Synthesis, structure and in vitro biological properties of a new copper(II) com­plex with 4-{[3-(pyri­din-2-yl)-1H-pyrazol-1-yl]meth­yl}benzoic acid

The new copper(II) com­plex di­chlorido­bis­(4-{[3-(pyri­din-2-yl-κN)-1H-pyrazol-1-yl-κN²]meth­yl}benzoic acid)copper(II) methanol sesquisolvate hemihydrate, [CuCl₂L₂]·1.5CH₃OH·0.5H₂O, (1), has been synthesized from CuCl₂·2H₂O and the ligand 4-{[3-(pyri­din-2-yl)-1H-pyrazol-1-yl]meth­yl}benzoic acid (L, C₁₅H₁₁N₃O₂). The com­plex was characterized by elemental analysis, Fourier transform IR spectroscopy, electrospray ionization mass spectrometry and single-crystal X-ray diffraction. Two chloride ligands and two bidentate L ligands coordinate the Cu^II centre in 1 in a Jahn–Teller-distorted octa­hedral geometry of rather unusual configuration: a chloride substituent and a pyrazole N atom of an N,N′-chelating ligand occupy the more distant axial positions. Classical O—H...O hydrogen bonds and O—H...Cl inter­actions link neighbouring com­plex mol­ecules and cocrystallized methanol molecules into chains that propagate parallel to the b direction. The title com­pound shows intriguing bioactivity: the effects of 1 on the enzymatic activity of protein tyrosine phosphatase 1B (PTP1B) and on the viability of human breast cancer cells of cell line MCF7 were evaluated. Complex 1, with an IC₅₀ value of 0.51 µM, can efficiently inhibit PTP1B activity. An enzyme kinetic assay suggests that 1 inhibits PTP1B in a non­com­petitive manner. A fluorescence titration assay indicates that 1 has a strong affinity for PTP1B, with a binding constant of 4.39 × 10⁶ M⁻¹. Complex 1 may also effectively decrease the viability of MCF7 cells in an extent com­parable to that of cisplatin (IC₅₀ = 6.3 µM). The new copper com­plex therefore represents a promising PTP1B inhibitor and an efficient anti­proliferation reagent against MCF7 cells.

Computing details

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015b).

Dichloridobis(4-{[3-(pyridin-2-yl-κN)-1H-pyrazol-1-yl-κN²]methyl}benzoic acid)copper(II) methanol sesquisolvate hemihydrate

Crystal data

[CuCl2(C15H11N3O2)2]·1.5CH4O·0.5H2O	Z = 2
Mr = 722.05	F(000) = 742
Triclinic, P1	Dx = 1.490 Mg m^−3
a = 8.4226 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.4978 (8) Å	Cell parameters from 6208 reflections
c = 15.2060 (8) Å	θ = 3.0–27.6°
α = 74.260 (2)°	µ = 0.90 mm^−1
β = 82.358 (2)°	T = 297 K
γ = 75.781 (2)°	Block, green
V = 1608.84 (16) Å^3	0.28 × 0.26 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer	5359 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.039
φ and ω scans	θmax = 28.2°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.678, Tmax = 0.746	k = −17→17
17964 measured reflections	l = −20→18
7757 independent reflections

Refinement

Refinement on F^2	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.048	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.039P)^2 + 1.P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.005
7757 reflections	Δρmax = 0.47 e Å^−3
447 parameters	Δρmin = −0.38 e Å^−3
7 restraints

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.37742 (4)	−0.01188 (3)	0.26715 (2)	0.03278 (11)
Cl1	0.27265 (9)	−0.15825 (6)	0.39997 (5)	0.04631 (19)
Cl2	0.15234 (9)	0.06521 (7)	0.17762 (5)	0.0470 (2)
O1	0.9310 (4)	−0.4878 (3)	0.1717 (3)	0.1239 (15)
O2	1.1126 (5)	−0.3983 (3)	0.0933 (3)	0.1181 (13)
H2A	1.135 (8)	−0.441 (4)	0.058 (4)	0.177*
O3	0.2450 (5)	0.5122 (3)	0.3271 (2)	0.0966 (10)
H3A	0.223 (7)	0.546 (4)	0.368 (3)	0.145*
O4	0.4949 (4)	0.5360 (3)	0.3315 (2)	0.1038 (11)
N1	0.3018 (3)	0.08863 (17)	0.34925 (15)	0.0336 (5)
N2	0.5944 (3)	−0.03577 (17)	0.33778 (14)	0.0318 (5)
N3	0.7564 (3)	−0.07953 (18)	0.33099 (15)	0.0342 (5)
N4	0.4683 (3)	−0.10692 (18)	0.18145 (14)	0.0340 (5)
N5	0.5556 (3)	0.08162 (19)	0.15063 (15)	0.0392 (6)
N6	0.6388 (3)	0.1590 (2)	0.13135 (17)	0.0457 (6)
C1	0.1467 (4)	0.1408 (2)	0.3614 (2)	0.0445 (7)
H1	0.065102	0.128298	0.332885	0.053*
C2	0.1037 (4)	0.2123 (3)	0.4148 (2)	0.0527 (8)
H2	−0.005362	0.246569	0.422720	0.063*
C3	0.2236 (4)	0.2325 (2)	0.4562 (2)	0.0508 (8)
H3	0.197138	0.282065	0.491002	0.061*
C4	0.3836 (4)	0.1785 (2)	0.44532 (19)	0.0410 (7)
H4	0.466643	0.190872	0.472800	0.049*
C5	0.4186 (3)	0.1056 (2)	0.39296 (17)	0.0324 (6)
C6	0.5818 (3)	0.0409 (2)	0.37963 (17)	0.0320 (6)
C7	0.7357 (3)	0.0453 (2)	0.40164 (19)	0.0401 (7)
H7	0.758914	0.091049	0.431652	0.048*
C8	0.8440 (4)	−0.0322 (2)	0.3695 (2)	0.0420 (7)
H8	0.957167	−0.049505	0.373299	0.050*
C9	0.8187 (3)	−0.1667 (2)	0.29030 (18)	0.0349 (6)
C10	0.7388 (3)	−0.2486 (2)	0.30945 (19)	0.0385 (6)
H10	0.646072	−0.248948	0.350125	0.046*
C11	0.7991 (4)	−0.3300 (2)	0.2672 (2)	0.0441 (7)
H11	0.747723	−0.386483	0.279874	0.053*
C12	0.9369 (4)	−0.3278 (3)	0.2054 (2)	0.0493 (8)
C13	1.0157 (4)	−0.2455 (3)	0.1891 (2)	0.0508 (8)
H13	1.109086	−0.244951	0.148888	0.061*
C14	0.9582 (3)	−0.1645 (3)	0.2313 (2)	0.0440 (7)
H14	1.011918	−0.109305	0.220413	0.053*
C15	0.9943 (5)	−0.4111 (4)	0.1548 (3)	0.0735 (12)
C16	0.4143 (4)	−0.1947 (2)	0.1910 (2)	0.0412 (7)
H16	0.336933	−0.211973	0.238808	0.049*
C17	0.4682 (4)	−0.2608 (3)	0.1330 (2)	0.0470 (8)
H17	0.428295	−0.321450	0.141965	0.056*
C18	0.5818 (4)	−0.2355 (3)	0.0618 (2)	0.0497 (8)
H18	0.620160	−0.278959	0.021947	0.060*
C19	0.6379 (4)	−0.1453 (2)	0.0503 (2)	0.0447 (7)
H19	0.714336	−0.126814	0.002300	0.054*
C20	0.5798 (3)	−0.0821 (2)	0.11092 (18)	0.0346 (6)
C21	0.6357 (3)	0.0149 (2)	0.10151 (18)	0.0373 (6)
C22	0.7688 (4)	0.0514 (3)	0.0481 (2)	0.0516 (8)
H22	0.841641	0.019594	0.007019	0.062*
C23	0.7685 (4)	0.1427 (3)	0.0689 (2)	0.0569 (9)
H23	0.842477	0.185986	0.045284	0.068*
C24	0.5821 (4)	0.2446 (2)	0.1738 (2)	0.0500 (8)
C25	0.6923 (5)	0.2891 (3)	0.2012 (2)	0.0652 (10)
H25	0.804794	0.264624	0.191136	0.078*
C26	0.6319 (6)	0.3711 (3)	0.2440 (3)	0.0723 (11)
H26	0.704617	0.402935	0.261512	0.087*
C27	0.4642 (6)	0.4058 (3)	0.2608 (2)	0.0625 (10)
C28	0.3567 (5)	0.3601 (3)	0.2330 (2)	0.0579 (9)
H28	0.244223	0.383853	0.243797	0.069*
C29	0.4141 (5)	0.2795 (2)	0.1894 (2)	0.0525 (8)
H29	0.341022	0.248906	0.170705	0.063*
C30	0.4062 (7)	0.4911 (3)	0.3100 (3)	0.0738 (12)
O5	0.1491 (4)	0.6324 (2)	0.4403 (2)	0.0838 (9)
H5	0.180 (6)	0.692 (2)	0.427 (3)	0.126*
C31	0.2226 (9)	0.5699 (4)	0.5213 (3)	0.147 (3)
H31A	0.323769	0.524833	0.505728	0.221*
H31B	0.149613	0.527499	0.557641	0.221*
H31C	0.244281	0.614774	0.555446	0.221*
O6	0.7403 (10)	−0.4787 (5)	0.0072 (4)	0.107 (2)	0.5
H6	0.778 (8)	−0.474 (8)	0.055 (5)	0.161*	0.5
C32	0.5670 (11)	−0.4887 (8)	0.0141 (7)	0.097 (3)	0.5
H32A	0.528949	−0.508411	0.077481	0.145*	0.5
H32B	0.560145	−0.541880	−0.015413	0.145*	0.5
H32C	0.499824	−0.422433	−0.015192	0.145*	0.5
O7	0.0478 (8)	0.3356 (6)	0.0974 (7)	0.161 (4)	0.5
H7A	0.033837	0.375984	0.130687	0.241*	0.5
H7B	0.111077	0.350994	0.052477	0.241*	0.5

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02966 (18)	0.0412 (2)	0.03133 (18)	−0.00584 (14)	0.00008 (13)	−0.01833 (14)
Cl1	0.0455 (4)	0.0564 (5)	0.0451 (4)	−0.0183 (4)	0.0042 (3)	−0.0232 (4)
Cl2	0.0368 (4)	0.0663 (5)	0.0414 (4)	−0.0102 (4)	−0.0039 (3)	−0.0197 (4)
O1	0.100 (2)	0.128 (3)	0.196 (4)	−0.059 (2)	0.047 (2)	−0.125 (3)
O2	0.108 (3)	0.129 (3)	0.142 (3)	−0.034 (2)	0.053 (2)	−0.097 (3)
O3	0.113 (3)	0.078 (2)	0.111 (3)	−0.013 (2)	−0.003 (2)	−0.0551 (19)
O4	0.133 (3)	0.094 (2)	0.113 (3)	−0.060 (2)	0.024 (2)	−0.059 (2)
N1	0.0326 (12)	0.0383 (13)	0.0305 (12)	−0.0078 (10)	0.0032 (10)	−0.0120 (10)
N2	0.0312 (11)	0.0373 (13)	0.0296 (12)	−0.0087 (10)	0.0008 (9)	−0.0130 (10)
N3	0.0307 (11)	0.0416 (13)	0.0340 (12)	−0.0111 (10)	−0.0001 (10)	−0.0139 (10)
N4	0.0317 (12)	0.0432 (14)	0.0294 (12)	−0.0059 (11)	−0.0018 (9)	−0.0151 (10)
N5	0.0432 (14)	0.0439 (14)	0.0321 (13)	−0.0142 (12)	0.0002 (11)	−0.0092 (11)
N6	0.0511 (15)	0.0479 (15)	0.0407 (14)	−0.0168 (13)	−0.0007 (12)	−0.0112 (12)
C1	0.0400 (16)	0.0507 (19)	0.0437 (17)	−0.0056 (15)	0.0028 (13)	−0.0199 (14)
C2	0.0462 (18)	0.056 (2)	0.051 (2)	0.0057 (16)	0.0042 (15)	−0.0240 (16)
C3	0.068 (2)	0.0417 (18)	0.0412 (18)	−0.0016 (17)	0.0036 (16)	−0.0212 (14)
C4	0.0581 (19)	0.0377 (16)	0.0324 (15)	−0.0134 (15)	−0.0017 (14)	−0.0153 (12)
C5	0.0402 (15)	0.0329 (14)	0.0244 (13)	−0.0117 (12)	0.0033 (11)	−0.0071 (11)
C6	0.0385 (15)	0.0363 (15)	0.0241 (13)	−0.0142 (12)	0.0001 (11)	−0.0080 (11)
C7	0.0428 (16)	0.0458 (17)	0.0398 (16)	−0.0159 (14)	−0.0050 (13)	−0.0176 (13)
C8	0.0352 (15)	0.0512 (18)	0.0457 (17)	−0.0154 (14)	−0.0051 (13)	−0.0159 (14)
C9	0.0312 (14)	0.0407 (16)	0.0335 (15)	−0.0034 (12)	−0.0045 (11)	−0.0134 (12)
C10	0.0340 (15)	0.0450 (17)	0.0375 (16)	−0.0095 (13)	−0.0006 (12)	−0.0123 (13)
C11	0.0415 (16)	0.0421 (17)	0.0526 (19)	−0.0100 (14)	−0.0104 (14)	−0.0144 (14)
C12	0.0377 (16)	0.058 (2)	0.059 (2)	−0.0030 (15)	−0.0043 (15)	−0.0324 (17)
C13	0.0313 (15)	0.072 (2)	0.058 (2)	−0.0121 (16)	0.0070 (14)	−0.0342 (17)
C14	0.0342 (15)	0.0562 (19)	0.0485 (18)	−0.0142 (14)	0.0031 (13)	−0.0232 (15)
C15	0.059 (2)	0.086 (3)	0.092 (3)	−0.020 (2)	0.010 (2)	−0.054 (3)
C16	0.0393 (16)	0.0501 (18)	0.0392 (16)	−0.0108 (14)	−0.0004 (13)	−0.0195 (14)
C17	0.0541 (19)	0.0474 (18)	0.0472 (18)	−0.0103 (15)	−0.0086 (15)	−0.0230 (15)
C18	0.0537 (19)	0.056 (2)	0.0418 (18)	0.0021 (16)	−0.0053 (15)	−0.0281 (15)
C19	0.0421 (16)	0.057 (2)	0.0326 (15)	−0.0021 (15)	0.0024 (13)	−0.0168 (14)
C20	0.0300 (13)	0.0434 (16)	0.0283 (14)	−0.0002 (12)	−0.0058 (11)	−0.0107 (12)
C21	0.0337 (14)	0.0473 (17)	0.0279 (14)	−0.0043 (13)	−0.0024 (12)	−0.0086 (12)
C22	0.0396 (17)	0.065 (2)	0.0503 (19)	−0.0130 (16)	0.0105 (15)	−0.0190 (16)
C23	0.050 (2)	0.071 (2)	0.053 (2)	−0.0281 (18)	0.0099 (16)	−0.0147 (18)
C24	0.070 (2)	0.0432 (18)	0.0380 (17)	−0.0212 (17)	0.0000 (16)	−0.0055 (14)
C25	0.074 (3)	0.066 (2)	0.064 (2)	−0.031 (2)	0.000 (2)	−0.0193 (19)
C26	0.104 (3)	0.065 (3)	0.065 (2)	−0.045 (2)	−0.003 (2)	−0.023 (2)
C27	0.098 (3)	0.046 (2)	0.047 (2)	−0.028 (2)	0.005 (2)	−0.0094 (16)
C28	0.078 (2)	0.0443 (19)	0.048 (2)	−0.0170 (18)	0.0026 (18)	−0.0075 (15)
C29	0.071 (2)	0.0443 (19)	0.0442 (18)	−0.0192 (17)	−0.0010 (17)	−0.0092 (15)
C30	0.111 (4)	0.051 (2)	0.063 (3)	−0.032 (3)	0.006 (2)	−0.0138 (19)
O5	0.105 (2)	0.0609 (18)	0.087 (2)	−0.0198 (17)	0.0028 (18)	−0.0243 (17)
C31	0.223 (7)	0.094 (4)	0.079 (4)	0.045 (4)	−0.016 (4)	−0.014 (3)
O6	0.174 (7)	0.084 (4)	0.073 (4)	−0.018 (5)	0.000 (4)	−0.046 (4)
C32	0.124 (10)	0.084 (7)	0.072 (6)	−0.023 (7)	0.006 (7)	−0.006 (5)
O7	0.088 (5)	0.120 (6)	0.313 (13)	−0.027 (5)	0.021 (6)	−0.131 (8)

Geometric parameters (Å, º)

Cu1—N1	2.022 (2)	C11—H11	0.9300
Cu1—N4	2.022 (2)	C12—C13	1.380 (4)
Cu1—N2	2.155 (2)	C12—C15	1.482 (5)
Cu1—Cl2	2.3407 (8)	C13—C14	1.371 (4)
Cu1—N5	2.448 (2)	C13—H13	0.9300
Cu1—Cl1	2.6418 (9)	C14—H14	0.9300
O1—C15	1.229 (5)	C16—C17	1.377 (4)
O2—C15	1.282 (5)	C16—H16	0.9300
O2—H2A	0.861 (19)	C17—C18	1.375 (4)
O3—C30	1.322 (5)	C17—H17	0.9300
O3—H3A	0.844 (19)	C18—C19	1.371 (4)
O4—C30	1.195 (5)	C18—H18	0.9300
N1—C1	1.339 (3)	C19—C20	1.385 (4)
N1—C5	1.353 (3)	C19—H19	0.9300
N2—C6	1.332 (3)	C20—C21	1.462 (4)
N2—N3	1.350 (3)	C21—C22	1.404 (4)
N3—C8	1.358 (3)	C22—C23	1.352 (5)
N3—C9	1.431 (3)	C22—H22	0.9300
N4—C16	1.336 (4)	C23—H23	0.9300
N4—C20	1.355 (3)	C24—C25	1.381 (5)
N5—C21	1.325 (3)	C24—C29	1.387 (5)
N5—N6	1.344 (3)	C25—C26	1.391 (5)
N6—C23	1.365 (4)	C25—H25	0.9300
N6—C24	1.424 (4)	C26—C27	1.387 (6)
C1—C2	1.377 (4)	C26—H26	0.9300
C1—H1	0.9300	C27—C28	1.376 (5)
C2—C3	1.374 (5)	C27—C30	1.489 (5)
C2—H2	0.9300	C28—C29	1.381 (4)
C3—C4	1.378 (4)	C28—H28	0.9300
C3—H3	0.9300	C29—H29	0.9300
C4—C5	1.382 (3)	O5—C31	1.412 (5)
C4—H4	0.9300	O5—H5	0.871 (19)
C5—C6	1.457 (4)	C31—H31A	0.9600
C6—C7	1.399 (4)	C31—H31B	0.9600
C7—C8	1.361 (4)	C31—H31C	0.9600
C7—H7	0.9300	O6—C32	1.487 (8)
C8—H8	0.9300	O6—H6	0.85 (2)
C9—C10	1.378 (4)	C32—H32A	0.9600
C9—C14	1.382 (4)	C32—H32B	0.9600
C10—C11	1.379 (4)	C32—H32C	0.9600
C10—H10	0.9300	O7—H7A	0.8193
C11—C12	1.394 (4)	O7—H7B	0.8208
N1—Cu1—N4	175.47 (9)	C11—C12—C15	120.0 (3)
N1—Cu1—N2	78.11 (8)	C14—C13—C12	120.9 (3)
N4—Cu1—N2	99.13 (8)	C14—C13—H13	119.5
N1—Cu1—Cl2	92.71 (7)	C12—C13—H13	119.5
N4—Cu1—Cl2	89.06 (6)	C13—C14—C9	118.5 (3)
N2—Cu1—Cl2	163.07 (6)	C13—C14—H14	120.8
N1—Cu1—N5	101.40 (8)	C9—C14—H14	120.8
N4—Cu1—N5	74.38 (9)	O1—C15—O2	122.7 (4)
N2—Cu1—N5	77.00 (8)	O1—C15—C12	121.1 (4)
Cl2—Cu1—N5	91.15 (6)	O2—C15—C12	116.2 (4)
N1—Cu1—Cl1	88.13 (6)	N4—C16—C17	122.9 (3)
N4—Cu1—Cl1	95.50 (7)	N4—C16—H16	118.5
N2—Cu1—Cl1	90.11 (6)	C17—C16—H16	118.5
Cl2—Cu1—Cl1	103.92 (3)	C18—C17—C16	118.9 (3)
N5—Cu1—Cl1	161.84 (6)	C18—C17—H17	120.6
C15—O2—H2A	116 (4)	C16—C17—H17	120.6
C30—O3—H3A	108 (4)	C19—C18—C17	119.2 (3)
C1—N1—C5	118.3 (2)	C19—C18—H18	120.4
C1—N1—Cu1	124.86 (19)	C17—C18—H18	120.4
C5—N1—Cu1	116.85 (17)	C18—C19—C20	119.4 (3)
C6—N2—N3	105.3 (2)	C18—C19—H19	120.3
C6—N2—Cu1	110.71 (17)	C20—C19—H19	120.3
N3—N2—Cu1	139.38 (16)	N4—C20—C19	121.6 (3)
N2—N3—C8	111.1 (2)	N4—C20—C21	116.9 (2)
N2—N3—C9	121.8 (2)	C19—C20—C21	121.5 (3)
C8—N3—C9	127.1 (2)	N5—C21—C22	111.0 (3)
C16—N4—C20	118.0 (2)	N5—C21—C20	118.7 (2)
C16—N4—Cu1	120.38 (18)	C22—C21—C20	130.3 (3)
C20—N4—Cu1	121.59 (19)	C23—C22—C21	105.4 (3)
C21—N5—N6	105.2 (2)	C23—C22—H22	127.3
C21—N5—Cu1	106.93 (18)	C21—C22—H22	127.3
N6—N5—Cu1	144.08 (18)	C22—C23—N6	106.9 (3)
N5—N6—C23	111.5 (3)	C22—C23—H23	126.6
N5—N6—C24	119.0 (2)	N6—C23—H23	126.6
C23—N6—C24	129.4 (3)	C25—C24—C29	121.1 (3)
N1—C1—C2	122.3 (3)	C25—C24—N6	120.5 (3)
N1—C1—H1	118.9	C29—C24—N6	118.3 (3)
C2—C1—H1	118.9	C24—C25—C26	118.8 (4)
C3—C2—C1	119.4 (3)	C24—C25—H25	120.6
C3—C2—H2	120.3	C26—C25—H25	120.6
C1—C2—H2	120.3	C27—C26—C25	120.5 (4)
C2—C3—C4	119.1 (3)	C27—C26—H26	119.7
C2—C3—H3	120.4	C25—C26—H26	119.7
C4—C3—H3	120.4	C28—C27—C26	119.7 (3)
C3—C4—C5	118.9 (3)	C28—C27—C30	121.9 (4)
C3—C4—H4	120.5	C26—C27—C30	118.4 (4)
C5—C4—H4	120.5	C27—C28—C29	120.7 (4)
N1—C5—C4	122.0 (3)	C27—C28—H28	119.7
N1—C5—C6	114.2 (2)	C29—C28—H28	119.7
C4—C5—C6	123.8 (3)	C28—C29—C24	119.2 (3)
N2—C6—C7	111.2 (2)	C28—C29—H29	120.4
N2—C6—C5	117.4 (2)	C24—C29—H29	120.4
C7—C6—C5	131.4 (3)	O4—C30—O3	123.5 (4)
C8—C7—C6	105.0 (2)	O4—C30—C27	124.0 (5)
C8—C7—H7	127.5	O3—C30—C27	112.6 (4)
C6—C7—H7	127.5	C31—O5—H5	107 (4)
N3—C8—C7	107.5 (3)	O5—C31—H31A	109.5
N3—C8—H8	126.3	O5—C31—H31B	109.5
C7—C8—H8	126.3	H31A—C31—H31B	109.5
C10—C9—C14	122.1 (3)	O5—C31—H31C	109.5
C10—C9—N3	120.1 (2)	H31A—C31—H31C	109.5
C14—C9—N3	117.8 (2)	H31B—C31—H31C	109.5
C9—C10—C11	118.8 (3)	C32—O6—H6	118 (6)
C9—C10—H10	120.6	O6—C32—H32A	109.5
C11—C10—H10	120.6	O6—C32—H32B	109.5
C10—C11—C12	120.0 (3)	H32A—C32—H32B	109.5
C10—C11—H11	120.0	O6—C32—H32C	109.5
C12—C11—H11	120.0	H32A—C32—H32C	109.5
C13—C12—C11	119.7 (3)	H32B—C32—H32C	109.5
C13—C12—C15	120.2 (3)	H7A—O7—H7B	112.3
C6—N2—N3—C8	1.1 (3)	C13—C12—C15—O1	176.3 (4)
Cu1—N2—N3—C8	152.9 (2)	C11—C12—C15—O1	−6.2 (6)
C6—N2—N3—C9	179.2 (2)	C13—C12—C15—O2	−3.6 (6)
Cu1—N2—N3—C9	−29.0 (4)	C11—C12—C15—O2	173.9 (4)
C21—N5—N6—C23	1.3 (3)	C20—N4—C16—C17	0.6 (4)
Cu1—N5—N6—C23	154.2 (3)	Cu1—N4—C16—C17	178.1 (2)
C21—N5—N6—C24	179.7 (3)	N4—C16—C17—C18	−0.4 (5)
Cu1—N5—N6—C24	−27.4 (5)	C16—C17—C18—C19	−0.2 (5)
C5—N1—C1—C2	1.6 (4)	C17—C18—C19—C20	0.4 (5)
Cu1—N1—C1—C2	−176.7 (2)	C16—N4—C20—C19	−0.4 (4)
N1—C1—C2—C3	1.0 (5)	Cu1—N4—C20—C19	−177.8 (2)
C1—C2—C3—C4	−1.8 (5)	C16—N4—C20—C21	179.4 (2)
C2—C3—C4—C5	0.1 (5)	Cu1—N4—C20—C21	2.0 (3)
C1—N1—C5—C4	−3.4 (4)	C18—C19—C20—N4	−0.1 (4)
Cu1—N1—C5—C4	175.1 (2)	C18—C19—C20—C21	−179.9 (3)
C1—N1—C5—C6	176.7 (2)	N6—N5—C21—C22	−1.8 (3)
Cu1—N1—C5—C6	−4.9 (3)	Cu1—N5—C21—C22	−165.6 (2)
C3—C4—C5—N1	2.6 (4)	N6—N5—C21—C20	177.0 (2)
C3—C4—C5—C6	−177.5 (3)	Cu1—N5—C21—C20	13.2 (3)
N3—N2—C6—C7	−1.3 (3)	N4—C20—C21—N5	−11.7 (4)
Cu1—N2—C6—C7	−162.05 (18)	C19—C20—C21—N5	168.1 (3)
N3—N2—C6—C5	177.5 (2)	N4—C20—C21—C22	166.8 (3)
Cu1—N2—C6—C5	16.7 (3)	C19—C20—C21—C22	−13.4 (5)
N1—C5—C6—N2	−8.8 (3)	N5—C21—C22—C23	1.6 (4)
C4—C5—C6—N2	171.3 (2)	C20—C21—C22—C23	−177.0 (3)
N1—C5—C6—C7	169.7 (3)	C21—C22—C23—N6	−0.7 (4)
C4—C5—C6—C7	−10.3 (5)	N5—N6—C23—C22	−0.4 (4)
N2—C6—C7—C8	1.0 (3)	C24—N6—C23—C22	−178.5 (3)
C5—C6—C7—C8	−177.6 (3)	N5—N6—C24—C25	142.7 (3)
N2—N3—C8—C7	−0.5 (3)	C23—N6—C24—C25	−39.3 (5)
C9—N3—C8—C7	−178.5 (3)	N5—N6—C24—C29	−35.3 (4)
C6—C7—C8—N3	−0.2 (3)	C23—N6—C24—C29	142.7 (3)
N2—N3—C9—C10	−42.3 (4)	C29—C24—C25—C26	−0.8 (5)
C8—N3—C9—C10	135.5 (3)	N6—C24—C25—C26	−178.7 (3)
N2—N3—C9—C14	136.9 (3)	C24—C25—C26—C27	1.5 (6)
C8—N3—C9—C14	−45.3 (4)	C25—C26—C27—C28	−1.4 (6)
C14—C9—C10—C11	−1.0 (4)	C25—C26—C27—C30	177.7 (3)
N3—C9—C10—C11	178.2 (3)	C26—C27—C28—C29	0.6 (5)
C9—C10—C11—C12	−0.9 (4)	C30—C27—C28—C29	−178.5 (3)
C10—C11—C12—C13	2.1 (5)	C27—C28—C29—C24	0.1 (5)
C10—C11—C12—C15	−175.4 (3)	C25—C24—C29—C28	0.1 (5)
C11—C12—C13—C14	−1.4 (5)	N6—C24—C29—C28	178.0 (3)
C15—C12—C13—C14	176.1 (3)	C28—C27—C30—O4	−176.4 (4)
C12—C13—C14—C9	−0.4 (5)	C26—C27—C30—O4	4.5 (6)
C10—C9—C14—C13	1.6 (4)	C28—C27—C30—O3	3.3 (5)
N3—C9—C14—C13	−177.6 (3)	C26—C27—C30—O3	−175.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O6^i	0.86 (2)	1.74 (3)	2.548 (6)	156 (6)
O3—H3A···O5	0.84 (2)	1.76 (2)	2.598 (4)	169 (6)
O5—H5···Cl1^ii	0.87 (2)	2.26 (2)	3.126 (3)	176 (5)
O6—H6···O1	0.85 (2)	2.27 (3)	3.107 (8)	166 (5)
O7—H7A···O1^iii	0.82	2.05	2.819 (7)	155
O7—H7B···O6^iv	0.82	2.30	2.953 (11)	137

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