The crystal structures of tetra­kis­(μ-n-butyrato-κ2O:O′)bis[bromidorhenium(III)] and tetra­kis­(μ-n-butyrato-κ2O:O′)bis[chlorido­rhenium(III)] aceto­nitrile disolvate

Reed, C.R.; Brennessel, W.W.

doi:10.1107/S2056989015020563

research communications

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ISSN: 2056-9890

Volume 71| Part 12| December 2015| Pages 1480-1484

https://doi.org/10.1107/S2056989015020563

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The crystal structures of tetrakis(μ-n-butyrato-κ²O:O′)bis[bromidorhenium(III)] and tetrakis(μ-n-butyrato-κ²O:O′)bis[chloridorhenium(III)] acetonitrile disolvate

Carly R. Reed ^a ^* and William W. Brennessel ^b

^aDepartment of Chemistry and Biochemistry, The College at Brockport, SUNY, Brockport, NY 14420, USA, and ^bDepartment of Chemistry, University of Rochester, Rochester, NY 14627, USA
^*Correspondence e-mail: creed@brockport.edu

Edited by T. J. Prior, University of Hull, England (Received 16 October 2015; accepted 29 October 2015; online 7 November 2015)

The title complexes, [Re₂Br₂(O₂CC₃H₇)₄], (1), and [Re₂(O₂CC₃H₇)₄Cl₂]·2CH₃CN, (2), both exhibit paddlewheel structures with four carboxylate ligands bridging two Re^III atoms. The Re—Re distances are 2.2325 (2) and 2.2299 (3) Å, indicating quadruple bonds between the Re^III atoms in each complex. Both complexes contain an inversion center at the mid-point of the Re—Re bond. The Re—Br bond [2.6712 (3) Å] in (1) is 0.1656 (6) Å longer than the Re—Cl distance [2.5056 (5) Å] of (2). In (2), the N atom of each co-crystallized acetonitrile solvent molecule is nearly equidistant between and in close contact with two carboxylate C atoms.

Keywords: crystal structure; dihalidotetrakis(butyrato)dirhenium(III,III); dirhenium tetracarboxylate; quadruple bond; paddlewheel complex.

CCDC references: 1434257; 1434256

1. Chemical context

The first compound discovered to contain a metal–metal quadruple bond was K₂Re₂Cl₈·2H₂O (Cotton & Harris, 1965 ); since then numerous other quadruply bonded complexes have been isolated (Cotton et al., 2005 ). Dirhenium quadruply bonded complexes are of interest due to their ability to act as molecular building blocks for the formation of molecular triangles and other multiple-metal arrays in which electronic coupling and delocalization between metal sites can be explored (Bera, Angaridis et al. 2001 ; Bera, Smucker et al., 2001 ; Vega et al., 2002 ). The title complexes are of the structural type classified as paddlewheel complexes, where the four carboxylate ligands bridge the two metal atoms, creating a paddlewheel appearance. A variety of these dirhenium(III) tetracarboxylate complexes were synthesized by Cotton et al. (1966 ) and in subsequent years the crystal structures of [Re₂Cl₂(O₂CCH₃)₄], [Re₂Cl₂(O₂CC₆H₅)₄] (Bennett et al., 1968 ), [Re₂(ReO₄)₂(O₂CC₃H₇)₄] (Calvo et al., 1970 ), [Re₂X₂{O₂CC(CH₃)₃}₄], where X = Cl or Br (Collins et al., 1979 ), [Re₂Cl₂(O₂CCH₃)₄] (Koz'min et al., 1980 ), and [Re₂Cl₂(O₂CC₃H₇)₄] (Thomson et al., 2014 ) have been reported. For additional dirhenium tetracarboxylate structures, see: Shtemenko et al. (2001 ), Cotton et al. (1997 ), and Vega et al. (2002). This communication reports and compares the structures of [Re₂Br₂(O₂CC₃H₇)₄], (1), and [Re₂(O₂CC₃H₇)₄Cl₂]·2CH₃CN, (2).

2. Structural commentary

Both of the title dirhenium metal complexes are located on crystallographic inversion centers that coincide with the midpoint of the Re—Re bonds. The short Re—Re bond lengths of 2.2325 (2) and 2.2299 (3) Å, in (1) and (2), respectively, are indicative of quadruple bonds (Tables 1 and 2). The four butyrate groups bridge the two Re^III metal atoms in both cases, forming the anticipated paddlewheel structures (Figs. 1 and 2).

Table 1
Selected geometric parameters (Å, °) for (1)

Re1—O4ⁱ	2.0102 (15)	Re1—O3	2.0295 (14)
Re1—O2ⁱ	2.0159 (14)	Re1—Re1ⁱ	2.2325 (2)
Re1—O1	2.0225 (15)	Re1—Br1	2.6712 (3)

O4ⁱ—Re1—O2ⁱ	89.22 (6)	O1—Re1—O3	89.64 (6)
O4ⁱ—Re1—O1	90.42 (6)	Re1ⁱ—Re1—Br1	175.018 (7)
O2ⁱ—Re1—O3	90.72 (6)

C1—C2—C3—C4	−177.54 (19)	C5—C6—C7—C8	56.0 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Selected geometric parameters (Å, °) for (2)

Re1—O1	2.0216 (12)	Re1—O4	2.0255 (12)
Re1—O2ⁱ	2.0217 (12)	Re1—Re1ⁱ	2.2299 (3)
Re1—O3ⁱ	2.0238 (12)	Re1—Cl1	2.5056 (5)

O1—Re1—O3ⁱ	89.75 (5)	O2ⁱ—Re1—O4	89.75 (5)
O2ⁱ—Re1—O3ⁱ	90.13 (5)	Re1ⁱ—Re1—Cl1	178.254 (11)
O1—Re1—O4	90.37 (5)

C1—C2—C3—C4	−70.2 (2)	C5—C6—C7—C8	−67.9 (2)
Symmetry code: (i) -x, -y, -z+1.

Figure 1
The molecular structure of title compound (1), with displacement ellipsoids drawn at the 50% probability level. The symmetry-equivalent half is generated by operator (−x + 1, −y + 1, −z + 1).

Figure 2
The molecular structure of title compound (2), with displacement ellipsoids drawn at the 50% probability level. The symmetry-equivalent half is generated by operator (−x, −y, −z + 1).

The asymmetric unit of (2) also contains one co-crystallized acetonitrile solvent molecule in a general position, thus giving rise to twice that in the formula unit.

The X—Re—Re—X bonds in (1) and (2) are nearly linear, as can be seen in the Re—Re—Br [175.018 (7)°] and Re—Re—Cl [178.254 (11)°] bond angles, and are comparable to those observed in similar compounds (Collins et al., 1979; Thomson et al., 2014). The Re—Cl bond length [2.5056 (5) Å] of (2) is similar to those of the previously published analog without co-crystallized acetonitrile (Thomson et al., 2014), [Re₂Cl₂(O₂CC(CH₃)₃)₄], and [Re₂Cl₂(O₂CC₆H₅)₄]·2CHCl₃ (Bennett et al., 1968; Collins et al., 1979). The Re—Br bond length [2.6712 (3) Å] of (1) is slightly longer than the Re—Br bond [2.603 (1) Å] found in [Re₂Br₂(O₂CC(CH₃)₃)₄] (Collins et al., 1979). The Re—Br and Re—Cl distances of (1) and (2) differ by 0.1656 (6) Å and those of Cotton and coworkers differ by 0.126 (3), both of which are consistent with the difference in covalent radii of Cl and Br (0.15 Å).

The structure of (1) is isotypic with the chlorido analog published by Thomson et al. (2014). Inspection of the torsion angles of the hydrocarbon chains reveals the possible effect of the co-crystallization of solvent in [Re₂Cl₂(O₂CC₃H₇)₄]. In compound (2), the C1—C2—C3—C4 torsion angle is −70.2 (2)°, comparable to −67.9 (2)° for C5—C6—C7—C8 (Fig. 1). In the structure of [Re₂Cl₂(O₂CC₃H₇)₄] without co-crystallizing solvent, the torsion angles vary more [C1—C2—C3—C4 = −55.2 (5) and C5—C6—C7—C8, 179.5 (4)°] (Thomson et al., 2014), similar to those observed in (1) (Table 1).

3. Supramolecular features

Packing arrangements are shown in Figs. 3 and 4. In (2) nitrogen atom N1 of the co-crystallized acetonitrile solvent molecule is located at distances of 3.197 (3) and 3.216 (3) Å from the carboxylate carbon atoms C1 and C5, respectively. This is just within the sum of the van der Waals radii of 3.25 Å (Bondi, 1964 ), and suggests the presence of a weak electrostatic interaction between the solvent and dirhenium species.

Figure 3
The packing arrangements of (1).

Figure 4
The packing arrangements of (2).

4. Database survey

There are 145 structures in the Cambridge Structural Database to date (CSD, Version 5.36, update No. 3, May 2015; Groom & Allen, 2014 ) that have explicitly defined Re—Re quadruple bonds. However, this appears to be an inconsistent denotation, as many other structures that contain quadruple bonds are not presented as such. For instance only six of the eleven carboxylate paddlewheel complexes in the CSD (to date) have their Re—Re bonds defined as quadruple. Thus a better way to search appears to be by bond length. There are 298 entries with Re—Re bond lengths ≤ 2.29 Å. The only examples of defined quadruple bonds greater than this (excluding obviously disordered structures) are two dirhenium structures with bridging hydride ligands (CSD refcodes BIBLED and BIBLIH; Green et al., 1982 ) and two with bridging di-p-tolylformamidine ligands (CSD refcodes KOZFUA and KOZGEL; Cotton & Ren, 1992 ).

5. Synthesis and crystallization

The title compounds were previously synthesized via microwave irradiation and fully characterized by elemental analysis and UV–Vis and IR spectroscopies (Reed et al., 2015 ). For crystallization each compound was dissolved in acetonitrile and a few drops of diethyl ether were added to the acetonitrile solution which produced seed crystals. Slow evaporation of the solvent at room temperature in a glovebox produced single crystals suitable for X-ray diffraction.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. H atoms were placed geometrically and treated as riding atoms: methylene, C—H = 0.99 Å, with U_iso(H) = 1.2U_eq(C) and methyl, C—H = 0.98 Å, with U_iso(H) = 1.5U_eq(C).

Table 3
Experimental details

	(1)	(2)
Crystal data
Chemical formula	[Re₂Br₂(C₄H₇O₂)₄]	[Re₂(C₄H₇O₂)₄Cl₂]·2C₂H₃N
M_r	880.60	873.79
Crystal system, space group	Monoclinic, P2₁/n	Monoclinic, P2₁/c
Temperature (K)	100	100
a, b, c (Å)	6.6833 (5), 12.2817 (10), 14.6134 (12)	8.5589 (13), 17.097 (3), 10.0494 (15)
β (°)	100.5380 (16)	105.830 (3)
V (Å³)	1179.27 (16)	1414.8 (4)
Z	2	2
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	13.68	8.78
Crystal size (mm)	0.36 × 0.16 × 0.12	0.36 × 0.34 × 0.12

Data collection
Diffractometer	Bruker SMART APEXII CCD platform	Bruker SMART APEXII CCD platform
Absorption correction	Multi-scan (SADABS; Sheldrick, 2014 )	Multi-scan (SADABS; Sheldrick, 2014)
T_min, T_max	0.161, 0.440	0.187, 0.440
No. of measured, independent and observed [I > 2σ(I)] reflections	43018, 6464, 5503	51215, 7730, 6874
R_int	0.039	0.038
(sin θ/λ)_max (Å⁻¹)	0.875	0.876

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.047, 1.04	0.021, 0.040, 1.15
No. of reflections	6464	7730
No. of parameters	129	157
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.11, −1.56	1.42, −1.61
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SIR2011 (Burla et al., 2012 ), SHELXL2014 (Sheldrick, 2015 ) and SHELXTL (Sheldrick, 2008 ).

Supporting information

CCDC references: 1434257; 1434256

Crystal structure: contains datablocks 1, 2, global. DOI: https://doi.org/10.1107/S2056989015020563/pj2025sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989015020563/pj20251sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989015020563/pj20252sup3.hkl

checkCIF report

Computing details top

For both compounds, data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(1) Tetrakis(µ-n-butyrato-κ²O:O')bis[bromidorhenium(III)] top

Crystal data top

[Re₂Br₂(C₄H₇O₂)₄]	F(000) = 816
M_r = 880.60	D_x = 2.480 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.6833 (5) Å	Cell parameters from 3849 reflections
b = 12.2817 (10) Å	θ = 3.3–38.2°
c = 14.6134 (12) Å	µ = 13.68 mm⁻¹
β = 100.5380 (16)°	T = 100 K
V = 1179.27 (16) Å³	Needle, orange
Z = 2	0.36 × 0.16 × 0.12 mm

Data collection top

Bruker SMART APEXII CCD platform diffractometer	5503 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.039
ω scans	θ_max = 38.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2014)	h = −11→11
T_min = 0.161, T_max = 0.440	k = −21→21
43018 measured reflections	l = −25→25
6464 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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.047	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0202P)² + 0.9723P] where P = (F_o² + 2F_c²)/3
6464 reflections	(Δ/σ)_max = 0.001
129 parameters	Δρ_max = 2.11 e Å⁻³
0 restraints	Δρ_min = −1.56 e Å⁻³

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	0.41766 (2)	0.44073 (2)	0.53764 (2)	0.00983 (2)
Br1	0.19163 (3)	0.30257 (2)	0.61673 (2)	0.01786 (4)
O1	0.5665 (2)	0.31578 (12)	0.48971 (10)	0.0133 (2)
O2	0.7293 (2)	0.43464 (12)	0.41390 (10)	0.0128 (2)
O3	0.1966 (2)	0.43002 (12)	0.42259 (10)	0.0130 (2)
O4	0.3633 (2)	0.54841 (12)	0.34843 (10)	0.0131 (2)
C1	0.6954 (3)	0.33636 (16)	0.43620 (13)	0.0122 (3)
C2	0.8048 (3)	0.24669 (16)	0.39774 (14)	0.0146 (3)
H2A	0.9528	0.2611	0.4142	0.018*
H2B	0.7672	0.2486	0.3290	0.018*
C3	0.7644 (4)	0.13262 (17)	0.43061 (16)	0.0182 (4)
H3A	0.6184	0.1147	0.4112	0.022*
H3B	0.7982	0.1293	0.4994	0.022*
C4	0.8936 (4)	0.05015 (19)	0.38890 (18)	0.0239 (5)
H4A	0.8633	−0.0234	0.4084	0.036*
H4B	1.0381	0.0661	0.4107	0.036*
H4C	0.8622	0.0549	0.3208	0.036*
C5	0.2113 (3)	0.48493 (16)	0.34960 (13)	0.0124 (3)
C6	0.0567 (3)	0.47160 (19)	0.26301 (14)	0.0165 (4)
H6A	0.0077	0.5441	0.2391	0.020*
H6B	−0.0611	0.4302	0.2771	0.020*
C7	0.1485 (4)	0.4111 (2)	0.18869 (17)	0.0251 (5)
H7A	0.0414	0.3999	0.1330	0.030*
H7B	0.2565	0.4566	0.1701	0.030*
C8	0.2376 (4)	0.3019 (3)	0.2226 (2)	0.0373 (7)
H8A	0.2849	0.2640	0.1715	0.056*
H8B	0.1331	0.2579	0.2443	0.056*
H8C	0.3524	0.3130	0.2740	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.01032 (3)	0.01015 (3)	0.00965 (3)	−0.00067 (2)	0.00351 (2)	−0.00002 (2)
Br1	0.01861 (9)	0.01864 (9)	0.01763 (9)	−0.00465 (7)	0.00674 (7)	0.00246 (7)
O1	0.0140 (6)	0.0128 (6)	0.0137 (6)	0.0002 (5)	0.0045 (5)	−0.0012 (5)
O2	0.0124 (6)	0.0132 (6)	0.0139 (6)	0.0008 (5)	0.0050 (5)	−0.0011 (5)
O3	0.0125 (6)	0.0153 (6)	0.0115 (6)	−0.0009 (5)	0.0029 (4)	−0.0002 (5)
O4	0.0140 (6)	0.0141 (6)	0.0115 (6)	−0.0006 (5)	0.0028 (5)	0.0014 (5)
C1	0.0113 (7)	0.0139 (8)	0.0112 (7)	0.0004 (6)	0.0018 (6)	−0.0007 (6)
C2	0.0143 (8)	0.0129 (8)	0.0174 (8)	0.0029 (6)	0.0049 (7)	−0.0030 (6)
C3	0.0219 (10)	0.0139 (8)	0.0198 (9)	0.0030 (7)	0.0060 (7)	−0.0017 (7)
C4	0.0274 (12)	0.0185 (10)	0.0258 (11)	0.0081 (8)	0.0048 (9)	−0.0023 (8)
C5	0.0122 (8)	0.0126 (8)	0.0125 (7)	0.0002 (6)	0.0030 (6)	−0.0020 (6)
C6	0.0162 (9)	0.0210 (9)	0.0114 (8)	−0.0008 (7)	0.0002 (6)	−0.0004 (7)
C7	0.0222 (11)	0.0361 (13)	0.0183 (9)	−0.0110 (10)	0.0068 (8)	−0.0097 (9)
C8	0.0262 (13)	0.0418 (17)	0.0430 (16)	0.0033 (12)	0.0035 (11)	−0.0264 (13)

Geometric parameters (Å, º) top

Re1—O4ⁱ	2.0102 (15)	C3—C4	1.528 (3)
Re1—O2ⁱ	2.0159 (14)	C3—H3A	0.9900
Re1—O1	2.0225 (15)	C3—H3B	0.9900
Re1—O3	2.0295 (14)	C4—H4A	0.9800
Re1—Re1ⁱ	2.2325 (2)	C4—H4B	0.9800
Re1—Br1	2.6712 (3)	C4—H4C	0.9800
O1—C1	1.290 (2)	C5—C6	1.489 (3)
O2—C1	1.281 (2)	C6—C7	1.533 (3)
O2—Re1ⁱ	2.0159 (14)	C6—H6A	0.9900
O3—C5	1.281 (2)	C6—H6B	0.9900
O4—C5	1.283 (2)	C7—C8	1.514 (4)
O4—Re1ⁱ	2.0102 (14)	C7—H7A	0.9900
C1—C2	1.488 (3)	C7—H7B	0.9900
C2—C3	1.521 (3)	C8—H8A	0.9800
C2—H2A	0.9900	C8—H8B	0.9800
C2—H2B	0.9900	C8—H8C	0.9800

O4ⁱ—Re1—O2ⁱ	89.22 (6)	C2—C3—H3B	109.7
O4ⁱ—Re1—O1	90.42 (6)	C4—C3—H3B	109.7
O2ⁱ—Re1—O1	179.64 (6)	H3A—C3—H3B	108.2
O4ⁱ—Re1—O3	179.91 (6)	C3—C4—H4A	109.5
O2ⁱ—Re1—O3	90.72 (6)	C3—C4—H4B	109.5
O1—Re1—O3	89.64 (6)	H4A—C4—H4B	109.5
O4ⁱ—Re1—Re1ⁱ	90.86 (4)	C3—C4—H4C	109.5
O2ⁱ—Re1—Re1ⁱ	89.64 (4)	H4A—C4—H4C	109.5
O1—Re1—Re1ⁱ	90.35 (4)	H4B—C4—H4C	109.5
O3—Re1—Re1ⁱ	89.08 (4)	O3—C5—O4	120.85 (18)
O4ⁱ—Re1—Br1	93.87 (4)	O3—C5—C6	120.16 (18)
O2ⁱ—Re1—Br1	88.85 (4)	O4—C5—C6	118.92 (18)
O1—Re1—Br1	91.19 (4)	C5—C6—C7	110.48 (19)
O3—Re1—Br1	86.19 (4)	C5—C6—H6A	109.6
Re1ⁱ—Re1—Br1	175.018 (7)	C7—C6—H6A	109.6
C1—O1—Re1	119.12 (13)	C5—C6—H6B	109.6
C1—O2—Re1ⁱ	120.39 (13)	C7—C6—H6B	109.6
C5—O3—Re1	120.03 (13)	H6A—C6—H6B	108.1
C5—O4—Re1ⁱ	119.18 (13)	C8—C7—C6	112.4 (2)
O2—C1—O1	120.51 (18)	C8—C7—H7A	109.1
O2—C1—C2	118.63 (18)	C6—C7—H7A	109.1
O1—C1—C2	120.85 (18)	C8—C7—H7B	109.1
C1—C2—C3	115.75 (18)	C6—C7—H7B	109.1
C1—C2—H2A	108.3	H7A—C7—H7B	107.8
C3—C2—H2A	108.3	C7—C8—H8A	109.5
C1—C2—H2B	108.3	C7—C8—H8B	109.5
C3—C2—H2B	108.3	H8A—C8—H8B	109.5
H2A—C2—H2B	107.4	C7—C8—H8C	109.5
C2—C3—C4	109.79 (19)	H8A—C8—H8C	109.5
C2—C3—H3A	109.7	H8B—C8—H8C	109.5
C4—C3—H3A	109.7

Re1ⁱ—O2—C1—O1	0.2 (2)	Re1—O3—C5—O4	−1.1 (3)
Re1ⁱ—O2—C1—C2	179.10 (13)	Re1—O3—C5—C6	175.86 (14)
Re1—O1—C1—O2	0.2 (2)	Re1ⁱ—O4—C5—O3	1.0 (3)
Re1—O1—C1—C2	−178.66 (14)	Re1ⁱ—O4—C5—C6	−175.98 (14)
O2—C1—C2—C3	177.34 (18)	O3—C5—C6—C7	−108.8 (2)
O1—C1—C2—C3	−3.7 (3)	O4—C5—C6—C7	68.2 (3)
C1—C2—C3—C4	−177.54 (19)	C5—C6—C7—C8	56.0 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

(2) Tetrakis(µ-n-butyrato-κ²O:O')bis[chloridorhenium(III)] top

Crystal data top

[Re₂(C₄H₇O₂)₄Cl₂]·2C₂H₃N	F(000) = 832
M_r = 873.79	D_x = 2.051 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.5589 (13) Å	Cell parameters from 3912 reflections
b = 17.097 (3) Å	θ = 2.4–38.3°
c = 10.0494 (15) Å	µ = 8.78 mm⁻¹
β = 105.830 (3)°	T = 100 K
V = 1414.8 (4) Å³	Plate, orange
Z = 2	0.36 × 0.34 × 0.12 mm

Data collection top

Bruker SMART APEXII CCD platform diffractometer	6874 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.038
ω scans	θ_max = 38.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2014)	h = −14→14
T_min = 0.187, T_max = 0.440	k = −29→29
51215 measured reflections	l = −17→17
7730 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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.040	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.0071P)² + 1.4405P] where P = (F_o² + 2F_c²)/3
7730 reflections	(Δ/σ)_max = 0.002
157 parameters	Δρ_max = 1.42 e Å⁻³
0 restraints	Δρ_min = −1.61 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
Re1	0.03406 (2)	0.02939 (2)	0.41289 (2)	0.00845 (2)
Cl1	0.11816 (5)	0.09708 (2)	0.22230 (4)	0.01465 (7)
O1	0.11825 (15)	0.12189 (7)	0.53706 (12)	0.0114 (2)
O2	0.05072 (15)	0.06310 (7)	0.71113 (12)	0.0116 (2)
O3	0.18769 (15)	−0.08019 (7)	0.64715 (13)	0.0119 (2)
O4	0.25576 (15)	−0.02169 (7)	0.47284 (13)	0.0125 (2)
C1	0.1121 (2)	0.12144 (9)	0.66290 (17)	0.0110 (3)
C2	0.1786 (2)	0.18996 (10)	0.75268 (19)	0.0155 (3)
H2A	0.1391	0.2384	0.7004	0.019*
H2B	0.2984	0.1894	0.7726	0.019*
C3	0.1342 (3)	0.19286 (11)	0.88930 (19)	0.0190 (3)
H3A	0.1606	0.1419	0.9367	0.023*
H3B	0.2011	0.2333	0.9491	0.023*
C4	−0.0440 (3)	0.21089 (13)	0.8716 (3)	0.0272 (4)
H4A	−0.0650	0.2134	0.9626	0.041*
H4B	−0.1109	0.1697	0.8162	0.041*
H4C	−0.0711	0.2613	0.8244	0.041*
C5	0.2915 (2)	−0.06622 (10)	0.57910 (18)	0.0128 (3)
C6	0.4563 (2)	−0.10219 (12)	0.6230 (2)	0.0185 (3)
H6A	0.4641	−0.1352	0.7055	0.022*
H6B	0.5385	−0.0602	0.6497	0.022*
C7	0.4947 (2)	−0.15213 (12)	0.5097 (2)	0.0226 (4)
H7A	0.4768	−0.1204	0.4245	0.027*
H7B	0.6109	−0.1670	0.5391	0.027*
C8	0.3925 (3)	−0.22572 (15)	0.4773 (3)	0.0392 (6)
H8A	0.4236	−0.2555	0.4053	0.059*
H8B	0.2775	−0.2114	0.4447	0.059*
H8C	0.4104	−0.2577	0.5610	0.059*
N1	0.4670 (3)	0.05726 (13)	0.8138 (2)	0.0299 (4)
C9	0.5906 (3)	0.05264 (13)	0.8933 (2)	0.0221 (4)
C10	0.7485 (3)	0.04674 (14)	0.9950 (2)	0.0255 (4)
H10A	0.7727	0.0959	1.0466	0.038*
H10B	0.8324	0.0365	0.9475	0.038*
H10C	0.7465	0.0038	1.0591	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Re1	0.00949 (2)	0.00778 (2)	0.00844 (2)	−0.00046 (2)	0.00305 (2)	0.00032 (2)
Cl1	0.01616 (16)	0.01644 (16)	0.01207 (15)	−0.00189 (13)	0.00506 (13)	0.00287 (13)
O1	0.0142 (5)	0.0097 (5)	0.0105 (5)	−0.0014 (4)	0.0037 (4)	−0.0004 (4)
O2	0.0149 (5)	0.0103 (5)	0.0097 (5)	−0.0016 (4)	0.0035 (4)	−0.0003 (4)
O3	0.0118 (5)	0.0115 (5)	0.0122 (5)	0.0009 (4)	0.0032 (4)	0.0012 (4)
O4	0.0112 (5)	0.0129 (5)	0.0140 (5)	0.0013 (4)	0.0048 (4)	0.0016 (4)
C1	0.0118 (6)	0.0094 (6)	0.0117 (6)	−0.0007 (5)	0.0031 (5)	−0.0006 (5)
C2	0.0198 (8)	0.0115 (6)	0.0151 (7)	−0.0042 (6)	0.0049 (6)	−0.0036 (6)
C3	0.0290 (9)	0.0148 (7)	0.0136 (7)	−0.0054 (7)	0.0067 (7)	−0.0046 (6)
C4	0.0316 (11)	0.0234 (9)	0.0325 (11)	−0.0057 (8)	0.0185 (9)	−0.0097 (8)
C5	0.0118 (6)	0.0123 (6)	0.0136 (7)	0.0008 (5)	0.0022 (5)	0.0002 (5)
C6	0.0114 (7)	0.0213 (8)	0.0217 (8)	0.0047 (6)	0.0027 (6)	0.0018 (7)
C7	0.0172 (8)	0.0225 (9)	0.0296 (10)	0.0056 (7)	0.0092 (7)	0.0004 (8)
C8	0.0315 (12)	0.0256 (11)	0.0572 (18)	0.0014 (9)	0.0066 (12)	−0.0116 (11)
N1	0.0290 (10)	0.0304 (10)	0.0270 (9)	0.0018 (8)	0.0018 (8)	0.0006 (8)
C9	0.0257 (9)	0.0199 (8)	0.0200 (8)	−0.0010 (7)	0.0050 (7)	0.0002 (7)
C10	0.0235 (9)	0.0288 (10)	0.0210 (9)	−0.0006 (8)	0.0005 (8)	0.0001 (8)

Geometric parameters (Å, º) top

Re1—O1	2.0216 (12)	C4—H4A	0.9800
Re1—O2ⁱ	2.0217 (12)	C4—H4B	0.9800
Re1—O3ⁱ	2.0238 (12)	C4—H4C	0.9800
Re1—O4	2.0255 (12)	C5—C6	1.490 (2)
Re1—Re1ⁱ	2.2299 (3)	C6—C7	1.529 (3)
Re1—Cl1	2.5056 (5)	C6—H6A	0.9900
O1—C1	1.280 (2)	C6—H6B	0.9900
O2—C1	1.282 (2)	C7—C8	1.516 (3)
O2—Re1ⁱ	2.0217 (12)	C7—H7A	0.9900
O3—C5	1.283 (2)	C7—H7B	0.9900
O3—Re1ⁱ	2.0238 (12)	C8—H8A	0.9800
O4—C5	1.279 (2)	C8—H8B	0.9800
C1—C2	1.493 (2)	C8—H8C	0.9800
C2—C3	1.522 (3)	N1—C9	1.141 (3)
C2—H2A	0.9900	C9—C10	1.459 (3)
C2—H2B	0.9900	C10—H10A	0.9800
C3—C4	1.518 (3)	C10—H10B	0.9800
C3—H3A	0.9900	C10—H10C	0.9800
C3—H3B	0.9900

O1—Re1—O2ⁱ	179.84 (5)	C3—C4—H4A	109.5
O1—Re1—O3ⁱ	89.75 (5)	C3—C4—H4B	109.5
O2ⁱ—Re1—O3ⁱ	90.13 (5)	H4A—C4—H4B	109.5
O1—Re1—O4	90.37 (5)	C3—C4—H4C	109.5
O2ⁱ—Re1—O4	89.75 (5)	H4A—C4—H4C	109.5
O3ⁱ—Re1—O4	179.87 (5)	H4B—C4—H4C	109.5
O1—Re1—Re1ⁱ	89.63 (4)	O4—C5—O3	120.86 (15)
O2ⁱ—Re1—Re1ⁱ	90.27 (4)	O4—C5—C6	118.98 (16)
O3ⁱ—Re1—Re1ⁱ	90.15 (4)	O3—C5—C6	120.16 (16)
O4—Re1—Re1ⁱ	89.80 (4)	C5—C6—C7	112.87 (16)
O1—Re1—Cl1	88.98 (4)	C5—C6—H6A	109.0
O2ⁱ—Re1—Cl1	91.13 (4)	C7—C6—H6A	109.0
O3ⁱ—Re1—Cl1	90.89 (4)	C5—C6—H6B	109.0
O4—Re1—Cl1	89.16 (4)	C7—C6—H6B	109.0
Re1ⁱ—Re1—Cl1	178.254 (11)	H6A—C6—H6B	107.8
C1—O1—Re1	120.09 (10)	C8—C7—C6	113.24 (19)
C1—O2—Re1ⁱ	119.38 (11)	C8—C7—H7A	108.9
C5—O3—Re1ⁱ	119.40 (11)	C6—C7—H7A	108.9
C5—O4—Re1	119.78 (11)	C8—C7—H7B	108.9
O1—C1—O2	120.63 (15)	C6—C7—H7B	108.9
O1—C1—C2	118.72 (15)	H7A—C7—H7B	107.7
O2—C1—C2	120.64 (15)	C7—C8—H8A	109.5
C1—C2—C3	115.01 (15)	C7—C8—H8B	109.5
C1—C2—H2A	108.5	H8A—C8—H8B	109.5
C3—C2—H2A	108.5	C7—C8—H8C	109.5
C1—C2—H2B	108.5	H8A—C8—H8C	109.5
C3—C2—H2B	108.5	H8B—C8—H8C	109.5
H2A—C2—H2B	107.5	N1—C9—C10	180.0 (3)
C4—C3—C2	113.00 (17)	C9—C10—H10A	109.5
C4—C3—H3A	109.0	C9—C10—H10B	109.5
C2—C3—H3A	109.0	H10A—C10—H10B	109.5
C4—C3—H3B	109.0	C9—C10—H10C	109.5
C2—C3—H3B	109.0	H10A—C10—H10C	109.5
H3A—C3—H3B	107.8	H10B—C10—H10C	109.5

Re1—O1—C1—O2	−1.0 (2)	Re1—O4—C5—O3	1.2 (2)
Re1—O1—C1—C2	178.70 (12)	Re1—O4—C5—C6	−178.97 (12)
Re1ⁱ—O2—C1—O1	0.8 (2)	Re1ⁱ—O3—C5—O4	−1.1 (2)
Re1ⁱ—O2—C1—C2	−178.84 (12)	Re1ⁱ—O3—C5—C6	179.11 (12)
O1—C1—C2—C3	167.38 (16)	O4—C5—C6—C7	−58.1 (2)
O2—C1—C2—C3	−12.9 (2)	O3—C5—C6—C7	121.71 (19)
C1—C2—C3—C4	−70.2 (2)	C5—C6—C7—C8	−67.9 (2)

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

The authors thank The College at Brockport, SUNY, and the University of Rochester Chemistry Department for financial support as well as Marcy A. Merritt and Callen Feeney who contributed to the initial preparation of the compounds.

References

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