[2,6-Bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine-κ³N]trichlororhodium(III) monohydrate

In the solid state, the title mononuclear octahedral rho­dium(III) complex, [RhCl₃(C₁₃H₁₅N₃)]·H₂O, shows a hydrogen bond between the equatorial Cl atom and the solvent water mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.036
• wR factor = 0.079
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .....       0.98
PLAT355_ALERT_3_A Long    O-H Bond (0.82A)   O1     -   H1W    =       1.21 Ang.

Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR) is > 1.10
            Tmin and Tmax reported:      0.798     0.820
            Tmin and Tmax expected:      0.725     0.820
            RR =      1.101
            Please check that your absorption correction is appropriate.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ..          ?
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ..           C2
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O1     -   H2W    =       1.07 Ang.

   2 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

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

---

S1. Comment

The tridentate ligand 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine (L; Bernauer & Gretillat, 1989) has been used extensively for the synthesis of mononuclear complexes containing one L (Cabort Therrien et al., 2003) or two L units around a transition metal (Cabort Therrien Stoeckli-Evans et al., 2002; Cabort Michel et al., 2003). To the best of our knowledge, L has never been used as a monodentate, bidentate, or bridging ligand. To investigate these other possible coordination modes, we decided to react L with [RhCp^*(µ-Cl)₂Cl] (White et al., 1992). However, under the reaction conditions of refluxing MeOH in the presence of NaBF₄, the 1,2,3,4,5-pentamethylcyclopentadienyl (Cp^*) moiety is removed, and the title mononuclear complex, [RhCl₃(L)], (I), is formed. Complex (I) has been reported previously by Cabort et al. (Cabort Therrien Bernauer & Süss-Fink, 2002). Unlike Cabort et al., where compound (I) crystallized with two benzene molecules per asymmetric unit, we obtained crystals of complex (I) with one molecule of water per asymmetric unit, giving rise to a different packing arrangement and to the formation of an intermolecular hydrogen bond between the equatorial Cl atom and the water molecule.

The three N atoms of the tridentate ligand, along with the three Cl atoms, form a distorted octahedral geometry around the metal in (I) (Fig.1, Table 1). The bond distances and angles are similar to those found in other [RhCl₃(η³-L)] complexes, where L is bis(oxazolinyl)pyridine (Nishiyama et al., 1991), bis(pyrazolyl)pyridine (Christenson et al., 1995), 2,6-bis(ethylidyneimino)pyridine (Haarman et al., 1997), 2,3,6-tris(2-pyridyl)-1,3,5-triazine (Paul et al., 1998), 2,2':6',2"-terpyridine (Ziegler et al., 1999; Kwong et al., 2001) or 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine (Cabort Therrien Bernauer & Süss-Fink, 2002).

The formation of five-membered chelate rings significantly distorts the geometry around the Rh atom. The N1—Rh1—N2 [78.12 (15)°], N2—Rh1—N3 [78.03 (14)°] and N1—Rh1—N3 [156.08 (15)°] angles are significantly smaller than the values of 90 and 180° expected for an ideal octahedral geometry. The equatorial plane formed by L and atoms Rh1 and Cl1 is planar, with an average deviation of 0.0692 Å; only atoms C3 and C12 of the pyrrol fragment and atom Cl1 are significantly out of this plane, by −0.135 (4), −0.178 (5) and 0.145 (2) Å, respectively. The distance between Rh and the central N2 atom [1.975 (3) Å] is shorter than the other Rh—N bonds [Rh1—N1 2.064 (4) and Rh1—N3 2.071 (4) Å].

In the crystal of (I), a weak intermolecular hydrogen bond is formed between atom Cl1 and the water molecule, with Cl1—O1 3.153 (5) and Cl1···H1W—O1 142.0°.

S2. Experimental

To a methanol solution (10 ml) of [RhCp^*(µ-Cl)₂Cl] (30 mg, 0.05 mmol) were added 2,6-bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine (20 mg, 0.1 mmol) and NaBF₄ (11 mg, 0.1 mmol). The orange solution was stirred and refluxed for 12 h. After cooling to room temperature, a brown precipitate was observed. The precipitate was dissolved in a methanol-water solution (Ratio?). Crystals of (I) were observed after two weeks. ¹H NMR (200 MHz, CDCl₃, δ, p.p.m.): 8.44 (t, 1H), 8.32 (d, 2H), 4.14 (m, 4H), 3.48 (m, 4H), 2.48 (m, 4H). MS (ESI, m/z): 423. [RhCl₃(L)] analysis, calculated for C₁₃H₁₅Cl₃N₃Rh·H₂O: C 35.44, H 3.89, N 9.54%; found: C 35.30, H 3.98, N 9.48%.

S3. Refinement

The H atoms were included in calculated positions and treated as riding atoms using the SHELXL97 (Sheldrick, 1997) default parameters, except for the H atoms of the water molecule, which were located from a Fourier difference map and fixed at their positions.

Computing details

Data collection: EXPOSE in IPDS (Stoe & Cie, 2000); cell refinement: CELL in IPDS; data reduction: INTEGRATE in IPDS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecular structure of (I) (Farrugia, 1997). Displacement ellipsoids are drawn at the 50% probability level.

[2,6-Bis(3,4-dihydro-2H-pyrrol-5-yl)pyridine-κ³N]trichlororhodium(III) monohydrate

Crystal data

[RhCl3(C13H15N3)]·H2O	F(000) = 1760
Mr = 440.56	Dx = 1.776 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6717 reflections
a = 18.682 (4) Å	θ = 1.9–25.9°
b = 14.821 (3) Å	µ = 1.52 mm^−1
c = 14.819 (3) Å	T = 153 K
β = 126.57 (3)°	Block, red
V = 3295.4 (17) Å^3	0.23 × 0.18 × 0.13 mm
Z = 8

Data collection

Stoe IPDS diffractometer	3136 independent reflections
Radiation source: fine-focus sealed tube	2127 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
Detector resolution: 0.81Å pixels mm^-1	θmax = 25.9°, θmin = 1.9°
ϕ oscillation scans	h = −21→22
Absorption correction: multi-scan (Blessing, 1995)	k = −16→18
Tmin = 0.798, Tmax = 0.820	l = −18→18
8555 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.079	H atoms treated by a mixture of independent and constrained refinement
S = 0.89	w = 1/[σ^2(Fo^2) + (0.0406P)^2] where P = (Fo^2 + 2Fc^2)/3
3136 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

Experimental. A crystal was mounted at 153 K on a Stoe Image Plate Diffraction System (Stoe & Cie, 2000) using Mo Kα graphite monochromated radiation. Image plate distance 70 mm, ϕ oscillation scans 0 − 180°, step Δϕ = 1.5°, 10 minutes per frame.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1537 (4)	0.1416 (3)	0.4399 (5)	0.0394 (13)
H1A	0.1287	0.1825	0.3767	0.047*
H1B	0.2039	0.1707	0.5067	0.047*
C2	0.0837 (4)	0.1143 (4)	0.4563 (6)	0.0561 (16)
H2A	0.0308	0.1514	0.4103	0.067*
H2B	0.1068	0.1214	0.5344	0.067*
C3	0.0619 (3)	0.0159 (3)	0.4212 (4)	0.0325 (11)
H3A	0.0651	−0.0200	0.4782	0.039*
H3B	0.0030	0.0095	0.3506	0.039*
C4	0.1323 (3)	−0.0101 (3)	0.4093 (3)	0.0261 (10)
C5	0.1513 (3)	−0.0996 (3)	0.3850 (3)	0.0258 (10)
C6	0.1109 (3)	−0.1813 (3)	0.3746 (4)	0.0306 (11)
H6	0.0660	−0.1851	0.3840	0.037*
C7	0.1395 (3)	−0.2573 (3)	0.3498 (4)	0.0340 (12)
H7	0.1133	−0.3128	0.3423	0.041*
C8	0.2068 (3)	−0.2517 (3)	0.3358 (4)	0.0303 (11)
H8	0.2257	−0.3028	0.3191	0.036*
C9	0.2445 (3)	−0.1694 (3)	0.3472 (4)	0.0261 (10)
C10	0.3155 (3)	−0.1463 (3)	0.3357 (3)	0.0248 (10)
C11	0.3631 (4)	−0.2071 (3)	0.3082 (4)	0.0348 (12)
H11A	0.3217	−0.2396	0.2388	0.042*
H11B	0.4000	−0.2500	0.3682	0.042*
C12	0.4195 (4)	−0.1416 (3)	0.2961 (4)	0.0373 (12)
H12A	0.3975	−0.1373	0.2181	0.045*
H12B	0.4811	−0.1615	0.3406	0.045*
C13	0.4120 (3)	−0.0503 (3)	0.3383 (4)	0.0332 (11)
H13A	0.4678	−0.0344	0.4092	0.040*
H13B	0.3962	−0.0031	0.2840	0.040*
N1	0.1814 (3)	0.0558 (3)	0.4178 (3)	0.0272 (9)
N2	0.2167 (2)	−0.0958 (2)	0.3718 (3)	0.0215 (8)
N3	0.3408 (2)	−0.0632 (2)	0.3524 (3)	0.0234 (8)
O1	0.5096 (3)	0.1842 (3)	0.4181 (4)	0.0717 (13)
H1W	0.4313	0.1842	0.3792	0.086*
H2W	0.5230	0.1206	0.3962	0.086*
Cl1	0.34436 (9)	0.16333 (7)	0.42372 (10)	0.0354 (3)
Cl2	0.17228 (8)	0.05304 (8)	0.20050 (9)	0.0340 (3)
Cl3	0.37853 (8)	−0.01363 (8)	0.58291 (8)	0.0311 (3)
Rh1	0.27517 (3)	0.02125 (2)	0.39239 (3)	0.02457 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.049 (4)	0.028 (3)	0.049 (3)	0.005 (2)	0.034 (3)	−0.003 (2)
C2	0.060 (5)	0.040 (3)	0.095 (5)	−0.004 (3)	0.061 (4)	−0.009 (3)
C3	0.032 (3)	0.040 (3)	0.029 (2)	0.003 (2)	0.020 (2)	0.003 (2)
C4	0.025 (3)	0.027 (2)	0.025 (2)	−0.002 (2)	0.014 (2)	0.0012 (18)
C5	0.023 (3)	0.031 (3)	0.020 (2)	−0.001 (2)	0.011 (2)	0.0016 (18)
C6	0.033 (3)	0.031 (3)	0.030 (2)	−0.009 (2)	0.020 (2)	−0.0010 (19)
C7	0.040 (3)	0.026 (3)	0.033 (3)	−0.013 (2)	0.021 (3)	−0.001 (2)
C8	0.034 (3)	0.024 (2)	0.029 (2)	−0.002 (2)	0.016 (2)	−0.0029 (18)
C9	0.030 (3)	0.019 (2)	0.025 (2)	−0.0003 (19)	0.014 (2)	−0.0022 (17)
C10	0.027 (3)	0.021 (2)	0.023 (2)	−0.0020 (19)	0.012 (2)	−0.0051 (17)
C11	0.038 (3)	0.030 (3)	0.047 (3)	−0.002 (2)	0.031 (3)	−0.009 (2)
C12	0.048 (4)	0.033 (3)	0.045 (3)	0.003 (2)	0.035 (3)	−0.003 (2)
C13	0.036 (3)	0.036 (3)	0.039 (3)	−0.007 (2)	0.028 (3)	−0.006 (2)
N1	0.031 (3)	0.025 (2)	0.0293 (19)	0.0050 (18)	0.0198 (19)	0.0018 (15)
N2	0.025 (2)	0.0148 (18)	0.0217 (17)	−0.0027 (15)	0.0125 (17)	−0.0006 (13)
N3	0.028 (2)	0.0197 (19)	0.0213 (17)	−0.0007 (16)	0.0142 (17)	−0.0022 (14)
O1	0.069 (4)	0.062 (3)	0.090 (3)	−0.001 (2)	0.050 (3)	0.010 (2)
Cl1	0.0424 (8)	0.0208 (6)	0.0441 (7)	−0.0052 (5)	0.0264 (6)	−0.0031 (5)
Cl2	0.0342 (8)	0.0294 (6)	0.0309 (6)	0.0005 (5)	0.0155 (6)	0.0027 (5)
Cl3	0.0371 (7)	0.0300 (6)	0.0269 (5)	−0.0042 (5)	0.0194 (5)	−0.0027 (5)
Rh1	0.0296 (2)	0.01756 (17)	0.02976 (18)	−0.00054 (17)	0.01946 (16)	−0.00173 (16)

Geometric parameters (Å, º)

C1—N1	1.481 (6)	C9—C10	1.474 (7)
C1—C2	1.519 (7)	C10—N3	1.290 (5)
C1—H1A	0.9700	C10—C11	1.483 (6)
C1—H1B	0.9700	C11—C12	1.520 (7)
C2—C3	1.521 (7)	C11—H11A	0.9700
C2—H2A	0.9700	C11—H11B	0.9700
C2—H2B	0.9700	C12—C13	1.533 (6)
C3—C4	1.478 (6)	C12—H12A	0.9700
C3—H3A	0.9700	C12—H12B	0.9700
C3—H3B	0.9700	C13—N3	1.476 (6)
C4—N1	1.294 (6)	C13—H13A	0.9700
C4—C5	1.472 (6)	C13—H13B	0.9700
C5—N2	1.348 (6)	N1—Rh1	2.064 (4)
C5—C6	1.386 (6)	N2—Rh1	1.975 (3)
C6—C7	1.386 (7)	N3—Rh1	2.071 (4)
C6—H6	0.9300	O1—H1W	1.2117
C7—C8	1.393 (7)	O1—H2W	1.0731
C7—H7	0.9300	Cl1—Rh1	2.3677 (12)
C8—C9	1.368 (6)	Cl2—Rh1	2.3431 (16)
C8—H8	0.9300	Cl3—Rh1	2.3389 (15)
C9—N2	1.349 (5)
N1—C1—C2	104.7 (4)	C12—C11—H11A	111.3
N1—C1—H1A	110.8	C10—C11—H11B	111.3
C2—C1—H1A	110.8	C12—C11—H11B	111.3
N1—C1—H1B	110.8	H11A—C11—H11B	109.2
C2—C1—H1B	110.8	C11—C12—C13	106.1 (4)
H1A—C1—H1B	108.9	C11—C12—H12A	110.5
C1—C2—C3	106.3 (4)	C13—C12—H12A	110.5
C1—C2—H2A	110.5	C11—C12—H12B	110.5
C3—C2—H2A	110.5	C13—C12—H12B	110.5
C1—C2—H2B	110.5	H12A—C12—H12B	108.7
C3—C2—H2B	110.5	N3—C13—C12	104.6 (4)
H2A—C2—H2B	108.7	N3—C13—H13A	110.8
C4—C3—C2	102.4 (4)	C12—C13—H13A	110.8
C4—C3—H3A	111.3	N3—C13—H13B	110.8
C2—C3—H3A	111.3	C12—C13—H13B	110.8
C4—C3—H3B	111.3	H13A—C13—H13B	108.9
C2—C3—H3B	111.3	C4—N1—C1	110.4 (4)
H3A—C3—H3B	109.2	C4—N1—Rh1	115.1 (3)
N1—C4—C5	116.3 (4)	C1—N1—Rh1	134.4 (3)
N1—C4—C3	114.9 (4)	C5—N2—C9	122.3 (4)
C5—C4—C3	128.7 (4)	C5—N2—Rh1	118.7 (3)
N2—C5—C6	120.1 (4)	C9—N2—Rh1	119.0 (3)
N2—C5—C4	111.6 (4)	C10—N3—C13	110.8 (4)
C6—C5—C4	128.3 (4)	C10—N3—Rh1	114.8 (3)
C5—C6—C7	117.9 (5)	C13—N3—Rh1	134.4 (3)
C5—C6—H6	121.0	H1W—O1—H2W	106.8
C7—C6—H6	121.0	N2—Rh1—N1	78.12 (15)
C6—C7—C8	121.0 (4)	N2—Rh1—N3	78.03 (14)
C6—C7—H7	119.5	N1—Rh1—N3	156.08 (15)
C8—C7—H7	119.5	N2—Rh1—Cl3	88.58 (10)
C9—C8—C7	118.6 (4)	N1—Rh1—Cl3	90.85 (11)
C9—C8—H8	120.7	N3—Rh1—Cl3	90.46 (10)
C7—C8—H8	120.7	N2—Rh1—Cl2	90.62 (10)
N2—C9—C8	120.1 (4)	N1—Rh1—Cl2	89.98 (11)
N2—C9—C10	111.2 (4)	N3—Rh1—Cl2	88.37 (10)
C8—C9—C10	128.7 (4)	Cl3—Rh1—Cl2	178.70 (4)
N3—C10—C9	116.9 (4)	N2—Rh1—Cl1	177.27 (10)
N3—C10—C11	114.9 (4)	N1—Rh1—Cl1	99.64 (11)
C9—C10—C11	128.3 (4)	N3—Rh1—Cl1	104.25 (11)
C10—C11—C12	102.5 (4)	Cl3—Rh1—Cl1	89.90 (5)
C10—C11—H11A	111.3	Cl2—Rh1—Cl1	90.94 (5)
N1—C1—C2—C3	−10.4 (6)	C10—C9—N2—Rh1	−2.2 (5)
C1—C2—C3—C4	10.7 (6)	C9—C10—N3—C13	179.8 (4)
C2—C3—C4—N1	−7.6 (5)	C11—C10—N3—C13	0.5 (5)
C2—C3—C4—C5	174.9 (5)	C9—C10—N3—Rh1	0.0 (5)
N1—C4—C5—N2	−2.3 (5)	C11—C10—N3—Rh1	−179.4 (3)
C3—C4—C5—N2	175.2 (4)	C12—C13—N3—C10	6.1 (5)
N1—C4—C5—C6	178.2 (4)	C12—C13—N3—Rh1	−174.1 (3)
C3—C4—C5—C6	−4.4 (7)	C5—N2—Rh1—N1	−1.5 (3)
N2—C5—C6—C7	−0.4 (6)	C9—N2—Rh1—N1	179.8 (3)
C4—C5—C6—C7	179.1 (4)	C5—N2—Rh1—N3	−179.6 (3)
C5—C6—C7—C8	0.1 (7)	C9—N2—Rh1—N3	1.7 (3)
C6—C7—C8—C9	0.1 (7)	C5—N2—Rh1—Cl3	89.7 (3)
C7—C8—C9—N2	0.2 (7)	C9—N2—Rh1—Cl3	−89.0 (3)
C7—C8—C9—C10	−179.5 (4)	C5—N2—Rh1—Cl2	−91.4 (3)
N2—C9—C10—N3	1.4 (6)	C9—N2—Rh1—Cl2	90.0 (3)
C8—C9—C10—N3	−178.9 (4)	C4—N1—Rh1—N2	0.1 (3)
N2—C9—C10—C11	−179.4 (4)	C1—N1—Rh1—N2	−176.9 (5)
C8—C9—C10—C11	0.3 (8)	C4—N1—Rh1—N3	4.8 (5)
N3—C10—C11—C12	−6.8 (5)	C1—N1—Rh1—N3	−172.2 (4)
C9—C10—C11—C12	173.9 (4)	C4—N1—Rh1—Cl3	−88.2 (3)
C10—C11—C12—C13	9.9 (5)	C1—N1—Rh1—Cl3	94.7 (4)
C11—C12—C13—N3	−9.9 (5)	C4—N1—Rh1—Cl2	90.8 (3)
C5—C4—N1—C1	178.9 (4)	C1—N1—Rh1—Cl2	−86.3 (4)
C3—C4—N1—C1	1.1 (5)	C4—N1—Rh1—Cl1	−178.3 (3)
C5—C4—N1—Rh1	1.1 (5)	C1—N1—Rh1—Cl1	4.7 (4)
C3—C4—N1—Rh1	−176.7 (3)	C10—N3—Rh1—N2	−0.9 (3)
C2—C1—N1—C4	6.1 (6)	C13—N3—Rh1—N2	179.3 (4)
C2—C1—N1—Rh1	−176.8 (4)	C10—N3—Rh1—N1	−5.6 (5)
C6—C5—N2—C9	0.7 (6)	C13—N3—Rh1—N1	174.6 (4)
C4—C5—N2—C9	−178.9 (4)	C10—N3—Rh1—Cl3	87.6 (3)
C6—C5—N2—Rh1	−178.0 (3)	C13—N3—Rh1—Cl3	−92.3 (4)
C4—C5—N2—Rh1	2.4 (5)	C10—N3—Rh1—Cl2	−91.8 (3)
C8—C9—N2—C5	−0.6 (6)	C13—N3—Rh1—Cl2	88.3 (4)
C10—C9—N2—C5	179.2 (4)	C10—N3—Rh1—Cl1	177.6 (3)
C8—C9—N2—Rh1	178.1 (3)	C13—N3—Rh1—Cl1	−2.2 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···Cl1	1.21	2.11	3.153 (5)	142