trans-Di­chlorido­tetra­kis­(pyridine-κN)rhodium(III) chloride methanol tetra­solvate

Suzuki, T.; Tsujino, M.; Sunatsuki, Y.

doi:10.1107/S2414314618014827

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 10| October 2018| x181482

https://doi.org/10.1107/S2414314618014827

Open

access

trans-Dichloridotetrakis(pyridine-κN)rhodium(III) chloride methanol tetrasolvate

Takayoshi Suzuki,^a ^* Misaki Tsujino ^b and Yukinari Sunatsuki ^b

^aDepartment of Chemistry, Faculty of Science, Research Institute for Interdisciplinary Science, Okayama University, and ^bDepartment of Chemistry, Faculty of Science, Okayama University
^*Correspondence e-mail: suzuki@okayama-u.ac.jp

Edited by M. Weil, Vienna University of Technology, Austria (Received 17 October 2018; accepted 19 October 2018; online 26 October 2018)

In the solvated title salt, [RhCl₂(C₅H₅N)₄]Cl·4CH₃OH, the Rh^III atom lies on a special position of 2.22 site symmetry. Consequently, the cationic complex has molecular D₂ symmetry with a trans disposition for two equivalent Cl⁻ and four equivalent pyridine ligands. The Rh—Cl and Rh—N bond lengths are 2.3452 (7) and 2.064 (2) Å, respectively. The planes of the coordinating pyridine ligands are tilted synchronously, with a dihedral angle of 40.76 (9)° between the least-squares pyridine plane and the coordination plane defined by the Rh^III and four pyridine N atoms. The chloride counter-anion is located on a crystallographic $[\overline{4}]$ .. site, and is surrounded by four methanol molecules to which it is bound in a pseudo-tetrahedral arrangement by O—H⋯Cl hydrogen bonds.

Keywords: crystal structure; rhodium(III) complex; pyridine complex; hydrogen bonds.

CCDC reference: 1874254

Structure description

Mixed-ligand rhodium(III) complexes with chlorido and pyridine ligands have been known since the 1880s (Jörgensen, 1883 ). Their composition, structures and properties were reexamined very carefully by Gillard & Wilkinson (1964 ). They concluded that the highest stable species is the trans-dichloridotetrakis(pyridine)rhodium(III) cation. Up to now, several crystal structures of this complex with different counter-anions have been reported: hydrogen dinitrate (Dobinson et al., 1967 ), dinitratoargentate(I) (Gillard et al., 1990 ), perchlorate, perrhenate (Vasilchenko et al., 2009 ), thiocyanate and 2-hydroxybenzoate (Vasil'chenko et al., 2015 ). However, one of the most simple complex salts, the chloride, has not been reported so far.

The title complex salt, trans-[RhCl₂(C₅H₅N)₄]Cl, crystallizes with four molecules of methanol in the space group P $[\overline{4}]$ c2. The Rh^III atom lies on a special position of 2.22 site symmetry (Wyckhoff position 2a), the chlorido ligand (Cl1) on a position with ..2 symmetry (4f), and the non-coordinating Cl⁻ anion (Cl2) is located on a $[\overline{4}]$ .. site (2d). In addition, the asymmetric unit contains a molecule of pyridine (py) and a molecule of methanol, both in general sites. Expanding the symmetry operations gives molecular units of a cationic Rh^III complex, trans-[RhCl₂(py)₄]⁺, and a tetra(methanol) solvated Cl⁻ anion (Fig. 1). The resulting cationic complex exhibits molecular D₂ symmetry. The Rh—Cl and Rh—N bond lengths are 2.3452 (7) and 2.064 (2) Å, respectively. The Cl—Rh—N and N—Rh—N bond angles are close, but not strictly equal, to 90°. Similar to previously reported structures (Dobinson et al., 1967; Gillard et al., 1990; Vasilchenko et al., 2009; Vasil'chenko et al., 2015), the planes of the coordinating pyridine are tilted synchronously with respect to the RhN₄ coordination plane. The dihedral angle between the least-squares pyridine plane and the coordination plane defined by the Rh and four N atoms is 40.76 (9)°. The hydrogen-bonded anionic [Cl(CH₃OH)₄]⁻ unit exhibits a pseudo-tetrahedral arrangement (Fig. 1, Table 1). The packing of the molecular entities in the crystal structure is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯Cl2	0.84	2.32	3.110 (4)	156

Figure 1
View of the molecular components of the solvated title salt, showing the atom-numbering scheme and displacement ellipsoids drawn at the 50% probability level. Hydrogen atoms are shown as an ideal sphere with a radius of 0.15 Å. The striped bonds indicate hydrogen bonds between Cl and H atoms. [Symmetry codes: (i) −x, −y, z; (ii) −y, −x, −z + $[{1\over 2}]$ , (iii) y, x, −z + $[{1\over 2}]$ ; (iv) −x + 1, y + 1, z; (v) −y + 1, x, −z; (vi) y, x + 1, −z.]

Figure 2
A packing diagram of the solvated title salt, in a view along the b axis. Colour code: purple, Rh; green, Cl; red, O; blue, N; black, C; and white, H.

Synthesis and crystallization

The hydrated complex chloride, trans-[RhCl₂(py)₄]Cl·5H₂O, was prepared from RhCl₃·3H₂O and pyridine in refluxing water, according to the method described in our previous paper (Suzuki et al., 1995 ). The product was recrystallized from methanol, affording yellow platelet methanol tetrasolvate crystals of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[RhCl₂(C₅H₅N)₄]Cl·4CH₄O
M_r	653.83
Crystal system, space group	Tetragonal, P $[\overline{4}]$ c2
Temperature (K)	163
a, c (Å)	7.6130 (7), 26.461 (3)
V (Å³)	1533.7 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.85
Crystal size (mm)	0.70 × 0.60 × 0.30

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Numerical (NUMABS; Higashi, 1999 )
T_min, T_max	0.611, 0.775
No. of measured, independent and observed [I > 2σ(I)] reflections	13753, 1749, 1605
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.047, 1.03
No. of reflections	1749
No. of parameters	85
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.48
Absolute structure	Flack x determined using 652 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.043 (19)
Computer programs: RAPID-AUTO (Rigaku, 2006 ), SIR2014 (Burla et al., 2012 ), SHELXL2014 (Sheldrick, 2015 ) and CrystalMaker (Palmer et al., 2017 ).

Structural data

CCDC reference: 1874254

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618014827/wm4088sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618014827/wm4088Isup2.hkl

checkCIF report

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); program(s) used to solve structure: SIR2014 (Burla et al., 2012); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: CrystalMaker (Palmer et al., 2017); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

trans-Dichloridotetrakis(pyridine-κN)rhodium(III) chloride methanol tetrasolvate top

Crystal data top

[RhCl₂(C₅H₅N)₄]Cl·4CH₄O	D_x = 1.416 Mg m⁻³
M_r = 653.83	Mo Kα radiation, λ = 0.71075 Å
Tetragonal, P4c2	Cell parameters from 13381 reflections
a = 7.6130 (7) Å	θ = 3.1–27.5°
c = 26.461 (3) Å	µ = 0.85 mm⁻¹
V = 1533.7 (3) Å³	T = 163 K
Z = 2	Platelet, yellow
F(000) = 672	0.70 × 0.60 × 0.30 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1605 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.038
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −9→9
T_min = 0.611, T_max = 0.775	k = −8→9
13753 measured reflections	l = −34→34
1749 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.022	H-atom parameters constrained
wR(F²) = 0.047	w = 1/[σ²(F_o²) + (0.0221P)² + 0.2836P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1749 reflections	Δρ_max = 0.22 e Å⁻³
85 parameters	Δρ_min = −0.47 e Å⁻³
0 restraints	Absolute structure: Flack x determined using 652 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.043 (19)

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. The H atom of the methanol hydroxy group was located from a difference Fourier map. Afterwards it was refined using a riding model, with O—H = 0.84 Å. For other H atoms, C—H = 0.95 (aromatic) or 0.98 (methyl) Å, with U_iso(H) = 1.2 U_eq(C, O) were applied.

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

	x	y	z	U_iso*/U_eq
Rh1	0.0000	0.0000	0.2500	0.02029 (9)
Cl1	0.21783 (6)	−0.21783 (6)	0.2500	0.02777 (16)
Cl2	0.5000	0.5000	0.0000	0.0462 (3)
O1	0.7689 (6)	0.2828 (5)	0.06260 (15)	0.0971 (16)
H1	0.7245	0.3530	0.0417	0.116*
N1	0.1360 (4)	0.1368 (4)	0.19521 (6)	0.0238 (3)
C1	0.0516 (4)	0.2088 (4)	0.15529 (10)	0.0285 (6)
H1A	−0.0724	0.1973	0.1529	0.034*
C2	0.1408 (4)	0.2984 (4)	0.11805 (11)	0.0347 (6)
H2	0.0782	0.3457	0.0901	0.042*
C3	0.3185 (6)	0.3196 (6)	0.12101 (9)	0.0406 (6)
H3	0.3802	0.3823	0.0956	0.049*
C4	0.4079 (4)	0.2473 (4)	0.16217 (12)	0.0376 (7)
H4	0.5316	0.2598	0.1653	0.045*
C5	0.3125 (4)	0.1571 (4)	0.19829 (10)	0.0296 (6)
H5	0.3730	0.1075	0.2263	0.035*
C6	0.7411 (7)	0.1140 (7)	0.0467 (2)	0.0807 (15)
H6A	0.7246	0.1127	0.0100	0.097*
H6B	0.6359	0.0669	0.0632	0.097*
H6C	0.8429	0.0415	0.0556	0.097*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.02015 (11)	0.02015 (11)	0.02056 (14)	0.00233 (13)	0.000	0.000
Cl1	0.0266 (2)	0.0266 (2)	0.0301 (3)	0.0081 (3)	0.0019 (6)	0.0019 (6)
Cl2	0.0557 (4)	0.0557 (4)	0.0273 (5)	0.000	0.000	0.000
O1	0.095 (3)	0.082 (3)	0.115 (3)	0.028 (3)	−0.058 (3)	−0.027 (2)
N1	0.0238 (19)	0.0239 (19)	0.0236 (8)	0.0016 (7)	0.0009 (14)	−0.0002 (13)
C1	0.0256 (13)	0.0294 (14)	0.0305 (13)	0.0026 (10)	−0.0050 (10)	0.0010 (11)
C2	0.0383 (16)	0.0362 (16)	0.0297 (13)	0.0023 (13)	−0.0047 (12)	0.0102 (13)
C3	0.044 (3)	0.039 (3)	0.0387 (12)	−0.0061 (11)	0.006 (2)	0.014 (2)
C4	0.0258 (16)	0.0442 (19)	0.0428 (15)	−0.0060 (13)	−0.0012 (13)	0.0104 (14)
C5	0.0243 (14)	0.0344 (15)	0.0300 (12)	0.0014 (11)	−0.0031 (11)	0.0063 (11)
C6	0.072 (3)	0.059 (3)	0.111 (4)	0.013 (3)	−0.009 (3)	0.002 (3)

Geometric parameters (Å, º) top

Rh1—N1	2.0638 (17)	C1—H1A	0.9500
Rh1—N1ⁱ	2.0638 (17)	C2—C3	1.365 (5)
Rh1—N1ⁱⁱ	2.0638 (17)	C2—H2	0.9500
Rh1—N1ⁱⁱⁱ	2.0638 (17)	C3—C4	1.397 (5)
Rh1—Cl1	2.3452 (7)	C3—H3	0.9500
Rh1—Cl1ⁱⁱ	2.3452 (7)	C4—C5	1.383 (4)
O1—C6	1.368 (6)	C4—H4	0.9500
O1—H1	0.8400	C5—H5	0.9500
N1—C5	1.355 (4)	C6—H6A	0.9800
N1—C1	1.352 (4)	C6—H6B	0.9800
C1—C2	1.377 (4)	C6—H6C	0.9800

N1—Rh1—N1ⁱ	89.26 (10)	N1—C1—H1A	119.2
N1—Rh1—N1ⁱⁱ	90.74 (10)	C2—C1—H1A	119.2
N1ⁱ—Rh1—N1ⁱⁱ	179.7 (2)	C3—C2—C1	120.4 (3)
N1—Rh1—N1ⁱⁱⁱ	179.7 (2)	C3—C2—H2	119.8
N1ⁱ—Rh1—N1ⁱⁱⁱ	90.74 (10)	C1—C2—H2	119.8
N1ⁱⁱ—Rh1—N1ⁱⁱⁱ	89.26 (10)	C2—C3—C4	118.8 (2)
N1—Rh1—Cl1	90.13 (12)	C2—C3—H3	120.6
N1ⁱ—Rh1—Cl1	89.87 (12)	C4—C3—H3	120.6
N1ⁱⁱ—Rh1—Cl1	89.87 (12)	C5—C4—C3	118.6 (3)
N1ⁱⁱⁱ—Rh1—Cl1	90.13 (12)	C5—C4—H4	120.7
N1—Rh1—Cl1ⁱⁱ	89.87 (12)	C3—C4—H4	120.7
N1ⁱ—Rh1—Cl1ⁱⁱ	90.13 (12)	N1—C5—C4	122.4 (3)
N1ⁱⁱ—Rh1—Cl1ⁱⁱ	90.13 (12)	N1—C5—H5	118.8
N1ⁱⁱⁱ—Rh1—Cl1ⁱⁱ	89.87 (12)	C4—C5—H5	118.8
Cl1—Rh1—Cl1ⁱⁱ	180.0	O1—C6—H6A	109.5
C6—O1—H1	109.5	O1—C6—H6B	109.5
C5—N1—C1	118.2 (2)	H6A—C6—H6B	109.5
C5—N1—Rh1	120.8 (2)	O1—C6—H6C	109.5
C1—N1—Rh1	121.0 (2)	H6A—C6—H6C	109.5
N1—C1—C2	121.7 (3)	H6B—C6—H6C	109.5

C5—N1—C1—C2	1.0 (5)	C2—C3—C4—C5	0.0 (6)
Rh1—N1—C1—C2	−179.1 (2)	C1—N1—C5—C4	−0.3 (5)
N1—C1—C2—C3	−1.2 (6)	Rh1—N1—C5—C4	179.7 (2)
C1—C2—C3—C4	0.7 (6)	C3—C4—C5—N1	−0.2 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl2	0.84	2.32	3.110 (4)	156

Funding information

Funding for this research was provided by: Grant-in-Aid for Scientific Research No. 18K05146 from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., Giacovazzo, C., Mallamo, M., Mazzone, A., Polidori, G. & Spagna, R. (2012). J. Appl. Cryst. 45, 357–361. Web of Science CrossRef CAS IUCr Journals Google Scholar
Dobinson, G. C., Mason, R. & Russell, D. R. (1967). Chem. Commun. (London), pp. 62–63. Google Scholar
Gillard, R. D., Hanton, L. R. & Mitchell, S. H. (1990). Polyhedron, 9, 2127–2133. CrossRef Web of Science Google Scholar
Gillard, R. D. & Wilkinson, G. (1964). J. Chem. Soc. pp. 1224–1228. CrossRef Web of Science Google Scholar
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Jörgensen, S. M. (1883). J. Prakt. Chem. 27, 433–489. Google Scholar
Palmer, D., Conley, M., Parsonson, L., Rimmer, L. & Stenson, I. (2017). CrystalMaker. CrystalMaker Software Ltd, Bicester, England. Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rigaku (2006). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Suzuki, T., Isobe, K. & Kashiwabara, K. (1995). J. Chem. Soc. Dalton Trans. pp. 3609–3616. CrossRef Web of Science Google Scholar
Vasilchenko, D. B., Baidina, I. A., Filatov, E. Y. & Korenev, S. V. (2009). J. Struct. Chem. 50, 335–342. Web of Science CrossRef Google Scholar
Vasil'chenko, D. B., Venediktov, A. B., Baidina, I. A. & Korenev, S. V. (2015). J. Struct. Chem. 56, 310–316. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.