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Bis(diisopropylammonium) hexachloroiridate(IV), [{(H3C)2CH}2NH2]2[IrCl6], crystallizes in the monoclinic centrosymmetric space group P21/c with two crystallographically independent [IrCl6]2- anions, each located on a center of symmetry, and two crystallographically independent diisopropylammonium cations in general positions. Weak hydrogen bonding occurs between the cations and anions to form layers parallel to the bc plane. Each layer is built by annealed 24-membered rings that can be classified according to Etter's nomenclature as R88(24). The structural relationship between K3[IrCl6] and the title compound shows that a replacement of three potassium cations by two diisopropylammonium cations leads to a layered structure. The hydrophilic layers that are dominated by hexachloroiridate(IV) anions are separated by lipophilic regions in the planes at x = 1/4 and x = 3/4.
Supporting information
CCDC reference: 180757
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.009 Å
- R factor = 0.034
- wR factor = 0.094
- Data-to-parameter ratio = 19.2
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Data collection: CrysAlis (Kuma, 2000); cell refinement: CrysAlis RED (Kuma, 2000); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
bis(diisopropylammonium) hexachloroiridate(IV)
top
Crystal data top
(C6H16N)2[IrCl6] | F(000) = 1188 |
Mr = 609.30 | Dx = 1.802 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 693 reflections |
a = 16.0939 (14) Å | θ = 5–20° |
b = 10.3961 (12) Å | µ = 6.66 mm−1 |
c = 13.6382 (13) Å | T = 293 K |
β = 100.196 (9)° | Plate, dark red |
V = 2245.8 (4) Å3 | 0.20 × 0.10 × 0.05 mm |
Z = 4 | |
Data collection top
Stoe CCD diffractometer | 3932 independent reflections |
Radiation source: fine-focus sealed tube | 2977 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
ω scans | θmax = 25.0°, θmin = 4.1° |
Absorption correction: numerical (XRED; Stoe & Cie, 1999) | h = −19→19 |
Tmin = 0.294, Tmax = 0.712 | k = −12→12 |
25279 measured reflections | l = −16→16 |
Refinement top
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.04P)2 + 4P] where P = (Fo2 + 2Fc2)/3 |
3932 reflections | (Δ/σ)max = 0.001 |
205 parameters | Δρmax = 0.89 e Å−3 |
0 restraints | Δρmin = −0.83 e Å−3 |
Special details top
Experimental. A thin dark-red platelet of the title compound was mounted on Stoe four-circle
diffractometer equipped with a CCD-detector. For the data collection 21
omega-scans (0.7°) with different chi, phi and 2theta settings and a detector
to crystal distance of 80 mm were performed. Integration procedures using
variable integration masks and integration width of 0.75° yielded a data
completeness of 99.3%. |
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 (Å2) top | x | y | z | Uiso*/Ueq | |
Ir1 | 0.0000 | 0.0000 | 0.0000 | 0.04074 (11) | |
Cl1 | 0.06553 (10) | 0.16306 (14) | 0.10171 (12) | 0.0679 (4) | |
Cl2 | −0.12510 (9) | 0.04463 (15) | 0.05546 (13) | 0.0694 (4) | |
Cl3 | 0.03607 (11) | −0.14831 (15) | 0.12684 (12) | 0.0719 (4) | |
Ir2 | 0.5000 | 0.0000 | 0.5000 | 0.03860 (11) | |
Cl4 | 0.45159 (9) | 0.15270 (14) | 0.37918 (11) | 0.0617 (4) | |
Cl5 | 0.36823 (8) | −0.09812 (13) | 0.47392 (10) | 0.0569 (3) | |
Cl6 | 0.53933 (9) | −0.13088 (15) | 0.37709 (11) | 0.0649 (4) | |
N1 | 0.1171 (3) | 0.1428 (4) | 0.3486 (4) | 0.0573 (11) | |
H1 | 0.0886 | 0.2130 | 0.3627 | 0.073 (19)* | |
H2 | 0.1038 | 0.1302 | 0.2824 | 0.055 (16)* | |
C11 | 0.0840 (4) | 0.0300 (6) | 0.3986 (5) | 0.0618 (16) | |
H11 | 0.0891 | 0.0504 | 0.4696 | 0.074* | |
C12 | −0.0091 (4) | 0.0153 (6) | 0.3562 (6) | 0.077 (2) | |
H12A | −0.0164 | 0.0045 | 0.2852 | 0.116* | |
H12B | −0.0389 | 0.0907 | 0.3712 | 0.116* | |
H12C | −0.0309 | −0.0587 | 0.3852 | 0.116* | |
C13 | 0.1332 (4) | −0.0902 (6) | 0.3899 (5) | 0.0766 (18) | |
H13A | 0.1328 | −0.1087 | 0.3209 | 0.115* | |
H13B | 0.1080 | −0.1604 | 0.4198 | 0.115* | |
H13C | 0.1903 | −0.0786 | 0.4236 | 0.115* | |
C21 | 0.2101 (3) | 0.1741 (5) | 0.3727 (4) | 0.0565 (13) | |
H21 | 0.2416 | 0.0980 | 0.3579 | 0.068* | |
C22 | 0.2275 (4) | 0.2814 (6) | 0.3043 (5) | 0.0725 (17) | |
H22A | 0.1994 | 0.3583 | 0.3196 | 0.109* | |
H22B | 0.2070 | 0.2573 | 0.2363 | 0.109* | |
H22C | 0.2872 | 0.2967 | 0.3133 | 0.109* | |
C23 | 0.2366 (4) | 0.2051 (7) | 0.4810 (4) | 0.0753 (18) | |
H23A | 0.2081 | 0.2815 | 0.4967 | 0.113* | |
H23B | 0.2965 | 0.2189 | 0.4954 | 0.113* | |
H23C | 0.2221 | 0.1348 | 0.5204 | 0.113* | |
N2 | 0.3739 (3) | −0.2199 (4) | 0.1947 (3) | 0.0536 (11) | |
H3 | 0.4147 | −0.1883 | 0.2423 | 0.066 (17)* | |
H4 | 0.3987 | −0.2766 | 0.1591 | 0.072 (18)* | |
C31 | 0.3131 (4) | −0.2939 (6) | 0.2459 (4) | 0.0594 (14) | |
H31 | 0.2889 | −0.2342 | 0.2888 | 0.071* | |
C32 | 0.3627 (4) | −0.3946 (6) | 0.3110 (5) | 0.0798 (19) | |
H32A | 0.3856 | −0.4555 | 0.2700 | 0.120* | |
H32B | 0.3263 | −0.4383 | 0.3487 | 0.120* | |
H32C | 0.4080 | −0.3542 | 0.3557 | 0.120* | |
C33 | 0.2414 (4) | −0.3510 (7) | 0.1712 (5) | 0.082 (2) | |
H33A | 0.2639 | −0.4108 | 0.1290 | 0.122* | |
H33B | 0.2121 | −0.2835 | 0.1313 | 0.122* | |
H33C | 0.2029 | −0.3949 | 0.2061 | 0.122* | |
C41 | 0.3408 (4) | −0.1097 (6) | 0.1259 (4) | 0.0597 (15) | |
H41 | 0.3036 | −0.1451 | 0.0674 | 0.072* | |
C42 | 0.2905 (5) | −0.0175 (6) | 0.1774 (5) | 0.0749 (19) | |
H42A | 0.2420 | −0.0609 | 0.1936 | 0.112* | |
H42B | 0.2723 | 0.0537 | 0.1341 | 0.112* | |
H42C | 0.3250 | 0.0135 | 0.2374 | 0.112* | |
C43 | 0.4147 (5) | −0.0459 (7) | 0.0920 (6) | 0.0806 (19) | |
H43A | 0.3947 | 0.0210 | 0.0452 | 0.121* | |
H43B | 0.4453 | −0.1085 | 0.0607 | 0.121* | |
H43C | 0.4512 | −0.0095 | 0.1484 | 0.121* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Ir1 | 0.03911 (19) | 0.03179 (17) | 0.04803 (19) | −0.00652 (10) | −0.00129 (13) | 0.00310 (10) |
Cl1 | 0.0682 (10) | 0.0534 (8) | 0.0771 (10) | −0.0201 (7) | −0.0006 (7) | −0.0157 (7) |
Cl2 | 0.0547 (9) | 0.0601 (8) | 0.0943 (11) | −0.0056 (7) | 0.0154 (8) | −0.0026 (8) |
Cl3 | 0.0744 (10) | 0.0597 (9) | 0.0754 (10) | −0.0014 (7) | −0.0036 (8) | 0.0276 (7) |
Ir2 | 0.03071 (18) | 0.04358 (19) | 0.03962 (18) | −0.00631 (10) | 0.00109 (12) | 0.00257 (10) |
Cl4 | 0.0489 (8) | 0.0665 (9) | 0.0652 (8) | −0.0060 (6) | −0.0024 (6) | 0.0240 (7) |
Cl5 | 0.0370 (7) | 0.0630 (8) | 0.0685 (8) | −0.0126 (6) | 0.0031 (6) | 0.0038 (6) |
Cl6 | 0.0526 (8) | 0.0771 (10) | 0.0643 (8) | −0.0015 (7) | 0.0085 (6) | −0.0142 (7) |
N1 | 0.052 (3) | 0.055 (3) | 0.067 (3) | 0.008 (2) | 0.018 (2) | 0.005 (2) |
C11 | 0.067 (4) | 0.057 (3) | 0.063 (4) | −0.003 (3) | 0.016 (3) | 0.005 (3) |
C12 | 0.059 (4) | 0.061 (4) | 0.120 (6) | −0.003 (3) | 0.037 (4) | −0.007 (3) |
C13 | 0.071 (4) | 0.063 (4) | 0.091 (5) | 0.004 (3) | 0.001 (4) | 0.010 (3) |
C21 | 0.043 (3) | 0.054 (3) | 0.072 (4) | 0.005 (2) | 0.011 (3) | −0.006 (3) |
C22 | 0.049 (4) | 0.065 (4) | 0.104 (5) | −0.009 (3) | 0.014 (3) | −0.003 (4) |
C23 | 0.073 (4) | 0.080 (4) | 0.070 (4) | 0.018 (3) | 0.004 (3) | −0.020 (3) |
N2 | 0.043 (2) | 0.056 (3) | 0.059 (3) | 0.005 (2) | 0.001 (2) | −0.009 (2) |
C31 | 0.051 (3) | 0.067 (4) | 0.061 (3) | −0.001 (3) | 0.014 (3) | −0.008 (3) |
C32 | 0.084 (5) | 0.064 (4) | 0.087 (5) | −0.006 (3) | 0.006 (4) | 0.002 (3) |
C33 | 0.057 (4) | 0.106 (5) | 0.079 (4) | −0.022 (4) | 0.004 (3) | −0.015 (4) |
C41 | 0.057 (4) | 0.060 (4) | 0.057 (3) | 0.011 (3) | −0.004 (3) | −0.007 (3) |
C42 | 0.079 (5) | 0.071 (4) | 0.071 (4) | 0.025 (3) | 0.002 (4) | −0.010 (3) |
C43 | 0.092 (6) | 0.072 (4) | 0.078 (5) | −0.003 (4) | 0.016 (4) | 0.002 (4) |
Geometric parameters (Å, º) top
Ir1—Cl3 | 2.3133 (14) | C11—C13 | 1.495 (9) |
Ir1—Cl1 | 2.3221 (13) | C21—C23 | 1.499 (8) |
Ir1—Cl2 | 2.3194 (15) | C21—C22 | 1.512 (8) |
Ir2—Cl4 | 2.3212 (13) | N2—C41 | 1.517 (7) |
Ir2—Cl5 | 2.3232 (12) | N2—C31 | 1.510 (7) |
Ir2—Cl6 | 2.3319 (14) | N2—H3 | 0.9000 |
N1—C11 | 1.501 (7) | N2—H4 | 0.9000 |
N1—C21 | 1.510 (7) | C31—C32 | 1.508 (8) |
N1—H1 | 0.9000 | C31—C33 | 1.518 (8) |
N1—H2 | 0.9000 | C41—C42 | 1.507 (8) |
C11—C12 | 1.514 (10) | C41—C43 | 1.504 (9) |
| | | |
Cl1—Ir1—Cl2 | 89.30 (6) | C23—C21—C22 | 113.5 (5) |
Cl1—Ir1—Cl3 | 90.72 (6) | N1—C21—C22 | 108.0 (4) |
Cl2—Ir1—Cl3 | 90.40 (6) | C23—C21—H21 | 108.0 |
Cl4—Ir2—Cl5 | 90.52 (5) | N1—C21—H21 | 108.0 |
Cl4—Ir2—Cl6 | 89.34 (6) | C41—N2—C31 | 119.0 (4) |
Cl5—Ir2—Cl6 | 89.45 (5) | C41—N2—H3 | 107.6 |
C11—N1—C21 | 119.2 (5) | C31—N2—H3 | 107.6 |
C11—N1—H1 | 107.5 | C41—N2—H4 | 107.6 |
C21—N1—H1 | 107.5 | C31—N2—H4 | 107.6 |
C11—N1—H2 | 107.5 | H3—N2—H4 | 107.0 |
C21—N1—H2 | 107.5 | C32—C31—N2 | 107.8 (5) |
H1—N1—H2 | 107.0 | C32—C31—C33 | 112.6 (5) |
C12—C11—N1 | 108.2 (5) | N2—C31—C33 | 111.5 (5) |
C12—C11—C13 | 112.8 (6) | C42—C41—C43 | 112.5 (6) |
N1—C11—C13 | 112.4 (5) | C42—C41—N2 | 110.6 (5) |
C23—C21—N1 | 111.0 (5) | C43—C41—N2 | 108.2 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···Cl3i | 0.90 | 2.50 | 3.346 (5) | 158 |
N1—H2···Cl1 | 0.90 | 2.46 | 3.329 (5) | 164 |
N2—H3···Cl6 | 0.90 | 2.54 | 3.434 (4) | 172 |
N2—H4···Cl4ii | 0.90 | 2.66 | 3.414 (5) | 142 |
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2. |
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