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

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 .. site, and is surrounded by four methanol mol­ecules to which it is bound in a pseudo-tetra­hedral arrangement by O—H...Cl hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 163 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.022
• wR factor = 0.047
• Data-to-parameter ratio = 20.6

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT260_ALERT_2_C Large Average Ueq of Residue Including        O1      0.089 Check

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          1 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.70 mm
PLAT304_ALERT_4_G Non-Integer Number of Atoms in ...... Resd  3          0.25 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Rh1       (III)     .       2.97 Info
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min).          2 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          6 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          1 Info

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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Computing details

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

Crystal data

[RhCl2(C5H5N)4]Cl·4CH4O	Dx = 1.416 Mg m^−3
Mr = 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) Å^3	T = 163 K
Z = 2	Platelet, yellow
F(000) = 672	0.70 × 0.60 × 0.30 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.022	H-atom parameters constrained
wR(F^2) = 0.047	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 0.2836P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
1749 reflections	Δρmax = 0.22 e Å^−3
85 parameters	Δρmin = −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

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Rh1—N1	2.0638 (17)	C1—H1A	0.9500
Rh1—N1^i	2.0638 (17)	C2—C3	1.365 (5)
Rh1—N1^ii	2.0638 (17)	C2—H2	0.9500
Rh1—N1^iii	2.0638 (17)	C3—C4	1.397 (5)
Rh1—Cl1	2.3452 (7)	C3—H3	0.9500
Rh1—Cl1^ii	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—N1^i	89.26 (10)	N1—C1—H1A	119.2
N1—Rh1—N1^ii	90.74 (10)	C2—C1—H1A	119.2
N1^i—Rh1—N1^ii	179.7 (2)	C3—C2—C1	120.4 (3)
N1—Rh1—N1^iii	179.7 (2)	C3—C2—H2	119.8
N1^i—Rh1—N1^iii	90.74 (10)	C1—C2—H2	119.8
N1^ii—Rh1—N1^iii	89.26 (10)	C2—C3—C4	118.8 (2)
N1—Rh1—Cl1	90.13 (12)	C2—C3—H3	120.6
N1^i—Rh1—Cl1	89.87 (12)	C4—C3—H3	120.6
N1^ii—Rh1—Cl1	89.87 (12)	C5—C4—C3	118.6 (3)
N1^iii—Rh1—Cl1	90.13 (12)	C5—C4—H4	120.7
N1—Rh1—Cl1^ii	89.87 (12)	C3—C4—H4	120.7
N1^i—Rh1—Cl1^ii	90.13 (12)	N1—C5—C4	122.4 (3)
N1^ii—Rh1—Cl1^ii	90.13 (12)	N1—C5—H5	118.8
N1^iii—Rh1—Cl1^ii	89.87 (12)	C4—C5—H5	118.8
Cl1—Rh1—Cl1^ii	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)

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