20C	0.599920	0.868494	0.357705	0.141*
C21	0.8659 (15)	0.918 (3)	1.1661 (14)	0.116 (7)
H21A	0.921768	1.007527	1.193555	0.140*
H21B	0.816487	0.939170	1.199213	0.140*
C22	0.6451 (16)	0.326 (3)	0.8212 (13)	0.114 (7)
H22A	0.690966	0.367215	0.884153	0.170*
H22B	0.616129	0.202800	0.828446	0.170*
H22C	0.591904	0.420340	0.797202	0.170*
O9	1.0255 (11)	0.525 (3)	0.5997 (15)	0.140 (6)
H9A	1.024891	0.443450	0.643878	0.209*
H9B	1.080235	0.501315	0.588130	0.209*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0586 (7)	0.0441 (6)	0.0467 (6)	−0.0118 (5)	0.0211 (5)	−0.0021 (5)
O1	0.064 (5)	0.055 (4)	0.058 (4)	−0.010 (4)	0.025 (4)	−0.007 (4)
O2	0.080 (5)	0.044 (5)	0.073 (5)	−0.017 (3)	0.034 (4)	−0.003 (3)
O3	0.067 (5)	0.049 (4)	0.053 (4)	−0.014 (3)	0.019 (4)	−0.005 (3)
O4	0.104 (8)	0.109 (9)	0.058 (5)	0.009 (7)	0.019 (5)	−0.013 (5)
O5	0.082 (6)	0.101 (7)	0.060 (5)	−0.001 (5)	0.027 (4)	−0.008 (5)
O6	0.054 (5)	0.124 (8)	0.069 (5)	0.001 (5)	0.016 (4)	−0.013 (6)
O7	0.153 (9)	0.074 (8)	0.080 (6)	−0.062 (7)	0.067 (6)	−0.020 (5)
O8	0.096 (7)	0.092 (9)	0.100 (7)	0.023 (6)	0.006 (6)	−0.035 (6)
N1	0.039 (4)	0.059 (5)	0.043 (4)	−0.001 (5)	0.014 (3)	0.002 (5)
N2	0.051 (4)	0.035 (4)	0.048 (4)	0.001 (4)	0.019 (3)	−0.002 (4)
N3	0.056 (6)	0.052 (5)	0.076 (6)	0.007 (4)	0.005 (5)	−0.003 (5)
N4	0.062 (6)	0.048 (5)	0.060 (5)	−0.001 (4)	0.020 (4)	−0.009 (4)
C1	0.058 (6)	0.032 (5)	0.046 (5)	0.003 (4)	0.017 (4)	−0.009 (4)
C2	0.062 (6)	0.031 (5)	0.058 (6)	0.001 (4)	0.016 (5)	−0.004 (5)
C3	0.047 (6)	0.076 (8)	0.061 (7)	−0.005 (5)	0.017 (5)	−0.013 (6)
C4	0.071 (7)	0.038 (5)	0.046 (5)	0.002 (5)	0.022 (5)	−0.004 (4)
C5	0.039 (5)	0.060 (6)	0.060 (6)	−0.010 (4)	0.008 (5)	0.000 (5)
C6	0.061 (6)	0.049 (6)	0.067 (7)	0.002 (5)	0.039 (5)	0.001 (5)
C7	0.064 (7)	0.061 (6)	0.061 (6)	0.002 (5)	0.037 (5)	−0.010 (5)
C8	0.043 (5)	0.047 (6)	0.066 (7)	0.002 (4)	0.020 (5)	−0.011 (5)
C9	0.077 (7)	0.055 (6)	0.049 (6)	−0.013 (5)	0.036 (5)	−0.004 (5)
C10	0.062 (6)	0.064 (7)	0.052 (6)	−0.007 (5)	0.027 (5)	0.004 (5)
C11	0.051 (6)	0.052 (6)	0.065 (7)	0.004 (5)	0.021 (5)	−0.008 (5)
C12	0.050 (6)	0.056 (6)	0.066 (7)	−0.002 (5)	0.004 (5)	−0.006 (5)
C13	0.059 (6)	0.038 (6)	0.067 (7)	0.001 (5)	0.029 (5)	−0.003 (5)
C14	0.051 (6)	0.063 (8)	0.078 (8)	0.008 (5)	0.018 (5)	0.002 (6)
C15	0.049 (6)	0.099 (11)	0.055 (6)	−0.019 (6)	0.023 (5)	−0.002 (6)
C16	0.069 (7)	0.035 (5)	0.062 (6)	−0.011 (5)	0.033 (5)	−0.004 (5)
C17	0.060 (6)	0.076 (8)	0.057 (6)	0.015 (7)	0.001 (5)	0.010 (7)
C18	0.073 (8)	0.053 (7)	0.070 (8)	0.000 (6)	0.017 (6)	0.007 (6)
C19	0.063 (7)	0.057 (7)	0.082 (9)	0.002 (5)	0.014 (6)	−0.010 (6)
C20	0.146 (14)	0.055 (8)	0.061 (8)	−0.011 (8)	0.007 (8)	0.012 (6)
C21	0.092 (12)	0.139 (17)	0.109 (14)	0.012 (10)	0.020 (10)	−0.060 (12)
C22	0.151 (15)	0.134 (15)	0.094 (11)	−0.069 (13)	0.092 (11)	−0.042 (11)
O9	0.112 (9)	0.117 (11)	0.227 (18)	−0.008 (9)	0.106 (11)	−0.004 (13)

Geometric parameters (Å, º) top

Cu1—O1	1.953 (8)	C3—C17	1.36 (2)
Cu1—O3	1.949 (7)	C4—C7	1.342 (16)
Cu1—N1	2.014 (7)	C4—C11	1.357 (15)
Cu1—N2	2.030 (7)	C5—C14	1.330 (16)
Cu1—N3	2.456 (10)	C5—C15	1.502 (16)
Cu1—N4	2.440 (9)	C5—C18	1.399 (18)
O1—C9	1.236 (13)	C6—H6	0.9300
O2—C13	1.234 (13)	C6—C11	1.371 (16)
O3—C13	1.250 (13)	C7—H7	0.9300
O4—C3	1.388 (15)	C7—C8	1.399 (16)
O4—C21	1.42 (2)	C8—H8	0.9300
O5—C4	1.389 (14)	C9—C10	1.558 (17)
O5—C19	1.445 (15)	C10—H10	0.9800
O6—C11	1.376 (14)	C10—C22	1.525 (15)
O6—C19	1.426 (16)	C12—C18	1.332 (18)
O7—C9	1.231 (14)	C13—C16	1.549 (16)
O8—C12	1.397 (16)	C14—H14	0.9300
O8—C21	1.43 (2)	C14—C17	1.422 (17)
N1—H1	0.9800	C15—H15A	0.9700
N1—C10	1.467 (17)	C15—H15B	0.9700
N1—C15	1.498 (13)	C16—H16	0.9800
N2—H2	0.9800	C16—C20	1.480 (19)
N2—C2	1.460 (14)	C17—H17	0.9300
N2—C16	1.488 (15)	C18—H18	0.9300
N3—H3A	0.8900	C19—H19A	0.9700
N3—H3B	0.8900	C19—H19B	0.9700
N3—H3C	0.8900	C20—H20A	0.9600
N4—H4A	0.8900	C20—H20B	0.9600
N4—H4B	0.8900	C20—H20C	0.9600
N4—H4C	0.8900	C21—H21A	0.9700
C1—C2	1.540 (14)	C21—H21B	0.9700
C1—C6	1.414 (15)	C22—H22A	0.9600
C1—C8	1.382 (14)	C22—H22B	0.9600
C2—H2A	0.9700	C22—H22C	0.9600
C2—H2B	0.9700	O9—H9A	0.8502
C3—C12	1.377 (18)	O9—H9B	0.8502

O1—Cu1—N1	84.4 (4)	C8—C7—H7	121.9
O1—Cu1—N2	95.1 (4)	C1—C8—C7	121.5 (10)
O1—Cu1—N3	89.3 (4)	C1—C8—H8	119.2
O1—Cu1—N4	88.1 (3)	C7—C8—H8	119.2
O3—Cu1—O1	179.0 (4)	O1—C9—C10	117.5 (10)
O3—Cu1—N1	95.5 (4)	O7—C9—O1	124.7 (12)
O3—Cu1—N2	84.9 (4)	O7—C9—C10	117.8 (10)
O3—Cu1—N3	89.7 (3)	N1—C10—C9	110.6 (9)
O3—Cu1—N4	92.9 (4)	N1—C10—H10	107.4
N1—Cu1—N2	174.6 (4)	N1—C10—C22	113.1 (12)
N1—Cu1—N3	83.6 (4)	C9—C10—H10	107.4
N1—Cu1—N4	87.9 (4)	C22—C10—C9	110.8 (11)
N2—Cu1—N3	91.1 (3)	C22—C10—H10	107.4
N2—Cu1—N4	97.4 (3)	C4—C11—O6	110.9 (10)
N4—Cu1—N3	171.3 (4)	C4—C11—C6	123.0 (10)
C9—O1—Cu1	116.8 (8)	C6—C11—O6	126.0 (10)
C13—O3—Cu1	116.2 (7)	C3—C12—O8	108.3 (11)
C3—O4—C21	104.2 (12)	C18—C12—O8	129.5 (12)
C4—O5—C19	106.6 (9)	C18—C12—C3	122.2 (12)
C11—O6—C19	106.6 (9)	O2—C13—O3	123.9 (11)
C12—O8—C21	105.4 (12)	O2—C13—C16	117.0 (10)
Cu1—N1—H1	106.0	O3—C13—C16	119.1 (10)
C10—N1—Cu1	109.4 (8)	C5—C14—H14	119.6
C10—N1—H1	106.0	C5—C14—C17	120.8 (12)
C10—N1—C15	113.1 (9)	C17—C14—H14	119.6
C15—N1—Cu1	115.6 (6)	N1—C15—C5	117.0 (8)
C15—N1—H1	106.0	N1—C15—H15A	108.0
Cu1—N2—H2	106.5	N1—C15—H15B	108.0
C2—N2—Cu1	112.8 (7)	C5—C15—H15A	108.0
C2—N2—H2	106.5	C5—C15—H15B	108.0
C2—N2—C16	114.2 (7)	H15A—C15—H15B	107.3
C16—N2—Cu1	109.7 (7)	N2—C16—C13	110.1 (9)
C16—N2—H2	106.5	N2—C16—H16	107.7
Cu1—N3—H3A	109.5	C13—C16—H16	107.7
Cu1—N3—H3B	109.5	C20—C16—N2	112.6 (10)
Cu1—N3—H3C	109.5	C20—C16—C13	110.8 (10)
H3A—N3—H3B	109.5	C20—C16—H16	107.7
H3A—N3—H3C	109.5	C3—C17—C14	117.1 (12)
H3B—N3—H3C	109.5	C3—C17—H17	121.4
Cu1—N4—H4A	109.5	C14—C17—H17	121.4
Cu1—N4—H4B	109.5	C5—C18—H18	121.0
Cu1—N4—H4C	109.5	C12—C18—C5	118.0 (11)
H4A—N4—H4B	109.5	C12—C18—H18	121.0
H4A—N4—H4C	109.5	O5—C19—H19A	110.4
H4B—N4—H4C	109.5	O5—C19—H19B	110.4
C6—C1—C2	116.9 (9)	O6—C19—O5	106.5 (10)
C8—C1—C2	122.2 (9)	O6—C19—H19A	110.4
C8—C1—C6	120.9 (9)	O6—C19—H19B	110.4
N2—C2—C1	114.0 (8)	H19A—C19—H19B	108.6
N2—C2—H2A	108.7	C16—C20—H20A	109.5
N2—C2—H2B	108.7	C16—C20—H20B	109.5
C1—C2—H2A	108.7	C16—C20—H20C	109.5
C1—C2—H2B	108.7	H20A—C20—H20B	109.5
H2A—C2—H2B	107.6	H20A—C20—H20C	109.5
C12—C3—O4	111.5 (12)	H20B—C20—H20C	109.5
C17—C3—O4	127.8 (12)	O4—C21—O8	109.6 (12)
C17—C3—C12	120.8 (11)	O4—C21—H21A	109.8
C7—C4—O5	127.8 (10)	O4—C21—H21B	109.8
C7—C4—C11	123.2 (10)	O8—C21—H21A	109.8
C11—C4—O5	108.9 (10)	O8—C21—H21B	109.8
C14—C5—C15	120.6 (12)	H21A—C21—H21B	108.2
C14—C5—C18	121.1 (11)	C10—C22—H22A	109.5
C18—C5—C15	118.3 (11)	C10—C22—H22B	109.5
C1—C6—H6	122.4	C10—C22—H22C	109.5
C11—C6—C1	115.1 (9)	H22A—C22—H22B	109.5
C11—C6—H6	122.4	H22A—C22—H22C	109.5
C4—C7—H7	121.9	H22B—C22—H22C	109.5
C4—C7—C8	116.2 (9)	H9A—O9—H9B	104.5

Cu1—O1—C9—O7	179.7 (11)	C4—O5—C19—O6	−6.6 (13)
Cu1—O1—C9—C10	1.0 (14)	C4—C7—C8—C1	1.6 (16)
Cu1—O3—C13—O2	180.0 (8)	C5—C14—C17—C3	−0.5 (18)
Cu1—O3—C13—C16	0.5 (13)	C6—C1—C2—N2	−72.6 (12)
Cu1—N1—C10—C9	−12.1 (11)	C6—C1—C8—C7	−0.1 (16)
Cu1—N1—C10—C22	−137.0 (11)	C7—C4—C11—O6	−178.6 (11)
Cu1—N1—C15—C5	167.9 (9)	C7—C4—C11—C6	0.4 (18)
Cu1—N2—C2—C1	171.9 (7)	C8—C1—C2—N2	108.6 (11)
Cu1—N2—C16—C13	−1.9 (10)	C8—C1—C6—C11	−1.2 (14)
Cu1—N2—C16—C20	−126.1 (10)	C10—N1—C15—C5	−64.9 (15)
O1—C9—C10—N1	7.9 (15)	C11—O6—C19—O5	6.9 (13)
O1—C9—C10—C22	134.1 (14)	C11—C4—C7—C8	−1.8 (17)
O2—C13—C16—N2	−178.5 (9)	C12—O8—C21—O4	−10.0 (19)
O2—C13—C16—C20	−53.3 (15)	C12—C3—C17—C14	0.6 (18)
O3—C13—C16—N2	1.0 (14)	C14—C5—C15—N1	104.0 (14)
O3—C13—C16—C20	126.2 (12)	C14—C5—C18—C12	−0.6 (17)
O4—C3—C12—O8	−1.2 (14)	C15—N1—C10—C9	−142.4 (10)
O4—C3—C12—C18	179.0 (11)	C15—N1—C10—C22	92.7 (14)
O4—C3—C17—C14	−179.1 (11)	C15—C5—C14—C17	178.8 (10)
O5—C4—C7—C8	179.2 (10)	C15—C5—C18—C12	−178.9 (10)
O5—C4—C11—O6	0.5 (14)	C16—N2—C2—C1	−62.0 (12)
O5—C4—C11—C6	179.6 (10)	C17—C3—C12—O8	179.0 (11)
O7—C9—C10—N1	−170.9 (11)	C17—C3—C12—C18	−0.8 (19)
O7—C9—C10—C22	−44.7 (18)	C18—C5—C14—C17	0.5 (17)
O8—C12—C18—C5	−179.0 (12)	C18—C5—C15—N1	−77.6 (15)
C1—C6—C11—O6	−180.0 (11)	C19—O5—C4—C7	−177.0 (11)
C1—C6—C11—C4	1.1 (16)	C19—O5—C4—C11	3.9 (13)
C2—N2—C16—C13	−129.7 (9)	C19—O6—C11—C4	−4.7 (14)
C2—N2—C16—C20	106.1 (12)	C19—O6—C11—C6	176.3 (11)
C2—C1—C6—C11	179.9 (9)	C21—O4—C3—C12	−4.9 (15)
C2—C1—C8—C7	178.7 (9)	C21—O4—C3—C17	174.8 (15)
C3—O4—C21—O8	9.2 (18)	C21—O8—C12—C3	6.8 (16)
C3—C12—C18—C5	0.7 (18)	C21—O8—C12—C18	−173.4 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O1ⁱ	0.89	2.22	2.871 (13)	129
N3—H3B···O7ⁱⁱ	0.89	1.89	2.740 (14)	160
N4—H4A···O2ⁱⁱⁱ	0.89	1.99	2.864 (12)	169
N4—H4C···O9	0.89	1.95	2.791 (18)	156
O9—H9B···O2^iv	0.85	1.92	2.737 (14)	160

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

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