Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102018231/ob1082sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102018231/ob1082Isup2.hkl |
CCDC reference: 199406
The starting material trans-[CrCl2(Me2tn)2]ClO4 was synthesized according to the literature method of House (1986). The complex trans-[CrCl2(Me2tn)2]ClO4 (1.0 g) and NaOH (1.0 g) were suspended in water (10 ml) and heated at 333 K for 15 min. HBr (48%, 10 ml) and HClO4 (60%, 5 ml) were added to the mixture. The solution was concentrated at 333 K until green crystals appeared. The reaction mixture was then placed in an ice bath and the crystalline product which was deposited was filtered off, washed with cold 2-propanol and then diethyl ether. Recrystallization of the crude product from 0.5 M HBr solution afforded green crystals of (I) suitable for X-ray analysis.
The water H atoms were located from difference syntheses and refined as parts of rigid groups, with O—H = 0.90 Å and Uiso(H) = 0.044 Å2. The position of the H+ ion (H00) was fixed at the midpoint between the atoms O1 and O1(1 - x, y, -z). Other H atoms were placed geometrically and refined using a riding model, with N—H = 0.90 Å, C—H = 0.96 (for methyl H) or 0.97 Å (for methylene H), and Uiso(H) = 1.2Uiso(N or C). The H atoms of the methyl groups (C24, C25, C29 and C30) were treated as positionally disordered over two sites.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: TEXSAN (Molecular Structure Cooperation & Rigaku, 2000); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1970); software used to prepare material for publication: SHELXL97.
[CrBr2(C5H14N2)2]2Br2·HClO4·6H2O | F(000) = 2400 |
Mr = 1200.74 | Dx = 1.731 Mg m−3 |
Monoclinic, C2/m | Mo Kα radiation, λ = 0.71069 Å |
a = 22.3862 (8) Å | Cell parameters from 24876 reflections |
b = 24.7393 (8) Å | θ = 1.6–27.5° |
c = 8.3230 (3) Å | µ = 5.78 mm−1 |
β = 91.624 (1)° | T = 293 K |
V = 4607.6 (3) Å3 | Plate, green |
Z = 8 | 0.32 × 0.32 × 0.10 mm |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 5320 independent reflections |
Radiation source: fine-focus sealed tube | 4188 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
Detector resolution: 10.00 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
ω scans | h = −26→26 |
Absorption correction: multi-scan (Higashi, 1995) | k = −30→32 |
Tmin = 0.188, Tmax = 0.560 | l = −10→10 |
20618 measured 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.052P)2 + 9.0033P] where P = (Fo2 + 2Fc2)/3 |
5320 reflections | (Δ/σ)max = 0.002 |
228 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −0.60 e Å−3 |
[CrBr2(C5H14N2)2]2Br2·HClO4·6H2O | V = 4607.6 (3) Å3 |
Mr = 1200.74 | Z = 8 |
Monoclinic, C2/m | Mo Kα radiation |
a = 22.3862 (8) Å | µ = 5.78 mm−1 |
b = 24.7393 (8) Å | T = 293 K |
c = 8.3230 (3) Å | 0.32 × 0.32 × 0.10 mm |
β = 91.624 (1)° |
Rigaku R-AXIS RAPID Imaging Plate diffractometer | 5320 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 4188 reflections with I > 2σ(I) |
Tmin = 0.188, Tmax = 0.560 | Rint = 0.052 |
20618 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.108 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.73 e Å−3 |
5320 reflections | Δρmin = −0.60 e Å−3 |
228 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) | |
Br3 | 0.29087 (2) | 0.176534 (16) | 0.50962 (4) | 0.04806 (13) | |
Br11 | 0.19102 (2) | 0.335225 (17) | −0.00718 (5) | 0.05015 (13) | |
Br21 | 0.21757 (3) | 0.0000 | 0.10304 (7) | 0.05798 (18) | |
Br22 | 0.31308 (3) | 0.0000 | 0.64692 (6) | 0.05400 (17) | |
Cr1 | 0.2500 | 0.2500 | 0.0000 | 0.03191 (18) | |
Cr2 | 0.26574 (4) | 0.0000 | 0.37796 (9) | 0.03325 (18) | |
Cl | 0.0000 | 0.16923 (8) | 0.5000 | 0.0705 (5) | |
O1 | 0.4979 (2) | 0.1581 (2) | 0.1407 (6) | 0.1096 (16) | |
O2 | 0.4230 (2) | 0.2077 (2) | 0.3351 (6) | 0.1109 (16) | |
O3 | 0.0933 (2) | 0.3843 (2) | 0.2930 (6) | 0.1143 (16) | |
O41 | 0.0122 (4) | 0.1410 (4) | 0.6354 (7) | 0.201 (4) | |
O42 | 0.0445 (6) | 0.2016 (5) | 0.4612 (12) | 0.318 (8) | |
N11 | 0.19109 (14) | 0.21564 (14) | −0.1693 (3) | 0.0415 (7) | |
H11M | 0.1638 | 0.2410 | −0.1963 | 0.049* | |
H11N | 0.2120 | 0.2089 | −0.2578 | 0.049* | |
N12 | 0.19988 (14) | 0.22128 (13) | 0.1883 (3) | 0.0377 (7) | |
H12M | 0.2250 | 0.2175 | 0.2739 | 0.047* | |
H12N | 0.1738 | 0.2474 | 0.2130 | 0.047* | |
N21 | 0.32399 (15) | −0.05930 (13) | 0.3001 (4) | 0.0432 (7) | |
H21M | 0.3167 | −0.0894 | 0.3572 | 0.053* | |
H21N | 0.3136 | −0.0667 | 0.1972 | 0.053* | |
N22 | 0.20486 (15) | −0.05914 (13) | 0.4460 (4) | 0.0446 (7) | |
H22M | 0.1816 | −0.0665 | 0.3588 | 0.055* | |
H22N | 0.2261 | −0.0893 | 0.4680 | 0.055* | |
C11 | 0.15758 (19) | 0.16518 (17) | −0.1308 (5) | 0.0479 (10) | |
H11A | 0.1857 | 0.1354 | −0.1225 | 0.061* | |
H11B | 0.1297 | 0.1573 | −0.2191 | 0.061* | |
C12 | 0.12281 (18) | 0.16832 (18) | 0.0254 (5) | 0.0477 (9) | |
C13 | 0.16552 (19) | 0.17025 (16) | 0.1717 (5) | 0.0448 (9) | |
H13A | 0.1427 | 0.1651 | 0.2677 | 0.057* | |
H13B | 0.1934 | 0.1404 | 0.1649 | 0.057* | |
C14 | 0.07988 (19) | 0.2160 (2) | 0.0238 (6) | 0.0610 (12) | |
H14A | 0.1021 | 0.2491 | 0.0172 | 0.073* | |
H14B | 0.0576 | 0.2159 | 0.1206 | 0.073* | |
H14C | 0.0529 | 0.2132 | −0.0675 | 0.073* | |
C15 | 0.0877 (2) | 0.1150 (2) | 0.0352 (7) | 0.0693 (13) | |
H15A | 0.0641 | 0.1152 | 0.1297 | 0.090* | |
H15B | 0.1151 | 0.0852 | 0.0403 | 0.090* | |
H15C | 0.0619 | 0.1114 | −0.0584 | 0.090* | |
C21 | 0.38967 (19) | −0.05071 (17) | 0.3070 (5) | 0.0501 (10) | |
H21A | 0.4087 | −0.0816 | 0.2583 | 0.065* | |
H21B | 0.4030 | −0.0493 | 0.4188 | 0.065* | |
C22 | 0.4106 (3) | 0.0000 | 0.2241 (7) | 0.0453 (13) | |
C24 | 0.3906 (3) | 0.0000 | 0.0467 (7) | 0.0617 (17) | |
H24A | 0.3478 | 0.0006 | 0.0384 | 0.075* | 0.5 |
H24B | 0.4052 | −0.0320 | −0.0043 | 0.075* | 0.50 |
H24C | 0.4064 | 0.0314 | −0.0052 | 0.075* | 0.50 |
C25 | 0.4793 (3) | 0.0000 | 0.2378 (9) | 0.0667 (19) | |
H25A | 0.4917 | −0.0006 | 0.3491 | 0.080* | 0.5 |
H25B | 0.4945 | 0.0320 | 0.1880 | 0.080* | 0.50 |
H25C | 0.4945 | −0.0314 | 0.1847 | 0.080* | 0.50 |
C27 | 0.1262 (3) | 0.0000 | 0.5701 (7) | 0.0495 (14) | |
C28 | 0.16419 (19) | −0.05075 (17) | 0.5826 (5) | 0.0500 (10) | |
H28A | 0.1881 | −0.0492 | 0.6816 | 0.066* | |
H28B | 0.1379 | −0.0818 | 0.5895 | 0.066* | |
C29 | 0.0869 (3) | 0.0000 | 0.4162 (8) | 0.0617 (17) | |
H29A | 0.1118 | 0.0000 | 0.3242 | 0.075* | |
H29B | 0.0621 | 0.0317 | 0.4141 | 0.075* | 0.50 |
H29C | 0.0621 | −0.0317 | 0.4141 | 0.075* | 0.50 |
C30 | 0.0858 (3) | 0.0000 | 0.7148 (9) | 0.071 (2) | |
H30A | 0.1099 | −0.0006 | 0.8120 | 0.083* | 0.5 |
H30B | 0.0606 | −0.0314 | 0.7107 | 0.083* | 0.50 |
H30C | 0.0615 | 0.0320 | 0.7127 | 0.083* | 0.50 |
H00 | 0.5000 | 0.1581 | 0.0000 | 0.044* | |
H01A | 0.5313 | 0.1449 | 0.1884 | 0.044* | |
H01B | 0.4810 | 0.1723 | 0.2281 | 0.044* | |
H02A | 0.4405 | 0.2375 | 0.3768 | 0.044* | |
H02B | 0.3923 | 0.1870 | 0.3665 | 0.044* | |
H03A | 0.1308 | 0.3890 | 0.3327 | 0.044* | |
H03B | 0.0890 | 0.3490 | 0.2657 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br3 | 0.0635 (3) | 0.0428 (2) | 0.0376 (2) | 0.00513 (19) | −0.00295 (17) | −0.00615 (15) |
Br11 | 0.0553 (3) | 0.0492 (2) | 0.0461 (2) | 0.01554 (19) | 0.00436 (18) | 0.00421 (17) |
Br21 | 0.0621 (4) | 0.0722 (4) | 0.0390 (3) | 0.000 | −0.0088 (3) | 0.000 |
Br22 | 0.0600 (4) | 0.0684 (4) | 0.0333 (3) | 0.000 | −0.0032 (2) | 0.000 |
Cr1 | 0.0350 (4) | 0.0382 (4) | 0.0225 (3) | 0.0071 (3) | −0.0011 (3) | −0.0005 (3) |
Cr2 | 0.0405 (4) | 0.0301 (4) | 0.0292 (4) | 0.000 | 0.0011 (3) | 0.000 |
Cl | 0.0839 (13) | 0.0729 (12) | 0.0548 (9) | 0.000 | 0.0051 (9) | 0.000 |
O1 | 0.103 (4) | 0.140 (4) | 0.085 (3) | 0.014 (3) | 0.006 (3) | 0.003 (3) |
O2 | 0.107 (3) | 0.120 (4) | 0.107 (3) | −0.051 (3) | 0.017 (3) | −0.021 (3) |
O3 | 0.083 (3) | 0.123 (4) | 0.135 (4) | 0.019 (3) | −0.024 (3) | −0.015 (3) |
O41 | 0.229 (8) | 0.272 (10) | 0.100 (4) | 0.049 (8) | −0.016 (5) | 0.061 (5) |
O42 | 0.378 (15) | 0.376 (15) | 0.209 (9) | −0.260 (13) | 0.142 (10) | −0.129 (10) |
N11 | 0.0428 (17) | 0.0543 (19) | 0.0273 (14) | 0.0076 (15) | −0.0021 (12) | −0.0061 (13) |
N12 | 0.0426 (17) | 0.0448 (17) | 0.0256 (13) | 0.0050 (14) | 0.0011 (12) | −0.0008 (12) |
N21 | 0.0513 (19) | 0.0370 (17) | 0.0417 (16) | −0.0012 (15) | 0.0080 (14) | −0.0012 (13) |
N22 | 0.0498 (19) | 0.0364 (17) | 0.0478 (17) | 0.0001 (15) | 0.0044 (14) | 0.0025 (14) |
C11 | 0.045 (2) | 0.055 (2) | 0.043 (2) | −0.0019 (19) | −0.0074 (17) | −0.0087 (18) |
C12 | 0.038 (2) | 0.057 (3) | 0.048 (2) | −0.0012 (19) | 0.0007 (17) | 0.0016 (18) |
C13 | 0.048 (2) | 0.047 (2) | 0.0397 (19) | 0.0021 (18) | 0.0034 (17) | 0.0055 (17) |
C14 | 0.041 (2) | 0.084 (3) | 0.058 (3) | 0.011 (2) | 0.0035 (19) | −0.001 (2) |
C15 | 0.058 (3) | 0.072 (3) | 0.078 (3) | −0.016 (3) | 0.001 (2) | 0.001 (3) |
C21 | 0.050 (2) | 0.051 (2) | 0.050 (2) | 0.011 (2) | 0.0063 (18) | 0.0009 (19) |
C22 | 0.041 (3) | 0.053 (3) | 0.042 (3) | 0.000 | 0.006 (2) | 0.000 |
C24 | 0.066 (4) | 0.080 (5) | 0.039 (3) | 0.000 | 0.015 (3) | 0.000 |
C25 | 0.048 (4) | 0.076 (5) | 0.077 (5) | 0.000 | 0.016 (3) | 0.000 |
C27 | 0.041 (3) | 0.056 (4) | 0.052 (3) | 0.000 | 0.010 (2) | 0.000 |
C28 | 0.052 (2) | 0.046 (2) | 0.052 (2) | −0.004 (2) | 0.0099 (18) | 0.0080 (18) |
C29 | 0.048 (4) | 0.072 (5) | 0.065 (4) | 0.000 | 0.001 (3) | 0.000 |
C30 | 0.058 (4) | 0.084 (5) | 0.072 (5) | 0.000 | 0.016 (3) | 0.000 |
Br11—Cr1 | 2.4876 (4) | C11—H11B | 0.9700 |
Br21—Cr2 | 2.5017 (9) | C12—C14 | 1.522 (6) |
Br22—Cr2 | 2.4495 (9) | C12—C13 | 1.527 (6) |
Cr1—N12i | 2.078 (3) | C12—C15 | 1.539 (6) |
Cr1—N12 | 2.078 (3) | C13—H13A | 0.9700 |
Cr1—N11 | 2.084 (3) | C13—H13B | 0.9700 |
Cr1—N11i | 2.084 (3) | C14—H14A | 0.9600 |
Cr1—Br11i | 2.4876 (4) | C14—H14B | 0.9600 |
Cr2—N21 | 2.078 (3) | C14—H14C | 0.9600 |
Cr2—N21ii | 2.079 (3) | C15—H15A | 0.9600 |
Cr2—N22 | 2.089 (3) | C15—H15B | 0.9600 |
Cr2—N22ii | 2.089 (3) | C15—H15C | 0.9600 |
Cl—O42 | 1.325 (8) | C21—C22 | 1.512 (5) |
Cl—O42iii | 1.325 (8) | C21—H21A | 0.9700 |
Cl—O41iii | 1.347 (6) | C21—H21B | 0.9700 |
Cl—O41 | 1.348 (6) | C22—C21ii | 1.512 (5) |
O1—H00 | 1.173 | C22—C24 | 1.530 (8) |
O1—H01A | 0.899 | C22—C25 | 1.539 (9) |
O1—H01B | 0.899 | C24—H24A | 0.9600 |
O2—H02A | 0.899 | C24—H24B | 0.9600 |
O2—H02B | 0.900 | C24—H24C | 0.9600 |
O3—H03A | 0.902 | C25—H25A | 0.9600 |
O3—H03B | 0.905 | C25—H25B | 0.9600 |
N11—C11 | 1.496 (5) | C25—H25C | 0.9600 |
N11—H11M | 0.9000 | C27—C28 | 1.518 (5) |
N11—H11N | 0.9000 | C27—C28ii | 1.518 (5) |
N12—C13 | 1.483 (5) | C27—C30 | 1.527 (9) |
N12—H12M | 0.9000 | C27—C29 | 1.534 (9) |
N12—H12N | 0.9000 | C28—H28A | 0.9700 |
N21—C21 | 1.485 (5) | C28—H28B | 0.9700 |
N21—H21M | 0.9000 | C29—H29A | 0.9600 |
N21—H21N | 0.9000 | C29—H29B | 0.9600 |
N22—C28 | 1.491 (5) | C29—H29C | 0.9600 |
N22—H22M | 0.9000 | C30—H30A | 0.9600 |
N22—H22N | 0.9000 | C30—H30B | 0.9600 |
C11—C12 | 1.536 (6) | C30—H30C | 0.9600 |
C11—H11A | 0.9700 | ||
N12i—Cr1—N12 | 180.0 | C14—C12—C11 | 111.5 (4) |
N12i—Cr1—N11 | 88.54 (12) | C13—C12—C11 | 110.8 (3) |
N12—Cr1—N11 | 91.46 (12) | C14—C12—C15 | 110.0 (4) |
N12i—Cr1—N11i | 91.46 (12) | C13—C12—C15 | 107.1 (4) |
N12—Cr1—N11i | 88.54 (12) | C11—C12—C15 | 105.9 (4) |
N11—Cr1—N11i | 180.0 | N12—C13—C12 | 114.4 (3) |
N12i—Cr1—Br11 | 89.41 (9) | N12—C13—H13A | 108.7 |
N12—Cr1—Br11 | 90.59 (9) | C12—C13—H13A | 108.7 |
N11—Cr1—Br11 | 90.24 (9) | N12—C13—H13B | 108.7 |
N11i—Cr1—Br11 | 89.76 (9) | C12—C13—H13B | 108.7 |
N12i—Cr1—Br11i | 90.59 (9) | H13A—C13—H13B | 107.6 |
N12—Cr1—Br11i | 89.41 (9) | C12—C14—H14A | 109.5 |
N11—Cr1—Br11i | 89.76 (9) | C12—C14—H14B | 109.5 |
N11i—Cr1—Br11i | 90.24 (9) | H14A—C14—H14B | 109.5 |
Br11—Cr1—Br11i | 180.0 | C12—C14—H14C | 109.5 |
N21—Cr2—N21ii | 89.79 (18) | H14A—C14—H14C | 109.5 |
N21—Cr2—N22 | 90.57 (13) | H14B—C14—H14C | 109.5 |
N21ii—Cr2—N22 | 177.29 (14) | C12—C15—H15A | 109.5 |
N21—Cr2—N22ii | 177.29 (14) | C12—C15—H15B | 109.5 |
N21ii—Cr2—N22ii | 90.57 (13) | H15A—C15—H15B | 109.5 |
N22—Cr2—N22ii | 88.94 (18) | C12—C15—H15C | 109.5 |
N21—Cr2—Br22 | 91.47 (9) | H15A—C15—H15C | 109.5 |
N21ii—Cr2—Br22 | 91.47 (9) | H15B—C15—H15C | 109.5 |
N22—Cr2—Br22 | 91.20 (10) | N21—C21—C22 | 114.8 (4) |
N22ii—Cr2—Br22 | 91.20 (10) | N21—C21—H21A | 108.6 |
N21—Cr2—Br21 | 88.45 (9) | C22—C21—H21A | 108.6 |
N21ii—Cr2—Br21 | 88.45 (9) | N21—C21—H21B | 108.6 |
N22—Cr2—Br21 | 88.87 (10) | C22—C21—H21B | 108.6 |
N22ii—Cr2—Br21 | 88.88 (10) | H21A—C21—H21B | 107.5 |
Br22—Cr2—Br21 | 179.89 (4) | C21ii—C22—C21 | 112.1 (5) |
O42—Cl—O42iii | 105.6 (13) | C21ii—C22—C24 | 110.8 (3) |
O42—Cl—O41iii | 104.2 (5) | C21—C22—C24 | 110.8 (3) |
O42iii—Cl—O41iii | 112.5 (8) | C21ii—C22—C25 | 106.7 (3) |
O42—Cl—O41 | 112.5 (8) | C21—C22—C25 | 106.7 (3) |
O42iii—Cl—O41 | 104.2 (5) | C24—C22—C25 | 109.6 (5) |
O41iii—Cl—O41 | 117.5 (9) | C22—C24—H24A | 109.5 |
H00—O1—H01A | 112.6 | C22—C24—H24B | 109.5 |
H00—O1—H01B | 146.7 | H24A—C24—H24B | 109.5 |
H01A—O1—H01B | 98.5 | C22—C24—H24C | 109.5 |
H02A—O2—H02B | 132.8 | H24A—C24—H24C | 109.5 |
H03A—O3—H03B | 107.9 | H24B—C24—H24C | 109.5 |
C11—N11—Cr1 | 120.5 (2) | C22—C25—H25A | 109.5 |
C11—N11—H11M | 107.2 | C22—C25—H25B | 109.5 |
Cr1—N11—H11M | 107.2 | H25A—C25—H25B | 109.5 |
C11—N11—H11N | 107.2 | C22—C25—H25C | 109.5 |
Cr1—N11—H11N | 107.2 | H25A—C25—H25C | 109.5 |
H11M—N11—H11N | 106.8 | H25B—C25—H25C | 109.5 |
C13—N12—Cr1 | 120.7 (2) | C28—C27—C28ii | 111.6 (5) |
C13—N12—H12M | 107.2 | C28—C27—C30 | 106.8 (3) |
Cr1—N12—H12M | 107.2 | C28ii—C27—C30 | 106.8 (3) |
C13—N12—H12N | 107.2 | C28—C27—C29 | 111.4 (3) |
Cr1—N12—H12N | 107.2 | C28ii—C27—C29 | 111.4 (3) |
H12M—N12—H12N | 106.8 | C30—C27—C29 | 108.6 (5) |
C21—N21—Cr2 | 121.1 (2) | N22—C28—C27 | 114.5 (4) |
C21—N21—H21M | 107.1 | N22—C28—H28A | 108.6 |
Cr2—N21—H21M | 107.1 | C27—C28—H28A | 108.6 |
C21—N21—H21N | 107.1 | N22—C28—H28B | 108.6 |
Cr2—N21—H21N | 107.1 | C27—C28—H28B | 108.6 |
H21M—N21—H21N | 106.8 | H28A—C28—H28B | 107.6 |
C28—N22—Cr2 | 121.8 (3) | C27—C29—H29A | 109.5 |
C28—N22—H22M | 106.9 | C27—C29—H29B | 109.5 |
Cr2—N22—H22M | 106.9 | H29A—C29—H29B | 109.5 |
C28—N22—H22N | 106.9 | C27—C29—H29C | 109.5 |
Cr2—N22—H22N | 106.9 | H29A—C29—H29C | 109.5 |
H22M—N22—H22N | 106.7 | H29B—C29—H29C | 109.5 |
N11—C11—C12 | 114.1 (3) | C27—C30—H30A | 109.5 |
N11—C11—H11A | 108.7 | C27—C30—H30B | 109.5 |
C12—C11—H11A | 108.7 | H30A—C30—H30B | 109.5 |
N11—C11—H11B | 108.7 | C27—C30—H30C | 109.5 |
C12—C11—H11B | 108.7 | H30A—C30—H30C | 109.5 |
H11A—C11—H11B | 107.6 | H30B—C30—H30C | 109.5 |
C14—C12—C13 | 111.3 (4) | ||
N12i—Cr1—N11—C11 | 149.8 (3) | Cr1—N11—C11—C12 | 52.9 (4) |
N12—Cr1—N11—C11 | −30.2 (3) | N11—C11—C12—C14 | 55.7 (5) |
Br11—Cr1—N11—C11 | −120.8 (3) | N11—C11—C12—C13 | −68.9 (4) |
Br11i—Cr1—N11—C11 | 59.2 (3) | N11—C11—C12—C15 | 175.3 (3) |
N11—Cr1—N12—C13 | 30.6 (3) | Cr1—N12—C13—C12 | −53.9 (4) |
N11i—Cr1—N12—C13 | −149.4 (3) | C14—C12—C13—N12 | −55.2 (5) |
Br11—Cr1—N12—C13 | 120.8 (3) | C11—C12—C13—N12 | 69.5 (4) |
Br11i—Cr1—N12—C13 | −59.2 (3) | C15—C12—C13—N12 | −175.5 (4) |
N21ii—Cr2—N21—C21 | 33.2 (3) | Cr2—N21—C21—C22 | −54.1 (4) |
N22—Cr2—N21—C21 | −149.5 (3) | N21—C21—C22—C21ii | 66.1 (6) |
Br22—Cr2—N21—C21 | −58.3 (3) | N21—C21—C22—C24 | −58.2 (5) |
Br21—Cr2—N21—C21 | 121.7 (3) | N21—C21—C22—C25 | −177.4 (4) |
N21—Cr2—N22—C28 | 149.5 (3) | Cr2—N22—C28—C27 | 54.6 (5) |
N22ii—Cr2—N22—C28 | −33.2 (4) | C28ii—C27—C28—N22 | −66.4 (6) |
Br22—Cr2—N22—C28 | 58.0 (3) | C30—C27—C28—N22 | 177.2 (4) |
Br21—Cr2—N22—C28 | −122.1 (3) | C29—C27—C28—N22 | 58.8 (5) |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x, −y, z; (iii) −x, y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11M···O2i | 0.90 | 2.57 | 3.438 (6) | 163 |
N11—H11N···Br3iv | 0.90 | 2.77 | 3.661 (3) | 169 |
N12—H12M···Br3 | 0.90 | 2.62 | 3.496 (3) | 163 |
N12—H12N···Br3v | 0.90 | 3.06 | 3.567 (3) | 117 |
N21—H21M···Br3ii | 0.90 | 2.58 | 3.475 (3) | 177 |
N21—H21N···Br11vi | 0.90 | 2.90 | 3.580 (3) | 134 |
N22—H22N···Br3ii | 0.90 | 2.62 | 3.516 (3) | 176 |
O1—H00···O1vii | 1.17 | 1.17 | 2.347 (9) | 180 |
O1—H01A···O3viii | 0.90 | 1.77 | 2.667 (7) | 175 |
O1—H01B···O2 | 0.90 | 1.82 | 2.662 (7) | 155 |
O2—H02A···O42v | 0.90 | 2.05 | 2.89 (1) | 157 |
O2—H02B···Br3 | 0.90 | 2.61 | 3.420 (5) | 150 |
O3—H03A···Br3v | 0.90 | 2.70 | 3.383 (5) | 133 |
O3—H03A···Br22v | 0.90 | 3.02 | 3.575 (5) | 121 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z; (ii) x, −y, z; (iv) x, y, z−1; (v) −x+1/2, −y+1/2, −z+1; (vi) −x+1/2, y−1/2, −z; (vii) −x+1, y, −z; (viii) x+1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [CrBr2(C5H14N2)2]2Br2·HClO4·6H2O |
Mr | 1200.74 |
Crystal system, space group | Monoclinic, C2/m |
Temperature (K) | 293 |
a, b, c (Å) | 22.3862 (8), 24.7393 (8), 8.3230 (3) |
β (°) | 91.624 (1) |
V (Å3) | 4607.6 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 5.78 |
Crystal size (mm) | 0.32 × 0.32 × 0.10 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID Imaging Plate diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.188, 0.560 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20618, 5320, 4188 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.108, 1.05 |
No. of reflections | 5320 |
No. of parameters | 228 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −0.60 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, TEXSAN (Molecular Structure Cooperation & Rigaku, 2000), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP (Johnson, 1970), SHELXL97.
Br11—Cr1 | 2.4876 (4) | Cr1—N11 | 2.084 (3) |
Br21—Cr2 | 2.5017 (9) | Cr2—N21 | 2.078 (3) |
Br22—Cr2 | 2.4495 (9) | Cr2—N22 | 2.089 (3) |
Cr1—N12 | 2.078 (3) | ||
N12—Cr1—N11 | 91.46 (12) | N22—Cr2—N22i | 88.94 (18) |
N12—Cr1—Br11 | 90.59 (9) | N21—Cr2—Br22 | 91.47 (9) |
N11—Cr1—Br11 | 90.24 (9) | N22—Cr2—Br22 | 91.20 (10) |
N21—Cr2—N21i | 89.79 (18) | N21—Cr2—Br21 | 88.45 (9) |
N21—Cr2—N22 | 90.57 (13) | N22—Cr2—Br21 | 88.87 (10) |
N21—Cr2—N22i | 177.29 (14) |
Symmetry code: (i) x, −y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N11—H11M···O2ii | 0.90 | 2.57 | 3.438 (6) | 163 |
N11—H11N···Br3iii | 0.90 | 2.77 | 3.661 (3) | 169 |
N12—H12M···Br3 | 0.90 | 2.62 | 3.496 (3) | 163 |
N12—H12N···Br3iv | 0.90 | 3.06 | 3.567 (3) | 117 |
N21—H21M···Br3i | 0.90 | 2.58 | 3.475 (3) | 177 |
N21—H21N···Br11v | 0.90 | 2.90 | 3.580 (3) | 134 |
N22—H22N···Br3i | 0.90 | 2.62 | 3.516 (3) | 176 |
O1—H00···O1vi | 1.17 | 1.17 | 2.347 (9) | 180 |
O1—H01A···O3vii | 0.90 | 1.77 | 2.667 (7) | 175 |
O1—H01B···O2 | 0.90 | 1.82 | 2.662 (7) | 155 |
O2—H02A···O42iv | 0.90 | 2.05 | 2.89 (1) | 157 |
O2—H02B···Br3 | 0.90 | 2.61 | 3.420 (5) | 150 |
O3—H03A···Br3iv | 0.90 | 2.70 | 3.383 (5) | 133 |
O3—H03A···Br22iv | 0.90 | 3.02 | 3.575 (5) | 121 |
Symmetry codes: (i) x, −y, z; (ii) −x+1/2, −y+1/2, −z; (iii) x, y, z−1; (iv) −x+1/2, −y+1/2, −z+1; (v) −x+1/2, y−1/2, −z; (vi) −x+1, y, −z; (vii) x+1/2, −y+1/2, z. |
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2,2-Dimethyl-1,3-diaminopropane (Me2tn) can coordinate to a central metal ion as a bidentate ligand, forming a six-membered chelate ring, similar to the situation for unsubstituted 1,3-diaminopropane (tn; House, 1986). In addition to the conformational isomerism resulting from the six-membered chelate rings, the [CrBr2(tn/Me2tn)2]+ complex cation can exist as a cis or trans isomer. Although electronic absorption and IR spectra have been used to identify the geometrical structures of chromium(III) complexes (Choi et al., 2002; Poon & Pun, 1980), assignments based on spectral data are not always conclusive (Stearns & Armstrong, 1992). Furthermore, since the structural chemistry of complexes of the type [CrIIIL4Br2]X is rare (Lisgarten et al., 1990), we prepared the title complex, (I), which contains the [CrBr2(Me2tn)2]+ cation, and determined its crystal structure by X-ray analysis.
The structure analysis of (I) revealed that the crystal contains two crystallographically independent CrIII complex moieties. As atom Cr1 is located at a crystallographic center of symmetry, this CrIII complex cation has a molecular Ci symmetry, while the other complex cation, containing atom Cr2, has molecular Cs symmetry; atoms Cr2, Br21, Br22, C22, C24, C25, C27, C29 and C30 atoms are located on a crystallographic mirror plane. It was found that in both complex cations, the two Br atoms are coordinated to the central Cr atom in a trans arrangement. The Cr—Br bond lengths [2.4495 (9)–2.5017 (9) Å] are close to the value found in trans-[CrBr2(cyclam)2]Br (cyclam is 1,4,8,11-tetraazacyclotetradecane; Lisgarten et al., 1990). The Cr—-N bond lengths are in the range 2.078 (3)–2.089 (3) Å, which are typical values for CrIII—N(primary amine) bonds. All of the six-membered chelate rings formed by the Me2tn ligand adopt chair conformations, but two complex cations were so-called conformational (Ci and Cs) isomers due to the relative conformation of the two Me2tn chelate rings, as shown in Fig. 1.
As well as the complex cations, the asymmetric unit of (I) also contains a Br- ion (Br3), a half ClO4- anion and three O atoms (O1, O2 and O3) corresponding to the hydrated water molecules. Owing to charge balance, a half equivalent amount of H+ per CrIII complex cation should be included in the crystal. We suspected that such an H+ ion was trapped between atoms O1 and O1iii [symmetry code: (iii) 1 - x, y, -z], because the O1···O1iii distance was only 2.347 (9) Å, pointing to the existence of a strong hydrogen-bonding interaction between these atoms (Minkwitz et al., 1998). Since atom O1 is also involved in a hydrogen bond with both O2 and O3iv [O1···O2 2.662 (7) Å and O1···O3iv 2.667 (7) Å; symmetry code: (iv) 1/2 + x, 1/2 - y, z], the hydrated H+ cation in this crystal forms an [H13O6]+ cluster cation (Fig. 2). Although both Eigen-type and chain-like structures of [H9O4]+ clusters are often observed (Frank & Reiss, 1997; Hassaballa et al., 1998), the H-shaped [H13O6]+ cluster cation found in the crystal of (I) has,to our best knowledge, not been reported previously.
Hence, (I) can be formulated as (H13O6){trans-[CrBr2(Me2tn)2]}2Br2(ClO4). For help in visualizing the complete structure of this compound, a drawing containing an H13O6+ cluster cation and two conformational isomers of the CrIII complex cation, together with two Br- anions and a ClO4- anion, is illustrated in Fig. 2.