Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010000038X/qb0165sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010000038X/qb0165Isup2.hkl |
CCDC reference: 142927
The protonated iridoxime, [IrCl2(Hdmg)(H2dmg)], (II), was prepared according to the procedure reported by Simonov et al. (1996). To the suspended aqueous solution of (II), ammoniac water was added to precipitate fine crystals of (NH4)[IrCl2(Hdmg)2], (I). By replacing ammoniac water with 10% methanol solution of NBu4OH, precipitate of (NBu4)[IrCl2(Hdmg)2], (III), soluble in organic solvents such as CH2Cl2, CH3CN etc., was obtained. Attempts to substitute the axial Cl− ligands with AgCl or NaBH4 have been unsuccessful.
The single crystals of (I) were obtained from ethanol solution of the precipitate by absorbing vaporized ether. Analysis found: C 18.52, H 3.50, N 13.86%; calculated for C8H18Cl2IrN5O4: C 18.79, H 3.55, N 13.69%.
1H NMR of (III) [CDCl3, 300 MHz, δ p.p.m.) 5.36 (s, 2H, OH), 2.40 (s, 12H, CH3), 3.18 (t, 8H, CH2(NBu4)], 1.58 [quintet, 8H, CH2(NBu4)], 1.40 [sextet, 8H, CH2(NBu4)], 0.99 [t, 12H, CH3(NBu4)]. The spectrum is consistent with the octahedral geometry of anionic complex of (I).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN PROCESS (Molecular Structure Corporation, 1993b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
(NH4)[IrCl2(C4H7N2O2)2] | F(000) = 976 |
Mr = 511.37 | Dx = 2.273 Mg m−3 Dm = 2.27 Mg m−3 Dm measured by flotation in CCl4/CBr4 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
a = 18.3948 (13) Å | Cell parameters from 25 reflections |
b = 7.4649 (14) Å | θ = 14.7–15.0° |
c = 13.2477 (16) Å | µ = 9.31 mm−1 |
β = 124.752 (4)° | T = 296 K |
V = 1494.6 (3) Å3 | Prism, intense green |
Z = 4 | 0.15 × 0.15 × 0.11 mm |
Rigaku AFC-7R diffractometer | 1686 reflections with I > 2σ(I) |
Radiation source: rotating Mo anticathode | Rint = 0.014 |
Graphite monochromator | θmax = 30.0°, θmin = 2.7° |
ω/2θ scans | h = −21→25 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→10 |
Tmin = 0.282, Tmax = 0.359 | l = −18→0 |
2266 measured reflections | 3 standard reflections every 150 reflections |
2177 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.014 | All H-atom parameters refined |
wR(F2) = 0.035 | w = 1/[σ2(Fo2) + (0.0167P)2 + 1.024P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2177 reflections | Δρmax = 0.57 e Å−3 |
130 parameters | Δρmin = −0.75 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00299 (8) |
(NH4)[IrCl2(C4H7N2O2)2] | V = 1494.6 (3) Å3 |
Mr = 511.37 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 18.3948 (13) Å | µ = 9.31 mm−1 |
b = 7.4649 (14) Å | T = 296 K |
c = 13.2477 (16) Å | 0.15 × 0.15 × 0.11 mm |
β = 124.752 (4)° |
Rigaku AFC-7R diffractometer | 1686 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.014 |
Tmin = 0.282, Tmax = 0.359 | 3 standard reflections every 150 reflections |
2266 measured reflections | intensity decay: none |
2177 independent reflections |
R[F2 > 2σ(F2)] = 0.014 | 0 restraints |
wR(F2) = 0.035 | All H-atom parameters refined |
S = 1.05 | Δρmax = 0.57 e Å−3 |
2177 reflections | Δρmin = −0.75 e Å−3 |
130 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 | ||
Ir | 0.0000 | 0.5000 | 0.0000 | 0.01648 (5) | |
Cl | −0.09255 (4) | 0.57499 (11) | 0.06226 (6) | 0.03066 (14) | |
O1 | 0.01829 (13) | 0.1423 (2) | 0.09772 (17) | 0.0307 (4) | |
O2 | 0.11906 (13) | 0.8025 (3) | 0.14412 (19) | 0.0319 (4) | |
N1 | 0.05479 (14) | 0.3033 (3) | 0.12534 (18) | 0.0206 (4) | |
N2 | 0.10257 (13) | 0.6226 (3) | 0.14552 (18) | 0.0210 (4) | |
C1 | 0.1770 (2) | 0.2074 (5) | 0.3320 (3) | 0.0349 (7) | |
C2 | 0.12787 (16) | 0.3419 (4) | 0.2317 (2) | 0.0231 (5) | |
C3 | 0.15551 (16) | 0.5294 (3) | 0.2429 (2) | 0.0213 (5) | |
C4 | 0.23678 (19) | 0.6037 (5) | 0.3550 (3) | 0.0301 (6) | |
N3 | 0 | −0.0810 (6) | 0.25 | 0.0373 (8) | |
H1 | 0.165 (2) | 0.094 (6) | 0.301 (3) | 0.038 (9)* | |
H2 | 0.156 (2) | 0.211 (5) | 0.378 (3) | 0.056 (11)* | |
H3 | 0.239 (3) | 0.234 (6) | 0.384 (3) | 0.062 (12)* | |
H4 | 0.241 (3) | 0.578 (7) | 0.427 (4) | 0.078 (14)* | |
H5 | 0.285 (3) | 0.555 (6) | 0.362 (4) | 0.065 (13)* | |
H6 | 0.239 (3) | 0.727 (7) | 0.352 (4) | 0.073 (14)* | |
H7 | 0.080 (3) | 0.832 (6) | 0.070 (4) | 0.069 (14)* | |
H8 | 0.012 (3) | −0.003 (5) | 0.204 (4) | 0.059 (13)* | |
H9 | −0.044 (3) | −0.146 (6) | 0.199 (4) | 0.073 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ir | 0.01911 (7) | 0.01424 (6) | 0.01536 (6) | −0.00020 (6) | 0.00940 (5) | −0.00001 (5) |
Cl | 0.0311 (3) | 0.0362 (3) | 0.0319 (3) | 0.0011 (3) | 0.0222 (3) | −0.0037 (3) |
O1 | 0.0410 (11) | 0.0160 (9) | 0.0275 (9) | −0.0061 (8) | 0.0151 (8) | 0.0003 (7) |
O2 | 0.0354 (11) | 0.0176 (9) | 0.0329 (10) | −0.0063 (8) | 0.0137 (9) | −0.0005 (8) |
N1 | 0.0268 (10) | 0.0162 (10) | 0.0194 (9) | 0.0004 (8) | 0.0136 (8) | 0.0024 (8) |
N2 | 0.0235 (9) | 0.0174 (10) | 0.0206 (9) | −0.0027 (8) | 0.0116 (8) | −0.0028 (8) |
C1 | 0.0406 (17) | 0.0290 (16) | 0.0237 (13) | 0.0046 (13) | 0.0117 (13) | 0.0062 (12) |
C2 | 0.0258 (11) | 0.0237 (13) | 0.0188 (11) | 0.0027 (10) | 0.0121 (9) | 0.0016 (9) |
C3 | 0.0222 (10) | 0.0221 (15) | 0.0202 (10) | 0.0001 (9) | 0.0124 (9) | −0.0037 (9) |
C4 | 0.0244 (12) | 0.0362 (17) | 0.0236 (12) | −0.0024 (12) | 0.0101 (10) | −0.0036 (12) |
N3 | 0.053 (2) | 0.027 (2) | 0.038 (2) | 0.000 | 0.030 (2) | 0.000 |
Ir—N1 | 2.005 (2) | C1—H1 | 0.91 (4) |
Ir—N2 | 1.992 (2) | C1—H2 | 0.90 (4) |
Ir—Cl | 2.3437 (6) | C1—H3 | 0.96 (4) |
O1—N1 | 1.323 (3) | C4—H4 | 0.92 (5) |
O2—N2 | 1.380 (3) | C4—H5 | 0.92 (5) |
N1—C2 | 1.310 (3) | C4—H6 | 0.92 (5) |
N2—C3 | 1.290 (3) | O2—H7 | 0.85 (4) |
C1—C2 | 1.490 (4) | N3—H8 | 0.96 (4) |
C2—C3 | 1.468 (3) | N3—H9 | 0.85 (4) |
C3—C4 | 1.489 (4) | ||
N1—Ir—N2 | 77.48 (8) | C2—C1—H1 | 111 (2) |
N1—Ir—Cl | 90.38 (6) | C2—C1—H2 | 108 (2) |
N2—Ir—Cl | 91.55 (6) | H1—C1—H2 | 105 (3) |
C2—N1—O1 | 123.0 (2) | C2—C1—H3 | 112 (2) |
C2—N1—Ir | 116.9 (2) | H1—C1—H3 | 113 (3) |
O1—N1—Ir | 120.0 (2) | H2—C1—H3 | 108 (3) |
C3—N2—O2 | 119.5 (2) | C3—C4—H4 | 113 (3) |
C3—N2—Ir | 118.6 (2) | C3—C4—H5 | 109 (3) |
O2—N2—Ir | 121.9 (2) | H4—C4—H5 | 108 (4) |
N1—C2—C3 | 113.7 (2) | C3—C4—H6 | 112 (3) |
N1—C2—C1 | 122.6 (3) | H4—C4—H6 | 106 (4) |
C3—C2—C1 | 123.6 (2) | H5—C4—H6 | 110 (4) |
N2—C3—C2 | 113.1 (2) | N2—O2—H7 | 103 (3) |
N2—C3—C4 | 123.6 (2) | H8—N3—H9 | 108 (4) |
C2—C3—C4 | 123.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H7···O1i | 0.85 (4) | 1.92 (4) | 2.755 (3) | 170 (4) |
N3—H8···O1 | 0.96 (4) | 1.83 (4) | 2.781 (3) | 172 (4) |
N3—H9···Clii | 0.85 (4) | 2.56 (5) | 3.294 (4) | 144 (4) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | (NH4)[IrCl2(C4H7N2O2)2] |
Mr | 511.37 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 296 |
a, b, c (Å) | 18.3948 (13), 7.4649 (14), 13.2477 (16) |
β (°) | 124.752 (4) |
V (Å3) | 1494.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 9.31 |
Crystal size (mm) | 0.15 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.282, 0.359 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2266, 2177, 1686 |
Rint | 0.014 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.014, 0.035, 1.05 |
No. of reflections | 2177 |
No. of parameters | 130 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.57, −0.75 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993a), MSC/AFC Diffractometer Control Software, TEXSAN PROCESS (Molecular Structure Corporation, 1993b), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).
Ir—N1 | 2.005 (2) | O2—N2 | 1.380 (3) |
Ir—N2 | 1.992 (2) | N1—C2 | 1.310 (3) |
Ir—Cl | 2.3437 (6) | N2—C3 | 1.290 (3) |
O1—N1 | 1.323 (3) | C2—C3 | 1.468 (3) |
N1—Ir—N2 | 77.48 (8) | N2—Ir—Cl | 91.55 (6) |
N1—Ir—Cl | 90.38 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H7···O1i | 0.85 (4) | 1.92 (4) | 2.755 (3) | 170 (4) |
N3—H8···O1 | 0.96 (4) | 1.83 (4) | 2.781 (3) | 172 (4) |
N3—H9···Clii | 0.85 (4) | 2.56 (5) | 3.294 (4) | 144 (4) |
Symmetry codes: (i) −x, −y+1, −z; (ii) x, y−1, z. |
Among compounds of the elements in Group 9 with dimethylglyoxime (H2dmg), cobalt complexes, the so-called cobaloximes, have been well studied from the bioinorganic aspects as useful vitamin B12 models (Randaccio et al., 1989). Some rhodium complexes are known, but have not been often applied to biological investigation in comparison with the cobalt complexes. The cobaloximes and rhodoximes commonly have octahedral geometry with equatorial coordination of two Hdmg− anions. As for the iridium complex, more inert than the rhodium, the structure of [IrCl2(Hdmg)(H2dmg)], (II), was only reported (Simonov et al., 1996); the geometry about iridium is octahedral, similar to the cobaloximes and rhodoximes. Its properties remain unexplored owing to the low solubility in solvents. We attempted to derive salts by replacement of onium ions such as NH4+, NBu4+ etc. in order to examine chemical and physical properties in solutions. Single crystals of the ammonium salt, (NH4)[IrCl2(Hdmg)2], (I), were obtained from ethanol solution.
The crystal structure of (I) is constructed of NH4+ cations and octahedral [IrCl2(Hdmg)2]− anions. The iridium atom on the inversion center is coordinated by two Cl atoms in trans and two Hdmg− chelate ligands in the equatorial plane, similarly to (II). A pair of the Hdmg− are planar with a maximum deviation of 0.138 (5) Å of C4 and linked with each other by the O1···H7—O2 intramolecular hydrogen bonds to form a 14-membered macrocycle. The intermolecular hydrogen bonds between the oxime groups of the [IrCl2(Hdmg)2] moieties are observed in (II) but not in (I). Insteadly, two-dimensional hydrogen-bond network along the bc plane is formed between NH4+ and, Cl and O1 atoms of [IrCl2(Hdmg)2]− moieties.
The notable difference between (II) and (I) is found in the O—N distances of the Hdmg moieties. In (I), the O1—N1 distance [1.323 (3) Å] is distinctly shorter than the O2—N2 distance [1.380 (3) Å], while the O—N distances of the two independent molecules in (II) are within a small range (1.36–1.37 Å). The discrepancy of the O—N distances in (I) shows that the H atom is strongly bonded to the O2 atom; such a phenomenon has been found in the cobaloximes or rhodoximes, e.g. [Rh(Hdmg)2(H2O)2](ClO4) (Moszner et al., 1997). In (I), the O—N distances seem quite close to each other owing to the delocalized distribution of the protonated oxime groups. Other bond distances and angles are reasonable within the standard deviations.