Crystal structure of bromido-fac-tricarbon­yl[5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ2N,N′]rhenium(I)

Piletska, K.; Domasevitch, K.V.; Shtemenko, A.V.

doi:10.1107/S1600536814025604

research communications

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ISSN: 2056-9890

Volume 70| Part 12| December 2014| Pages 587-589

doi:10.1107/S1600536814025604

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Crystal structure of bromido-fac-tricarbonyl[5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N,N′]rhenium(I)

Kseniia Piletska,^a ^* Konstantin V. Domasevitch ^b and Alexander V. Shtemenko ^a

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

Edited by M. Weil, Vienna University of Technology, Austria (Received 4 November 2014; accepted 23 November 2014; online 29 November 2014)

In the title compound, [ReBr(C₁₃H₁₀N₄)(CO)₃], the Re^I atom has a distorted octahedral coordination environment. Two N atoms of the 5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole ligand and two of the three carbonyl groups occupy the equatorial plane of the complex, with the third carbonyl ligand and the bromide ligand in the axial positions. The three carbonyl ligands are arranged in a fac configuration around the Re^I atom. Mutual N—H⋯Br hydrogen bonds arrange molecules into centrosymmetric dimers. Additional stabilization within the crystal structure is provided by C—H⋯O and C—H⋯Br hydrogen bonds, as well as by slipped π–π stacking interactions [centroid-to-centroid distance = 3.785 (5) Å], defining a three-dimensional network.

Keywords: Crystal structure; rhenium carbonyl complex; 5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole; hydrogen bonding; slipped π–π stacking interactions.

CCDC reference: 1031232

1. Chemical context

The coordination chemistry of rhenium and technetium has been well studied over the last half century, particularly in view of the potential applications of their ^186/188Re and ^99mTc isotopes in therapeutic and diagnostic agents in nuclear medicine (Volkert & Hoffman, 1999 ; Alberto et al., 1999 ). Complexes of the type [M(CO)₃(NN)X] (M = Tc, Re; NN = bidentate nitrogen donor; X = anionic ligand) have been shown to possess interesting photophysical, photochemical and excited-state redox properties (Striplin & Crosby, 2001 ; Stufkens & Vlcěk, 1998 ), making this class of complexes applicable as fluorescent probes, in addition to their potential usage as radio-imaging and therapeutic agents. Moreover, metal carbonyls display intense infrared absorptions in the range 1800 to 2200 cm⁻¹, which is the IR transparency window for biological media (Hildebrandt, 2010 ). In addition to their luminescent properties, the vibrational signature of fac-[Re(CO)₃(NN)] is appropriate for IR imaging (Policar et al., 2011 ; Clède et al., 2012 ). They are thus valuable as small molecular units enabling multimodal imaging involving vibrational-based detections (IR, Raman) and fluorescence (Clède et al., 2012). In [Re(CO)₃(NN)X] compounds, the photophysical properties of the complexes are closely dependent on the ligand. When NN is a ligand with low π* orbitals, the corresponding [Re(CO)₃(NN)] unit is luminescent (Wrighton & Morse, 1974 ) and this property has often been used in subcellular bio-imaging (Lo et al., 2012 ; Baggaley et al., 2012 ; Xiang et al., 2013 ; Coogan & Fernandez-Moreira, 2014 ).

In this communication, we report the synthesis and crystal structure analysis of a novel Re^I complex which contains the triazole ligand 5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole, [Re(CO)₃(C₁₃H₁₀N₄)Br]. Its luminescent properties will be reported in a forthcoming article.

2. Structural commentary

In the title compound, the Re^I atom is in a slightly distorted octahedral coordination environment (Fig. 1). The three carbonyl ligands bonded to the Re^I atom are arranged in a fac-configuration. The distances of C1, C2, and C3 to the Re^I atom are 1.905 (4), 1.915 (4), and 1.922 (6) Å, respectively, and the Re—N bonds lengths are 2.201 (3) and 2.164 (3) Å. The CO ligands are almost linearly coordinated with O—C—Re bond angles of 178.4 (4), 175.6 (3) and 179.0 (4)°. The C—Re—C bond angles between CO carbon atoms are 87.78 (17), 90.4 (2) and 89.18 (19)°, close to ideal values, whereas the cis equatorial bite angle [N1—Re1—N2] is 74.33 (11)°. All other bond lengths and angles are comparable to those found for related Re^I complexes (Rajendran et al., 2000 ).

Figure 1
The structure of the title complex, showing the association of molecules into a centrosymmetric dimer by means of mutual hydrogen bonds of the N—H⋯Br and C—H⋯Br types. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry code: (i) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z.]

3. Supramolecular features

The title compound adopts a typical molecular structure. There is only one relatively strong donor (N—H) and one acceptor (Br) site for hydrogen-bonding interactions, which arrange molecules into dimers (Table 1, Fig. 1). Weak hydrogen bonds of the type C—H⋯O with carbonyl O atoms as acceptor groups play a supporting role in the crystal packing. Nevertheless, these interactions demonstrate a clear discrimination of the C—H binding sites that follow a common pattern. The C—H⋯O hydrogen bonds present are provided by the 2- and 4-C—H protons of the pyridine ring, which are the most polarized and acidic. Besides C—H⋯Br interactions, weak slipped π–π stacking interactions between pyridine and phenyl rings (symmetry code: 1 − x, −y, −z) [with a shortest separation of C6⋯C11(1 − x, −y, −z) = 3.265 (6) Å, a centroid-to-centroid distance of 3.785 (5) Å and an interplanar angle of 7.1 (3)°] also appear to be involved in the stabilization of the crystal structure (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Br1ⁱ	0.87	2.51	3.360 (3)	168
C16—H16⋯Br1ⁱ	0.94	2.87	3.784 (4)	165
C6—H6⋯O2ⁱⁱ	0.94	2.38	3.194 (5)	145
C8—H8⋯O1ⁱⁱⁱ	0.94	2.56	3.285 (5)	134
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Figure 2
The crystal structure of the title complex, showing weak hydrogen-bonding interactions (indicated by dotted lines) of the type C—H⋯O between carbonyl O atoms and pyridyl C—H groups of the organic ligands. [Symmetry codes: (i) −x + $[{1\over 2}]$ , −y + $[{1\over 2}]$ , −z; (iii) −x + 1, y, −z + $[{1\over 2}]$ .]

4. Synthesis and crystallization

Pentacarbonylrhenium(I) bromide (0.1 g, 0.246 mmol) was reacted with 5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole (0.1 g, 0.492 mmol) in benzene at 353 K, with stirring, under a steady stream of argon for five h. The dark-yellow solution was removed from the heat and allowed to cool overnight. The yellow product was collected by suction filtration, washed with a 50 ml portion of petroleum ether and dried. Yield = 0.107g, (76.4%). Crystals suitable for X-ray diffraction were obtained by slow diffusion of hexane into a methanol solution of the complex. IR (KBr, cm⁻¹): ν_as(CO) 2028 (s), ν_s(CO) 1912 (s).

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were positioned with idealized geometry and were refined with C—H = 0.94, N—H = 0.87 Å and U_iso(H) = 1.2U_eq(C,N).

Table 2
Experimental details

Crystal data
Chemical formula	[ReBr(C₁₃H₁₀N₄)(CO)₃]
M_r	572.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	213
a, b, c (Å)	20.8082 (15), 7.2521 (4), 24.386 (2)
β (°)	111.599 (7)
V (Å³)	3421.5 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	9.46
Crystal size (mm)	0.14 × 0.12 × 0.11

Data collection
Diffractometer	Stoe Imaging plate diffraction system
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe & Cie, 2001 )
T_min, T_max	0.319, 0.385
No. of measured, independent and observed [I > 2σ(I)] reflections	14578, 4092, 2844
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.050, 0.84
No. of reflections	4092
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.03, −1.14
Computer programs: IPDS (Stoe & Cie, 2001), SHELXS97 and SHELXL2014 (Sheldrick, 2008 ), DIAMOND (Brandenburg, 1999 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1031232

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814025604/wm5089sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814025604/wm5089Isup2.hkl

checkCIF report

Chemical context top

The coordination chemistry of rhenium and technetium has been well studied over the last half century, particularly in view of the potential applications of their ^186/188Re and ^99mTc isotopes in therapeutic and diagnostic agents in nuclear medicine (Volkert & Hoffman, 1999; Alberto et al., 1999). Complexes of the type [M(CO)₃(NN)X] (M = Tc, Re; NN = bidentate nitrogen donor; X = anionic ligand) have been shown to possess interesting photophysical, photochemical and excited-state redox properties (Striplin & Crosby, 2001; Stufkens & Vlcěk, (1998), making this class of complexes applicable as fluorescent probes, in addition to their potential usage as radio-imaging and therapeutic agents. Moreover, metal carbonyls display intense infrared absorptions in the range 1800 to 2200 cm^-1, which is the IR transparency window for biological media (Hildebrandt, 2010). In addition to their luminescent properties, the vibrational signature of fac-[Re(CO)₃(NN)] is appropriate for IR imaging (Policar et al., 2011; Clède et al., 2012). They are thus valuable as small molecular units enabling multimodal imaging involving vibrational-based detections (IR, Raman) and fluorescence (Clède et al., 2012). In [Re(CO)₃(NN)X] compounds, the photophysical properties of the complexes are closely dependent on the ligand. When NN is a ligand with low π* orbitals, the corresponding [Re(CO)₃(NN)] unit is luminescent (Wrighton & Morse, 1974) and this property has often been used in subcellular bio-imaging (Lo et al., 2012; Baggaley et al., 2012; Xiang et al., 2013; Coogan & Fernandez-Moreira, 2014).

Structural commentary top

Supramolecular features top

The title compound adopts a typical molecular structure. There is only one relatively strong donor (N—H) and one acceptor (Br) site for hydrogen-bonding interactions, which arrange molecules into dimers (Table 1, Fig. 1). Weak hydrogen bonds of the type C—H···O with carbonyl O atoms as acceptor groups play a supporting role in the crystal packing. Nevertheless, these interactions demonstrate a clear discrimination of the C—H binding sites that follow a common pattern. The C—H···O hydrogen bonds present are provided by the 2- and 4-C—H protons of the pyridine ring, which are the most polarized and acidic. Besides C—H···Br interactions, weak slipped π–π stacking interactions between pyridine and phenyl rings (symmetry code: 1 - x, -y, -z) [with a shortest separation of C6···C11(1 - x, -y, -z) = 3.265 (6), a centroid-to-centroid distance of 3.785 (5) Å and an interplanar angle of 7.1 (3)°] also appear to be involved in the stabilization of the crystal structure (Fig. 2).

Synthesis and crystallization top

Pentacarbonylrhenium(I) bromide (0.1 g, 0.246 mmol) was reacted with 5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole (0.1 g, 0.492 mmol) in benzene at 353 K, with stirring, under a steady stream of argon for five hours. The dark-yellow solution was removed from the heat and allowed to cool overnight. The yellow product was collected by suction filtration, washed with a 50 ml portion of petroleum ether and dried. Yield = 0.107g, (76.4 %). Crystals suitable for X-ray diffraction were obtained by slow diffusion of hexane into a methanol solution of the complex. IR (KBr, cm^-1): ν_as(CO) 2028 (s), ν_s(CO) 1912 (s).

Refinement top

Related literature top

For related literature, see: Alberto et al. (1999); Baggaley et al. (2012); Clède et al. (2012); Coogan & Fernandez-Moreira (2014); Hildebrandt (2010); Lo et al. (2012); Policar et al. (2011); Rajendran et al. (2000); Striplin & Crosby (2001); Stufkens & Vlcěk (1998); Volkert & Hoffman (1999); Wrighton & Morse (1974); Xiang et al. (2013).

Computing details top

Data collection: IPDS (Stoe & Cie, 2001); cell refinement: IPDS (Stoe & Cie, 2001); data reduction: IPDS (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

The structure of the title complex, showing the association of molecules into a centrosymmetric dimer by means of mutual hydrogen bonds of the N—H···Br and C—H···Br types. Displacement ellipsoids are drawn at the 40% probability level. [Symmetry code: (i) -x + 1/2, -y + 1/2, -z.]

The crystal structure of the title complex, showing weak hydrogen-bonding interactions (indicated by dotted lines) of the type C—H···O between carbonyl O atoms and pyridyl C—H groups of the organic ligands. [Symmetry codes: (i) -x + 1/2, -y + 1/2, -z; (iii) -x + 1, y, -z + 1/2.]

Bromido-fac-tricarbonyl[5-phenyl-3-(pyridin-2-yl)-1H-1,2,4-triazole-κ²N,N']rhenium(I) top

Crystal data top

[ReBr(C₁₃H₁₀N₄)(CO)₃]	F(000) = 2144
M_r = 572.39	D_x = 2.222 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.8082 (15) Å	Cell parameters from 8000 reflections
b = 7.2521 (4) Å	θ = 3.0–28.0°
c = 24.386 (2) Å	µ = 9.46 mm⁻¹
β = 111.599 (7)°	T = 213 K
V = 3421.5 (4) Å³	Prism, yellow
Z = 8	0.14 × 0.12 × 0.11 mm

Data collection top

Stoe Imaging plate diffraction system diffractometer	2844 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.057
ϕ oscillation scans	θ_max = 28.0°, θ_min = 3.0°
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2001)	h = −27→27
T_min = 0.319, T_max = 0.385	k = −9→8
14578 measured reflections	l = −32→32
4092 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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.050	H-atom parameters constrained
S = 0.84	w = 1/[σ²(F_o²) + (0.0225P)²] where P = (F_o² + 2F_c²)/3
4092 reflections	(Δ/σ)_max = 0.001
226 parameters	Δρ_max = 1.03 e Å⁻³
0 restraints	Δρ_min = −1.14 e Å⁻³

Crystal data top

[ReBr(C₁₃H₁₀N₄)(CO)₃]	V = 3421.5 (4) Å³
M_r = 572.39	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.8082 (15) Å	µ = 9.46 mm⁻¹
b = 7.2521 (4) Å	T = 213 K
c = 24.386 (2) Å	0.14 × 0.12 × 0.11 mm
β = 111.599 (7)°

Data collection top

Stoe Imaging plate diffraction system diffractometer	4092 independent reflections
Absorption correction: numerical (X-RED and X-SHAPE; Stoe & Cie, 2001)	2844 reflections with I > 2σ(I)
T_min = 0.319, T_max = 0.385	R_int = 0.057
14578 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.050	H-atom parameters constrained
S = 0.84	Δρ_max = 1.03 e Å⁻³
4092 reflections	Δρ_min = −1.14 e Å⁻³
226 parameters

Special details top

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

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

	x	y	z	U_iso*/U_eq
Re1	0.38382 (2)	0.25265 (3)	0.10559 (2)	0.02798 (5)
Br1	0.32731 (2)	0.54427 (7)	0.04146 (2)	0.03557 (11)
O1	0.40827 (17)	0.4654 (6)	0.21974 (13)	0.0594 (10)
O2	0.24980 (15)	0.1146 (5)	0.11477 (13)	0.0516 (10)
O3	0.4540 (2)	−0.0838 (7)	0.17525 (18)	0.0796 (14)
N1	0.48045 (14)	0.3439 (5)	0.09681 (13)	0.0264 (7)
N2	0.38108 (14)	0.1420 (5)	0.02237 (12)	0.0244 (7)
N3	0.33622 (14)	0.0546 (5)	−0.02600 (12)	0.0258 (7)
H3	0.2960	0.0108	−0.0295	0.031*
N4	0.42685 (15)	0.1255 (5)	−0.04749 (13)	0.0255 (7)
C1	0.3988 (2)	0.3830 (7)	0.17704 (17)	0.0372 (12)
C2	0.2983 (2)	0.1674 (7)	0.10904 (15)	0.0361 (11)
C3	0.4289 (2)	0.0391 (9)	0.14970 (19)	0.0463 (13)
C4	0.49040 (18)	0.2879 (5)	0.04763 (16)	0.0246 (9)
C5	0.54965 (18)	0.3314 (7)	0.03688 (17)	0.0297 (9)
H5	0.5554	0.2910	0.0024	0.036*
C6	0.59958 (19)	0.4352 (7)	0.07811 (18)	0.0341 (10)
H6	0.6407	0.4653	0.0725	0.041*
C7	0.58898 (19)	0.4942 (6)	0.12745 (18)	0.0347 (10)
H7	0.6225	0.5668	0.1557	0.042*
C8	0.5289 (2)	0.4467 (7)	0.13551 (17)	0.0340 (10)
H8	0.5220	0.4883	0.1694	0.041*
C9	0.43441 (18)	0.1817 (6)	0.00714 (16)	0.0258 (8)
C10	0.36475 (18)	0.0474 (6)	−0.06765 (15)	0.0246 (8)
C11	0.33235 (18)	−0.0329 (6)	−0.12595 (15)	0.0268 (9)
C12	0.3677 (2)	−0.0228 (7)	−0.16469 (17)	0.0337 (10)
H12	0.4104	0.0389	−0.1534	0.040*
C13	0.3397 (3)	−0.1037 (7)	−0.21942 (18)	0.0426 (12)
H13	0.3636	−0.0967	−0.2454	0.051*
C14	0.2775 (3)	−0.1946 (7)	−0.23681 (19)	0.0448 (12)
H14	0.2592	−0.2506	−0.2741	0.054*
C15	0.2425 (2)	−0.2025 (7)	−0.19894 (19)	0.0403 (12)
H15	0.1998	−0.2636	−0.2106	0.048*
C16	0.2693 (2)	−0.1219 (7)	−0.14401 (18)	0.0369 (11)
H16	0.2446	−0.1276	−0.1187	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.02700 (7)	0.03224 (11)	0.02386 (7)	−0.00874 (8)	0.00836 (5)	0.00069 (8)
Br1	0.03230 (18)	0.0375 (3)	0.03867 (19)	−0.0024 (2)	0.01516 (15)	0.0035 (2)
O1	0.068 (2)	0.075 (3)	0.0338 (16)	−0.021 (2)	0.0179 (15)	−0.0196 (19)
O2	0.0364 (15)	0.077 (3)	0.0440 (17)	−0.0237 (18)	0.0178 (13)	−0.0038 (18)
O3	0.081 (3)	0.071 (4)	0.079 (3)	0.009 (3)	0.020 (2)	0.034 (3)
N1	0.0216 (14)	0.022 (2)	0.0309 (15)	−0.0032 (15)	0.0036 (12)	0.0023 (15)
N2	0.0224 (14)	0.019 (2)	0.0291 (15)	−0.0061 (14)	0.0071 (12)	0.0002 (14)
N3	0.0250 (14)	0.023 (2)	0.0270 (14)	−0.0053 (15)	0.0074 (11)	−0.0012 (15)
N4	0.0240 (14)	0.018 (2)	0.0350 (16)	−0.0011 (14)	0.0116 (12)	0.0018 (15)
C1	0.032 (2)	0.049 (4)	0.0275 (19)	−0.009 (2)	0.0074 (15)	0.004 (2)
C2	0.036 (2)	0.047 (3)	0.0221 (17)	−0.013 (2)	0.0068 (15)	−0.0053 (19)
C3	0.041 (2)	0.053 (4)	0.043 (2)	−0.007 (3)	0.0144 (19)	0.017 (3)
C4	0.0250 (16)	0.015 (3)	0.0322 (17)	0.0002 (15)	0.0084 (13)	0.0071 (15)
C5	0.0245 (17)	0.023 (3)	0.042 (2)	0.0009 (18)	0.0128 (16)	0.009 (2)
C6	0.0243 (18)	0.021 (3)	0.052 (2)	−0.0034 (19)	0.0086 (17)	0.014 (2)
C7	0.0268 (18)	0.018 (3)	0.047 (2)	−0.0065 (18)	−0.0005 (16)	0.009 (2)
C8	0.038 (2)	0.024 (3)	0.0353 (19)	−0.007 (2)	0.0078 (16)	−0.003 (2)
C9	0.0266 (17)	0.016 (2)	0.0354 (19)	0.0016 (17)	0.0123 (15)	0.0062 (17)
C10	0.0298 (18)	0.013 (2)	0.0293 (17)	0.0031 (17)	0.0089 (14)	0.0020 (17)
C11	0.0324 (19)	0.018 (3)	0.0287 (17)	0.0041 (18)	0.0099 (15)	−0.0024 (17)
C12	0.044 (2)	0.022 (3)	0.037 (2)	0.005 (2)	0.0161 (17)	0.0047 (19)
C13	0.065 (3)	0.030 (3)	0.039 (2)	0.012 (2)	0.025 (2)	0.002 (2)
C14	0.066 (3)	0.030 (3)	0.033 (2)	0.002 (2)	0.012 (2)	−0.008 (2)
C15	0.048 (2)	0.027 (4)	0.041 (2)	−0.006 (2)	0.0107 (19)	−0.013 (2)
C16	0.037 (2)	0.033 (3)	0.042 (2)	0.001 (2)	0.0155 (18)	−0.008 (2)

Geometric parameters (Å, º) top

Re1—C1	1.905 (4)	C5—C6	1.374 (6)
Re1—C2	1.915 (4)	C5—H5	0.9400
Re1—C3	1.922 (6)	C6—C7	1.369 (6)
Re1—N2	2.164 (3)	C6—H6	0.9400
Re1—N1	2.201 (3)	C7—C8	1.380 (5)
Re1—Br1	2.6357 (5)	C7—H7	0.9400
O1—C1	1.153 (5)	C8—H8	0.9400
O2—C2	1.135 (4)	C10—C11	1.453 (5)
O3—C3	1.103 (6)	C11—C16	1.380 (6)
N1—C8	1.327 (5)	C11—C12	1.397 (5)
N1—C4	1.352 (5)	C12—C13	1.376 (6)
N2—C9	1.325 (4)	C12—H12	0.9400
N2—N3	1.361 (4)	C13—C14	1.373 (7)
N3—C10	1.353 (4)	C13—H13	0.9400
N3—H3	0.8700	C14—C15	1.371 (6)
N4—C10	1.328 (5)	C14—H14	0.9400
N4—C9	1.346 (5)	C15—C16	1.377 (6)
C4—C5	1.388 (5)	C15—H15	0.9400
C4—C9	1.442 (5)	C16—H16	0.9400

C1—Re1—C2	87.78 (17)	C7—C6—C5	119.4 (3)
C1—Re1—C3	90.4 (2)	C7—C6—H6	120.3
C2—Re1—C3	89.18 (19)	C5—C6—H6	120.3
C1—Re1—N2	168.91 (15)	C6—C7—C8	119.7 (4)
C2—Re1—N2	102.56 (14)	C6—C7—H7	120.2
C3—Re1—N2	93.71 (18)	C8—C7—H7	120.2
C1—Re1—N1	95.31 (14)	N1—C8—C7	122.0 (4)
C2—Re1—N1	176.88 (13)	N1—C8—H8	119.0
C3—Re1—N1	91.22 (15)	C7—C8—H8	119.0
N2—Re1—N1	74.33 (11)	N2—C9—N4	114.0 (3)
C1—Re1—Br1	91.81 (14)	N2—C9—C4	118.2 (3)
C2—Re1—Br1	93.80 (15)	N4—C9—C4	127.6 (3)
C3—Re1—Br1	176.38 (12)	N4—C10—N3	110.0 (3)
N2—Re1—Br1	83.63 (9)	N4—C10—C11	124.8 (3)
N1—Re1—Br1	85.69 (9)	N3—C10—C11	125.2 (3)
C8—N1—C4	118.4 (3)	C16—C11—C12	118.9 (4)
C8—N1—Re1	125.5 (3)	C16—C11—C10	122.9 (3)
C4—N1—Re1	116.1 (2)	C12—C11—C10	118.1 (3)
C9—N2—N3	103.7 (3)	C13—C12—C11	119.6 (4)
C9—N2—Re1	116.5 (3)	C13—C12—H12	120.2
N3—N2—Re1	139.3 (2)	C11—C12—H12	120.2
C10—N3—N2	108.5 (3)	C14—C13—C12	121.3 (4)
C10—N3—H3	125.7	C14—C13—H13	119.4
N2—N3—H3	125.7	C12—C13—H13	119.4
C10—N4—C9	103.8 (3)	C15—C14—C13	119.0 (4)
O1—C1—Re1	178.4 (4)	C15—C14—H14	120.5
O2—C2—Re1	175.6 (3)	C13—C14—H14	120.5
O3—C3—Re1	179.0 (4)	C14—C15—C16	120.8 (4)
N1—C4—C5	122.4 (4)	C14—C15—H15	119.6
N1—C4—C9	114.8 (3)	C16—C15—H15	119.6
C5—C4—C9	122.8 (3)	C15—C16—C11	120.4 (4)
C6—C5—C4	118.1 (4)	C15—C16—H16	119.8
C6—C5—H5	120.9	C11—C16—H16	119.8
C4—C5—H5	120.9

C9—N2—N3—C10	−0.3 (4)	C5—C4—C9—N2	177.7 (4)
Re1—N2—N3—C10	170.7 (3)	N1—C4—C9—N4	172.3 (4)
C8—N1—C4—C5	1.1 (6)	C5—C4—C9—N4	−7.0 (7)
Re1—N1—C4—C5	−178.5 (3)	C9—N4—C10—N3	−0.7 (5)
C8—N1—C4—C9	−178.2 (4)	C9—N4—C10—C11	179.0 (4)
Re1—N1—C4—C9	2.2 (4)	N2—N3—C10—N4	0.7 (5)
N1—C4—C5—C6	0.0 (6)	N2—N3—C10—C11	−179.1 (4)
C9—C4—C5—C6	179.3 (4)	N4—C10—C11—C16	176.3 (4)
C4—C5—C6—C7	−1.0 (6)	N3—C10—C11—C16	−4.0 (7)
C5—C6—C7—C8	0.9 (7)	N4—C10—C11—C12	−2.2 (6)
C4—N1—C8—C7	−1.3 (6)	N3—C10—C11—C12	177.5 (4)
Re1—N1—C8—C7	178.3 (3)	C16—C11—C12—C13	−1.0 (7)
C6—C7—C8—N1	0.3 (7)	C10—C11—C12—C13	177.5 (4)
N3—N2—C9—N4	−0.1 (5)	C11—C12—C13—C14	0.0 (7)
Re1—N2—C9—N4	−173.6 (3)	C12—C13—C14—C15	0.8 (7)
N3—N2—C9—C4	175.8 (3)	C13—C14—C15—C16	−0.5 (7)
Re1—N2—C9—C4	2.3 (5)	C14—C15—C16—C11	−0.5 (7)
C10—N4—C9—N2	0.5 (5)	C12—C11—C16—C15	1.2 (7)
C10—N4—C9—C4	−174.9 (4)	C10—C11—C16—C15	−177.1 (4)
N1—C4—C9—N2	−3.0 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Br1ⁱ	0.87	2.51	3.360 (3)	168
C16—H16···Br1ⁱ	0.94	2.87	3.784 (4)	165
C6—H6···O2ⁱⁱ	0.94	2.38	3.194 (5)	145
C8—H8···O1ⁱⁱⁱ	0.94	2.56	3.285 (5)	134

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···Br1ⁱ	0.87	2.51	3.360 (3)	168
C16—H16···Br1ⁱ	0.94	2.87	3.784 (4)	165
C6—H6···O2ⁱⁱ	0.94	2.38	3.194 (5)	145
C8—H8···O1ⁱⁱⁱ	0.94	2.56	3.285 (5)	134

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

Experimental details

Crystal data
Chemical formula	[ReBr(C₁₃H₁₀N₄)(CO)₃]
M_r	572.39
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	213
a, b, c (Å)	20.8082 (15), 7.2521 (4), 24.386 (2)
β (°)	111.599 (7)
V (Å³)	3421.5 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	9.46
Crystal size (mm)	0.14 × 0.12 × 0.11

Data collection
Diffractometer	Stoe Imaging plate diffraction system diffractometer
Absorption correction	Numerical (X-RED and X-SHAPE; Stoe & Cie, 2001)
T_min, T_max	0.319, 0.385
No. of measured, independent and observed [I > 2σ(I)] reflections	14578, 4092, 2844
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.050, 0.84
No. of reflections	4092
No. of parameters	226
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.03, −1.14

Computer programs: IPDS (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 2012).

Acknowledgements

This work was supported by the fund `Grant for Science Research' (No. 0111U000111) from the Ministry of Education and Science of Ukraine. We thank the Taurida National V. I. Vernadsky University, Crimea, Ukraine, for providing the ligand.

References

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Volume 70| Part 12| December 2014| Pages 587-589

doi:10.1107/S1600536814025604

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