Tetra­kis(μ-benzoato-κ2O:O′)bis­[(piperidine-κN)rhodium]

Selent, D.; Drexler, H.-J.

doi:10.1107/S241431461700205X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170205

https://doi.org/10.1107/S241431461700205X

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Tetrakis(μ-benzoato-κ²O:O′)bis[(piperidine-κN)rhodium]

Detlef Selent ^a ^* and Hans-Joachim Drexler ^a

^aLeibniz-Institut für Katalyse e. V. an der Universität Rostock, Albert-Einstein-Strasse 29a, 18059 Rostock, Germany
^*Correspondence e-mail: detlef.selent@catalysis.de

Edited by A. J. Lough, University of Toronto, Canada (Received 24 January 2017; accepted 8 February 2017; online 14 February 2017)

The title compound, [Rh₂(C₇H₅O₂)₄(C₅H₁₁N)₂], an adduct of dimeric rhodium(II) benzoate with piperidine, was prepared. The complex lies across an inversion centre with the unique Rh^II ion in a slightly distorted octahedral coordination environment.

Keywords: crystal structure; rhodium complex; benzoate; piperidine.

CCDC reference: 1531658

Structure description

The molecular structure lies across an inversion centre and the coordination geometry around the rhodium atoms is slightly distorted octahedral (Fig. 1). The Rh1—Rh1(−x, −y + 2, −z) distance is 2.4116 (2) Å, which is comparable to the value of 2.402 (2) Å determined for the corresponding bispyridine complex [Rh₂(bzt)₄(py)₂] (Mehmet & Tocher, 1991 ). As a result of the sp²-hybridized nitrogen atoms, the rhodium nitrogen distance of 2.246 (4) in the latter molecule is shorter, compared to the value of 2.3083 (13) Å found for the title compound. In [Rh₂(bzt)₄(pip)₂], individual C—O distances vary within a narrow range of 0.008 (2) Å thus pointing towards an almost symmetric charge distribution within the carboxylato groups. A deviation of 0.0763 (5) Å from the plane defined by the square arrangement of the oxygen atoms was determined for the symmetry-equivalent rhodium atoms. The piperidine molecules adopt chair conformations.

Figure 1
The molecular structure of the title compound, showing the atom labelling and displacement ellipsoids drawn at the 30% probability level [symmetry code: (A) (i) −x, −y + 2, −z].

Synthesis and crystallization

A procedure analogous to that for the pyridine adduct has been applied (Legzdins et al., 1970 ). A stirred solution of rhodium trichloride trihydrate (1 g, 0.0038 mol) in methanol (125 ml) was treated with solid benzoic acid (12 g, 0.098 mol), solid sodium benzoate (5 g, 0.0035 mol) and with piperidine (8.515 g, 0.1 mol). The reaction mixture was heated to reflux for 1 h, and the formed precipitate was filtered off. The product was then washed with methanol (2 × 5 ml) and recrystallized from chloroform/diethyl ether (2:1) to give the title compound as carmine, air-stable crystals. Yield: 0.290 g (0.340 mmol, 18%). Elemental analysis (calculated for Rh₂C₃₈H₄₂N₂O₈, M = 860.58 g mol⁻¹): C, 52.60 (53.04); H, 5.04 (4.92); N, 3.18 (3.26); Rh, 24.12 (23.92)%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	[Rh₂(C₇H₅O₂)₄(C₅H₁₁N)₂]
M_r	860.55
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	10.7224 (1), 11.1042 (2), 14.7761 (2)
β (°)	96.078 (1)
V (Å³)	1749.41 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.00
Crystal size (mm)	0.44 × 0.26 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.684, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	35557, 5343, 4939
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.055, 1.05
No. of reflections	5343
No. of parameters	230
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.54
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008), publCIF (Westrip, 2010 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1531658

Crystal structure: contains datablocks I, ax1215abs. DOI: https://doi.org/10.1107/S241431461700205X/lh4016sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431461700205X/lh4016Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Tetrakis(µ-benzoato-κ²O:O')bis[(piperidine-κN)rhodium] top

Crystal data top

[Rh₂(C₇H₅O₂)₄(C₅H₁₁N)₂]	F(000) = 876
M_r = 860.55	D_x = 1.634 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.7224 (1) Å	Cell parameters from 9954 reflections
b = 11.1042 (2) Å	θ = 2.9–30.5°
c = 14.7761 (2) Å	µ = 1.00 mm⁻¹
β = 96.078 (1)°	T = 150 K
V = 1749.41 (4) Å³	Prism, red
Z = 2	0.44 × 0.26 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	5343 independent reflections
Radiation source: fine-focus sealed tube	4939 reflections with I > 2σ(I)
Detector resolution: 8.3333 pixels mm^-1	R_int = 0.022
φ and ω scans	θ_max = 30.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −15→15
T_min = 0.684, T_max = 0.746	k = −15→14
35557 measured reflections	l = −21→20

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.021	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.055	w = 1/[σ²(F_o²) + (0.0255P)² + 1.4431P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5343 reflections	Δρ_max = 0.81 e Å⁻³
230 parameters	Δρ_min = −0.54 e Å⁻³

Special details top

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

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

	x	y	z	U_iso*/U_eq
Rh1	0.02361 (2)	0.95634 (2)	0.07456 (2)	0.01337 (4)
O1	0.07504 (10)	0.80446 (10)	0.01222 (7)	0.01890 (19)
O2	0.03436 (10)	0.88572 (10)	−0.12799 (7)	0.0193 (2)
O3	0.19998 (9)	1.02805 (10)	0.07472 (7)	0.0185 (2)
O4	0.15364 (9)	1.10880 (10)	−0.06514 (7)	0.0190 (2)
N1	0.04978 (12)	0.85729 (12)	0.21261 (8)	0.0204 (2)
H1	−0.026 (2)	0.821 (2)	0.2074 (14)	0.030 (5)*
C1	0.06780 (12)	0.80076 (13)	−0.07406 (9)	0.0161 (2)
C2	0.10317 (12)	0.68370 (13)	−0.11396 (9)	0.0172 (2)
C3	0.12819 (16)	0.67759 (15)	−0.20431 (10)	0.0252 (3)
H3	0.1216	0.7478	−0.2413	0.030*
C4	0.1627 (2)	0.56869 (17)	−0.24021 (12)	0.0364 (4)
H4	0.1824	0.5648	−0.3013	0.044*
C5	0.1687 (2)	0.46555 (17)	−0.18722 (13)	0.0381 (4)
H5	0.1911	0.3909	−0.2124	0.046*
C6	0.1421 (2)	0.47095 (16)	−0.09732 (12)	0.0321 (4)
H6	0.1446	0.3999	−0.0613	0.039*
C7	0.11185 (15)	0.58047 (14)	−0.06047 (10)	0.0228 (3)
H7	0.0970	0.5851	0.0017	0.027*
C8	0.22654 (12)	1.08853 (13)	0.00705 (9)	0.0159 (2)
C9	0.35458 (12)	1.14222 (13)	0.01039 (9)	0.0167 (2)
C10	0.45244 (13)	1.10339 (14)	0.07328 (10)	0.0206 (3)
H10	0.4379	1.0437	0.1170	0.025*
C11	0.57143 (14)	1.15254 (16)	0.07159 (11)	0.0262 (3)
H11	0.6385	1.1258	0.1140	0.031*
C12	0.59252 (15)	1.23997 (19)	0.00863 (13)	0.0340 (4)
H12	0.6741	1.2728	0.0075	0.041*
C13	0.49488 (16)	1.2798 (2)	−0.05281 (13)	0.0364 (4)
H13	0.5090	1.3411	−0.0954	0.044*
C14	0.37677 (14)	1.23026 (16)	−0.05219 (11)	0.0251 (3)
H14	0.3102	1.2569	−0.0951	0.030*
C15	0.05381 (15)	0.93372 (16)	0.29481 (11)	0.0251 (3)
H15A	0.0422	0.8833	0.3486	0.030*
H15B	−0.0148	0.9937	0.2874	0.030*
C16	0.17947 (16)	0.99760 (16)	0.30890 (12)	0.0279 (3)
H16A	0.1831	1.0475	0.3646	0.033*
H16B	0.1881	1.0517	0.2567	0.033*
C17	0.28741 (16)	0.90793 (17)	0.31786 (13)	0.0312 (4)
H17A	0.3682	0.9518	0.3221	0.037*
H17B	0.2850	0.8602	0.3742	0.037*
C18	0.27784 (15)	0.82436 (16)	0.23619 (12)	0.0272 (3)
H18A	0.3435	0.7615	0.2456	0.033*
H18B	0.2925	0.8708	0.1811	0.033*
C19	0.14973 (16)	0.76498 (14)	0.22207 (11)	0.0249 (3)
H19A	0.1441	0.7144	0.1666	0.030*
H19B	0.1382	0.7122	0.2746	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.01245 (5)	0.01576 (6)	0.01178 (5)	−0.00098 (3)	0.00075 (3)	0.00050 (3)
O1	0.0226 (5)	0.0191 (5)	0.0148 (4)	0.0022 (4)	0.0014 (4)	0.0000 (4)
O2	0.0235 (5)	0.0195 (5)	0.0149 (4)	0.0023 (4)	0.0017 (4)	−0.0004 (4)
O3	0.0146 (4)	0.0238 (5)	0.0168 (5)	−0.0037 (4)	−0.0003 (3)	0.0037 (4)
O4	0.0139 (4)	0.0266 (5)	0.0163 (4)	−0.0044 (4)	0.0002 (3)	0.0036 (4)
N1	0.0206 (6)	0.0227 (6)	0.0176 (5)	−0.0028 (5)	0.0011 (4)	0.0012 (5)
C1	0.0130 (5)	0.0181 (6)	0.0171 (6)	−0.0012 (5)	0.0011 (4)	−0.0016 (5)
C2	0.0148 (5)	0.0187 (6)	0.0178 (6)	0.0010 (5)	−0.0003 (4)	−0.0021 (5)
C3	0.0344 (8)	0.0227 (7)	0.0184 (7)	0.0040 (6)	0.0029 (6)	−0.0004 (5)
C4	0.0587 (12)	0.0303 (9)	0.0209 (8)	0.0126 (8)	0.0081 (8)	−0.0032 (7)
C5	0.0615 (13)	0.0258 (9)	0.0270 (8)	0.0161 (8)	0.0047 (8)	−0.0037 (7)
C6	0.0470 (10)	0.0222 (8)	0.0268 (8)	0.0089 (7)	0.0026 (7)	0.0012 (6)
C7	0.0271 (7)	0.0215 (7)	0.0196 (6)	0.0023 (6)	0.0019 (5)	0.0002 (5)
C8	0.0137 (5)	0.0174 (6)	0.0167 (6)	−0.0007 (5)	0.0021 (4)	−0.0007 (5)
C9	0.0130 (5)	0.0201 (6)	0.0171 (6)	−0.0020 (5)	0.0021 (4)	−0.0018 (5)
C10	0.0183 (6)	0.0226 (7)	0.0205 (6)	−0.0019 (5)	−0.0004 (5)	0.0018 (5)
C11	0.0167 (6)	0.0329 (8)	0.0278 (8)	−0.0022 (6)	−0.0040 (5)	0.0027 (6)
C12	0.0168 (7)	0.0468 (11)	0.0375 (9)	−0.0113 (7)	−0.0012 (6)	0.0094 (8)
C13	0.0240 (8)	0.0479 (11)	0.0365 (9)	−0.0133 (7)	−0.0015 (7)	0.0198 (8)
C14	0.0170 (6)	0.0310 (8)	0.0265 (7)	−0.0044 (6)	−0.0014 (5)	0.0077 (6)
C15	0.0254 (7)	0.0315 (8)	0.0186 (7)	0.0033 (6)	0.0032 (5)	−0.0008 (6)
C16	0.0281 (8)	0.0270 (8)	0.0272 (8)	0.0024 (6)	−0.0038 (6)	−0.0066 (6)
C17	0.0255 (7)	0.0317 (9)	0.0342 (9)	0.0033 (6)	−0.0073 (6)	−0.0023 (7)
C18	0.0251 (7)	0.0257 (8)	0.0305 (8)	0.0060 (6)	0.0009 (6)	0.0016 (6)
C19	0.0313 (8)	0.0206 (7)	0.0220 (7)	0.0023 (6)	−0.0011 (6)	0.0016 (5)

Geometric parameters (Å, º) top

Rh1—O4ⁱ	2.0245 (10)	C8—C9	1.4927 (18)
Rh1—O1	2.0260 (10)	C9—C14	1.383 (2)
Rh1—O2ⁱ	2.0469 (10)	C9—C10	1.3943 (19)
Rh1—O3	2.0517 (10)	C10—C11	1.390 (2)
Rh1—N1	2.3083 (12)	C10—H10	0.9500
Rh1—Rh1ⁱ	2.4116 (2)	C11—C12	1.380 (2)
O1—C1	1.2696 (16)	C11—H11	0.9500
O2—C1	1.2623 (17)	C12—C13	1.384 (2)
O2—Rh1ⁱ	2.0468 (10)	C12—H12	0.9500
O3—C8	1.2619 (17)	C13—C14	1.382 (2)
O4—C8	1.2740 (16)	C13—H13	0.9500
O4—Rh1ⁱ	2.0244 (10)	C14—H14	0.9500
N1—C15	1.479 (2)	C15—C16	1.517 (2)
N1—C19	1.479 (2)	C15—H15A	0.9900
N1—H1	0.91 (2)	C15—H15B	0.9900
C1—C2	1.4927 (19)	C16—C17	1.522 (2)
C2—C7	1.390 (2)	C16—H16A	0.9900
C2—C3	1.391 (2)	C16—H16B	0.9900
C3—C4	1.387 (2)	C17—C18	1.517 (2)
C3—H3	0.9500	C17—H17A	0.9900
C4—C5	1.385 (3)	C17—H17B	0.9900
C4—H4	0.9500	C18—C19	1.518 (2)
C5—C6	1.389 (3)	C18—H18A	0.9900
C5—H5	0.9500	C18—H18B	0.9900
C6—C7	1.385 (2)	C19—H19A	0.9900
C6—H6	0.9500	C19—H19B	0.9900
C7—H7	0.9500

O4ⁱ—Rh1—O1	88.29 (4)	C14—C9—C10	119.57 (13)
O4ⁱ—Rh1—O2ⁱ	90.66 (4)	C14—C9—C8	118.87 (12)
O1—Rh1—O2ⁱ	175.60 (4)	C10—C9—C8	121.54 (13)
O4ⁱ—Rh1—O3	175.72 (4)	C11—C10—C9	119.60 (14)
O1—Rh1—O3	91.63 (4)	C11—C10—H10	120.2
O2ⁱ—Rh1—O3	89.11 (4)	C9—C10—H10	120.2
O4ⁱ—Rh1—N1	85.18 (4)	C12—C11—C10	120.30 (15)
O1—Rh1—N1	89.53 (4)	C12—C11—H11	119.9
O2ⁱ—Rh1—N1	94.64 (4)	C10—C11—H11	119.9
O3—Rh1—N1	99.10 (4)	C11—C12—C13	120.05 (15)
O4ⁱ—Rh1—Rh1ⁱ	88.63 (3)	C11—C12—H12	120.0
O1—Rh1—Rh1ⁱ	87.72 (3)	C13—C12—H12	120.0
O2ⁱ—Rh1—Rh1ⁱ	87.99 (3)	C14—C13—C12	119.91 (16)
O3—Rh1—Rh1ⁱ	87.09 (3)	C14—C13—H13	120.0
N1—Rh1—Rh1ⁱ	173.29 (3)	C12—C13—H13	120.0
C1—O1—Rh1	119.53 (9)	C13—C14—C9	120.56 (15)
C1—O2—Rh1ⁱ	118.32 (9)	C13—C14—H14	119.7
C8—O3—Rh1	119.41 (9)	C9—C14—H14	119.7
C8—O4—Rh1ⁱ	118.87 (9)	N1—C15—C16	109.23 (13)
C15—N1—C19	111.24 (12)	N1—C15—H15A	109.8
C15—N1—Rh1	116.27 (10)	C16—C15—H15A	109.8
C19—N1—Rh1	115.65 (9)	N1—C15—H15B	109.8
C15—N1—H1	105.9 (14)	C16—C15—H15B	109.8
C19—N1—H1	109.5 (14)	H15A—C15—H15B	108.3
Rh1—N1—H1	96.6 (14)	C15—C16—C17	111.23 (15)
O2—C1—O1	126.36 (13)	C15—C16—H16A	109.4
O2—C1—C2	117.94 (12)	C17—C16—H16A	109.4
O1—C1—C2	115.70 (12)	C15—C16—H16B	109.4
C7—C2—C3	119.83 (14)	C17—C16—H16B	109.4
C7—C2—C1	119.87 (13)	H16A—C16—H16B	108.0
C3—C2—C1	120.30 (13)	C18—C17—C16	110.14 (14)
C4—C3—C2	119.75 (15)	C18—C17—H17A	109.6
C4—C3—H3	120.1	C16—C17—H17A	109.6
C2—C3—H3	120.1	C18—C17—H17B	109.6
C5—C4—C3	120.21 (16)	C16—C17—H17B	109.6
C5—C4—H4	119.9	H17A—C17—H17B	108.1
C3—C4—H4	119.9	C17—C18—C19	111.04 (14)
C4—C5—C6	120.19 (16)	C17—C18—H18A	109.4
C4—C5—H5	119.9	C19—C18—H18A	109.4
C6—C5—H5	119.9	C17—C18—H18B	109.4
C7—C6—C5	119.62 (16)	C19—C18—H18B	109.4
C7—C6—H6	120.2	H18A—C18—H18B	108.0
C5—C6—H6	120.2	N1—C19—C18	110.38 (13)
C6—C7—C2	120.33 (14)	N1—C19—H19A	109.6
C6—C7—H7	119.8	C18—C19—H19A	109.6
C2—C7—H7	119.8	N1—C19—H19B	109.6
O3—C8—O4	125.99 (12)	C18—C19—H19B	109.6
O3—C8—C9	118.06 (12)	H19A—C19—H19B	108.1
O4—C8—C9	115.96 (12)

Rh1ⁱ—O2—C1—O1	−3.53 (19)	O3—C8—C9—C14	−165.39 (14)
Rh1ⁱ—O2—C1—C2	176.69 (9)	O4—C8—C9—C14	14.5 (2)
Rh1—O1—C1—O2	2.40 (19)	O3—C8—C9—C10	16.4 (2)
Rh1—O1—C1—C2	−177.82 (8)	O4—C8—C9—C10	−163.70 (14)
O2—C1—C2—C7	−164.88 (13)	C14—C9—C10—C11	−0.8 (2)
O1—C1—C2—C7	15.32 (19)	C8—C9—C10—C11	177.43 (14)
O2—C1—C2—C3	15.5 (2)	C9—C10—C11—C12	0.6 (3)
O1—C1—C2—C3	−164.31 (14)	C10—C11—C12—C13	0.5 (3)
C7—C2—C3—C4	−0.6 (2)	C11—C12—C13—C14	−1.2 (3)
C1—C2—C3—C4	179.06 (16)	C12—C13—C14—C9	1.0 (3)
C2—C3—C4—C5	1.9 (3)	C10—C9—C14—C13	0.0 (3)
C3—C4—C5—C6	−1.0 (3)	C8—C9—C14—C13	−178.26 (17)
C4—C5—C6—C7	−1.2 (3)	C19—N1—C15—C16	60.57 (17)
C5—C6—C7—C2	2.6 (3)	Rh1—N1—C15—C16	−74.65 (14)
C3—C2—C7—C6	−1.7 (2)	N1—C15—C16—C17	−57.91 (18)
C1—C2—C7—C6	178.67 (15)	C15—C16—C17—C18	54.8 (2)
Rh1—O3—C8—O4	−1.5 (2)	C16—C17—C18—C19	−53.59 (19)
Rh1—O3—C8—C9	178.39 (9)	C15—N1—C19—C18	−60.09 (16)
Rh1ⁱ—O4—C8—O3	1.6 (2)	Rh1—N1—C19—C18	75.43 (14)
Rh1ⁱ—O4—C8—C9	−178.30 (9)	C17—C18—C19—N1	56.22 (17)

Symmetry code: (i) −x, −y+2, −z.

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