[Bis(pyridin-2-ylmeth-yl) ether]trichlorido-rhodium(III) dichloro-methane monosolvate: unusual hydrolysis of the methyl-ene bridge in (pyrazolylmeth-yl)pyridine.

In the title compound, [RhCl(3)(C(12)H(12)N(2)O)]·CH(2)Cl(2), the Rh(III) atom shows a slightly distorted octa-hedral geometry being coordinated by two N atoms and one O atom from the 2,2'-(oxydimethanedi-yl)dipyridine ligand and three Cl atoms. Two Cl atoms adopt a trans arrangement to the two pyridyl N atoms, while the third Cl atom and the O atoms occupy the axial site. The Rh-Cl bonds that are trans to the pyridyl N atoms are slightly longer than the Rh-Cl bond distance trans to the O atom.

Related literature

For hydrogenation of n class="Chemical">olefins, see: Samec et al. (2006 ▶); Xu et al. (2009 ▶); Chalid et al. (2011 ▶); Liu et al. (2011 ▶). For multidentate N-containing ligands, see: Dayan & Centikaya (2007 ▶); Deng et al. (2005 ▶). For pyrazolyl-based transition metal complexes as catalysts, see: Ojwach & Darkwa (2010 ▶) and references therein. For structures bearing the 2,2′-(oxydimethanedi­yl)dipyridine ligand, see: Nanty et al. (2000 ▶) and references therein.

Experimental

Crystal data

[RhCl3(C12n class="Species">H12N2O)]·CH2Cl2

M = 494.42

Monoclinic,

a = 9.5360 (18) Å

b = 12.527 (2) Å

c = 14.340 (3) Å

β = 95.071 (4)°

V = 1706.3 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.78 mm−1

T = 100 K

0.14 × 0.13 × 0.05 mm

Data collection

Bruker X8 APEXII 4K KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.788, T max = 0.916

30694 measured reflections

4276 independent reflections

2925 reflections with I > 2σ(I)

R int = 0.102

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.139

S = 1.08

4276 reflections

199 parameters

H-atom parameters constrained

Δρmax = 1.50 e Å−3

Δρmin = −1.25 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT-Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus and XPREP (Bruker, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811027644/om2440sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027644/om2440Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[RhCl3(C12H12N2O)]·CH2Cl2	F(000) = 976
Mr = 494.42	Dx = 1.925 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 31705 reflections
a = 9.5360 (18) Å	θ = 2.1–28.6°
b = 12.527 (2) Å	µ = 1.78 mm−1
c = 14.340 (3) Å	T = 100 K
β = 95.071 (4)°	Block, brown
V = 1706.3 (6) Å3	0.14 × 0.13 × 0.05 mm
Z = 4

Bruker X8 APEXII 4K KappaCCD diffractometer	2925 reflections with I > 2σ(I)
graphite	Rint = 0.102
φ and ω scans	θmax = 28.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −12→12
Tmin = 0.788, Tmax = 0.916	k = −15→16
30694 measured reflections	l = −19→19
4276 independent reflections

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0602P)2 + 6.0697P] where P = (Fo2 + 2Fc2)/3
4276 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 1.50 e Å−3
0 restraints	Δρmin = −1.25 e Å−3

Experimental. The intensity data was collected on a Bruker X8 Apex 4 K CCD diffractometer using an exposure time of 20 sec/per frame. A total of 3527 frames were collected with a frame width of 0.5° covering upto θ = 28.57° with 99.8% completeness accomplished.

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.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. >>> The Following ALERTS were generated <<< Format: alert-number_ALERT_alert-type_alert-level text 973_ALERT_2_B Large Calcd. Positive Residual Density on Rh1 1.53 e A-3 Difference map does not reveal any missing peaks, R factor is 4.8% 342_ALERT_3_C Low Bond Precision on C—C Bonds (x 1000) Ang.. 9 083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large. 6.07 960_ALERT_3_G Number of Intensities with I. LT. - 2*sig(I).. 7 912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 76Noted.

	x	y	z	Uiso*/Ueq
C1	0.9453 (6)	0.3170 (5)	0.5707 (4)	0.0220 (12)
C2	0.9516 (6)	0.3990 (5)	0.6344 (4)	0.0250 (13)
H2	0.9982	0.3893	0.6952	0.03*
C3	0.8896 (7)	0.4959 (5)	0.6095 (4)	0.0286 (14)
H3	0.8936	0.5538	0.6525	0.034*
C4	0.8218 (7)	0.5068 (5)	0.5210 (4)	0.0284 (14)
H4	0.7789	0.5727	0.5022	0.034*
C5	0.8166 (6)	0.4224 (5)	0.4604 (4)	0.0238 (13)
H5	0.7684	0.43	0.3999	0.029*
C6	1.0152 (6)	0.2118 (5)	0.5914 (4)	0.0213 (12)
H6A	1.1158	0.2167	0.5797	0.026*
H6B	1.0101	0.194	0.6583	0.026*
C7	0.8409 (6)	0.0651 (5)	0.5762 (4)	0.0240 (13)
H7A	0.8595	0.0672	0.6452	0.029*
H7B	0.8459	−0.0103	0.556	0.029*
C8	0.6967 (6)	0.1079 (5)	0.5489 (4)	0.0217 (12)
C9	0.5837 (6)	0.0877 (5)	0.6005 (4)	0.0248 (13)
H9	0.5973	0.05	0.6581	0.03*
C10	0.4508 (7)	0.1230 (5)	0.5677 (4)	0.0285 (14)
H10	0.372	0.11	0.6023	0.034*
C11	0.4352 (6)	0.1776 (5)	0.4833 (4)	0.0284 (14)
H11	0.3447	0.2014	0.4589	0.034*
C12	0.5499 (6)	0.1970 (5)	0.4353 (4)	0.0272 (13)
H12	0.5381	0.2353	0.378	0.033*
C13	0.5353 (9)	0.4120 (7)	0.6578 (7)	0.053 (2)
H13A	0.6165	0.3889	0.7009	0.064*
H13B	0.5467	0.3812	0.5953	0.064*
N1	0.8778 (5)	0.3292 (4)	0.4846 (3)	0.0179 (10)
N2	0.6797 (5)	0.1632 (4)	0.4675 (3)	0.0212 (10)
O1	0.9483 (4)	0.1273 (3)	0.5336 (3)	0.0204 (8)
Cl1	1.08727 (15)	0.21896 (12)	0.35869 (10)	0.0231 (3)
Cl2	0.76119 (16)	0.27205 (13)	0.27541 (10)	0.0255 (3)
Cl3	0.83695 (15)	0.02382 (12)	0.33886 (9)	0.0231 (3)
Cl4	0.5347 (2)	0.55102 (18)	0.64998 (18)	0.0583 (6)
Cl5	0.3773 (2)	0.36285 (18)	0.69904 (14)	0.0513 (5)
Rh1	0.86208 (5)	0.19166 (4)	0.40861 (3)	0.01818 (13)

	U11	U22	U33	U12	U13	U23
C1	0.020 (3)	0.023 (3)	0.025 (3)	−0.002 (2)	0.010 (2)	0.002 (2)
C2	0.026 (3)	0.028 (4)	0.021 (3)	−0.007 (3)	0.006 (2)	0.003 (2)
C3	0.037 (4)	0.018 (3)	0.032 (3)	−0.002 (3)	0.014 (3)	−0.004 (2)
C4	0.030 (3)	0.018 (3)	0.039 (3)	0.003 (2)	0.011 (3)	0.002 (3)
C5	0.023 (3)	0.025 (3)	0.024 (3)	0.002 (2)	0.006 (2)	0.006 (2)
C6	0.018 (3)	0.019 (3)	0.026 (3)	−0.001 (2)	0.001 (2)	−0.001 (2)
C7	0.025 (3)	0.023 (3)	0.024 (3)	−0.002 (2)	0.007 (2)	0.005 (2)
C8	0.023 (3)	0.018 (3)	0.024 (3)	−0.003 (2)	0.005 (2)	0.000 (2)
C9	0.026 (3)	0.025 (3)	0.024 (3)	−0.007 (3)	0.007 (2)	−0.002 (2)
C10	0.023 (3)	0.029 (4)	0.035 (3)	−0.006 (3)	0.010 (3)	−0.006 (3)
C11	0.016 (3)	0.029 (4)	0.039 (3)	−0.002 (2)	−0.001 (2)	−0.004 (3)
C12	0.024 (3)	0.027 (4)	0.029 (3)	−0.004 (3)	0.000 (2)	−0.005 (3)
C13	0.042 (5)	0.040 (5)	0.077 (6)	0.013 (4)	0.008 (4)	0.013 (4)
N1	0.016 (2)	0.016 (3)	0.023 (2)	−0.0009 (18)	0.0045 (18)	0.0013 (18)
N2	0.020 (2)	0.021 (3)	0.023 (2)	−0.0013 (19)	0.0039 (19)	−0.0011 (19)
O1	0.018 (2)	0.022 (2)	0.0219 (19)	−0.0005 (16)	0.0038 (15)	0.0005 (16)
Cl1	0.0195 (7)	0.0223 (8)	0.0283 (7)	−0.0014 (5)	0.0060 (5)	−0.0002 (5)
Cl2	0.0257 (7)	0.0280 (8)	0.0227 (7)	0.0011 (6)	0.0018 (5)	0.0037 (6)
Cl3	0.0247 (7)	0.0205 (8)	0.0244 (6)	−0.0026 (6)	0.0041 (5)	−0.0008 (5)
Cl4	0.0419 (12)	0.0495 (13)	0.0855 (16)	0.0110 (9)	0.0173 (11)	0.0111 (11)
Cl5	0.0472 (12)	0.0535 (13)	0.0525 (11)	0.0010 (9)	0.0010 (9)	0.0028 (9)
Rh1	0.0174 (2)	0.0170 (2)	0.0204 (2)	−0.00075 (18)	0.00326 (15)	0.00144 (18)

C1—N1	1.349 (7)	C8—C9	1.383 (8)
C1—C2	1.373 (8)	C9—C10	1.385 (9)
C1—C6	1.495 (8)	C9—H9	0.95
C2—C3	1.384 (9)	C10—C11	1.387 (9)
C2—H2	0.95	C10—H10	0.95
C3—C4	1.380 (9)	C11—C12	1.365 (8)
C3—H3	0.95	C11—H11	0.95
C4—C5	1.367 (9)	C12—N2	1.350 (8)
C4—H4	0.95	C12—H12	0.95
C5—N1	1.336 (7)	C13—Cl4	1.745 (9)
C5—H5	0.95	C13—Cl5	1.777 (9)
C6—O1	1.456 (7)	C13—H13A	0.99
C6—H6A	0.99	C13—H13B	0.99
C6—H6B	0.99	N1—Rh1	2.037 (5)
C7—O1	1.462 (7)	N2—Rh1	2.031 (5)
C7—C8	1.496 (8)	O1—Rh1	2.069 (4)
C7—H7A	0.99	Cl1—Rh1	2.3479 (15)
C7—H7B	0.99	Cl2—Rh1	2.2941 (15)
C8—N2	1.355 (7)	Cl3—Rh1	2.3315 (15)
N1—C1—C2	120.8 (5)	C12—C11—C10	120.0 (6)
N1—C1—C6	116.8 (5)	C12—C11—H11	120
C2—C1—C6	122.3 (5)	C10—C11—H11	120
C1—C2—C3	119.5 (6)	N2—C12—C11	121.5 (6)
C1—C2—H2	120.2	N2—C12—H12	119.2
C3—C2—H2	120.2	C11—C12—H12	119.2
C4—C3—C2	118.6 (6)	Cl4—C13—Cl5	111.6 (4)
C4—C3—H3	120.7	Cl4—C13—H13A	109.3
C2—C3—H3	120.7	Cl5—C13—H13A	109.3
C5—C4—C3	119.8 (6)	Cl4—C13—H13B	109.3
C5—C4—H4	120.1	Cl5—C13—H13B	109.3
C3—C4—H4	120.1	H13A—C13—H13B	108
N1—C5—C4	121.3 (6)	C5—N1—C1	119.9 (5)
N1—C5—H5	119.3	C5—N1—Rh1	126.1 (4)
C4—C5—H5	119.3	C1—N1—Rh1	113.5 (4)
O1—C6—C1	111.2 (5)	C12—N2—C8	119.4 (5)
O1—C6—H6A	109.4	C12—N2—Rh1	126.6 (4)
C1—C6—H6A	109.4	C8—N2—Rh1	114.0 (4)
O1—C6—H6B	109.4	C6—O1—C7	116.0 (4)
C1—C6—H6B	109.4	C6—O1—Rh1	109.3 (3)
H6A—C6—H6B	108	C7—O1—Rh1	109.3 (3)
O1—C7—C8	111.2 (5)	N2—Rh1—N1	87.23 (19)
O1—C7—H7A	109.4	N2—Rh1—O1	81.99 (17)
C8—C7—H7A	109.4	N1—Rh1—O1	82.03 (17)
O1—C7—H7B	109.4	N2—Rh1—Cl2	96.40 (14)
C8—C7—H7B	109.4	N1—Rh1—Cl2	94.57 (13)
H7A—C7—H7B	108	N2—Rh1—Cl3	87.75 (14)
N2—C8—C9	121.0 (6)	O1—Rh1—Cl3	92.19 (12)
N2—C8—C7	116.5 (5)	Cl2—Rh1—Cl3	91.09 (6)
C9—C8—C7	122.4 (5)	N1—Rh1—Cl1	90.78 (13)
C8—C9—C10	119.5 (6)	O1—Rh1—Cl1	90.98 (11)
C8—C9—H9	120.2	Cl2—Rh1—Cl1	90.56 (5)
C10—C9—H9	120.2	Cl3—Rh1—Cl1	93.59 (5)
C9—C10—C11	118.5 (6)	N1—Rh1—Cl3	172.82 (13)
C9—C10—H10	120.7	N2—Rh1—Cl1	172.89 (14)
C11—C10—H10	120.7	O1—Rh1—Cl2	176.29 (12)
N1—C1—C2—C3	−0.9 (9)	C12—N2—Rh1—N1	87.7 (5)
C6—C1—C2—C3	177.4 (5)	C8—N2—Rh1—N1	−89.7 (4)
C1—C2—C3—C4	0.6 (9)	C12—N2—Rh1—O1	170.1 (5)
C2—C3—C4—C5	0.4 (9)	C8—N2—Rh1—O1	−7.3 (4)
C3—C4—C5—N1	−1.0 (9)	C12—N2—Rh1—Cl2	−6.6 (5)
N1—C1—C6—O1	−25.6 (7)	C8—N2—Rh1—Cl2	176.1 (4)
C2—C1—C6—O1	156.1 (5)	C12—N2—Rh1—Cl3	−97.4 (5)
O1—C7—C8—N2	24.6 (7)	C8—N2—Rh1—Cl3	85.2 (4)
O1—C7—C8—C9	−158.8 (5)	C12—N2—Rh1—Cl1	161.6 (9)
N2—C8—C9—C10	1.2 (9)	C8—N2—Rh1—Cl1	−15.8 (15)
C7—C8—C9—C10	−175.2 (6)	C5—N1—Rh1—N2	−84.2 (5)
C8—C9—C10—C11	0.1 (9)	C1—N1—Rh1—N2	88.5 (4)
C9—C10—C11—C12	−1.1 (9)	C5—N1—Rh1—O1	−166.5 (5)
C10—C11—C12—N2	0.8 (10)	C1—N1—Rh1—O1	6.2 (4)
C4—C5—N1—C1	0.7 (8)	C5—N1—Rh1—Cl2	12.0 (5)
C4—C5—N1—Rh1	173.0 (4)	C1—N1—Rh1—Cl2	−175.3 (3)
C2—C1—N1—C5	0.3 (8)	C5—N1—Rh1—Cl3	−129.9 (10)
C6—C1—N1—C5	−178.1 (5)	C1—N1—Rh1—Cl3	42.8 (13)
C2—C1—N1—Rh1	−172.9 (4)	C5—N1—Rh1—Cl1	102.6 (4)
C6—C1—N1—Rh1	8.7 (6)	C1—N1—Rh1—Cl1	−84.7 (4)
C11—C12—N2—C8	0.6 (9)	C6—O1—Rh1—N2	−107.8 (3)
C11—C12—N2—Rh1	−176.7 (5)	C7—O1—Rh1—N2	20.1 (4)
C9—C8—N2—C12	−1.6 (9)	C6—O1—Rh1—N1	−19.5 (3)
C7—C8—N2—C12	175.1 (5)	C7—O1—Rh1—N1	108.4 (4)
C9—C8—N2—Rh1	176.0 (4)	C6—O1—Rh1—Cl2	−43 (2)
C7—C8—N2—Rh1	−7.4 (7)	C7—O1—Rh1—Cl2	84.6 (19)
C1—C6—O1—C7	−95.4 (5)	C6—O1—Rh1—Cl3	164.8 (3)
C1—C6—O1—Rh1	28.7 (5)	C7—O1—Rh1—Cl3	−67.3 (3)
C8—C7—O1—C6	95.3 (5)	C6—O1—Rh1—Cl1	71.2 (3)
C8—C7—O1—Rh1	−28.7 (5)	C7—O1—Rh1—Cl1	−161.0 (3)

Table 1

Selected bond lengths (Å)

N1—Rh1	2.037 (5)
N2—Rh1	2.031 (5)
O1—Rh1	2.069 (4)
Cl1—Rh1	2.3479 (15)
Cl2—Rh1	2.2941 (15)
Cl3—Rh1	2.3315 (15)