metal-organic compounds
fac-{2-[Bis(2-aminoethyl)amino]ethanaminium}trichloridorhodium(III) chloride hemihydrate
aFachrichtung Chemie, Universität des Saarlandes, Postfach 151150, D-66041 Saarbrücken, Germany
*Correspondence e-mail: hegetschweiler@mx.uni-saarland.de
The 6H19N4)Cl3]Cl·0.5H2O, is isotypic with the previously reported Ru analogue. The structure contains two crystallographically independent [Rh(Htren)Cl3]+ cations with a facial tridentate coordination of the monoprotonated tren ligand [tren = tris(2-aminoethyl)amine], leading to an overall distorted octahedral coordination environment around the Rh(III) atom. In one of the two cations, the ethylene groups of the two chelate rings as well as the non-coordinating ethylammonium group are disordered over two sets of sites [0.579 (3):0.421 (3) occupancy ratio]. A series of N—H⋯Cl and O—H⋯Cl hydrogen bonds stabilizes the structure.
of the title compound, [Rh(CRelated literature
The preparation of the title compound has been described by Hyvärinen et al. (2009) and the of the isotypic RuIII complex has been reported by Sakai et al. (1996). Disorder phenomena, caused by a superposition of differently folded chelate rings of the tren ligand have been observed by Düpre et al. (1999). Hypodentate coordination of polyamine ligands has been discussed by Blackman (2005) and Neis et al. (2010). For disorder phenomena, see: Hirshfeld (1976).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2010); cell SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536810051846/si2315sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810051846/si2315Isup2.hkl
Orange crystals of the title compound were grown from aqueous 1 mol/L HCl. 1H-NMR (D2O): δ (p.p.m.) = 3.06 (2H), 3.20 (4H), 3.35 (2H), 3.60 (2H), 3.91 (2H), 5.52 (broad, 2NH), 5.62 (broad, 2NH). 13C-NMR (D2O): δ (p.p.m.)= 35.1, 46.1, 59.6, 62.2. UV/Vis (H2O) λmax (nm) = 396, 313.
In the second cation (Rh2), the ethylene groups of both chelate rings as well as the non-coordinating ethylammonium group are disordered, and were considered as a major and minor component with an occupancy of 57.9 (3) % and 42.1 (3) %, respectively. The partially occupied positions of all non hydrogen atoms (major component: C7, C9, C11, C13, C15, C17, N81; minor compounent: C8, C10, C12, C14, C16, C18, N82) could be refined anisotropically. C7 and C8, C11 and C12, N81 and N82 were each refined with equal displacement parameters. However, the disorder obviously generated some inequality of the displacement parameters for neighboring atoms such as N7 and C9 or C14 (Hirshfeld, 1976). H atoms bonded to the water O atom were located in an
and refined with distance restraints of O—H = 0.84 (2) Å, and with Uiso(H) = 1.2Ueq(O). Other H atoms bonded to C- and N-atoms were positioned geometrically and refined using a riding model with about the C—NH3 bond, with C—H = 0.99 Å, N—H = 0.91 (NH3 groups) or 0.92 Å (NH2 groups), and Uiso(H) = 1.2 or 1.5 (NH3 groups) of Ueq of the pivot atom.The title compound has recently been obtained as a byproduct in the synthesis of [RhCl2(tren)]+. Based on the slightly longer wave lengths of the d-d transitions, a partial coordination of the tren ligand was assigned to [RhCl3(Htren)]+. Considering a step by step binding of the nitrogen donors to a mononuclear aqua-chlorido-RhIII precursor, such an intermediate with three coordinated amino groups could either have a meridional or a facial geometry. The two forms cannot be distinguished by NMR spectroscopy, because both
exhibit Cs symmetry for the averaged solution structure.The
analysis confirmed tridentate binding for the Htren+ ligand and exhibited a facial geometry for the coordinated diethylenetriamine unit (Fig. 1). Partial metal binding ("hypodentate coordination") of polyamine ligands is well known. Hypodentate coordination can either be caused by the specific steric requirements of the ligand or by slow ligand substitution. The observation, that vigorous conditions in the synthetic procedure resulted in an exclusive formation of [RhCl2(tren)]+ indicates that the incompletely coordinated ligand of the title compound is due to kinetic rather than thermodynamic reasons. [RhCl3(Htren)]+ should thus be regarded as an intermediate, trapped on its way to [RhCl2(tren)]+.The structure of the title compound is isotypic with the previously reported Ru analogue. The λ and δ conformation. The second cation exhibited some disorder for the five membered Rh—N—C—C—N rings and the non coordinating ethylammonium group. This disorder could be resolved and has been refined as a superposition of two distinct conformers. Within one particular form, the same type of conformation (i.e. λ/λ or δ/δ) was observed for the two chelate rings.
contains two crystallographically independent [RhCl3(Htren)]+ cations, two crystallographically independent chloride anions and one water molecule. The entire structure is stabilized by a three dimensional network of hydrogen bonds (Table 2). Notably, one of the hydrogen atoms of the water molecule (H1WB) has no acceptor: its nearest neighbors are the hydrogen atoms of an ethylenediamine group. Two coordinated chloride ions (Cl2 and Cl3) already exhibit O···Cl separations of 3.675 and 3.784 Å. The molecular structure of one of the cations closely approaches Cs symmetry with the two chelate rings having aIn comparison to the isotypic Ru complex, the M—N and M—Cl bonds of the title compound are, as expected, slightly shorter. In both congeners, the M—N bonds of the tertiary nitrogen atoms were slightly longer. In addition, a trans influence (push-pull mechanism) has found to be operative (Table 1). However, for the Ru congener, these effects were - if at all - barely significant. This is now different for the title compound, where the accuracy of the structure has been increased by almost one order of magnitude.
The preparation of the title compound has been described by Hyvärinen et al. (2009) and the
of the isotypic RuIII complex has been reported by Sakai et al. (1996). Disorder phenomena, caused by a superposition of differently folded chelate rings of the tren ligand have been observed by Düpre et al. (1999). Hypodentate coordination of polyamine ligands has been discussed by Blackman (2005) and Neis et al. (2010). For disorder phenomena, see: Hirshfeld (1976).Data collection: APEX2 (Bruker, 2010); cell
SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. Molecular structure of the title compound. a) The [Rh1Cl3(Htren)]+ cation together with the water molecule; b) the disordered [Rh2Cl3(Htren)]+ cation together with the two chloride counter ions. Displacement ellipsoids are drawn at the 30% probability level. |
[Rh(C6H19N4)Cl3]Cl·0.5H2O | F(000) = 1608 |
Mr = 400.97 | Dx = 1.996 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.8022 (6) Å | Cell parameters from 9299 reflections |
b = 14.1954 (5) Å | θ = 3.2–39.4° |
c = 13.6208 (5) Å | µ = 2.06 mm−1 |
β = 91.196 (1)° | T = 100 K |
V = 2668.11 (18) Å3 | Prism, orange |
Z = 8 | 0.15 × 0.05 × 0.03 mm |
Bruker X8 APEX KappaCCD diffractometer | 13775 independent reflections |
Radiation source: fine-focus sealed tube | 13026 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
phi and ω scans | θmax = 37.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2010) | h = −23→23 |
Tmin = 0.747, Tmax = 0.941 | k = −24→24 |
56384 measured reflections | l = −22→18 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.18 | w = 1/[σ2(Fo2) + (0.0142P)2 + 3.4613P] where P = (Fo2 + 2Fc2)/3 |
13775 reflections | (Δ/σ)max = 0.001 |
328 parameters | Δρmax = 1.79 e Å−3 |
2 restraints | Δρmin = −1.89 e Å−3 |
[Rh(C6H19N4)Cl3]Cl·0.5H2O | V = 2668.11 (18) Å3 |
Mr = 400.97 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 13.8022 (6) Å | µ = 2.06 mm−1 |
b = 14.1954 (5) Å | T = 100 K |
c = 13.6208 (5) Å | 0.15 × 0.05 × 0.03 mm |
β = 91.196 (1)° |
Bruker X8 APEX KappaCCD diffractometer | 13775 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2010) | 13026 reflections with I > 2σ(I) |
Tmin = 0.747, Tmax = 0.941 | Rint = 0.036 |
56384 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 2 restraints |
wR(F2) = 0.065 | H-atom parameters constrained |
S = 1.18 | Δρmax = 1.79 e Å−3 |
13775 reflections | Δρmin = −1.89 e Å−3 |
328 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Rh2 | 0.456131 (7) | 0.457663 (7) | 0.295722 (7) | 0.00764 (2) | |
Cl4 | 0.35083 (2) | 0.54510 (2) | 0.39418 (2) | 0.01355 (5) | |
Cl5 | 0.41181 (3) | 0.55130 (2) | 0.15758 (3) | 0.01525 (6) | |
Cl6 | 0.58495 (2) | 0.55887 (2) | 0.34534 (3) | 0.01457 (5) | |
N5 | 0.49273 (8) | 0.37552 (8) | 0.41469 (9) | 0.01239 (18) | |
H5C | 0.5065 | 0.4125 | 0.4687 | 0.015* | |
H5D | 0.4426 | 0.3355 | 0.4295 | 0.015* | |
N6 | 0.34500 (9) | 0.37247 (9) | 0.25038 (9) | 0.01339 (18) | |
H6C | 0.3199 | 0.3433 | 0.3045 | 0.016* | |
H6D | 0.2968 | 0.4094 | 0.2230 | 0.016* | |
N7 | 0.54171 (10) | 0.36156 (9) | 0.21917 (10) | 0.0158 (2) | |
N81 | 0.7151 (7) | 0.4973 (11) | 0.0537 (10) | 0.0137 (10) | 0.579 (3) |
H81A | 0.7110 | 0.5503 | 0.0162 | 0.021* | 0.579 (3) |
H81B | 0.7268 | 0.4467 | 0.0146 | 0.021* | 0.579 (3) |
H81C | 0.7643 | 0.5036 | 0.0988 | 0.021* | 0.579 (3) |
C11 | 0.5795 (8) | 0.3211 (6) | 0.3865 (7) | 0.0144 (8) | 0.579 (3) |
H11A | 0.5909 | 0.2688 | 0.4335 | 0.017* | 0.579 (3) |
H11B | 0.6373 | 0.3624 | 0.3878 | 0.017* | 0.579 (3) |
C7 | 0.3707 (4) | 0.3016 (5) | 0.1806 (5) | 0.0133 (6) | 0.579 (3) |
H7A | 0.3202 | 0.2980 | 0.1280 | 0.016* | 0.579 (3) |
H7B | 0.3744 | 0.2395 | 0.2135 | 0.016* | 0.579 (3) |
C9 | 0.46844 (17) | 0.32497 (16) | 0.13587 (17) | 0.0126 (4) | 0.579 (3) |
H9A | 0.4597 | 0.3741 | 0.0848 | 0.015* | 0.579 (3) |
H9B | 0.4953 | 0.2681 | 0.1044 | 0.015* | 0.579 (3) |
C13 | 0.56229 (18) | 0.28239 (16) | 0.28408 (18) | 0.0134 (4) | 0.579 (3) |
H13A | 0.6205 | 0.2482 | 0.2621 | 0.016* | 0.579 (3) |
H13B | 0.5069 | 0.2381 | 0.2835 | 0.016* | 0.579 (3) |
C15 | 0.62883 (18) | 0.39463 (17) | 0.1702 (2) | 0.0119 (4) | 0.579 (3) |
H15A | 0.6525 | 0.3428 | 0.1285 | 0.014* | 0.579 (3) |
H15B | 0.6793 | 0.4066 | 0.2213 | 0.014* | 0.579 (3) |
C17 | 0.61978 (18) | 0.48254 (17) | 0.1066 (2) | 0.0123 (4) | 0.579 (3) |
H17A | 0.6057 | 0.5379 | 0.1481 | 0.015* | 0.579 (3) |
H17B | 0.5660 | 0.4749 | 0.0581 | 0.015* | 0.579 (3) |
N82 | 0.7010 (11) | 0.5007 (16) | 0.0506 (15) | 0.0137 (10) | 0.421 (3) |
H82A | 0.7544 | 0.4635 | 0.0456 | 0.021* | 0.421 (3) |
H82B | 0.7189 | 0.5623 | 0.0482 | 0.021* | 0.421 (3) |
H82C | 0.6589 | 0.4879 | 0.0001 | 0.021* | 0.421 (3) |
C12 | 0.5738 (11) | 0.3072 (9) | 0.3985 (10) | 0.0144 (8) | 0.421 (3) |
H12A | 0.5479 | 0.2422 | 0.3950 | 0.017* | 0.421 (3) |
H12B | 0.6211 | 0.3105 | 0.4541 | 0.017* | 0.421 (3) |
C8 | 0.3877 (6) | 0.3096 (7) | 0.1675 (7) | 0.0133 (6) | 0.421 (3) |
H8A | 0.3451 | 0.2545 | 0.1552 | 0.016* | 0.421 (3) |
H8B | 0.3917 | 0.3462 | 0.1058 | 0.016* | 0.421 (3) |
C10 | 0.4876 (2) | 0.2769 (2) | 0.2001 (3) | 0.0139 (6) | 0.421 (3) |
H10A | 0.4841 | 0.2379 | 0.2601 | 0.017* | 0.421 (3) |
H10B | 0.5182 | 0.2394 | 0.1478 | 0.017* | 0.421 (3) |
C14 | 0.6233 (2) | 0.3313 (2) | 0.3038 (2) | 0.0136 (5) | 0.421 (3) |
H14A | 0.6606 | 0.2762 | 0.2810 | 0.016* | 0.421 (3) |
H14B | 0.6692 | 0.3840 | 0.3152 | 0.016* | 0.421 (3) |
C16 | 0.5993 (3) | 0.3907 (2) | 0.1350 (3) | 0.0132 (5) | 0.421 (3) |
H16A | 0.5551 | 0.3949 | 0.0770 | 0.020* | 0.421 (3) |
H16B | 0.6463 | 0.3398 | 0.1217 | 0.020* | 0.421 (3) |
C18 | 0.6550 (3) | 0.4822 (2) | 0.1422 (3) | 0.0135 (6) | 0.421 (3) |
H18A | 0.6103 | 0.5343 | 0.1578 | 0.020* | 0.421 (3) |
H18B | 0.7045 | 0.4779 | 0.1957 | 0.020* | 0.421 (3) |
Rh1 | −0.050193 (6) | 0.022538 (6) | 0.294250 (7) | 0.00769 (2) | |
Cl1 | −0.14238 (2) | −0.08013 (2) | 0.39188 (2) | 0.01218 (5) | |
Cl2 | −0.08326 (2) | −0.07112 (2) | 0.15330 (2) | 0.01352 (5) | |
Cl3 | 0.09065 (2) | −0.06574 (2) | 0.33366 (3) | 0.01344 (5) | |
N1 | 0.02397 (8) | 0.12427 (8) | 0.21533 (9) | 0.01062 (16) | |
N2 | −0.01835 (8) | 0.10429 (8) | 0.41382 (9) | 0.01167 (17) | |
H2B | −0.0739 | 0.1151 | 0.4482 | 0.014* | |
H2A | 0.0249 | 0.0730 | 0.4545 | 0.014* | |
N3 | −0.17010 (8) | 0.10130 (8) | 0.26043 (9) | 0.01160 (17) | |
H3A | −0.2102 | 0.0679 | 0.2184 | 0.014* | |
H3B | −0.2036 | 0.1133 | 0.3168 | 0.014* | |
N4 | 0.22326 (9) | 0.09829 (9) | 0.02885 (9) | 0.01396 (19) | |
H4A | 0.2549 | 0.1396 | −0.0103 | 0.017* | |
H4B | 0.1881 | 0.0575 | −0.0091 | 0.017* | |
H4C | 0.2672 | 0.0656 | 0.0662 | 0.017* | |
C5 | 0.09455 (9) | 0.08094 (9) | 0.14742 (10) | 0.01189 (19) | |
H5A | 0.0583 | 0.0427 | 0.0983 | 0.014* | |
H5B | 0.1372 | 0.0377 | 0.1856 | 0.014* | |
C1 | 0.07923 (11) | 0.18286 (10) | 0.28988 (11) | 0.0156 (2) | |
H1A | 0.0927 | 0.2455 | 0.2614 | 0.019* | |
H1B | 0.1421 | 0.1522 | 0.3052 | 0.019* | |
C3 | −0.05095 (10) | 0.17878 (10) | 0.15695 (11) | 0.0154 (2) | |
H3C | −0.0661 | 0.1448 | 0.0950 | 0.018* | |
H3D | −0.0243 | 0.2413 | 0.1398 | 0.018* | |
C4 | −0.14309 (10) | 0.19188 (10) | 0.21365 (12) | 0.0155 (2) | |
H4D | −0.1331 | 0.2408 | 0.2647 | 0.019* | |
H4E | −0.1960 | 0.2129 | 0.1686 | 0.019* | |
C2 | 0.02394 (11) | 0.19537 (10) | 0.38390 (11) | 0.0162 (2) | |
H2C | 0.0682 | 0.2189 | 0.4365 | 0.019* | |
H2D | −0.0283 | 0.2423 | 0.3736 | 0.019* | |
C6 | 0.15742 (12) | 0.15079 (10) | 0.09370 (12) | 0.0185 (3) | |
H6A | 0.1162 | 0.1941 | 0.0541 | 0.022* | |
H6B | 0.1957 | 0.1887 | 0.1416 | 0.022* | |
O1W | 0.16704 (14) | 0.59698 (11) | 0.57048 (15) | 0.0440 (5) | |
H1WA | 0.1880 | 0.6496 | 0.5480 | 0.053* | |
H1WB | 0.1240 | 0.6050 | 0.6150 | 0.053* | |
Cl7 | 0.21905 (2) | 0.69611 (2) | 0.02866 (3) | 0.01468 (5) | |
Cl8 | 0.30749 (3) | 0.22405 (2) | 0.42426 (3) | 0.01559 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Rh2 | 0.00869 (4) | 0.00589 (4) | 0.00829 (4) | −0.00005 (2) | −0.00082 (3) | 0.00014 (2) |
Cl4 | 0.01259 (11) | 0.01427 (12) | 0.01383 (13) | 0.00339 (9) | 0.00147 (9) | −0.00073 (9) |
Cl5 | 0.01943 (14) | 0.01270 (12) | 0.01342 (13) | −0.00283 (10) | −0.00451 (10) | 0.00451 (9) |
Cl6 | 0.01406 (12) | 0.01173 (12) | 0.01772 (14) | −0.00389 (9) | −0.00425 (10) | 0.00080 (10) |
N5 | 0.0131 (4) | 0.0113 (4) | 0.0128 (5) | 0.0018 (3) | −0.0008 (3) | 0.0020 (3) |
N6 | 0.0156 (5) | 0.0122 (4) | 0.0123 (5) | −0.0047 (4) | −0.0014 (3) | 0.0008 (3) |
N7 | 0.0212 (5) | 0.0079 (4) | 0.0188 (5) | −0.0005 (4) | 0.0093 (4) | −0.0007 (4) |
N81 | 0.008 (3) | 0.0135 (11) | 0.0201 (10) | 0.002 (2) | 0.0063 (18) | 0.0006 (8) |
C11 | 0.0156 (13) | 0.010 (2) | 0.017 (2) | 0.0036 (15) | −0.0036 (14) | 0.0029 (14) |
C7 | 0.015 (2) | 0.0123 (13) | 0.0129 (18) | −0.0029 (13) | 0.0009 (12) | −0.0023 (11) |
C9 | 0.0148 (9) | 0.0105 (8) | 0.0126 (9) | −0.0014 (6) | 0.0004 (7) | −0.0029 (6) |
C13 | 0.0163 (9) | 0.0082 (8) | 0.0157 (9) | 0.0034 (7) | 0.0010 (7) | 0.0024 (7) |
C15 | 0.0104 (9) | 0.0115 (9) | 0.0140 (10) | 0.0025 (7) | 0.0020 (8) | 0.0018 (7) |
C17 | 0.0097 (8) | 0.0128 (9) | 0.0144 (10) | 0.0011 (6) | 0.0019 (8) | 0.0032 (7) |
N82 | 0.008 (3) | 0.0135 (11) | 0.0201 (10) | 0.002 (2) | 0.0063 (18) | 0.0006 (8) |
C12 | 0.0156 (13) | 0.010 (2) | 0.017 (2) | 0.0036 (15) | −0.0036 (14) | 0.0029 (14) |
C8 | 0.015 (2) | 0.0123 (13) | 0.0129 (18) | −0.0029 (13) | 0.0009 (12) | −0.0023 (11) |
C10 | 0.0157 (12) | 0.0090 (11) | 0.0170 (13) | −0.0014 (9) | −0.0004 (10) | −0.0027 (9) |
C14 | 0.0126 (11) | 0.0119 (12) | 0.0161 (13) | 0.0042 (9) | −0.0012 (9) | 0.0003 (9) |
C16 | 0.0155 (14) | 0.0123 (12) | 0.0118 (14) | 0.0002 (10) | 0.0027 (11) | −0.0015 (10) |
C18 | 0.0141 (13) | 0.0136 (13) | 0.0129 (13) | −0.0024 (10) | 0.0019 (11) | −0.0018 (10) |
Rh1 | 0.00765 (4) | 0.00523 (4) | 0.01013 (4) | −0.00032 (2) | −0.00141 (3) | −0.00011 (2) |
Cl1 | 0.01169 (11) | 0.01046 (11) | 0.01437 (12) | −0.00173 (9) | 0.00012 (9) | 0.00220 (9) |
Cl2 | 0.01728 (13) | 0.00891 (11) | 0.01422 (13) | −0.00154 (9) | −0.00346 (10) | −0.00250 (9) |
Cl3 | 0.01081 (11) | 0.01042 (11) | 0.01899 (14) | 0.00193 (9) | −0.00234 (9) | 0.00180 (10) |
N1 | 0.0113 (4) | 0.0078 (4) | 0.0128 (4) | −0.0003 (3) | 0.0010 (3) | 0.0000 (3) |
N2 | 0.0125 (4) | 0.0100 (4) | 0.0125 (4) | −0.0010 (3) | −0.0008 (3) | −0.0010 (3) |
N3 | 0.0106 (4) | 0.0095 (4) | 0.0146 (5) | 0.0004 (3) | −0.0017 (3) | 0.0008 (3) |
N4 | 0.0116 (4) | 0.0160 (5) | 0.0143 (5) | 0.0001 (4) | 0.0015 (3) | −0.0005 (4) |
C5 | 0.0125 (5) | 0.0092 (4) | 0.0141 (5) | −0.0001 (4) | 0.0016 (4) | 0.0001 (4) |
C1 | 0.0175 (5) | 0.0130 (5) | 0.0163 (6) | −0.0067 (4) | 0.0022 (4) | −0.0040 (4) |
C3 | 0.0162 (5) | 0.0126 (5) | 0.0174 (6) | 0.0032 (4) | 0.0019 (4) | 0.0050 (4) |
C4 | 0.0149 (5) | 0.0109 (5) | 0.0208 (6) | 0.0039 (4) | 0.0019 (4) | 0.0040 (4) |
C2 | 0.0211 (6) | 0.0117 (5) | 0.0159 (6) | −0.0053 (4) | 0.0022 (4) | −0.0041 (4) |
C6 | 0.0210 (6) | 0.0113 (5) | 0.0235 (7) | 0.0002 (4) | 0.0103 (5) | 0.0014 (5) |
O1W | 0.0534 (10) | 0.0139 (6) | 0.0662 (12) | −0.0023 (6) | 0.0344 (9) | 0.0031 (7) |
Cl7 | 0.01501 (12) | 0.01145 (12) | 0.01767 (14) | −0.00112 (9) | 0.00213 (10) | −0.00116 (10) |
Cl8 | 0.02018 (14) | 0.01051 (12) | 0.01618 (13) | −0.00098 (10) | 0.00267 (10) | 0.00115 (10) |
Rh2—N6 | 2.0389 (12) | C8—H8A | 0.9900 |
Rh2—N5 | 2.0510 (12) | C8—H8B | 0.9900 |
Rh2—N7 | 2.0964 (12) | C10—H10A | 0.9900 |
Rh2—Cl4 | 2.3522 (3) | C10—H10B | 0.9900 |
Rh2—Cl6 | 2.3731 (3) | C14—H14A | 0.9900 |
Rh2—Cl5 | 2.3735 (3) | C14—H14B | 0.9900 |
N5—C11 | 1.482 (12) | C16—C18 | 1.511 (5) |
N5—C12 | 1.501 (17) | C16—H16A | 0.9900 |
N5—H5C | 0.9200 | C16—H16B | 0.9900 |
N5—H5D | 0.9200 | C18—H18A | 0.9900 |
N6—C7 | 1.434 (7) | C18—H18B | 0.9900 |
N6—C8 | 1.564 (10) | Rh1—N2 | 2.0402 (11) |
N6—H6C | 0.9200 | Rh1—N3 | 2.0420 (11) |
N6—H6D | 0.9200 | Rh1—N1 | 2.0820 (11) |
N7—C10 | 1.435 (3) | Rh1—Cl1 | 2.3626 (3) |
N7—C13 | 1.454 (3) | Rh1—Cl3 | 2.3652 (3) |
N7—C15 | 1.465 (3) | Rh1—Cl2 | 2.3718 (3) |
N7—C16 | 1.468 (4) | N1—C5 | 1.4901 (18) |
N7—C9 | 1.591 (3) | N1—C3 | 1.5054 (18) |
N7—C14 | 1.652 (3) | N1—C1 | 1.5074 (18) |
N81—C17 | 1.527 (13) | N2—C2 | 1.4793 (18) |
N81—H81A | 0.9100 | N2—H2B | 0.9200 |
N81—H81B | 0.9100 | N2—H2A | 0.9200 |
N81—H81C | 0.9100 | N3—C4 | 1.4860 (18) |
C11—C13 | 1.514 (11) | N3—H3A | 0.9200 |
C11—H11A | 0.9900 | N3—H3B | 0.9200 |
C11—H11B | 0.9900 | N4—C6 | 1.4816 (19) |
C7—C9 | 1.529 (5) | N4—H4A | 0.9100 |
C7—H7A | 0.9900 | N4—H4B | 0.9100 |
C7—H7B | 0.9900 | N4—H4C | 0.9100 |
C9—H9A | 0.9900 | C5—C6 | 1.516 (2) |
C9—H9B | 0.9900 | C5—H5A | 0.9900 |
C13—H13A | 0.9900 | C5—H5B | 0.9900 |
C13—H13B | 0.9900 | C1—C2 | 1.515 (2) |
C15—C17 | 1.522 (3) | C1—H1A | 0.9900 |
C15—H15A | 0.9900 | C1—H1B | 0.9900 |
C15—H15B | 0.9900 | C3—C4 | 1.513 (2) |
C17—H17A | 0.9900 | C3—H3C | 0.9900 |
C17—H17B | 0.9900 | C3—H3D | 0.9900 |
N82—C18 | 1.44 (2) | C4—H4D | 0.9900 |
N82—H82A | 0.9100 | C4—H4E | 0.9900 |
N82—H82B | 0.9100 | C2—H2C | 0.9900 |
N82—H82C | 0.9100 | C2—H2D | 0.9900 |
C12—C14 | 1.511 (13) | C6—H6A | 0.9900 |
C12—H12A | 0.9900 | C6—H6B | 0.9900 |
C12—H12B | 0.9900 | O1W—H1WA | 0.8603 |
C8—C10 | 1.513 (11) | O1W—H1WB | 0.8650 |
N6—Rh2—N5 | 94.21 (5) | N6—C8—H8B | 110.0 |
N6—Rh2—N7 | 83.77 (5) | H8A—C8—H8B | 108.4 |
N5—Rh2—N7 | 83.74 (5) | N7—C10—C8 | 105.3 (4) |
N6—Rh2—Cl4 | 90.90 (4) | N7—C10—H10A | 110.7 |
N5—Rh2—Cl4 | 89.68 (3) | C8—C10—H10A | 110.7 |
N7—Rh2—Cl4 | 171.19 (3) | N7—C10—H10B | 110.7 |
N6—Rh2—Cl6 | 178.74 (4) | C8—C10—H10B | 110.7 |
N5—Rh2—Cl6 | 87.05 (3) | H10A—C10—H10B | 108.8 |
N7—Rh2—Cl6 | 96.26 (4) | C12—C14—N7 | 109.9 (6) |
Cl4—Rh2—Cl6 | 89.216 (13) | C12—C14—H14A | 109.7 |
N6—Rh2—Cl5 | 84.96 (4) | N7—C14—H14A | 109.7 |
N5—Rh2—Cl5 | 179.17 (4) | C12—C14—H14B | 109.7 |
N7—Rh2—Cl5 | 96.24 (4) | N7—C14—H14B | 109.7 |
Cl4—Rh2—Cl5 | 90.250 (13) | H14A—C14—H14B | 108.2 |
Cl6—Rh2—Cl5 | 93.777 (12) | N7—C16—C18 | 118.3 (3) |
C11—N5—Rh2 | 106.2 (3) | N7—C16—H16A | 107.7 |
C12—N5—Rh2 | 115.1 (5) | C18—C16—H16A | 107.7 |
C11—N5—H5C | 110.5 | N7—C16—H16B | 107.7 |
C12—N5—H5C | 110.1 | C18—C16—H16B | 107.7 |
Rh2—N5—H5C | 110.5 | H16A—C16—H16B | 107.1 |
C11—N5—H5D | 110.5 | N82—C18—C16 | 109.5 (9) |
C12—N5—H5D | 101.5 | N82—C18—H18A | 109.8 |
Rh2—N5—H5D | 110.5 | C16—C18—H18A | 109.8 |
H5C—N5—H5D | 108.7 | N82—C18—H18B | 109.8 |
C7—N6—Rh2 | 115.0 (2) | C16—C18—H18B | 109.8 |
C8—N6—Rh2 | 105.4 (3) | H18A—C18—H18B | 108.2 |
C7—N6—H6C | 108.5 | N2—Rh1—N3 | 91.65 (5) |
C8—N6—H6C | 118.4 | N2—Rh1—N1 | 85.27 (5) |
Rh2—N6—H6C | 108.5 | N3—Rh1—N1 | 84.76 (5) |
C7—N6—H6D | 108.5 | N2—Rh1—Cl1 | 90.64 (3) |
C8—N6—H6D | 108.2 | N3—Rh1—Cl1 | 91.22 (3) |
Rh2—N6—H6D | 108.5 | N1—Rh1—Cl1 | 174.17 (3) |
H6C—N6—H6D | 107.5 | N2—Rh1—Cl3 | 87.58 (3) |
C13—N7—C15 | 111.90 (16) | N3—Rh1—Cl3 | 178.79 (3) |
C10—N7—C16 | 112.5 (2) | N1—Rh1—Cl3 | 94.25 (3) |
C13—N7—C9 | 107.12 (15) | Cl1—Rh1—Cl3 | 89.722 (12) |
C15—N7—C9 | 107.18 (17) | N2—Rh1—Cl2 | 178.45 (3) |
C10—N7—C14 | 104.7 (2) | N3—Rh1—Cl2 | 89.02 (3) |
C16—N7—C14 | 104.2 (2) | N1—Rh1—Cl2 | 93.40 (3) |
C10—N7—Rh2 | 109.80 (15) | Cl1—Rh1—Cl2 | 90.746 (12) |
C13—N7—Rh2 | 107.78 (12) | Cl3—Rh1—Cl2 | 91.723 (12) |
C15—N7—Rh2 | 119.63 (12) | C5—N1—C3 | 109.57 (11) |
C16—N7—Rh2 | 121.67 (15) | C5—N1—C1 | 108.53 (10) |
C9—N7—Rh2 | 102.17 (11) | C3—N1—C1 | 113.87 (11) |
C14—N7—Rh2 | 101.84 (13) | C5—N1—Rh1 | 111.65 (8) |
C17—N81—H81A | 109.5 | C3—N1—Rh1 | 106.83 (8) |
C17—N81—H81B | 109.5 | C1—N1—Rh1 | 106.39 (8) |
H81A—N81—H81B | 109.5 | C2—N2—Rh1 | 110.91 (9) |
C17—N81—H81C | 109.5 | C2—N2—H2B | 109.5 |
H81A—N81—H81C | 109.5 | Rh1—N2—H2B | 109.5 |
H81B—N81—H81C | 109.5 | C2—N2—H2A | 109.5 |
N5—C11—C13 | 108.4 (6) | Rh1—N2—H2A | 109.5 |
N5—C11—H11A | 110.0 | H2B—N2—H2A | 108.0 |
C13—C11—H11A | 110.0 | C4—N3—Rh1 | 111.17 (8) |
N5—C11—H11B | 110.0 | C4—N3—H3A | 109.4 |
C13—C11—H11B | 110.0 | Rh1—N3—H3A | 109.4 |
H11A—C11—H11B | 108.4 | C4—N3—H3B | 109.4 |
N6—C7—C9 | 110.1 (4) | Rh1—N3—H3B | 109.4 |
N6—C7—H7A | 109.6 | H3A—N3—H3B | 108.0 |
C9—C7—H7A | 109.6 | C6—N4—H4A | 109.5 |
N6—C7—H7B | 109.6 | C6—N4—H4B | 109.5 |
C9—C7—H7B | 109.6 | H4A—N4—H4B | 109.5 |
H7A—C7—H7B | 108.1 | C6—N4—H4C | 109.5 |
C7—C9—N7 | 109.9 (3) | H4A—N4—H4C | 109.5 |
C7—C9—H9A | 109.7 | H4B—N4—H4C | 109.5 |
N7—C9—H9A | 109.7 | N1—C5—C6 | 114.70 (11) |
C7—C9—H9B | 109.7 | N1—C5—H5A | 108.6 |
N7—C9—H9B | 109.7 | C6—C5—H5A | 108.6 |
H9A—C9—H9B | 108.2 | N1—C5—H5B | 108.6 |
N7—C13—C11 | 107.7 (3) | C6—C5—H5B | 108.6 |
N7—C13—H13A | 110.2 | H5A—C5—H5B | 107.6 |
C11—C13—H13A | 110.2 | N1—C1—C2 | 112.17 (11) |
N7—C13—H13B | 110.2 | N1—C1—H1A | 109.2 |
C11—C13—H13B | 110.2 | C2—C1—H1A | 109.2 |
H13A—C13—H13B | 108.5 | N1—C1—H1B | 109.2 |
N7—C15—C17 | 117.61 (19) | C2—C1—H1B | 109.2 |
N7—C15—H15A | 107.9 | H1A—C1—H1B | 107.9 |
C17—C15—H15A | 107.9 | N1—C3—C4 | 111.65 (11) |
N7—C15—H15B | 107.9 | N1—C3—H3C | 109.3 |
C17—C15—H15B | 107.9 | C4—C3—H3C | 109.3 |
H15A—C15—H15B | 107.2 | N1—C3—H3D | 109.3 |
C15—C17—N81 | 108.6 (6) | C4—C3—H3D | 109.3 |
C15—C17—H17A | 110.0 | H3C—C3—H3D | 108.0 |
N81—C17—H17A | 110.0 | N3—C4—C3 | 109.49 (11) |
C15—C17—H17B | 110.0 | N3—C4—H4D | 109.8 |
N81—C17—H17B | 110.0 | C3—C4—H4D | 109.8 |
H17A—C17—H17B | 108.3 | N3—C4—H4E | 109.8 |
C18—N82—H82A | 109.5 | C3—C4—H4E | 109.8 |
C18—N82—H82B | 109.5 | H4D—C4—H4E | 108.2 |
H82A—N82—H82B | 109.5 | N2—C2—C1 | 109.82 (11) |
C18—N82—H82C | 109.5 | N2—C2—H2C | 109.7 |
H82A—N82—H82C | 109.5 | C1—C2—H2C | 109.7 |
H82B—N82—H82C | 109.5 | N2—C2—H2D | 109.7 |
N5—C12—C14 | 109.3 (7) | C1—C2—H2D | 109.7 |
N5—C12—H12A | 109.8 | H2C—C2—H2D | 108.2 |
C14—C12—H12A | 109.8 | N4—C6—C5 | 108.85 (12) |
N5—C12—H12B | 109.8 | N4—C6—H6A | 109.9 |
C14—C12—H12B | 109.8 | C5—C6—H6A | 109.9 |
H12A—C12—H12B | 108.3 | N4—C6—H6B | 109.9 |
C10—C8—N6 | 108.5 (7) | C5—C6—H6B | 109.9 |
C10—C8—H8A | 110.0 | H6A—C6—H6B | 108.3 |
N6—C8—H8A | 110.0 | H1WA—O1W—H1WB | 112.1 |
C10—C8—H8B | 110.0 | ||
N6—Rh2—N5—C11 | 102.0 (4) | Rh2—N7—C15—C17 | −47.5 (3) |
N7—Rh2—N5—C11 | 18.7 (4) | N7—C15—C17—N81 | −173.4 (6) |
Cl4—Rh2—N5—C11 | −167.1 (4) | Rh2—N5—C12—C14 | 12.4 (11) |
Cl6—Rh2—N5—C11 | −77.9 (4) | Rh2—N6—C8—C10 | 43.2 (5) |
N6—Rh2—N5—C12 | 96.3 (6) | C16—N7—C10—C8 | −95.7 (4) |
N7—Rh2—N5—C12 | 13.1 (6) | C9—N7—C10—C8 | −43.9 (4) |
Cl4—Rh2—N5—C12 | −172.8 (6) | C14—N7—C10—C8 | 151.7 (4) |
Cl6—Rh2—N5—C12 | −83.5 (6) | Rh2—N7—C10—C8 | 43.1 (4) |
N5—Rh2—N6—C7 | −92.1 (3) | N6—C8—C10—N7 | −57.6 (5) |
N7—Rh2—N6—C7 | −8.9 (3) | N5—C12—C14—N7 | −40.2 (10) |
Cl4—Rh2—N6—C7 | 178.1 (3) | C10—N7—C14—C12 | −66.4 (6) |
Cl5—Rh2—N6—C7 | 87.9 (3) | C16—N7—C14—C12 | 175.3 (6) |
N5—Rh2—N6—C8 | −98.1 (4) | Rh2—N7—C14—C12 | 47.9 (6) |
N7—Rh2—N6—C8 | −14.9 (4) | C10—N7—C16—C18 | 176.1 (3) |
Cl4—Rh2—N6—C8 | 172.1 (4) | C14—N7—C16—C18 | −71.1 (4) |
Cl5—Rh2—N6—C8 | 81.9 (4) | Rh2—N7—C16—C18 | 42.8 (4) |
N6—Rh2—N7—C10 | −15.86 (17) | N7—C16—C18—N82 | −176.3 (8) |
N5—Rh2—N7—C10 | 79.09 (17) | N2—Rh1—N1—C5 | 132.69 (9) |
Cl6—Rh2—N7—C10 | 165.41 (16) | N3—Rh1—N1—C5 | −135.22 (9) |
Cl5—Rh2—N7—C10 | −100.08 (16) | Cl3—Rh1—N1—C5 | 45.47 (8) |
N6—Rh2—N7—C13 | −83.64 (13) | Cl2—Rh1—N1—C5 | −46.51 (8) |
N5—Rh2—N7—C13 | 11.31 (13) | N2—Rh1—N1—C3 | −107.53 (9) |
Cl6—Rh2—N7—C13 | 97.63 (12) | N3—Rh1—N1—C3 | −15.44 (9) |
Cl5—Rh2—N7—C13 | −167.86 (12) | Cl3—Rh1—N1—C3 | 165.25 (8) |
N6—Rh2—N7—C15 | 147.09 (17) | Cl2—Rh1—N1—C3 | 73.27 (8) |
N5—Rh2—N7—C15 | −117.96 (17) | N2—Rh1—N1—C1 | 14.44 (9) |
Cl6—Rh2—N7—C15 | −31.64 (16) | N3—Rh1—N1—C1 | 106.54 (9) |
Cl5—Rh2—N7—C15 | 62.87 (16) | Cl3—Rh1—N1—C1 | −72.77 (8) |
N6—Rh2—N7—C16 | 118.5 (2) | Cl2—Rh1—N1—C1 | −164.76 (8) |
N5—Rh2—N7—C16 | −146.5 (2) | N3—Rh1—N2—C2 | −75.84 (10) |
Cl6—Rh2—N7—C16 | −60.2 (2) | N1—Rh1—N2—C2 | 8.76 (9) |
Cl5—Rh2—N7—C16 | 34.3 (2) | Cl1—Rh1—N2—C2 | −167.08 (9) |
N6—Rh2—N7—C9 | 29.04 (11) | Cl3—Rh1—N2—C2 | 103.23 (9) |
N5—Rh2—N7—C9 | 123.98 (11) | N2—Rh1—N3—C4 | 76.85 (10) |
Cl6—Rh2—N7—C9 | −149.69 (10) | N1—Rh1—N3—C4 | −8.24 (9) |
Cl5—Rh2—N7—C9 | −55.18 (10) | Cl1—Rh1—N3—C4 | 167.53 (9) |
N6—Rh2—N7—C14 | −126.39 (14) | Cl2—Rh1—N3—C4 | −101.75 (9) |
N5—Rh2—N7—C14 | −31.44 (14) | C3—N1—C5—C6 | 66.79 (15) |
Cl6—Rh2—N7—C14 | 54.89 (13) | C1—N1—C5—C6 | −58.10 (15) |
Cl5—Rh2—N7—C14 | 149.40 (13) | Rh1—N1—C5—C6 | −175.06 (10) |
Rh2—N5—C11—C13 | −45.3 (4) | C5—N1—C1—C2 | −155.76 (12) |
Rh2—N6—C7—C9 | −15.9 (5) | C3—N1—C1—C2 | 81.92 (15) |
N6—C7—C9—N7 | 41.9 (5) | Rh1—N1—C1—C2 | −35.48 (14) |
C13—N7—C9—C7 | 67.3 (3) | C5—N1—C3—C4 | 157.88 (12) |
C15—N7—C9—C7 | −172.5 (3) | C1—N1—C3—C4 | −80.38 (15) |
Rh2—N7—C9—C7 | −45.9 (3) | Rh1—N1—C3—C4 | 36.77 (13) |
C15—N7—C13—C11 | 94.9 (5) | Rh1—N3—C4—C3 | 30.36 (14) |
C9—N7—C13—C11 | −147.9 (4) | N1—C3—C4—N3 | −45.09 (16) |
Rh2—N7—C13—C11 | −38.6 (4) | Rh1—N2—C2—C1 | −30.32 (14) |
N5—C11—C13—N7 | 57.2 (4) | N1—C1—C2—N2 | 44.48 (17) |
C13—N7—C15—C17 | −174.9 (2) | N1—C5—C6—N4 | −179.70 (12) |
C9—N7—C15—C17 | 67.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···Cl7i | 0.92 | 2.42 | 3.2560 (13) | 150 |
N3—H3A···Cl4i | 0.92 | 2.47 | 3.3279 (12) | 155 |
N2—H2B···Cl7i | 0.92 | 2.34 | 3.1744 (12) | 151 |
N5—H5D···Cl8 | 0.92 | 2.45 | 3.3452 (13) | 166 |
N4—H4A···Cl8ii | 0.91 | 2.26 | 3.1322 (13) | 161 |
N5—H5C···Cl4iii | 0.92 | 2.75 | 3.5319 (12) | 143 |
N6—H6D···Cl1iv | 0.92 | 2.62 | 3.4354 (13) | 148 |
N4—H4C···Cl6v | 0.91 | 2.35 | 3.1729 (13) | 150 |
N81—H81B···Cl7vi | 0.91 | 2.24 | 3.109 (14) | 159 |
O1W—H1WA···Cl7vii | 0.86 | 2.25 | 3.0797 (15) | 163 |
N2—H2A···Cl1viii | 0.92 | 2.62 | 3.4348 (12) | 148 |
N6—H6C···Cl8 | 0.92 | 2.36 | 3.2199 (13) | 156 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x, y+1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x+1, −y+1, −z; (vii) x, −y+3/2, z+1/2; (viii) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Rh(C6H19N4)Cl3]Cl·0.5H2O |
Mr | 400.97 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 13.8022 (6), 14.1954 (5), 13.6208 (5) |
β (°) | 91.196 (1) |
V (Å3) | 2668.11 (18) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.06 |
Crystal size (mm) | 0.15 × 0.05 × 0.03 |
Data collection | |
Diffractometer | Bruker X8 APEX KappaCCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2010) |
Tmin, Tmax | 0.747, 0.941 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 56384, 13775, 13026 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.857 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.065, 1.18 |
No. of reflections | 13775 |
No. of parameters | 328 |
No. of restraints | 2 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.79, −1.89 |
Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Rh2—N6 | 2.0389 (12) | Rh1—N2 | 2.0402 (11) |
Rh2—N5 | 2.0510 (12) | Rh1—N3 | 2.0420 (11) |
Rh2—N7 | 2.0964 (12) | Rh1—N1 | 2.0820 (11) |
Rh2—Cl4 | 2.3522 (3) | Rh1—Cl1 | 2.3626 (3) |
Rh2—Cl6 | 2.3731 (3) | Rh1—Cl3 | 2.3652 (3) |
Rh2—Cl5 | 2.3735 (3) | Rh1—Cl2 | 2.3718 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···Cl7i | 0.92 | 2.42 | 3.2560 (13) | 150.4 |
N3—H3A···Cl4i | 0.92 | 2.47 | 3.3279 (12) | 155.4 |
N2—H2B···Cl7i | 0.92 | 2.34 | 3.1744 (12) | 151.2 |
N5—H5D···Cl8 | 0.92 | 2.45 | 3.3452 (13) | 165.6 |
N4—H4A···Cl8ii | 0.91 | 2.26 | 3.1322 (13) | 161.0 |
N5—H5C···Cl4iii | 0.92 | 2.75 | 3.5319 (12) | 143.1 |
N6—H6D···Cl1iv | 0.92 | 2.62 | 3.4354 (13) | 147.8 |
N4—H4C···Cl6v | 0.91 | 2.35 | 3.1729 (13) | 150.2 |
N81—H81B···Cl7vi | 0.91 | 2.24 | 3.109 (14) | 158.5 |
O1W—H1WA···Cl7vii | 0.86 | 2.25 | 3.0797 (15) | 162.6 |
N2—H2A···Cl1viii | 0.92 | 2.62 | 3.4348 (12) | 147.7 |
N6—H6C···Cl8 | 0.92 | 2.36 | 3.2199 (13) | 155.7 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) −x+1, −y+1, −z+1; (iv) −x, y+1/2, −z+1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x+1, −y+1, −z; (vii) x, −y+3/2, z+1/2; (viii) −x, −y, −z+1. |
Acknowledgements
We thank Dr Volker Huch (Universität des Saarlandes) for the data collection.
References
Blackman, A. G. (2005). C. R. Chim. 8, 107–119. CrossRef CAS Google Scholar
Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Düpre, Y., Bartscherer, E., Sander, J., Huch, V. & Hegetschweiler, K. (1999). Z. Kristallogr. New Cryst. Struct. 214, 407–409. Google Scholar
Hirshfeld, F. L. (1976). Acta Cryst. A32, 239–244. CrossRef IUCr Journals Web of Science Google Scholar
Hyvärinen, M., Vaara, J., Goldammer, A., Kutzky, B., Hegetschweiler, K., Kaupp, M. & Straka, M. (2009). J. Am. Chem. Soc. 131, 11909–11918. Web of Science PubMed Google Scholar
Neis, C., Petry, D., Demangeon, A., Morgenstern, B., Kuppert, D., Huppert, J., Stucky, S. & Hegetschweiler, K. (2010). Inorg. Chem. 49, 10092–10107. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sakai, K., Yamada, Y. & Tsubomura, T. (1996). Inorg. Chem. 35, 3163–3172. CSD CrossRef PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals 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.
The title compound has recently been obtained as a byproduct in the synthesis of [RhCl2(tren)]+. Based on the slightly longer wave lengths of the d-d transitions, a partial coordination of the tren ligand was assigned to [RhCl3(Htren)]+. Considering a step by step binding of the nitrogen donors to a mononuclear aqua-chlorido-RhIII precursor, such an intermediate with three coordinated amino groups could either have a meridional or a facial geometry. The two forms cannot be distinguished by NMR spectroscopy, because both diastereomers exhibit Cs symmetry for the averaged solution structure.
The crystal structure analysis confirmed tridentate binding for the Htren+ ligand and exhibited a facial geometry for the coordinated diethylenetriamine unit (Fig. 1). Partial metal binding ("hypodentate coordination") of polyamine ligands is well known. Hypodentate coordination can either be caused by the specific steric requirements of the ligand or by slow ligand substitution. The observation, that vigorous conditions in the synthetic procedure resulted in an exclusive formation of [RhCl2(tren)]+ indicates that the incompletely coordinated ligand of the title compound is due to kinetic rather than thermodynamic reasons. [RhCl3(Htren)]+ should thus be regarded as an intermediate, trapped on its way to [RhCl2(tren)]+.
The structure of the title compound is isotypic with the previously reported Ru analogue. The asymmetric unit contains two crystallographically independent [RhCl3(Htren)]+ cations, two crystallographically independent chloride anions and one water molecule. The entire structure is stabilized by a three dimensional network of hydrogen bonds (Table 2). Notably, one of the hydrogen atoms of the water molecule (H1WB) has no acceptor: its nearest neighbors are the hydrogen atoms of an ethylenediamine group. Two coordinated chloride ions (Cl2 and Cl3) already exhibit O···Cl separations of 3.675 and 3.784 Å. The molecular structure of one of the cations closely approaches Cs symmetry with the two chelate rings having a λ and δ conformation. The second cation exhibited some disorder for the five membered Rh—N—C—C—N rings and the non coordinating ethylammonium group. This disorder could be resolved and has been refined as a superposition of two distinct conformers. Within one particular form, the same type of conformation (i.e. λ/λ or δ/δ) was observed for the two chelate rings.
In comparison to the isotypic Ru complex, the M—N and M—Cl bonds of the title compound are, as expected, slightly shorter. In both congeners, the M—N bonds of the tertiary nitrogen atoms were slightly longer. In addition, a trans influence (push-pull mechanism) has found to be operative (Table 1). However, for the Ru congener, these effects were - if at all - barely significant. This is now different for the title compound, where the accuracy of the structure has been increased by almost one order of magnitude.