Crystal structure of the cis and trans polymorphs of bis­[μ-2-(1,3-benzo­thia­zol-2-yl)phenolato]-κ3N,O:O;κ3O:N,O-bis­[fac-tri­carbonyl­rhenium(I)]

Priyatharsini, M.; Shankar, B.; Sathiyendiran, M.; Srinivasan, N.; Krishnakumar, R.V.

doi:10.1107/S2056989017001347

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ISSN: 2056-9890

Volume 73| Part 2| February 2017| Pages 310-313

https://doi.org/10.1107/S2056989017001347

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Crystal structure of the cis and trans polymorphs of bis[μ-2-(1,3-benzothiazol-2-yl)phenolato]-κ³N,O:O;κ³O:N,O-bis[fac-tricarbonylrhenium(I)]¹

Maruthupandiyan Priyatharsini,^a Bhaskaran Shankar,^b Malaichamy Sathiyendiran,^b Navaneethakrishnan Srinivasan ^a and Rajaputi Venkatraman Krishnakumar ^a ^*

^aDepartment of Physics, Thiagarajar College, Madurai 625 009, Tamil Nadu, India, and ^bDepartment of Chemistry, University of Hyderabad, South Campus, Hyderabad 500 046, Telengana, India
^*Correspondence e-mail: mailtorvkk@yahoo.co.in

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 11 January 2017; accepted 26 January 2017; online 31 January 2017)

The title dinuclear complex, [Re₂(C₁₃H₈NOS)₂(CO)₆], crystallizes in two polymorphs where the 2-(1,3-benzothiazol-2-yl)phenolate ligands and two carbonyl groups are trans- (I) or cis-arranged (II) with respect to the [Re₂O₂(CO)₄] core. Polymorphs I and II exhibit a crystallographically imposed centre of symmetry and a twofold rotation axis, respectively. The structures may be described as being formed by two octahedrally distorted metal-coordinating units fused through μ-oxido bridges, leading to edge-sharing dimers. The crystal packing is governed by C—H⋯O hydrogen-bonding interactions, forming chains parallel to the c axis in I and a three-dimensional network in II.

Keywords: crystal structure; rhenium tricarbonyl complexes; polymorphism.

CCDC references: 1529701; 1529700

1. Chemical context

Organometallic complexes are regarded as interesting and important compounds owing to their versatile photophysical, photochemical and biological properties. In particular, the importance of the use of metal complexes in medicine began with the discovery of the anti-cancer activity of cis-platin (Rosenberg et al., 1965 ). Since then, attempts to synthesize and characterize novel organometallics with potential pharmaceutical applications remains the main focus of anticancer drug discovery.

While it has been discovered recently that some rhenium–indolato complexes exhibit light-induced anti-cancer activity (Kastl et al., 2013 ), a number of tricarbonyl–rhenium complexes are well known agents in the field of biomedical imaging (Lo et al., 2010 , 2011 ). Several rhenium(I) tricarbonyl heterocyclic complexes are known to exhibit intense luminescence in the visible region and, owing to their stability to photodecomposition, are promising candidates for solar energy conversion applications (Wallace & Rillema, 1993 ). In the context of earlier works (Shi et al., 1996 ; Bradshaw & Westwell, 2004 ; Potgieter et al., 2012 ) suggesting benzothiazole derivatives to be promising ligands for rhenium which possess potential usefulness in radiotherapy, the intra- and intermolecular features of the crystal structures of the title compound may well be regarded as relevant. More recently, a host of rhenium–tricarbonyl complexes containing heterocyclic derivatives have been shown to exhibit antimicrobial properties (Kumar et al., 2016 ). In a recent review, a systematic evaluation of neutral Re^I tricarbonyl complexes was undertaken for their suitability as organic light-emitting diodes (Zhao et al., 2016 ).

2. Structural commentary

The title compound, [Re(CO)₃(L)]₂ where L= 2-(1,3-benzothiazol-2-yl)phenolate, crystallizes in two different forms, viz. the trans form (I, Fig. 1) in the triclinic space group P $[\overline{1}]$ and the cis form (II, Fig. 2) in the orthorhombic space group Pbca. The structure of the compound may be described as being composed of two octahedral metal-coordinating units fused through μ-oxido bridges leading to edge-sharing dimers. The presence of the inversion centre in I leads to Re—O-bridged centrosymmetric dimeric molecular units. In II, dimerization through Re—O bridging is achieved through a twofold rotation axis. In both I and II, coordination around the rhenium atom is similar, the metal exhibiting a distorted octahedral environment with atoms C16 and N1 occupying the apical sites and atoms C14, C15, O1 and O1ⁱ/O1ⁱⁱ at the equatorial plane [symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) −x, y, $[{1\over 2}]$ − z]. The N1—Re01—O1ⁱ—C9ⁱ torsion angle associated with the Re—O bridging of symmetry-related molecules in trans polymorph I [137.1 (5)°] is distinctly different from the corresponding value in the cis polymorph II [−59.4 (3)°]. The Re⋯Re and O1⋯O1 separations in the Re₂O₂ core are 3.4799 (5) and 2.581 (8) Å, and 3.4332 (5) and 2.535 (4) Å in I and II, respectively.

Figure 1
The molecular structure of I, with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by (1 − x, 1 − y, 1 − z). H atoms have been omitted for clarity.

Figure 2
The molecular structure of II, with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by (−x, y, $[{1\over 2}]$ − z). H atoms have been omitted for clarity.

The conformation of the ligand in I and II is significantly different. The dihedral angles between the planar benzothiazole unit and the benzene rings in I and II are 32.23 (18) and 22.78 (8)°, respectively. The value observed in II closely agrees with that observed in the crystal structure of 2-(4-hydroxyphenyl)benzothiazole [18.49 (6)°; Teo et al., 1995 ], which interestingly crystallizes in the same space group. The larger value observed in I may be attributed to the `flipping' of the twofold symmetry into an inversion centre.

3. Supramolecular features

The crystal structures of I and II are governed by C—H⋯O hydrogen bonds which significantly differ in their strengths and the mode of participation of the carbonyl O atoms. In I, the O3 atom of the apical carbonyl group C16=O3 plays a role in connecting the molecules across inversion centres into a chain along the c axis (Fig. 3, Table 1). In addition, a short O4⋯O4ⁱⁱⁱ contact [symmetry code: (iii) –x + 1, –y + 2, –z + 1] involving centrosymmetrcally related carbonyl groups C15=O4 [2.792 (10) Å] is present, linking the chains along the b axis to form layers parallel to the bc plane.

Table 1
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O3ⁱ	0.95	2.52	3.276 (8)	137
Symmetry code: (i) x, y, z-1.

Figure 3
Crystal packing of I, showing the formation of molecular chains parallel to the c axis via C—H⋯O hydrogen bonds (dashed lines). H atoms not involved in hydrogen bonding are omitted.

In II, the oxygen atom of the equatorial carbonyl group C14=O2 links the molecules across the glide planes into a three-dimensional network (Fig. 4, Table 2). Similarly to that observed in I, a C—H⋯O hydrogen bond involving the O3 atom of the apical carbonyl group C16=O3 is present, which extends along the b axis through translation. Therefore it may be concluded that in both the trans and cis polymorphs, the mode of participation to the hydrogen-bonding network of the O atom of the apical carbonyl group is through simple translation, while there is a significant `switching' in the choice of the O atoms of the equatorial carbonyl groups. A common feature between the two structures is that one of the three carbonyl groups, namely C14=O2 in I and C15=O4 in II, forbids its O atom from participating in the intermolecular interactions.

Table 2
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O2ⁱ	0.93	2.49	3.387 (4)	163
C2—H2⋯O3ⁱⁱ	0.93	2.64	3.467 (5)	149
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) x, y+1, z.

Figure 4
Crystal packing of II approximately, viewed along the b axis, showing molecules linked into a the three-dimensional network through C—H⋯O hydrogen bonds (red dashed lines). H atoms not involved in hydrogen bonding are omitted.

4. Database survey

A search in the Cambridge structural Database (Version 5.35, November 2014 update; Groom et al., 2016 ) for μ-oxido bridging dinuclear complexes of rhenium having an octahedral coordination environment similar to that observed in the title compounds (i.e. involving three carbonyl C atoms, two oxygens and a nitrogen) was made. The search returned 45 crystal structures with three-dimensional coordinates determined, excluding duplicate structure determinations and having an R factor less than 0.075. Out of these 45 crystal structures, 25 crystallize in the monoclinic, nine in the triclinic, eight in the orthorhombic and three in the trigonal systems. In these compounds, the Re⋯Re distance ranges from 3.330 to 3.501 Å, the O⋯O separation within the Re₂O₂ core ranges from 2.485 to 2.701 Å, and Re—O bond lengths from 2.065 to 2.215 Å.

5. Synthesis and crystallization

For I:

A mixture of Re₂(CO)₁₀ (101.3 mg, 0.1552 mmol), 2-(1,3-benzothiazol-2-yl)phenol (69.7 mg, 0.307 mmol) and 2-phenyl-2-imidazoline (45.8 mg, 0.323 mmol) in toluene (10 ml) in a Teflon flask was placed in a steel bomb. The bomb was placed in an oven maintained at 433 K for 48 h and then cooled to 298 K. Pale-yellow crystals were obtained and separated by filtration.

For II:

A mixture of Re₂(CO)₁₀ (101.8 mg, 0.156 mmol), 2-(1,3-benzothiazol-2-yl)phenol (69.9 mg, 0.308 mmol) and 2-(pyridin-4-yl)-1-(2,4,6-trimethylbenzyl)-1H-benzo[d]imidazole (101.1 mg, 0.309 mmol) in toluene (10 ml) in a Teflon flask was placed in a steel bomb. The bomb was placed in an oven maintained at 433 K for 48 h and then cooled to 298 K. Pale-yellow crystals were obtained and separated by filtration.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. In both I and II, the H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set at 1.2–1.5U_eq(C). In I, two outliers (9 11 2, 2 2 4) were omitted in the last cycles of refinement.

Table 3
Experimental details

	I	II
Crystal data
Chemical formula	[Re₂(C₁₃H₈NOS)₂(CO)₆]	[Re₂(C₁₃H₈NOS)₂(CO)₆]
M_r	992.99	992.99
Crystal system, space group	Triclinic, P $[\overline{1}]$	Orthorhombic, Pbcn
Temperature (K)	100	296
a, b, c (Å)	8.9250 (11), 9.7342 (12), 10.0844 (12)	16.1480 (7), 11.6519 (5), 15.6329 (8)
α, β, γ (°)	66.438 (5), 75.636 (5), 63.585 (5)	90, 90, 90
V (Å³)	716.59 (16)	2941.4 (2)
Z	1	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	8.64	8.42
Crystal size (mm)	0.28 × 0.18 × 0.15	0.25 × 0.18 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.168, 0.357	0.18, 0.38
No. of measured, independent and observed [I > 2σ(I)] reflections	23724, 3325, 3113	11735, 3510, 2943
R_int	0.105	0.027
(sin θ/λ)_max (Å⁻¹)	0.654	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.088, 1.08	0.027, 0.060, 1.07
No. of reflections	3325	3510
No. of parameters	208	208
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.91, −2.74	1.09, −0.95
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2013 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), PLUTON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1529701; 1529700

Crystal structure: contains datablocks I, II. DOI: https://doi.org/10.1107/S2056989017001347/rz5204sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017001347/rz5204Isup6.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989017001347/rz5204IIsup7.hkl

checkCIF report

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: PLUTON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

(I) trans-Bis[µ-2-(1,3-benzothiazol-2-yl)phenolato]-κ³N,O:O;κ³O:N,O-bis[fac-tricarbonylrhenium(I)] top

Crystal data top

[Re₂(C₁₃H₈NOS)₂(CO)₆]	Z = 1
M_r = 992.99	F(000) = 468
Triclinic, P1	D_x = 2.301 Mg m⁻³
a = 8.9250 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7342 (12) Å	Cell parameters from 3113 reflections
c = 10.0844 (12) Å	θ = 2.5–27.7°
α = 66.438 (5)°	µ = 8.64 mm⁻¹
β = 75.636 (5)°	T = 100 K
γ = 63.585 (5)°	Needle, yellow
V = 716.59 (16) Å³	0.28 × 0.18 × 0.15 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3113 reflections with I > 2σ(I)
ω scans	R_int = 0.105
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θ_max = 27.7°, θ_min = 2.5°
T_min = 0.168, T_max = 0.357	h = −11→11
23724 measured reflections	k = −12→12
3325 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0558P)²] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
3325 reflections	Δρ_max = 2.91 e Å⁻³
208 parameters	Δρ_min = −2.74 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. Refined as a 2-component perfect inversion twin.

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

	x	y	z	U_iso*/U_eq
Re01	0.36347 (2)	0.70142 (2)	0.47571 (2)	0.01179 (10)
S1	0.5151 (2)	0.69074 (18)	−0.00066 (15)	0.0204 (3)
O1	0.3841 (5)	0.4733 (5)	0.4716 (4)	0.0136 (7)
O2	0.0115 (6)	0.9108 (6)	0.3751 (5)	0.0285 (11)
O3	0.2004 (7)	0.6662 (7)	0.7869 (5)	0.0329 (12)
O4	0.3450 (7)	1.0258 (6)	0.4663 (8)	0.0413 (14)
N1	0.4733 (6)	0.7154 (5)	0.2528 (5)	0.0143 (9)
C1	0.6280 (7)	0.7795 (7)	0.0280 (6)	0.0206 (12)
C2	0.7395 (9)	0.8452 (8)	−0.0704 (7)	0.0258 (14)
H2	0.7625	0.8448	−0.1674	0.031*
C3	0.8153 (8)	0.9111 (8)	−0.0215 (8)	0.0283 (15)
H3	0.8930	0.9550	−0.0856	0.034*
C4	0.7797 (8)	0.9142 (8)	0.1200 (8)	0.0267 (14)
H4	0.8337	0.9599	0.1507	0.032*
C5	0.6676 (8)	0.8521 (7)	0.2161 (7)	0.0201 (12)
H5	0.6427	0.8563	0.3120	0.024*
C6	0.5912 (7)	0.7828 (6)	0.1703 (6)	0.0164 (11)
C7	0.4244 (7)	0.6635 (6)	0.1754 (6)	0.0158 (10)
C8	0.3038 (7)	0.5852 (7)	0.2262 (6)	0.0173 (11)
C9	0.2952 (7)	0.4856 (6)	0.3742 (6)	0.0144 (10)
C10	0.1877 (8)	0.4040 (7)	0.4184 (7)	0.0214 (12)
H10	0.1813	0.3356	0.5164	0.026*
C11	0.0890 (9)	0.4215 (8)	0.3198 (7)	0.0255 (13)
H11	0.0175	0.3636	0.3513	0.031*
C12	0.0942 (8)	0.5229 (8)	0.1760 (7)	0.0225 (12)
H12	0.0248	0.5369	0.1101	0.027*
C13	0.2023 (8)	0.6028 (7)	0.1310 (6)	0.0208 (12)
H13	0.2073	0.6714	0.0329	0.025*
C14	0.1446 (8)	0.8311 (7)	0.4146 (6)	0.0203 (12)
C15	0.3586 (8)	0.9012 (7)	0.4703 (7)	0.0244 (13)
C16	0.2666 (8)	0.6763 (7)	0.6697 (6)	0.0176 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re01	0.01088 (13)	0.00927 (12)	0.01551 (13)	−0.00340 (8)	−0.00144 (7)	−0.00480 (8)
S1	0.0232 (7)	0.0199 (7)	0.0161 (6)	−0.0080 (6)	0.0009 (5)	−0.0060 (5)
O1	0.0121 (18)	0.0103 (17)	0.0185 (17)	−0.0032 (14)	0.0007 (14)	−0.0074 (14)
O2	0.016 (2)	0.029 (2)	0.032 (2)	0.0011 (18)	−0.0068 (18)	−0.0100 (19)
O3	0.027 (3)	0.042 (3)	0.025 (2)	−0.008 (2)	−0.0042 (19)	−0.012 (2)
O4	0.030 (3)	0.021 (2)	0.083 (4)	−0.010 (2)	−0.001 (3)	−0.029 (3)
N1	0.014 (2)	0.010 (2)	0.017 (2)	−0.0043 (17)	−0.0020 (17)	−0.0023 (16)
C1	0.016 (3)	0.013 (2)	0.024 (3)	−0.004 (2)	−0.001 (2)	−0.001 (2)
C2	0.024 (3)	0.020 (3)	0.022 (3)	−0.007 (2)	0.002 (2)	0.000 (2)
C3	0.016 (3)	0.021 (3)	0.035 (3)	−0.009 (2)	0.002 (2)	0.003 (2)
C4	0.020 (3)	0.020 (3)	0.036 (3)	−0.010 (2)	−0.005 (3)	−0.001 (2)
C5	0.015 (3)	0.017 (3)	0.025 (3)	−0.007 (2)	−0.003 (2)	−0.003 (2)
C6	0.014 (3)	0.011 (2)	0.021 (2)	−0.004 (2)	0.0010 (19)	−0.0040 (19)
C7	0.013 (3)	0.010 (2)	0.019 (2)	−0.0011 (19)	−0.0009 (19)	−0.0040 (19)
C8	0.015 (3)	0.016 (2)	0.020 (2)	−0.005 (2)	0.001 (2)	−0.009 (2)
C9	0.012 (2)	0.009 (2)	0.021 (2)	−0.0012 (19)	−0.0004 (19)	−0.0073 (19)
C10	0.018 (3)	0.019 (3)	0.027 (3)	−0.010 (2)	−0.004 (2)	−0.004 (2)
C11	0.026 (3)	0.025 (3)	0.032 (3)	−0.014 (3)	−0.008 (3)	−0.009 (2)
C12	0.022 (3)	0.024 (3)	0.028 (3)	−0.007 (2)	−0.009 (2)	−0.013 (2)
C13	0.020 (3)	0.018 (3)	0.020 (2)	−0.003 (2)	−0.003 (2)	−0.007 (2)
C14	0.028 (3)	0.017 (3)	0.017 (2)	−0.011 (2)	0.002 (2)	−0.006 (2)
C15	0.021 (3)	0.015 (3)	0.036 (3)	−0.004 (2)	0.000 (2)	−0.012 (2)
C16	0.014 (3)	0.022 (3)	0.018 (2)	−0.005 (2)	−0.006 (2)	−0.006 (2)

Geometric parameters (Å, º) top

Re01—C14	1.890 (7)	C2—H2	0.9500
Re01—C15	1.905 (7)	C3—C4	1.392 (11)
Re01—C16	1.898 (6)	C3—H3	0.9500
Re01—O1	2.162 (4)	C4—C5	1.376 (8)
Re01—O1ⁱ	2.171 (4)	C4—H4	0.9500
Re01—N1	2.194 (5)	C5—C6	1.396 (9)
S1—C1	1.722 (7)	C5—H5	0.9500
S1—C7	1.726 (6)	C7—C8	1.465 (8)
O1—C9	1.348 (7)	C8—C13	1.390 (9)
O1—Re01ⁱ	2.171 (4)	C8—C9	1.424 (7)
O2—C14	1.157 (8)	C9—C10	1.390 (8)
O3—C16	1.170 (8)	C10—C11	1.400 (9)
O4—C15	1.148 (9)	C10—H10	0.9500
N1—C7	1.317 (8)	C11—C12	1.394 (9)
N1—C6	1.405 (7)	C11—H11	0.9500
C1—C2	1.398 (8)	C12—C13	1.382 (9)
C1—C6	1.400 (8)	C12—H12	0.9500
C2—C3	1.384 (11)	C13—H13	0.9500

C14—Re01—C15	83.9 (3)	C5—C4—H4	119.4
C14—Re01—C16	87.9 (2)	C3—C4—H4	119.4
C15—Re01—C16	86.4 (3)	C4—C5—C6	118.8 (6)
C14—Re01—O1	98.2 (2)	C4—C5—H5	120.6
C15—Re01—O1	176.1 (2)	C6—C5—H5	120.6
C16—Re01—O1	97.0 (2)	C5—C6—C1	119.8 (5)
C14—Re01—O1ⁱ	170.6 (2)	C5—C6—N1	126.5 (5)
C15—Re01—O1ⁱ	104.5 (2)	C1—C6—N1	113.7 (5)
C16—Re01—O1ⁱ	96.8 (2)	N1—C7—C8	125.9 (5)
O1—Re01—O1ⁱ	73.12 (18)	N1—C7—S1	115.5 (4)
C14—Re01—N1	92.1 (2)	C8—C7—S1	118.6 (5)
C15—Re01—N1	97.5 (2)	C13—C8—C9	119.9 (5)
C16—Re01—N1	176.0 (2)	C13—C8—C7	120.9 (5)
O1—Re01—N1	79.11 (16)	C9—C8—C7	119.1 (5)
O1ⁱ—Re01—N1	82.68 (16)	O1—C9—C10	120.0 (5)
C1—S1—C7	89.8 (3)	O1—C9—C8	121.6 (5)
C9—O1—Re01	115.5 (3)	C10—C9—C8	118.3 (6)
C9—O1—Re01ⁱ	126.8 (3)	C9—C10—C11	120.6 (5)
Re01—O1—Re01ⁱ	106.88 (18)	C9—C10—H10	119.7
C7—N1—C6	110.7 (5)	C11—C10—H10	119.7
C7—N1—Re01	120.7 (4)	C12—C11—C10	120.8 (6)
C6—N1—Re01	128.5 (4)	C12—C11—H11	119.6
C2—C1—C6	121.4 (6)	C10—C11—H11	119.6
C2—C1—S1	128.4 (5)	C13—C12—C11	118.8 (6)
C6—C1—S1	110.2 (4)	C13—C12—H12	120.6
C3—C2—C1	117.7 (6)	C11—C12—H12	120.6
C3—C2—H2	121.2	C12—C13—C8	121.4 (5)
C1—C2—H2	121.2	C12—C13—H13	119.3
C2—C3—C4	121.2 (6)	C8—C13—H13	119.3
C2—C3—H3	119.4	O2—C14—Re01	179.0 (5)
C4—C3—H3	119.4	O4—C15—Re01	175.7 (6)
C5—C4—C3	121.2 (7)	O3—C16—Re01	177.0 (5)

C7—S1—C1—C2	−178.2 (6)	C1—S1—C7—N1	−0.3 (5)
C7—S1—C1—C6	0.3 (4)	C1—S1—C7—C8	−179.6 (4)
C6—C1—C2—C3	1.3 (9)	N1—C7—C8—C13	149.4 (6)
S1—C1—C2—C3	179.7 (5)	S1—C7—C8—C13	−31.3 (7)
C1—C2—C3—C4	−1.0 (9)	N1—C7—C8—C9	−32.5 (8)
C2—C3—C4—C5	−0.1 (10)	S1—C7—C8—C9	146.7 (4)
C3—C4—C5—C6	1.0 (9)	Re01—O1—C9—C10	−128.2 (5)
C4—C5—C6—C1	−0.8 (9)	Re01ⁱ—O1—C9—C10	92.4 (6)
C4—C5—C6—N1	−179.4 (5)	Re01—O1—C9—C8	49.8 (6)
C2—C1—C6—C5	−0.4 (8)	Re01ⁱ—O1—C9—C8	−89.7 (6)
S1—C1—C6—C5	−179.1 (4)	C13—C8—C9—O1	−175.9 (5)
C2—C1—C6—N1	178.4 (5)	C7—C8—C9—O1	6.0 (8)
S1—C1—C6—N1	−0.3 (6)	C13—C8—C9—C10	2.0 (9)
C7—N1—C6—C5	178.8 (6)	C7—C8—C9—C10	−176.0 (5)
Re01—N1—C6—C5	2.0 (8)	O1—C9—C10—C11	177.1 (6)
C7—N1—C6—C1	0.1 (7)	C8—C9—C10—C11	−0.9 (9)
Re01—N1—C6—C1	−176.7 (4)	C9—C10—C11—C12	−1.0 (10)
C6—N1—C7—C8	179.4 (5)	C10—C11—C12—C13	1.7 (10)
Re01—N1—C7—C8	−3.5 (8)	C11—C12—C13—C8	−0.6 (10)
C6—N1—C7—S1	0.1 (6)	C9—C8—C13—C12	−1.3 (9)
Re01—N1—C7—S1	177.2 (2)	C7—C8—C13—C12	176.7 (6)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O3ⁱⁱ	0.95	2.52	3.276 (8)	137

Symmetry code: (ii) x, y, z−1.

(II) cis-Bis[µ-2-(1,3-benzothiazol-2-yl)phenolato]-κ³N,O:O;κ³O:N,O-bis[fac-tricarbonylrhenium(I)] top

Crystal data top

[Re₂(C₁₃H₈NOS)₂(CO)₆]	D_x = 2.242 Mg m⁻³
M_r = 992.99	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 2943 reflections
a = 16.1480 (7) Å	θ = 2.9–28.0°
b = 11.6519 (5) Å	µ = 8.42 mm⁻¹
c = 15.6329 (8) Å	T = 296 K
V = 2941.4 (2) Å³	Needle, yellow
Z = 4	0.25 × 0.18 × 0.12 mm
F(000) = 1872

Data collection top

Bruker SMART APEX CCD diffractometer	2943 reflections with I > 2σ(I)
ω scans	R_int = 0.027
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θ_max = 29.3°, θ_min = 2.9°
T_min = 0.18, T_max = 0.38	h = −12→22
11735 measured reflections	k = −15→14
3510 independent reflections	l = −21→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0263P)²] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
3510 reflections	Δρ_max = 1.09 e Å⁻³
208 parameters	Δρ_min = −0.95 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
Re01	−0.00490 (2)	0.15435 (2)	0.35969 (2)	0.01406 (6)
S1	0.07316 (6)	0.54284 (8)	0.35632 (6)	0.0210 (2)
O1	0.07833 (17)	0.1789 (2)	0.25483 (14)	0.0159 (6)
O2	0.13167 (17)	0.1285 (2)	0.49308 (18)	0.0287 (7)
O3	−0.01421 (17)	−0.1089 (3)	0.34887 (19)	0.0293 (7)
O4	−0.13228 (17)	0.1328 (2)	0.50382 (18)	0.0302 (7)
N1	0.00453 (16)	0.3439 (3)	0.36089 (19)	0.0158 (8)
C1	−0.0277 (2)	0.5344 (3)	0.3923 (2)	0.0164 (8)
C2	−0.0769 (2)	0.6243 (3)	0.4226 (2)	0.0198 (8)
H2	−0.0566	0.6988	0.4265	0.024*
C3	−0.1569 (2)	0.5978 (3)	0.4467 (2)	0.0212 (8)
H3	−0.1914	0.6555	0.4672	0.025*
C4	−0.1866 (2)	0.4861 (3)	0.4407 (3)	0.0219 (9)
H4	−0.2410	0.4705	0.4562	0.026*
C5	−0.1369 (2)	0.3980 (3)	0.4121 (2)	0.0173 (8)
H5	−0.1576	0.3237	0.4083	0.021*
C6	−0.0555 (2)	0.4210 (3)	0.3892 (2)	0.0142 (7)
C7	0.0748 (2)	0.3953 (3)	0.3416 (2)	0.0159 (8)
C8	0.1503 (2)	0.3426 (3)	0.3103 (2)	0.0167 (8)
C9	0.1499 (2)	0.2380 (3)	0.2657 (2)	0.0165 (8)
C10	0.2230 (2)	0.1963 (3)	0.2318 (2)	0.0213 (9)
H10	0.2227	0.1273	0.2019	0.026*
C11	0.2959 (2)	0.2549 (4)	0.2414 (2)	0.0271 (10)
H11	0.3443	0.2262	0.2173	0.033*
C12	0.2980 (2)	0.3564 (3)	0.2867 (3)	0.0294 (10)
H12	0.3478	0.3950	0.2945	0.035*
C13	0.2258 (2)	0.4003 (3)	0.3203 (3)	0.0237 (9)
H13	0.2272	0.4694	0.3501	0.028*
C14	0.0788 (2)	0.1374 (3)	0.4440 (3)	0.0183 (8)
C15	−0.0848 (2)	0.1418 (3)	0.4488 (3)	0.0197 (8)
C16	−0.0108 (2)	−0.0097 (4)	0.3516 (2)	0.0189 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re01	0.01466 (9)	0.01247 (9)	0.01505 (10)	0.00037 (6)	0.00097 (6)	0.00113 (6)
S1	0.0214 (5)	0.0153 (4)	0.0264 (6)	−0.0040 (4)	0.0031 (4)	−0.0005 (4)
O1	0.0149 (13)	0.0178 (12)	0.0151 (14)	−0.0016 (10)	0.0013 (10)	−0.0023 (11)
O2	0.0307 (16)	0.0265 (14)	0.0288 (18)	0.0057 (12)	−0.0083 (14)	−0.0005 (13)
O3	0.0357 (17)	0.0147 (14)	0.038 (2)	−0.0035 (12)	0.0049 (14)	0.0005 (14)
O4	0.0323 (16)	0.0318 (15)	0.0265 (18)	0.0006 (13)	0.0133 (14)	0.0065 (13)
N1	0.0161 (17)	0.0151 (18)	0.0162 (19)	−0.0012 (12)	0.0013 (13)	0.0003 (12)
C1	0.0161 (17)	0.0199 (19)	0.0132 (19)	−0.0010 (15)	0.0031 (15)	0.0030 (17)
C2	0.028 (2)	0.0132 (17)	0.018 (2)	0.0005 (15)	−0.0005 (18)	0.0004 (16)
C3	0.027 (2)	0.0184 (19)	0.018 (2)	0.0071 (16)	−0.0001 (17)	−0.0029 (17)
C4	0.0179 (18)	0.025 (2)	0.022 (2)	0.0023 (16)	0.0024 (17)	0.0004 (17)
C5	0.0166 (18)	0.0140 (17)	0.021 (2)	−0.0012 (14)	−0.0008 (16)	−0.0004 (16)
C6	0.0168 (18)	0.0117 (16)	0.0142 (18)	0.0025 (14)	0.0014 (15)	−0.0007 (15)
C7	0.0168 (18)	0.0191 (19)	0.0120 (19)	−0.0018 (15)	−0.0010 (15)	−0.0024 (16)
C8	0.0138 (17)	0.0193 (19)	0.017 (2)	−0.0018 (15)	0.0004 (15)	−0.0007 (16)
C9	0.0137 (17)	0.0189 (18)	0.017 (2)	0.0020 (15)	−0.0012 (15)	0.0046 (16)
C10	0.0186 (19)	0.025 (2)	0.020 (2)	0.0063 (16)	0.0023 (16)	0.0014 (17)
C11	0.0165 (19)	0.039 (3)	0.026 (2)	0.0049 (18)	0.0050 (17)	−0.004 (2)
C12	0.0152 (19)	0.044 (3)	0.029 (3)	−0.0067 (18)	0.0014 (18)	−0.008 (2)
C13	0.0205 (19)	0.020 (2)	0.030 (2)	−0.0053 (17)	0.0003 (18)	−0.0063 (17)
C14	0.0218 (19)	0.0146 (18)	0.019 (2)	0.0011 (15)	0.0018 (17)	−0.0015 (16)
C15	0.0224 (19)	0.0132 (18)	0.023 (2)	0.0021 (15)	−0.0029 (17)	−0.0010 (16)
C16	0.0155 (18)	0.024 (2)	0.017 (2)	0.0015 (15)	0.0018 (15)	0.0019 (16)

Geometric parameters (Å, º) top

Re01—C14	1.898 (4)	C2—H2	0.9300
Re01—C15	1.904 (4)	C3—C4	1.390 (4)
Re01—C16	1.918 (4)	C3—H3	0.9300
Re01—O1	2.139 (2)	C4—C5	1.377 (4)
Re01—O1ⁱ	2.166 (2)	C4—H4	0.9300
Re01—N1	2.214 (3)	C5—C6	1.389 (5)
S1—C1	1.726 (4)	C5—H5	0.9300
S1—C7	1.735 (4)	C7—C8	1.450 (5)
O1—C9	1.355 (4)	C8—C13	1.401 (5)
O1—Re01ⁱ	2.166 (2)	C8—C9	1.404 (5)
O2—C14	1.153 (4)	C9—C10	1.382 (5)
O3—C16	1.158 (5)	C10—C11	1.370 (5)
O4—C15	1.157 (5)	C10—H10	0.9300
N1—C7	1.318 (4)	C11—C12	1.378 (6)
N1—C6	1.393 (4)	C11—H11	0.9300
C1—C6	1.396 (5)	C12—C13	1.377 (5)
C1—C2	1.398 (5)	C12—H12	0.9300
C2—C3	1.380 (5)	C13—H13	0.9300

C14—Re01—C15	88.10 (18)	C5—C4—H4	119.4
C14—Re01—C16	88.70 (15)	C3—C4—H4	119.4
C15—Re01—C16	86.45 (14)	C4—C5—C6	119.4 (3)
C14—Re01—O1	95.63 (14)	C4—C5—H5	120.3
C15—Re01—O1	175.25 (12)	C6—C5—H5	120.3
C16—Re01—O1	96.54 (13)	C5—C6—N1	128.0 (3)
C14—Re01—O1ⁱ	167.74 (13)	C5—C6—C1	118.5 (3)
C15—Re01—O1ⁱ	104.12 (14)	N1—C6—C1	113.5 (3)
C16—Re01—O1ⁱ	92.87 (13)	N1—C7—C8	127.5 (3)
O1—Re01—O1ⁱ	72.12 (12)	N1—C7—S1	114.0 (3)
C14—Re01—N1	92.80 (12)	C8—C7—S1	118.5 (3)
C15—Re01—N1	96.72 (12)	C13—C8—C9	118.4 (3)
C16—Re01—N1	176.53 (14)	C13—C8—C7	119.4 (3)
O1—Re01—N1	80.20 (10)	C9—C8—C7	122.1 (3)
O1ⁱ—Re01—N1	85.00 (10)	O1—C9—C10	120.1 (3)
C1—S1—C7	90.05 (17)	O1—C9—C8	120.5 (3)
C9—O1—Re01	120.5 (2)	C10—C9—C8	119.4 (3)
C9—O1—Re01ⁱ	129.6 (2)	C11—C10—C9	121.1 (4)
Re01—O1—Re01ⁱ	105.77 (11)	C11—C10—H10	119.4
C7—N1—C6	112.3 (3)	C9—C10—H10	119.4
C7—N1—Re01	120.7 (2)	C10—C11—C12	120.3 (4)
C6—N1—Re01	126.7 (2)	C10—C11—H11	119.8
C6—C1—C2	122.6 (3)	C12—C11—H11	119.8
C6—C1—S1	110.2 (3)	C13—C12—C11	119.6 (4)
C2—C1—S1	127.2 (3)	C13—C12—H12	120.2
C3—C2—C1	117.2 (3)	C11—C12—H12	120.2
C3—C2—H2	121.4	C12—C13—C8	121.0 (3)
C1—C2—H2	121.4	C12—C13—H13	119.5
C2—C3—C4	120.9 (3)	C8—C13—H13	119.5
C2—C3—H3	119.6	O2—C14—Re01	177.6 (3)
C4—C3—H3	119.6	O4—C15—Re01	178.7 (3)
C5—C4—C3	121.3 (3)	O3—C16—Re01	178.3 (3)

C7—S1—C1—C6	−1.5 (3)	C1—S1—C7—N1	1.0 (3)
C7—S1—C1—C2	177.1 (4)	C1—S1—C7—C8	−179.2 (3)
C6—C1—C2—C3	−2.7 (6)	N1—C7—C8—C13	−158.5 (4)
S1—C1—C2—C3	178.8 (3)	S1—C7—C8—C13	21.7 (5)
C1—C2—C3—C4	0.0 (6)	N1—C7—C8—C9	25.2 (6)
C2—C3—C4—C5	1.2 (6)	S1—C7—C8—C9	−154.6 (3)
C3—C4—C5—C6	0.2 (6)	Re01—O1—C9—C10	135.2 (3)
C4—C5—C6—N1	178.4 (4)	Re01ⁱ—O1—C9—C10	−71.1 (4)
C4—C5—C6—C1	−2.8 (5)	Re01—O1—C9—C8	−45.7 (4)
C7—N1—C6—C5	177.8 (4)	Re01ⁱ—O1—C9—C8	108.0 (3)
Re01—N1—C6—C5	−9.0 (5)	C13—C8—C9—O1	179.7 (3)
C7—N1—C6—C1	−1.0 (4)	C7—C8—C9—O1	−4.0 (5)
Re01—N1—C6—C1	172.2 (2)	C13—C8—C9—C10	−1.2 (5)
C2—C1—C6—C5	4.2 (6)	C7—C8—C9—C10	175.1 (3)
S1—C1—C6—C5	−177.2 (3)	O1—C9—C10—C11	179.5 (3)
C2—C1—C6—N1	−176.9 (3)	C8—C9—C10—C11	0.4 (6)
S1—C1—C6—N1	1.8 (4)	C9—C10—C11—C12	1.1 (6)
C6—N1—C7—C8	−180.0 (4)	C10—C11—C12—C13	−1.8 (6)
Re01—N1—C7—C8	6.3 (5)	C11—C12—C13—C8	0.9 (6)
C6—N1—C7—S1	−0.2 (4)	C9—C8—C13—C12	0.5 (6)
Re01—N1—C7—S1	−173.91 (16)	C7—C8—C13—C12	−175.9 (4)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O2ⁱⁱ	0.93	2.49	3.387 (4)	163
C2—H2···O3ⁱⁱⁱ	0.93	2.64	3.467 (5)	149

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

Footnotes

¹This paper is dedicated to the memory of Professor S. K. Mohanlal.

Acknowledgements

MP thanks the University Grants Commission, India, for a Rajiv Gandhi National Fellowship and for facilities availed at the Networking Resource Centre, School of Chemistry, University of Hyderabad, India.

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