Crystal structure of bromido-fac-tricarbon­yl[5-(3,4,5-tri­meth­oxy­phen­yl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ2N2,N3]rhenium(I) methanol monosolvate

Kharlova, M.I.; Piletska, K.O.; Domasevitch, K.V.; Shtemenko, A.V.

doi:10.1107/S2056989017003371

research communications

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ISSN: 2056-9890

Volume 73| Part 4| April 2017| Pages 484-487

https://doi.org/10.1107/S2056989017003371

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Crystal structure of bromido-fac-tricarbonyl[5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N²,N³]rhenium(I) methanol monosolvate

Marharyta I. Kharlova,^a ^* Kseniia O. Piletska,^a Kostiantyn V. Domasevitch ^b and Alexander V. Shtemenko ^a

^aDepartment of Inorganic Chemistry, Ukrainian State University of Chemical Technology, Gagarin Ave. 8, Dnipro 49005, Ukraine, and ^bInorganic Chemistry Department, National Taras Shevchenko University of Kyiv, Volodymyrska Street 64/13, Kyiv 01601, Ukraine
^*Correspondence e-mail: kharlovamargarita@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 21 February 2017; accepted 28 February 2017; online 10 March 2017)

In the title compound, [ReBr(C₁₆H₁₆N₄O₃)(CO)₃]·CH₃OH, the Re^I atom adopts a distorted octahedral coordination sphere with a facial arrangement of the three carbonyl ligands. Two N atoms of the chelating 5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole ligand and two carbonyl ligands define the equatorial plane of the complex, with the third carbonyl ligand and the bromide ligand in axial positions. Conventional hydrogen bonds including the methanol solvent molecules assemble the complex molecules through mutual N—H⋯O—H⋯Br links [N⋯O = 2.703 (3) Å and O⋯Br = 3.255 (2) Å] into centrosymmetric dimers, whereas weaker C—H⋯O and C—H⋯Br hydrogen bonds [C⋯O = 3.215 (3)–3.390 (4) Å and C⋯Br = 3.927 (3) Å] connect the dimers into double layers parallel to the (111) plane.

Keywords: crystal structure; rhenium(I) carbonyl complex; 5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole.

CCDC reference: 1535292

1. Chemical context

Rhenium(I) metal complexes have attracted attention because of their chemical characteristics exhibiting increased potentials for biochemical applications (Fernández-Moreira et al., 2010 ; Lo et al., 2012 ). Rhenium tricarbonyl complexes with the general formula fac-[Re(CO)₃(N^N)] (where N^N is an N,N′-chelating ligand) are kinetically stable and have luminescence properties with long life times (Kowalski et al., 2015 ; Guo et al., 1997 ), high photostability (Lo, 2015 ) and large Stokes shifts (Lo, 2015; Stephenson et al., 2004 ), which makes these compounds ideal candidates for either in vitro or in vivo visualization of biological processes (Shen et al., 2001 ; Thorp-Greenwood, 2012 ).

Triazole derivatives are an interesting type of ligand. 1,2,4-Triazoles have biological relevance since they show antiviral (Abdullah et al., 2012 ), antibacterial (Varvarason et al., 2000 ; Jassim et al., 2011 ), antifungal (Luo et al., 2009 ), anticancer (Sztanke et al., 2008 ) and antituberculous (Mandal et al., 2010 ) activities. Moreover, metal complexes containing triazole derivatives have interesting photophysical and photochemical properties (Piletska et al., 2015 ; Chen et al., 2013 ), and this class of complexes, apart from their biological activity (Chohan & Hanif, 2010 ), is used for fluorescent probing in addition to their potential use in radio-imaging. Introduction of substituents in the triazole derivatives affects the σ-donor and π-acceptor properties (Van Diemen et al., 1991 ), and consequently affects the photophysical properties of an organometallic compounds in which they are incorporated. In this context, we report here the synthesis and crystal structure analysis of a novel Re^I complex, i.e. [ReBr(C₁₆H₁₆N₄O₃)(CO)₃]·CH₃OH (Fig. 1), which contains the triazole ligand 5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole.

Figure 1
The structures of the molecular entities in the solvated title complex. Displacement ellipsoids are drawn at the 40% probability level and the dashed line indicates hydrogen bonding involving the methanol solvent molecule.

2. Structural commentary

The three carbonyl ligands bonded to the Re^I atom are arranged in a fac configuration. The distances of atoms C1, C2 and C3 to the Re^I atom are 1.902 (4), 1.910 (2) and 1.907 (2) Å, respectively, and the Re—N bond lengths involving the chelating organic ligand are 2.151 (2) and 2.205 (2) Å. The two N atoms and two carbonyl C atoms define the equatorial plane, while the octahedral coordination sphere is completed by the third carbonyl C atom and the Br atom [Re—Br = 2.6222 (3) Å] in axial positions. The CO ligands are almost linearly coordinated, with O—C—Re bond angles of 178.2 (3), 177.8 (3) and 177.8 (3)°. The C—Re—C bond angles between carbonyl C atoms are 90.6 (1), 90.2 (1) and 88.7 (1)°, close to ideal values, whereas the cis equatorial bite angle of the chelating ligand (N1—Re1—N4) is 73.42 (8)°.

3. Supramolecular features

In the crystal, the packing of the molecules is influenced by a set of weak interactions, including conventional hydrogen bonding with common NH and OH donor groups and weaker hydrogen bonds formed by CH groups (Table 1). Two pairs of relatively short hydrogen bonds (O7—H⋯Br1 and N2—H⋯O7), both involving the methanol solvent molecules, assemble the complex molecules into centrosymmetric dimers (Fig. 2). As may be compared with the closely related complex [ReBr(L)(CO)₃] [L = 5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole; Piletska et al., 2014 ], a key prerequisite for the formation of dimers is the presence of acidic NH functions and sterically accessible Br sites. In the latter, they afford two mutual N—H⋯Br hydrogen bonds, whereas in the present case, these links appear to be extended by the inclusion of methanol, resulting in an N—H⋯O(Me)—H⋯Br motif.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H1O⋯Br1	0.85	2.41	3.255 (2)	172
N2—H1N⋯O7ⁱ	0.87	1.89	2.703 (3)	154
C7—H7⋯Br1ⁱⁱ	0.94	3.01	3.927 (3)	165
C8—H8⋯O2ⁱⁱⁱ	0.94	2.52	3.390 (4)	153
C9—H9⋯O6^iv	0.94	2.49	3.278 (3)	142
C10—H10⋯O3^v	0.94	2.39	3.215 (3)	146
Symmetry codes: (i) -x+1, -y, -z; (ii) -x, -y+1, -z; (iii) x-1, y+1, z; (iv) x-1, y, z+1; (v) -x, -y, -z+1.

Figure 2
(a) Part of the crystal structure of the title complex, showing dimers formed by conventional hydrogen bonding involving the methanol solvent molecules and weak C—H⋯O interactions providing interconnection of the dimers into chains. (b) A partial view of the double layer in a projection approximately on the (111) plane; individual chains are marked in blue and grey and the dotted lines indicate hydrogen bonding within a layer. [Symmetry codes: (i) 1 − x, −y, −z; (ii) −x, −y, 1 − z; (iii) −1 + x, y, 1 + z; (iv) −1 + x, 1 + y, z; (v) −x, 1 − y, −z.]

Each of the four pyridine CH groups functions as a donor of weak hydrogen bonds (Fig. 2). These groups establish hydrogen bonds to two carbonyl O atoms (C8⋯O2^iv and C10⋯O3ⁱⁱ), a methoxy O atom (C9⋯O6ⁱⁱⁱ) and a very weak bond with bromine as acceptor (C7⋯Br^v) (for symmetry codes, see Table 1). These distal yet directional interactions (the hydrogen-bonding angles are in the range 142–165°; Table 1) unite the above dimers into flat double layers, which extend parallel to the (111) plane. Within a layer, the pyridine and triazole moieties of adjacent molecules are actually parallel, with shortest contacts of C7⋯N3^v = 3.430 (4) Å [symmetry code: (v) −x, 1 − y, −z]. However, this situation is unlikely to be a consequence of slipped π–π interactions, since the corresponding slippage angle exceeds 56° and the intercentroid distance is as long as Cg(C6–C10/N4)⋯Cg(C4/C5/N1–N3)^v = 4.090 (3) Å [for the lack of an overlap between heteroaromatic planes, see Fig. 2, part (B)]. At the same time, successive double layers are turned towards one another by methyl groups of the trimethoxyphenyl and methanol entities (Fig. 3). Thus, the interlayer interactions are very weak and the only remarkable contact is found between two inversion-related carbonyl groups [O1⋯C1^vi = 3.295 (3) Å and O1⋯Cg(C1=O1)^vi = 3.226 (3) Å; symmetry code (vi) −x, −y, −z]. Although such weak interactions are characteristic of related metal–carbonyl structures (Sparkes et al., 2006 ), in the present case, their significance is relatively minor.

Figure 3
Packing of successive double layers, which are turned towards one another by the methyl and carbonyl groups (the view is along the direction of the hydrogen-bonded chains indicated with blue and grey bonds). [Symmetry codes: (iv) −1 + x, 1 + y, z; (v) −x, 1 − y, −z.]

4. Synthesis and crystallization

Pentacarbonylrhenium(I) bromide (0.15 g, 0.369 mmol) was mixed with 5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole (0.138 g, 0.442 mmol) in benzene (30 ml). The mixture was refluxed for 4 h under a stream of argon and then allowed to cool to room temperature. The yellow product was collected by suction filtration, washed with hexane and dried (yield 0.138 g, 77%). Crystals suitable for X-ray diffraction were obtained by slow diffusion of hexane into a methanol–dichloromethane solution of the complex. IR (KBr, cm⁻¹): ν_as(CO) 2028 (s), ν_s(CO) 1894 (s). ¹H NMR (400 MHz, d⁶-DMSO): δ 9.02 (d, 1H, CH=N, Py), 8.39 (d, 1H, CH=C, Py), 8.35 (dd, 1H, CH, Py), 7.75 (dd, 1H, CH, Py), 7.44 [s, 2H, 2 CH, Ph(OCH₃)₃], 3.93 [s, 9H, 3 O-CH₃, Ph(OCH₃)₃].

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. C- and N-bound H atoms were positioned with idealized geometry and were refined with aryl C—H = 0.94 Å, methyl C—H = 0.97 Å and N—H = 0.87 Å, and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C,N) otherwise. The O-bound H atom of the methanol solvent molecule was found from a difference map and was refined with O—H = 0.95 Å and U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	[ReBr(C₁₆H₁₆N₄O₃)(CO)₃]·CH₄O
M_r	694.51
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	213
a, b, c (Å)	10.9569 (6), 11.0012 (6), 11.9738 (7)
α, β, γ (°)	69.073 (6), 75.593 (7), 61.409 (6)
V (Å³)	1178.37 (14)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	6.90
Crystal size (mm)	0.21 × 0.18 × 0.15

Data collection
Diffractometer	Stoe IPDS
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe & Cie, 1999 )
T_min, T_max	0.325, 0.424
No. of measured, independent and observed [I > 2σ(I)] reflections	22150, 5649, 4658
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.019, 0.034, 0.84
No. of reflections	5649
No. of parameters	302
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.98
Computer programs: IPDS (Stoe & Cie, 2000 ), SHELXS97 and SHELXL97 (Sheldrick, 2008 ), DIAMOND (Brandenburg, 1999 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1535292

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017003371/wm5372sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017003371/wm5372Isup2.hkl

checkCIF report

Computing details top

Data collection: IPDS (Stoe & Cie, 2000); cell refinement: IPDS (Stoe & Cie, 2000); data reduction: IPDS (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Bromido-fac-tricarbonyl[5-(3,4,5-trimethoxyphenyl)-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N²,N³]rhenium(I) methanol monosolvate top

Crystal data top

[ReBr(C₁₆H₁₆N₄O₃)(CO)₃]·CH₄O	Z = 2
M_r = 694.51	F(000) = 668
Triclinic, P1	D_x = 1.957 Mg m⁻³
a = 10.9569 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0012 (6) Å	Cell parameters from 8000 reflections
c = 11.9738 (7) Å	θ = 2.4–28.0°
α = 69.073 (6)°	µ = 6.90 mm⁻¹
β = 75.593 (7)°	T = 213 K
γ = 61.409 (6)°	Prism, yellow
V = 1178.37 (14) Å³	0.21 × 0.18 × 0.15 mm

Data collection top

Stoe IPDS diffractometer	5649 independent reflections
Radiation source: fine-focus sealed tube	4658 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
φ oscillation scans	θ_max = 28.0°, θ_min = 2.4°
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 1999)	h = −14→14
T_min = 0.325, T_max = 0.424	k = −14→14
22150 measured reflections	l = −15→15

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)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.034	H-atom parameters constrained
S = 0.84	w = 1/[σ²(F_o²) + (0.007P)²] where P = (F_o² + 2F_c²)/3
5649 reflections	(Δ/σ)_max = 0.002
302 parameters	Δρ_max = 0.77 e Å⁻³
0 restraints	Δρ_min = −0.98 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Re1	0.154206 (13)	0.050031 (12)	0.169575 (9)	0.02510 (3)
Br1	0.25284 (3)	0.20300 (3)	0.21180 (2)	0.03551 (7)
O1	0.0338 (3)	−0.1259 (3)	0.1269 (2)	0.0619 (7)
O2	0.4513 (3)	−0.1785 (3)	0.1342 (2)	0.0647 (7)
O3	0.1502 (3)	−0.1065 (3)	0.43714 (17)	0.0564 (6)
O4	0.0599 (2)	0.6925 (2)	−0.58379 (15)	0.0424 (5)
O5	0.3238 (2)	0.5465 (3)	−0.66521 (15)	0.0496 (6)
O6	0.4851 (2)	0.2842 (3)	−0.53647 (19)	0.0588 (7)
O7	0.5906 (2)	0.0402 (3)	0.1603 (2)	0.0607 (6)
H1O	0.5022	0.0743	0.1740	0.091*
N1	0.1308 (2)	0.1987 (2)	−0.00751 (16)	0.0251 (5)
N2	0.2059 (2)	0.2076 (2)	−0.11623 (17)	0.0277 (5)
H1N	0.2870	0.1422	−0.1341	0.042*
N3	0.0134 (2)	0.4101 (2)	−0.13551 (17)	0.0276 (5)
N4	−0.0517 (2)	0.2340 (2)	0.17886 (16)	0.0261 (5)
C1	0.0776 (3)	−0.0582 (3)	0.1415 (2)	0.0372 (7)
C2	0.3389 (3)	−0.0940 (3)	0.1465 (2)	0.0374 (7)
C3	0.1518 (3)	−0.0502 (3)	0.3364 (2)	0.0337 (6)
C4	0.0180 (3)	0.3209 (3)	−0.02390 (19)	0.0236 (5)
C5	0.1328 (3)	0.3353 (3)	−0.1915 (2)	0.0258 (5)
C6	−0.0881 (3)	0.3444 (3)	0.0779 (2)	0.0256 (5)
C7	−0.2134 (3)	0.4647 (3)	0.0716 (2)	0.0330 (6)
H7	−0.2349	0.5395	−0.0004	0.040*
C8	−0.3074 (3)	0.4739 (3)	0.1731 (3)	0.0393 (7)
H8	−0.3944	0.5547	0.1712	0.047*
C9	−0.2715 (3)	0.3632 (3)	0.2763 (2)	0.0402 (7)
H9	−0.3335	0.3675	0.3465	0.048*
C10	−0.1442 (3)	0.2460 (3)	0.2766 (2)	0.0346 (6)
H10	−0.1209	0.1709	0.3482	0.042*
C11	0.1808 (3)	0.3865 (3)	−0.3176 (2)	0.0292 (6)
C12	0.0921 (3)	0.5169 (3)	−0.3878 (2)	0.0311 (6)
H12	0.0019	0.5697	−0.3557	0.037*
C13	0.1380 (3)	0.5683 (3)	−0.5059 (2)	0.0335 (6)
C14	0.2732 (3)	0.4897 (3)	−0.5527 (2)	0.0374 (7)
C15	0.3585 (3)	0.3574 (3)	−0.4825 (2)	0.0392 (7)
C16	0.3131 (3)	0.3051 (3)	−0.3641 (2)	0.0363 (7)
H16	0.3713	0.2156	−0.3160	0.044*
C17	−0.0765 (4)	0.7778 (3)	−0.5387 (3)	0.0465 (8)
H17A	−0.1313	0.7229	−0.5112	0.070*
H17B	−0.1212	0.8642	−0.6019	0.070*
H17C	−0.0701	0.8046	−0.4721	0.070*
C18	0.2920 (4)	0.5205 (4)	−0.7592 (3)	0.0544 (9)
H18A	0.3399	0.4181	−0.7525	0.082*
H18B	0.3221	0.5733	−0.8358	0.082*
H18C	0.1920	0.5521	−0.7538	0.082*
C19	0.5582 (4)	0.1362 (5)	−0.4788 (4)	0.0857 (14)
H19A	0.5877	0.1254	−0.4045	0.128*
H19B	0.6395	0.0928	−0.5309	0.128*
H19C	0.4977	0.0888	−0.4613	0.128*
C20	0.6343 (5)	0.1423 (5)	0.1534 (5)	0.0861 (14)
H20A	0.6044	0.1685	0.2282	0.129*
H20B	0.5936	0.2272	0.0878	0.129*
H20C	0.7353	0.1024	0.1395	0.129*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.02840 (6)	0.02390 (6)	0.02089 (5)	−0.01144 (4)	−0.00314 (3)	−0.00318 (3)
Br1	0.03337 (16)	0.03401 (17)	0.04178 (14)	−0.01567 (13)	−0.00360 (12)	−0.01181 (12)
O1	0.088 (2)	0.0571 (16)	0.0582 (14)	−0.0442 (15)	−0.0299 (13)	−0.0010 (12)
O2	0.0457 (15)	0.0503 (16)	0.0727 (16)	0.0050 (13)	−0.0118 (12)	−0.0217 (12)
O3	0.0822 (18)	0.0659 (16)	0.0272 (10)	−0.0472 (15)	−0.0099 (10)	0.0052 (10)
O4	0.0561 (14)	0.0372 (12)	0.0284 (9)	−0.0229 (11)	−0.0026 (9)	−0.0001 (8)
O5	0.0627 (15)	0.0786 (16)	0.0239 (9)	−0.0539 (14)	0.0066 (9)	−0.0060 (9)
O6	0.0325 (12)	0.0807 (19)	0.0418 (11)	−0.0187 (13)	0.0098 (9)	−0.0108 (11)
O7	0.0342 (13)	0.0493 (15)	0.0909 (17)	−0.0084 (12)	0.0067 (12)	−0.0335 (13)
N1	0.0260 (12)	0.0283 (12)	0.0190 (9)	−0.0126 (10)	0.0005 (8)	−0.0049 (8)
N2	0.0231 (11)	0.0347 (13)	0.0223 (10)	−0.0118 (10)	0.0026 (8)	−0.0090 (9)
N3	0.0268 (12)	0.0283 (12)	0.0256 (10)	−0.0136 (10)	0.0001 (9)	−0.0045 (9)
N4	0.0261 (12)	0.0302 (12)	0.0223 (9)	−0.0149 (10)	0.0005 (8)	−0.0057 (8)
C1	0.055 (2)	0.0295 (16)	0.0275 (13)	−0.0215 (15)	−0.0095 (12)	0.0000 (11)
C2	0.0396 (18)	0.0311 (17)	0.0327 (14)	−0.0084 (15)	−0.0097 (12)	−0.0050 (12)
C3	0.0403 (17)	0.0340 (16)	0.0288 (13)	−0.0204 (14)	−0.0052 (11)	−0.0036 (11)
C4	0.0228 (13)	0.0272 (14)	0.0210 (10)	−0.0123 (11)	−0.0026 (9)	−0.0042 (9)
C5	0.0245 (13)	0.0302 (15)	0.0245 (11)	−0.0156 (12)	−0.0021 (10)	−0.0042 (10)
C6	0.0267 (14)	0.0281 (14)	0.0252 (11)	−0.0151 (12)	−0.0013 (10)	−0.0071 (10)
C7	0.0294 (15)	0.0302 (16)	0.0363 (13)	−0.0111 (13)	−0.0043 (11)	−0.0075 (11)
C8	0.0273 (15)	0.0377 (18)	0.0515 (16)	−0.0126 (14)	0.0053 (13)	−0.0190 (14)
C9	0.0362 (17)	0.049 (2)	0.0382 (14)	−0.0234 (16)	0.0148 (12)	−0.0212 (14)
C10	0.0394 (17)	0.0419 (18)	0.0258 (12)	−0.0254 (15)	0.0047 (11)	−0.0070 (11)
C11	0.0306 (15)	0.0369 (16)	0.0239 (11)	−0.0202 (13)	−0.0006 (10)	−0.0062 (10)
C12	0.0366 (16)	0.0359 (16)	0.0246 (11)	−0.0220 (13)	−0.0003 (11)	−0.0054 (11)
C13	0.0464 (18)	0.0344 (16)	0.0251 (12)	−0.0260 (15)	−0.0045 (12)	−0.0012 (11)
C14	0.0446 (18)	0.056 (2)	0.0238 (12)	−0.0368 (16)	0.0029 (12)	−0.0070 (12)
C15	0.0284 (15)	0.062 (2)	0.0294 (13)	−0.0249 (15)	0.0052 (11)	−0.0125 (13)
C16	0.0296 (15)	0.0466 (18)	0.0267 (12)	−0.0179 (14)	−0.0026 (11)	−0.0015 (12)
C17	0.053 (2)	0.0380 (19)	0.0382 (15)	−0.0163 (16)	−0.0077 (14)	−0.0012 (13)
C18	0.064 (2)	0.075 (3)	0.0333 (15)	−0.039 (2)	0.0008 (15)	−0.0156 (16)
C19	0.045 (2)	0.098 (4)	0.087 (3)	−0.021 (2)	0.031 (2)	−0.036 (3)
C20	0.060 (3)	0.086 (3)	0.134 (4)	−0.029 (3)	−0.005 (3)	−0.062 (3)

Geometric parameters (Å, º) top

Re1—C1	1.902 (3)	C7—C8	1.383 (4)
Re1—C3	1.907 (3)	C7—H7	0.9400
Re1—C2	1.910 (3)	C8—C9	1.369 (4)
Re1—N1	2.1515 (18)	C8—H8	0.9400
Re1—N4	2.205 (2)	C9—C10	1.373 (4)
Re1—Br1	2.6222 (3)	C9—H9	0.9400
O1—C1	1.137 (3)	C10—H10	0.9400
O2—C2	1.146 (4)	C11—C12	1.385 (4)
O3—C3	1.142 (3)	C11—C16	1.388 (4)
O4—C13	1.355 (3)	C12—C13	1.386 (3)
O4—C17	1.423 (4)	C12—H12	0.9400
O5—C14	1.368 (3)	C13—C14	1.401 (4)
O5—C18	1.410 (4)	C14—C15	1.383 (4)
O6—C15	1.359 (4)	C15—C16	1.389 (4)
O6—C19	1.412 (5)	C16—H16	0.9400
O7—C20	1.388 (5)	C17—H17A	0.9700
O7—H1O	0.8500	C17—H17B	0.9700
N1—C4	1.310 (3)	C17—H17C	0.9700
N1—N2	1.354 (3)	C18—H18A	0.9700
N2—C5	1.344 (3)	C18—H18B	0.9700
N2—H1N	0.8700	C18—H18C	0.9700
N3—C5	1.329 (3)	C19—H19A	0.9700
N3—C4	1.342 (3)	C19—H19B	0.9700
N4—C10	1.344 (3)	C19—H19C	0.9700
N4—C6	1.350 (3)	C20—H20A	0.9700
C4—C6	1.462 (3)	C20—H20B	0.9700
C5—C11	1.468 (3)	C20—H20C	0.9700
C6—C7	1.372 (4)

C1—Re1—C3	90.15 (11)	C8—C9—H9	120.2
C1—Re1—C2	90.62 (13)	C10—C9—H9	120.2
C3—Re1—C2	88.74 (12)	N4—C10—C9	122.8 (2)
C1—Re1—N1	95.06 (9)	N4—C10—H10	118.6
C3—Re1—N1	169.20 (10)	C9—C10—H10	118.6
C2—Re1—N1	100.64 (10)	C12—C11—C16	121.3 (2)
C1—Re1—N4	92.83 (11)	C12—C11—C5	118.7 (2)
C3—Re1—N4	96.92 (10)	C16—C11—C5	120.0 (2)
C2—Re1—N4	173.36 (10)	C11—C12—C13	119.2 (3)
N1—Re1—N4	73.41 (7)	C11—C12—H12	120.4
C1—Re1—Br1	178.32 (9)	C13—C12—H12	120.4
C3—Re1—Br1	89.23 (8)	O4—C13—C12	124.5 (3)
C2—Re1—Br1	90.92 (9)	O4—C13—C14	115.4 (2)
N1—Re1—Br1	85.31 (6)	C12—C13—C14	120.1 (3)
N4—Re1—Br1	85.70 (6)	O5—C14—C15	119.8 (3)
C13—O4—C17	117.1 (2)	O5—C14—C13	120.3 (3)
C14—O5—C18	114.9 (2)	C15—C14—C13	119.9 (2)
C15—O6—C19	117.1 (2)	O6—C15—C14	116.3 (2)
C20—O7—H1O	109.6	O6—C15—C16	123.4 (3)
C4—N1—N2	104.04 (18)	C14—C15—C16	120.3 (3)
C4—N1—Re1	118.20 (15)	C11—C16—C15	119.2 (3)
N2—N1—Re1	137.71 (17)	C11—C16—H16	120.4
C5—N2—N1	107.9 (2)	C15—C16—H16	120.4
C5—N2—H1N	126.1	O4—C17—H17A	109.5
N1—N2—H1N	126.1	O4—C17—H17B	109.5
C5—N3—C4	102.6 (2)	H17A—C17—H17B	109.5
C10—N4—C6	117.0 (2)	O4—C17—H17C	109.5
C10—N4—Re1	125.62 (18)	H17A—C17—H17C	109.5
C6—N4—Re1	117.35 (15)	H17B—C17—H17C	109.5
O1—C1—Re1	178.2 (3)	O5—C18—H18A	109.5
O2—C2—Re1	177.9 (3)	O5—C18—H18B	109.5
O3—C3—Re1	177.7 (3)	H18A—C18—H18B	109.5
N1—C4—N3	114.7 (2)	O5—C18—H18C	109.5
N1—C4—C6	117.8 (2)	H18A—C18—H18C	109.5
N3—C4—C6	127.5 (2)	H18B—C18—H18C	109.5
N3—C5—N2	110.8 (2)	O6—C19—H19A	109.5
N3—C5—C11	124.8 (2)	O6—C19—H19B	109.5
N2—C5—C11	124.4 (2)	H19A—C19—H19B	109.5
N4—C6—C7	123.1 (2)	O6—C19—H19C	109.5
N4—C6—C4	113.1 (2)	H19A—C19—H19C	109.5
C7—C6—C4	123.8 (2)	H19B—C19—H19C	109.5
C6—C7—C8	118.8 (3)	O7—C20—H20A	109.5
C6—C7—H7	120.6	O7—C20—H20B	109.5
C8—C7—H7	120.6	H20A—C20—H20B	109.5
C9—C8—C7	118.7 (3)	O7—C20—H20C	109.5
C9—C8—H8	120.6	H20A—C20—H20C	109.5
C7—C8—H8	120.6	H20B—C20—H20C	109.5
C8—C9—C10	119.5 (2)

C1—Re1—N1—C4	94.2 (2)	N1—C4—C6—C7	−177.2 (3)
C3—Re1—N1—C4	−24.3 (7)	N3—C4—C6—C7	1.7 (4)
C2—Re1—N1—C4	−174.2 (2)	N4—C6—C7—C8	−0.1 (4)
N4—Re1—N1—C4	2.79 (18)	C4—C6—C7—C8	178.5 (2)
Br1—Re1—N1—C4	−84.12 (18)	C6—C7—C8—C9	0.6 (4)
C1—Re1—N1—N2	−88.8 (3)	C7—C8—C9—C10	−0.4 (4)
C3—Re1—N1—N2	152.7 (5)	C6—N4—C10—C9	0.6 (4)
C2—Re1—N1—N2	2.8 (3)	Re1—N4—C10—C9	−179.5 (2)
N4—Re1—N1—N2	179.8 (3)	C8—C9—C10—N4	−0.2 (5)
Br1—Re1—N1—N2	92.9 (2)	N3—C5—C11—C12	−5.7 (4)
C4—N1—N2—C5	−0.1 (3)	N2—C5—C11—C12	176.3 (2)
Re1—N1—N2—C5	−177.32 (19)	N3—C5—C11—C16	174.0 (3)
C1—Re1—N4—C10	83.7 (2)	N2—C5—C11—C16	−4.0 (4)
C3—Re1—N4—C10	−6.7 (2)	C16—C11—C12—C13	−1.6 (4)
N1—Re1—N4—C10	178.2 (2)	C5—C11—C12—C13	178.1 (2)
Br1—Re1—N4—C10	−95.4 (2)	C17—O4—C13—C12	2.6 (4)
C1—Re1—N4—C6	−96.34 (19)	C17—O4—C13—C14	−178.0 (3)
C3—Re1—N4—C6	173.17 (19)	C11—C12—C13—O4	178.6 (3)
N1—Re1—N4—C6	−1.90 (18)	C11—C12—C13—C14	−0.8 (4)
Br1—Re1—N4—C6	84.47 (18)	C18—O5—C14—C15	96.3 (3)
N2—N1—C4—N3	−0.3 (3)	C18—O5—C14—C13	−87.1 (4)
Re1—N1—C4—N3	177.60 (16)	O4—C13—C14—O5	7.0 (4)
N2—N1—C4—C6	178.8 (2)	C12—C13—C14—O5	−173.6 (2)
Re1—N1—C4—C6	−3.3 (3)	O4—C13—C14—C15	−176.4 (3)
C5—N3—C4—N1	0.5 (3)	C12—C13—C14—C15	3.0 (4)
C5—N3—C4—C6	−178.4 (2)	C19—O6—C15—C14	−164.1 (3)
C4—N3—C5—N2	−0.6 (3)	C19—O6—C15—C16	15.2 (5)
C4—N3—C5—C11	−178.8 (2)	O5—C14—C15—O6	−6.9 (4)
N1—N2—C5—N3	0.4 (3)	C13—C14—C15—O6	176.4 (3)
N1—N2—C5—C11	178.7 (2)	O5—C14—C15—C16	173.7 (3)
C10—N4—C6—C7	−0.4 (4)	C13—C14—C15—C16	−2.9 (4)
Re1—N4—C6—C7	179.7 (2)	C12—C11—C16—C15	1.7 (4)
C10—N4—C6—C4	−179.2 (2)	C5—C11—C16—C15	−178.0 (3)
Re1—N4—C6—C4	0.9 (3)	O6—C15—C16—C11	−178.7 (3)
N1—C4—C6—N4	1.6 (3)	C14—C15—C16—C11	0.6 (4)
N3—C4—C6—N4	−179.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H1O···Br1	0.85	2.41	3.255 (2)	172
N2—H1N···O7ⁱ	0.87	1.89	2.703 (3)	154
C7—H7···Br1ⁱⁱ	0.94	3.01	3.927 (3)	165
C8—H8···O2ⁱⁱⁱ	0.94	2.52	3.390 (4)	153
C9—H9···O6^iv	0.94	2.49	3.278 (3)	142
C10—H10···O3^v	0.94	2.39	3.215 (3)	146

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

Funding information

Funding for this research was provided by: Ministry of Education and Science of Ukraine, Grant for Science Research (award No. 0114U002488).

References

Abdullah, H. M., Jassim, I. K. & Safi, M. N. (2012). Karbala J. Pharm. Sci, 4, 115–135. Google Scholar
Brandenburg, K. (1999). DIAMOND. University of Bonn, Germany. Google Scholar
Chen, J.-L., Cao, X.-F., Wang, J.-Y., He, L.-H., Liu, Z.-Y., Wen, H.-R. & Chen, Z.-N. (2013). Inorg. Chem. 52, 9727–9740. Web of Science CSD CrossRef CAS PubMed Google Scholar
Chohan, Z. H. & Hanif, M. (2010). J. Enzyme Inhib. Med. Chem. 25, 737–749. Web of Science CrossRef CAS PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fernández-Moreira, V., Thorp-Greenwood, F. L. & Coogan, M. P. (2010). Chem. Commun. 46, 186–202. Google Scholar
Guo, X., Castellano, F. N., Li, L., Szmacinski, H., Lakowicz, J. R. & Sipior, J. (1997). Anal. Biochem. 254, 179–186. Web of Science CrossRef CAS PubMed Google Scholar
Jassim, I. K., Fayad, A. A. & Jassim, W. K. (2011). Karbala J. Pharm. Sci. 2, 228–240. Google Scholar
Kowalski, K., Szczupak, Ł., Bernaś, T. & Czerwieniec, R. (2015). J. Organomet. Chem. 782, 124–130. Web of Science CrossRef CAS Google Scholar
Lo, K. K.-W. (2015). Acc. Chem. Res. 48, 2985–2995. Web of Science CrossRef CAS PubMed Google Scholar
Lo, K. K.-W., Choi, A. W.-T. & Law, W. H.-T. (2012). Dalton Trans. 41, 6021–6047. Web of Science CrossRef CAS PubMed Google Scholar
Luo, Y., Lu, Y.-H., Gan, L.-L., Zhou, C.-H., Wu, J., Geng, R.-X. & Zhang, Y.-Y. (2009). Arch. Pharm. Chem. Life Sci. 342, 386–393. Web of Science CrossRef CAS Google Scholar
Mandal, S. K., Saha, D., Jain, V. K. & Jain, B. (2010). Int. J. Pharm. Sci. Res. 1, 465–472. CAS Google Scholar
Piletska, K. O., Domasevitch, K. V., Gusev, A. N., Shul'gin, V. F. & Shtemenko, A. V. (2015). Polyhedron, 102, 699–704. Web of Science CSD CrossRef CAS Google Scholar
Piletska, K., Domasevitch, K. V. & Shtemenko, A. V. (2014). Acta Cryst. E70, 587–589. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, Y., Maliwal, B. P. & Lakowicz, J. R. (2001). J. Fluoresc. 11, 315–318. Web of Science CrossRef CAS Google Scholar
Sparkes, H. A., Raithby, P. R., Clot, E., Shields, G. P., Chisholm, J. A. & Allen, F. H. (2006). CrystEngComm, 8, 563–570. Web of Science CSD CrossRef CAS Google Scholar
Stephenson, K. A., Banerjee, S. R., Besanger, T., Sogbein, O. O., Levadala, M. K., McFarlane, N., Lemon, J. A., Boreham, D. R., Maresca, K. P., Brennan, J. D., Babich, J. W., Zubieta, J. & Valliant, J. F. (2004). J. Am. Chem. Soc. 126, 8598–8599. Web of Science CrossRef PubMed CAS Google Scholar
Stoe & Cie (1999). X-RED and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Stoe & Cie (2000). IPDS. Stoe & Cie, Darmstadt, Germany. Google Scholar
Sztanke, K., Tuzimski, T., Rzymowska, J., Pasternak, K. & Kandefer-Szerszeń, M. (2008). Eur. J. Med. Chem. 43, 404–419. Web of Science CrossRef PubMed CAS Google Scholar
Thorp-Greenwood, F. L. (2012). Organometallics, 31, 5686–5692. CAS Google Scholar
Van Diemen, J. H., Haasnoot, J. G., Hage, R., Reedijk, J., Vos, J. G. & Wang, R. (1991). Inorg. Chem. 30, 4038–4043. CSD CrossRef CAS Web of Science Google Scholar
Varvarason, A., Tantili-Kakoulidou, A., Siatra-Papastasikoudi, T. & Tiligada, E. (2000). Arzneim.-Forsch. 50, 48–54. Google Scholar

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