Crystal structure and Hirshfeld analysis of trans-bis­(5-fluoro­indoline-2,3-dione 3-oximato-κ2O2,N3)-trans-bis­(pyridine-κN)copper(II)

Melo, A.P.L. de; Bresolin, L.; Martins, B.B.; Gervini, V.C.; Oliveira, A.B. de

doi:10.1107/S2056989018003365

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 74| Part 4| April 2018| Pages 428-432

https://doi.org/10.1107/S2056989018003365

Open

access

Crystal structure and Hirshfeld analysis of trans-bis(5-fluoroindoline-2,3-dione 3-oximato-κ²O²,N³)-trans-bis(pyridine-κN)copper(II)

Ana Paula Lopes de Melo,^a Leandro Bresolin,^a ^* Bianca Barreto Martins,^a Vanessa Carratu Gervini ^a and Adriano Bof de Oliveira ^b

^aEscola de Química e Alimentos, Universidade Federal do Rio Grande, Av. Itália km 08, Campus Carreiros, 96203-900 Rio Grande-RS, Brazil, and ^bDepartamento de Química, Universidade Federal de Sergipe, Av. Marechal Rondon s/n, 49100-000 São Cristóvão-SE, Brazil
^*Correspondence e-mail: leandro_bresolin@yahoo.com.br

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 10 February 2018; accepted 27 February 2018; online 2 March 2018)

The reaction in methanol of Cu^II acetate monohydrate with 5-fluoroisatin 3-oxime deprotonated with KOH in a 1:2 molar ratio and recrystallization from pyridine yielded the title compound, [Cu(C₈H₄FN₂O₂)₂(C₅H₅N)₂]. In the centrosymmetric complex, the anionic form of the isatin oxime acts as a κ²N,O donor, building five-membered metallarings. The Cu^II cation is sixfold coordinated in a slightly distorted octahedral environment by two trans, equatorial, anionic isatin derivatives and two trans pyridine ligands in axial positions. The complexes are linked by hydrogen bonding into a three-dimensional network, which is also stabilized by π–π stacking interactions [centroid-to-centroid distance = 3.7352 (9) Å] and C—H⋯π contacts. The Hirshfeld surface analysis indicates that the major contributions for the crystal packing are H⋯H (31.80%), H⋯C (24.30%), H⋯O (15.20%) and H⋯F (10.80%). This work is the second report in the literature of a crystal structure of a coordination compound with isatin 3-oxime ligands (coordination chemistry).

Keywords: crystal structure; 5-fluoroisatin 3-oxime copper complex; Hirshfeld surface analysis.

CCDC reference: 1826012

1. Chemical context

By the first half of the 19th century, the first reports on the chemistry of the isatin fragment were published independently in Germany and France (Erdmann, 1841a ,b ; Laurent, 1841 ). One very nice review concerning the organic synthesis of the isatin derivatives was published 74 years ago (Sumpter, 1944 ) and the topic remains up-to-date. From the early years, the chemistry of isatin-based molecules emerged from the synthetic approach to a large class of organic compounds with applications in biochemistry and pharmacology. For two recent examples, see: 1-[(2-methylbenzimidazol-1-yl) methyl]-2-oxo-indolin-3-ylidene]amino]thiourea, a derivative with in silico and in vitro inhibition of Chikungunya virus replication (Mishra et al., 2016 ) and 5-chloroisatin-4-methylthiosemicarbazone, another derivative which appears as an intermediate in the synthesis of an HIV-1 RT inhibitor (Meleddu et al., 2017 ). The abbreviation HIV-1 RT stands for human immunodeficiency virus type 1 reverse transcriptase. Along the same line of research of the present work, the crystal structure, the Hirshfeld surface analysis and the lock-and-key supramolecular analysis through in silico evaluation with the vascular endothelial growth factor receptor-2 (VEGFR-2) of the isatin derivative ligand of the title complex were recently carried out. The (3Z)-5-fluoro-3-(hydroxyimino)-indolin-2-one molecule showed a structure–activity relationship with the selected biological target through hydrogen bonding (Martins et al., 2017 ). Although the chemistry of isatins is already well reported in several scientific disciplines, crystal structures of complexes with isatin 3-oxime derivatives are surprisingly few in number. Thus, the crystal structure determination of isatin-based molecules has become our major research interest and herein, the synthesis, crystal structure and Hirshfeld surface analysis of a 5-fluoroisatin 3-oxime complex with copper(II) is reported.

2. Structural commentary

The asymmetric unit of the title coordination compound consists of one Cu^II cation, which lies on an inversion center, and two ligands in general positions, the anionic form of 5-fluoroisatin 3-oxime and one pyridine molecule. The Cu^II atoms are sixfold coordinated in a slightly distorted octahedral environment by two five-membered chelate 5-fluoroisatin-3-oximate ligands, acting as κ²N,O-donors in equatorial positions, and by two pyridine ligands in axial positions (Fig. 1). The isatin 3-oxime derivative is nearly planar with an r.m.s. deviation from the mean plane of the non–H atoms of 0.0145 Å and a maximum deviation of 0.0344 (9) Å for the N2 atom. The dihedral angle between the pyridine ring and the mean plane through the indoline ring system is 73.82 (3)°. For the five-membered ring, the r.m.s. from the mean plane through the Cu1/C1/C2/N2/O1 fragment is 0.074 Å and the maximum deviation from that plane is 0.0945 (7) Å for the N2 atom. The N2—Cu1—N3 and O1—Cu1—N3 angles are 88.75 (4) and 89.01 (4)°, respectively. Four intramolecular C—H⋯O hydrogen bonds are observed for the title compound, forming rings with S(5) graph-set motif. As an interesting feature of the structure, a hydrogen-bonded macrocyclic coordination environment can be assumed based on the S(5) rings (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N3/C9–C13 ring

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H5⋯O1ⁱ	0.95	2.54	3.1424 (18)	121
C12—H8⋯F1ⁱⁱ	0.95	2.49	3.287 (2)	142
C13—H9⋯O1	0.95	2.54	3.1077 (19)	119
N1—H4⋯O2ⁱⁱⁱ	0.88	2.00	2.7529 (14)	143
C6—H2⋯Cg1^iv	0.95	2.79	3.7076 (17)	162
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) x, y-1, z; (iv) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 40% probability level. [Symmetry code: (i) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1.]

Figure 2
The intramolecular C—H⋯O hydrogen interactions of the title compound (dashed lines) forming a ring of S(5) graph-set motif.

3. Supramolecular features and Hirshfeld analysis

In the crystal, the molecules of the centrosymmetric title compound are connected into a three-dimensional hydrogen-bonded network (Table 1). The complexes are linked by centrosymmetric pairs of C—H⋯F interactions into dimers with graph-set motif R₂²(22). The dimers are the subunits of the periodic arrangement along the [110] direction (Fig. 3). The molecular units are also connected by C—H⋯O interactions into a one-dimensional hydrogen-bonded polymer along the [001] direction (Fig. 4) and finally, the complexes are linked by N—H⋯O interactions into centrosymmetric dimers with graph-set motif R₂²(14). Like the dimers of the first structural element, with C—H⋯F interactions connecting the molecules, the latter element is also based on dimers as subunits of the polymeric motif, connected through N—H⋯O interactions but in this case along the [010] direction (Fig. 5). In addition, π–π stacking interactions [centroid-to-centroid distance: 3.7352 (9) Å] and C—H⋯π contacts (Table 1) stabilize the crystal structure.

Figure 3
Partial crystal packing of the title compound, viewed down the c axis, showing the C—H⋯F interactions (dashed lines) forming rings of R₂²(22) graph-set motif connecting the molecules into a chain along the [110] direction.

Figure 4
Partial crystal packing of the title compound, viewed down the a axis, showing the C—H⋯O interactions (dashed lines) organized in a C(8) graph-set motif along the [001] direction.

Figure 5
Partial crystal packing of the title compound, viewed along the c axis, showing the C—H⋯O interactions (dashed lines) forming rings of R₂²(14) graph-set motif connecting the molecules into a chain along the [010] direction.

The Hirshfeld surface analysis (Hirshfeld, 1977 ) of the crystal structure suggests that the contributions of the H⋯H, H⋯C and H⋯O intermolecular interactions to the crystal packing amount to 31.80, 24.30 and 15.20%, respectively. Other important intermolecular contacts for the cohesion of the structure are (values given in %): H⋯F = 10.80, C⋯C = 6.20, and H⋯N = 4.30. The contributions to the crystal cohesion are shown as two-dimensional Hirshfeld surface fingerprint plots with cyan dots (Wolff et al., 2012 ). The d_e (y axis) and d_i (x axis) values are the closest external and internal distances (values in Å) from given points on the Hirshfeld surface contacts (Fig. 6). The graphical representation of the Hirshfeld surface for the title compound with transparency and labelled atoms (Fig. 7) indicates, in magenta, the locations of the strongest intermolecular contacts, e.g. the H4, H7, H8, O2 and F1 atoms.

Figure 6
Hirshfeld surface two-dimensional fingerprint plot for the title compound showing (a) H⋯H, (b) H⋯C, (c) O⋯H and (d) H⋯F, (e) C⋯C and (f) H⋯N contacts in detail (cyan dots). The contribution of the interactions to the crystal packing amounts to 31.80, 24.30, 15.20, 10.80, 06.20 and 04.30%, respectively. The d_e (y axis) and d_i (x axis) values are the closest external and internal distances (values in Å) from given points on the Hirshfeld surface contacts.

Figure 7
Graphical representation of the Hirshfeld surface (d_norm) for the title compound. The surface is drawn with transparency and simplified for clarity. The surface regions with strongest intermolecular interactions are drawn in magenta and the respective atoms are labelled. [Symmetry code: (i) −x + $[{3\over 2}]$ , −y + $[{3\over 2}]$ , −z + 1.]

4. Database survey

A search of SciFinder (SciFinder, 2018 ) revealed a single report in the literature about the crystal structure of coordination compounds with isatin 3-oxime derivatives, i.e. the one-dimensional coordination polymer, catena-poly[[[aquasodium]-di-μ-aqua-[aquasodium]-bis(μ-2-oxoindoline-2,3-dione 3-oximato)] tetrakis(oxoindoline-2,3-dione 3-oxime)] (Barreto Martins et al., 2011 ). For that complex, the Na cations shows an octahedral coordination environment builded by the anionic form of the isatin 3-oxime and water molecules (Fig. 8).

Figure 8
Partial view of the structure of catena-poly[[[aquasodium]-di-μ-aqua-[aquasodium]-bis(μ-2-oxoindoline-2,3-dione 3-oximato)] tetrakis(oxoindoline-2,3-dione 3-oxime)].

5. Synthesis and crystallization

All the starting materials were commercially available and were used without further purification. The synthesis of the ligand followed the procedure reported previously (Martins et al., 2017). 5-Fluoroisatin 3-oxime was dissolved in methanol (4 mmol, 50 mL) and deprotonated with one pellet of KOH with stirring maintained for 60 min. Simultaneously, a green solution of copper acetate monohydrate in methanol (2 mmol, 50 mL) was prepared under continuous stirring. A dark-coloured mixture of both solutions was maintained with stirring at room temperature for 8 h. A crude dark-red material was obtained by evaporation of the solvent. Purple crystals of the complex, suitable for X-ray analysis, were obtained by recrystallization of the solid from a pyridine/methanol (1:10 v/v) solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Hydrogen atoms were located in a difference-Fourier map, but were positioned with idealized geometry and refined isotropically using a riding model, with U_iso(H) = 1.2U_eq(C, N), and with C—H = 0.95 and N—H = 0.88 Å.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₈H₄FN₂O₂)₂(C₅H₅N)₂]
M_r	580.00
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	200
a, b, c (Å)	19.9709 (14), 7.2155 (5), 17.1989 (12)
β (°)	98.579 (2)
V (Å³)	2450.6 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.95
Crystal size (mm)	0.40 × 0.24 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.674, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	18806, 4481, 3966
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 1.12
No. of reflections	4481
No. of parameters	178
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.34
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), WinGX (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ), CrystalExplorer (Wolff et al., 2012), publCIF (Westrip, 2010 ) and enCIFer (Allen et al., 2004 ).

Supporting information

CCDC reference: 1826012

Crystal structure: contains datablocks I, publication_text. DOI: https://doi.org/10.1107/S2056989018003365/rz5228sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018003365/rz5228Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: WinGX (Farrugia, 2012), DIAMOND (Brandenburg, 2006) and CrystalExplorer (Wolff et al., 2012); software used to prepare material for publication: publCIF (Westrip, 2010) and enCIFer (Allen et al., 2004).

trans-Bis(5-fluoroindoline-2,3-dione 3-oximato-κ²O²,N³)-trans-bis(pyridine-κN)copper(II) top

Crystal data top

[Cu(C₈H₄FN₂O₂)₂(C₅H₅N)₂]	F(000) = 1180
M_r = 580.00	D_x = 1.572 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.9709 (14) Å	Cell parameters from 9537 reflections
b = 7.2155 (5) Å	θ = 2.4–32.7°
c = 17.1989 (12) Å	µ = 0.95 mm⁻¹
β = 98.579 (2)°	T = 200 K
V = 2450.6 (3) Å³	Prismatic, purple
Z = 4	0.40 × 0.24 × 0.20 mm

Data collection top

Bruker APEXII CCD diffractometer	3966 reflections with I > 2σ(I)
Radiation source: fine-focus sealed X-ray tube, Bruker APEX2 CCD	R_int = 0.017
φ and ω scans	θ_max = 32.7°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −30→30
T_min = 0.674, T_max = 0.746	k = −10→7
18806 measured reflections	l = −26→26
4481 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.035P)² + 2.817P] where P = (F_o² + 2F_c²)/3
4481 reflections	(Δ/σ)_max < 0.001
178 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

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
C1	0.66193 (6)	0.43044 (17)	0.51144 (7)	0.0202 (2)
C2	0.62981 (6)	0.59529 (16)	0.54136 (7)	0.0179 (2)
C3	0.57200 (6)	0.53285 (17)	0.57616 (7)	0.0190 (2)
C4	0.52421 (7)	0.6220 (2)	0.61397 (8)	0.0252 (2)
H1	0.524139	0.752687	0.620565	0.030*
C5	0.47665 (7)	0.5092 (2)	0.64150 (10)	0.0308 (3)
C6	0.47458 (7)	0.3189 (2)	0.63286 (10)	0.0330 (3)
H2	0.440637	0.248844	0.652851	0.040*
C7	0.52236 (8)	0.2300 (2)	0.59479 (10)	0.0292 (3)
H3	0.521610	0.099354	0.587721	0.035*
C8	0.57102 (6)	0.33887 (17)	0.56761 (8)	0.0213 (2)
C9	0.79324 (7)	0.8070 (2)	0.66905 (8)	0.0271 (3)
H5	0.778142	0.929489	0.656022	0.033*
C10	0.81834 (9)	0.7655 (3)	0.74669 (9)	0.0361 (3)
H6	0.820299	0.858192	0.786181	0.043*
C11	0.84039 (8)	0.5880 (3)	0.76578 (9)	0.0374 (4)
H7	0.857425	0.556392	0.818653	0.045*
C12	0.83737 (9)	0.4571 (3)	0.70703 (10)	0.0359 (3)
H8	0.852688	0.334216	0.718775	0.043*
C13	0.81167 (8)	0.5072 (2)	0.63051 (9)	0.0285 (3)
H9	0.809607	0.416673	0.590100	0.034*
Cu1	0.750000	0.750000	0.500000	0.01704 (6)
F1	0.42924 (6)	0.59199 (17)	0.67886 (8)	0.0505 (3)
N1	0.62487 (6)	0.28139 (15)	0.52904 (8)	0.0242 (2)
H4	0.633443	0.165583	0.517849	0.029*
N2	0.65751 (5)	0.75711 (14)	0.53373 (6)	0.01704 (17)
N3	0.78961 (5)	0.67952 (17)	0.61181 (6)	0.0208 (2)
O1	0.71204 (5)	0.42959 (14)	0.47722 (6)	0.02501 (19)
O2	0.62959 (5)	0.90531 (12)	0.55624 (6)	0.02333 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0261 (5)	0.0133 (5)	0.0219 (5)	0.0016 (4)	0.0052 (4)	0.0011 (4)
C2	0.0209 (5)	0.0130 (5)	0.0204 (5)	0.0011 (4)	0.0051 (4)	0.0007 (4)
C3	0.0205 (5)	0.0150 (5)	0.0215 (5)	−0.0005 (4)	0.0041 (4)	0.0022 (4)
C4	0.0254 (6)	0.0219 (6)	0.0299 (6)	0.0018 (5)	0.0092 (5)	0.0011 (5)
C5	0.0246 (6)	0.0335 (8)	0.0367 (7)	0.0022 (5)	0.0131 (5)	0.0036 (6)
C6	0.0254 (6)	0.0329 (8)	0.0420 (8)	−0.0059 (6)	0.0098 (6)	0.0092 (7)
C7	0.0292 (6)	0.0201 (6)	0.0386 (7)	−0.0053 (5)	0.0057 (5)	0.0062 (5)
C8	0.0237 (5)	0.0145 (5)	0.0255 (5)	−0.0007 (4)	0.0036 (4)	0.0033 (4)
C9	0.0295 (6)	0.0297 (7)	0.0220 (6)	0.0023 (5)	0.0034 (5)	−0.0005 (5)
C10	0.0398 (8)	0.0476 (10)	0.0199 (6)	−0.0019 (7)	0.0009 (5)	−0.0030 (6)
C11	0.0345 (7)	0.0532 (11)	0.0230 (6)	−0.0028 (7)	−0.0006 (5)	0.0120 (6)
C12	0.0375 (8)	0.0367 (8)	0.0327 (7)	0.0066 (7)	0.0026 (6)	0.0141 (6)
C13	0.0322 (6)	0.0278 (7)	0.0262 (6)	0.0071 (5)	0.0069 (5)	0.0045 (5)
Cu1	0.01925 (10)	0.01681 (10)	0.01575 (9)	0.00118 (7)	0.00488 (6)	0.00176 (7)
F1	0.0404 (5)	0.0492 (7)	0.0705 (8)	0.0048 (5)	0.0367 (5)	0.0016 (6)
N1	0.0325 (6)	0.0093 (4)	0.0326 (6)	0.0007 (4)	0.0108 (5)	0.0011 (4)
N2	0.0204 (4)	0.0131 (4)	0.0179 (4)	0.0018 (3)	0.0040 (3)	0.0000 (3)
N3	0.0203 (4)	0.0249 (5)	0.0182 (4)	0.0027 (4)	0.0064 (3)	0.0029 (4)
O1	0.0308 (5)	0.0182 (4)	0.0284 (5)	0.0044 (4)	0.0123 (4)	0.0013 (4)
O2	0.0297 (4)	0.0122 (4)	0.0301 (5)	0.0025 (3)	0.0113 (4)	−0.0021 (3)

Geometric parameters (Å, º) top

C1—O1	1.2342 (15)	C9—N3	1.3412 (19)
C1—N1	1.3649 (16)	C9—C10	1.387 (2)
C1—C2	1.4798 (17)	C9—H5	0.9500
C2—N2	1.3070 (15)	C10—C11	1.378 (3)
C2—C3	1.4493 (16)	C10—H6	0.9500
C3—C4	1.3901 (18)	C11—C12	1.378 (3)
C3—C8	1.4072 (17)	C11—H7	0.9500
C4—C5	1.386 (2)	C12—C13	1.387 (2)
C4—H1	0.9500	C12—H8	0.9500
C5—F1	1.3591 (17)	C13—N3	1.3423 (19)
C5—C6	1.382 (2)	C13—H9	0.9500
C6—C7	1.392 (2)	Cu1—N2	2.0176 (10)
C6—H2	0.9500	Cu1—N3	2.0319 (11)
C7—C8	1.3841 (18)	N1—H4	0.8800
C7—H3	0.9500	N2—O2	1.2917 (13)
C8—N1	1.4077 (17)

O1—C1—N1	127.37 (12)	N3—C9—H5	119.0
O1—C1—C2	126.46 (12)	C10—C9—H5	119.0
N1—C1—C2	106.18 (11)	C11—C10—C9	119.13 (15)
N2—C2—C3	133.98 (11)	C11—C10—H6	120.4
N2—C2—C1	118.12 (10)	C9—C10—H6	120.4
C3—C2—C1	107.89 (10)	C10—C11—C12	119.00 (14)
C4—C3—C8	120.61 (12)	C10—C11—H7	120.5
C4—C3—C2	133.96 (12)	C12—C11—H7	120.5
C8—C3—C2	105.40 (11)	C11—C12—C13	119.13 (15)
C5—C4—C3	116.20 (13)	C11—C12—H8	120.4
C5—C4—H1	121.9	C13—C12—H8	120.4
C3—C4—H1	121.9	N3—C13—C12	122.02 (15)
F1—C5—C6	118.42 (13)	N3—C13—H9	119.0
F1—C5—C4	117.69 (14)	C12—C13—H9	119.0
C6—C5—C4	123.89 (14)	N2—Cu1—N3	88.75 (4)
C5—C6—C7	119.82 (13)	O1—Cu1—N3	89.01 (4)
C5—C6—H2	120.1	C1—N1—C8	110.49 (10)
C7—C6—H2	120.1	C1—N1—H4	124.8
C8—C7—C6	117.53 (13)	C8—N1—H4	124.8
C8—C7—H3	121.2	O2—N2—C2	120.09 (10)
C6—C7—H3	121.2	O2—N2—Cu1	124.18 (8)
C7—C8—C3	121.93 (13)	C2—N2—Cu1	115.18 (8)
C7—C8—N1	128.03 (12)	C9—N3—C13	118.66 (12)
C3—C8—N1	110.04 (11)	C9—N3—Cu1	119.59 (10)
N3—C9—C10	122.06 (15)	C13—N3—Cu1	121.74 (10)

O1—C1—C2—N2	−2.32 (19)	C4—C3—C8—N1	−178.83 (12)
N1—C1—C2—N2	177.94 (12)	C2—C3—C8—N1	−0.40 (14)
O1—C1—C2—C3	179.09 (13)	N3—C9—C10—C11	0.1 (2)
N1—C1—C2—C3	−0.65 (14)	C9—C10—C11—C12	0.5 (3)
N2—C2—C3—C4	0.5 (3)	C10—C11—C12—C13	−0.6 (3)
C1—C2—C3—C4	178.76 (14)	C11—C12—C13—N3	0.0 (2)
N2—C2—C3—C8	−177.63 (14)	O1—C1—N1—C8	−179.33 (13)
C1—C2—C3—C8	0.63 (13)	C2—C1—N1—C8	0.41 (14)
C8—C3—C4—C5	−0.3 (2)	C7—C8—N1—C1	179.97 (14)
C2—C3—C4—C5	−178.20 (14)	C3—C8—N1—C1	−0.01 (16)
C3—C4—C5—F1	179.91 (13)	C3—C2—N2—O2	−4.6 (2)
C3—C4—C5—C6	−0.4 (2)	C1—C2—N2—O2	177.27 (11)
F1—C5—C6—C7	179.92 (15)	C3—C2—N2—Cu1	167.30 (11)
C4—C5—C6—C7	0.2 (3)	C1—C2—N2—Cu1	−10.83 (14)
C5—C6—C7—C8	0.6 (2)	C10—C9—N3—C13	−0.7 (2)
C6—C7—C8—C3	−1.3 (2)	C10—C9—N3—Cu1	178.48 (12)
C6—C7—C8—N1	178.68 (14)	C12—C13—N3—C9	0.6 (2)
C4—C3—C8—C7	1.2 (2)	C12—C13—N3—Cu1	−178.54 (12)
C2—C3—C8—C7	179.62 (13)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N3/C9–C13 ring

D—H···A	D—H	H···A	D···A	D—H···A
C9—H5···O1ⁱ	0.95	2.54	3.1424 (18)	121
C12—H8···F1ⁱⁱ	0.95	2.49	3.287 (2)	142
C13—H9···O1	0.95	2.54	3.1077 (19)	119
N1—H4···O2ⁱⁱⁱ	0.88	2.00	2.7529 (14)	143
C6—H2···Cg1^iv	0.95	2.79	3.7076 (17)	162

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

Acknowledgements

ABO is a former DAAD scholarship holder and alumnus of the University of Bonn, Germany, and thanks both of the institutions for long-term support, in particular Professor Johannes Beck and Dr Jörg Daniels.

Funding information

APLM thanks the CAPES foundation for a scholarship.

References

Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Barreto Martins, B., Bresolin, L., Santana Carratu, V., Boneberger Behm, M. & Bof de Oliveira, A. (2011). Acta Cryst. E67, m790–m791. Web of Science CSD CrossRef IUCr Journals Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2014). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Erdmann, O. L. (1841a). Ann. Chim. Phys. 3, 355–371. Google Scholar
Erdmann, O. L. (1841b). J. Prakt. Chem. 22, 257–299. CrossRef Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Hirshfeld, H. L. (1977). Theor. Chim. Acta, 44, 129–138. CrossRef CAS Web of Science Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Laurent, A. (1841). Ann. Chim. Phys. 3, 371–383. Google Scholar
Martins, B. B., Bresolin, L., Farias, R. L. de, Oliveira, A. B. de & Gervini, V. C. (2017). Acta Cryst. E73, 987–992. Web of Science CSD CrossRef IUCr Journals Google Scholar
Meleddu, R., Distinto, S., Corona, A., Tramontano, E., Bianco, G., Melis, C., Cottiglia, F. & Maccioni, E. (2017). J. Enzyme Inhib. Med. Chem. 32, 130–136. Web of Science CrossRef CAS PubMed Google Scholar
Mishra, P., Kumar, A., Mamidi, P., Kumar, S., Basantray, I., Saswat, T., Das, I., Nayak, T. K., Chattopadhyay, S., Subudhi, B. B. & Chattopadhyay, S. (2016). Sci. Rep. 6, 20122. Web of Science CrossRef PubMed Google Scholar
SciFinder (2018). Chemical Abstracts Service: Columbus, OH, 2010; RN 58-08-2 (accessed Feb 08, 2018). Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sumpter, W. C. (1944). Chem. Rev. 34, 393–434. CrossRef CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). CRYSTAL EXPLORER. University of Western Australia, Perth, Australia. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.