Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029923/hb2433sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029923/hb2433Isup2.hkl |
CCDC reference: 654803
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean (C-C) = 0.009 Å
- R factor = 0.036
- wR factor = 0.062
- Data-to-parameter ratio = 20.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 9 PLAT431_ALERT_2_C Short Inter HL..A Contact Br3 .. N2 .. 3.38 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Re1 (4) 3.89 PLAT794_ALERT_5_G Check Predicted Bond Valency for Re2 (3) 2.34 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 4
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 3 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 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
(NH4)2ReBr6 was obtained by the method of Watt & Thompson (1963). A mixture of (NH4)2ReBr6 (0.46 g) and the terpy lignad (0.50 g) was dissolved in 50-ml of 1:1 v/v water-ethanol solution. Then it was sealed under nitrogen and heated for 15 h to 423 K. After the reaction the mixture colour was yellow orange. The solution was diluted with ethanol and left standing for evaporation. After five days orange plates of (I) appeared. Anal. Calc. C23.69 H 1.98 N 5.52 /% found C 21.40 H 1.20 N 5.14 /%.
The water H atoms were located in a difference map and refined as riding in their as-found relative positions with Uiso(H) = 1.2Ueq(O). The other H atoms were placed in idealized positions (N—H = 0.86 Å, C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier).
This paper reports the crystal structure of the title mixed valence rhenium compound, (I). One of rhenium atoms lies on a centre of symmetry and other one in general position.
Compound (I) (Fig. 1) and some of its derivatives show interesting magnetic properties (Rose et al., 1996). Several papers describing the crystal structures of bromorhenates are available in the literature (Preetz & Struess, 1988, Chiozzone et al., 2006) but surprisingly the crystal structure of (I) has not been determined yet.
The [ReO(H2O)Br4]- units in (I) shows a distorted octahedral geometry about the Re(V) site defined by the terminal oxo ligand, the trans aqua ligand, and four bromide ions (Table 1). The Re—Br bond lengths in (I) agree with those in related crystal structures (Kochel, 2007; Abram et al., 1996).
In the crystal packing of (I), layers of rhenate anions and terpyridinium cations could be distinguished. However, the anion layer is additionally filled with the water molecules and bromide anions. The crystal structure is consolidated by a complex hydrogen bond system including various C—H···O links (Table 2).
For related literature, see: Abram et al. (1996); Chiozzone et al. (2006); Kochel (2007); Rose et al. (1996); Preetz & Struess (1988); Watt & Thompson (1963).
Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP (Bruker, 1999); software used to prepare material for publication: SHELXL97.
Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). Symmetry code: (i) -x, 1 - y, 1 - z. | |
Fig. 2. The crystal packing in (I). |
(C15H13N3)4[ReBr6][ReBr4O(H2O)]2Br4·2H2O | Z = 1 |
Mr = 3042.03 | F(000) = 1407 |
Triclinic, P1 | Dx = 2.578 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.3458 (6) Å | Cell parameters from 5311 reflections |
b = 10.3563 (6) Å | θ = 2.7–28.6° |
c = 19.0582 (14) Å | µ = 13.85 mm−1 |
α = 81.361 (6)° | T = 100 K |
β = 79.041 (6)° | Prism, orange |
γ = 79.987 (5)° | 0.10 × 0.10 × 0.05 mm |
V = 1959.7 (2) Å3 |
Oxford Diffraction KM-4-CCD diffractometer | 9275 independent reflections |
Radiation source: fine-focus sealed tube | 5991 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.056 |
ω scans | θmax = 28.6°, θmin = 2.7° |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2003) | h = −13→13 |
Tmin = 0.456, Tmax = 0.794 | k = −13→13 |
24231 measured reflections | l = −25→25 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0215P)2] where P = (Fo2 + 2Fc2)/3 |
9275 reflections | (Δ/σ)max < 0.001 |
448 parameters | Δρmax = 1.24 e Å−3 |
4 restraints | Δρmin = −0.94 e Å−3 |
(C15H13N3)4[ReBr6][ReBr4O(H2O)]2Br4·2H2O | γ = 79.987 (5)° |
Mr = 3042.03 | V = 1959.7 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.3458 (6) Å | Mo Kα radiation |
b = 10.3563 (6) Å | µ = 13.85 mm−1 |
c = 19.0582 (14) Å | T = 100 K |
α = 81.361 (6)° | 0.10 × 0.10 × 0.05 mm |
β = 79.041 (6)° |
Oxford Diffraction KM-4-CCD diffractometer | 9275 independent reflections |
Absorption correction: numerical (CrysAlis RED; Oxford Diffraction, 2003) | 5991 reflections with I > 2σ(I) |
Tmin = 0.456, Tmax = 0.794 | Rint = 0.056 |
24231 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 4 restraints |
wR(F2) = 0.062 | H-atom parameters constrained |
S = 0.94 | Δρmax = 1.24 e Å−3 |
9275 reflections | Δρmin = −0.94 e Å−3 |
448 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 | ||
N1 | 0.1742 (5) | 0.0591 (5) | 0.6381 (3) | 0.0177 (12) | |
H1N | 0.1977 | 0.1054 | 0.6661 | 0.021* | |
N2 | 0.3703 (5) | 0.2058 (5) | 0.6009 (3) | 0.0173 (12) | |
N3 | 0.3926 (5) | 0.3432 (5) | 0.7045 (3) | 0.0186 (12) | |
H3N | 0.3393 | 0.2863 | 0.7089 | 0.022* | |
C1 | 0.0747 (7) | −0.0095 (6) | 0.6643 (4) | 0.0261 (16) | |
H1 | 0.0315 | −0.0047 | 0.7116 | 0.031* | |
C2 | 0.0346 (6) | −0.0877 (6) | 0.6222 (3) | 0.0210 (15) | |
H2 | −0.0351 | −0.1356 | 0.6403 | 0.025* | |
C3 | 0.1013 (6) | −0.0925 (6) | 0.5524 (4) | 0.0255 (16) | |
H3 | 0.0786 | −0.1473 | 0.5237 | 0.031* | |
C4 | 0.2019 (6) | −0.0166 (6) | 0.5246 (3) | 0.0193 (14) | |
H4 | 0.2430 | −0.0165 | 0.4768 | 0.023* | |
C5 | 0.2408 (6) | 0.0599 (5) | 0.5696 (3) | 0.0155 (14) | |
C6 | 0.3483 (6) | 0.1416 (5) | 0.5493 (3) | 0.0145 (13) | |
C7 | 0.4232 (6) | 0.1521 (6) | 0.4791 (3) | 0.0211 (15) | |
H7 | 0.4062 | 0.1074 | 0.4439 | 0.025* | |
C8 | 0.5220 (7) | 0.2300 (6) | 0.4644 (3) | 0.0215 (15) | |
H8 | 0.5728 | 0.2386 | 0.4186 | 0.026* | |
C9 | 0.5459 (6) | 0.2957 (6) | 0.5175 (3) | 0.0190 (14) | |
H9 | 0.6139 | 0.3472 | 0.5084 | 0.023* | |
C10 | 0.4666 (6) | 0.2831 (6) | 0.5845 (3) | 0.0160 (14) | |
C11 | 0.4774 (6) | 0.3597 (6) | 0.6420 (3) | 0.0168 (14) | |
C12 | 0.5655 (6) | 0.4496 (6) | 0.6356 (3) | 0.0206 (15) | |
H12 | 0.6271 | 0.4617 | 0.5937 | 0.025* | |
C13 | 0.5607 (6) | 0.5214 (6) | 0.6924 (3) | 0.0201 (15) | |
H13 | 0.6187 | 0.5824 | 0.6883 | 0.024* | |
C14 | 0.4699 (6) | 0.5021 (6) | 0.7550 (3) | 0.0214 (15) | |
H14 | 0.4654 | 0.5506 | 0.7929 | 0.026* | |
C15 | 0.3863 (6) | 0.4102 (6) | 0.7604 (3) | 0.0206 (15) | |
H15 | 0.3259 | 0.3945 | 0.8024 | 0.025* | |
N4 | 0.2439 (5) | 0.5363 (5) | 0.1040 (3) | 0.0184 (12) | |
H4N | 0.2335 | 0.4798 | 0.0775 | 0.022* | |
N5 | 0.0414 (5) | 0.3972 (5) | 0.1317 (2) | 0.0158 (11) | |
N6 | 0.0141 (5) | 0.2830 (5) | 0.0195 (3) | 0.0218 (13) | |
H6N | 0.0713 | 0.3348 | 0.0182 | 0.026* | |
C21 | 0.3407 (6) | 0.6082 (6) | 0.0809 (4) | 0.0235 (15) | |
H21 | 0.3943 | 0.5978 | 0.0364 | 0.028* | |
C22 | 0.3632 (7) | 0.6978 (6) | 0.1214 (4) | 0.0251 (16) | |
H22 | 0.4321 | 0.7476 | 0.1055 | 0.030* | |
C23 | 0.2800 (7) | 0.7120 (6) | 0.1872 (4) | 0.0245 (16) | |
H23 | 0.2921 | 0.7732 | 0.2155 | 0.029* | |
C24 | 0.1791 (6) | 0.6352 (6) | 0.2107 (3) | 0.0222 (15) | |
H24 | 0.1249 | 0.6432 | 0.2552 | 0.027* | |
C25 | 0.1599 (6) | 0.5473 (6) | 0.1676 (3) | 0.0182 (14) | |
C26 | 0.0557 (6) | 0.4606 (6) | 0.1854 (3) | 0.0173 (14) | |
C27 | −0.0240 (6) | 0.4503 (6) | 0.2539 (3) | 0.0203 (15) | |
H27 | −0.0135 | 0.4973 | 0.2898 | 0.024* | |
C28 | −0.1191 (6) | 0.3664 (6) | 0.2652 (3) | 0.0244 (16) | |
H28 | −0.1721 | 0.3543 | 0.3103 | 0.029* | |
C29 | −0.1359 (6) | 0.3010 (6) | 0.2104 (3) | 0.0203 (15) | |
H29 | −0.2008 | 0.2462 | 0.2175 | 0.024* | |
C30 | −0.0533 (6) | 0.3188 (6) | 0.1443 (3) | 0.0186 (14) | |
C31 | −0.0661 (6) | 0.2550 (6) | 0.0832 (3) | 0.0182 (14) | |
C32 | −0.1550 (6) | 0.1664 (6) | 0.0841 (4) | 0.0265 (16) | |
H32 | −0.2101 | 0.1411 | 0.1267 | 0.032* | |
C33 | −0.1602 (6) | 0.1163 (6) | 0.0211 (4) | 0.0243 (16) | |
H33 | −0.2198 | 0.0584 | 0.0216 | 0.029* | |
C34 | −0.0770 (6) | 0.1524 (6) | −0.0426 (4) | 0.0256 (16) | |
H34 | −0.0807 | 0.1205 | −0.0851 | 0.031* | |
C35 | 0.0101 (6) | 0.2361 (6) | −0.0406 (3) | 0.0220 (15) | |
H35 | 0.0682 | 0.2601 | −0.0822 | 0.026* | |
Re2 | 0.38002 (2) | 0.12190 (2) | 0.218448 (13) | 0.01424 (7) | |
Br4 | 0.56622 (6) | 0.13304 (6) | 0.28386 (3) | 0.01760 (14) | |
Br5 | 0.23701 (6) | 0.05495 (6) | 0.14103 (3) | 0.02149 (15) | |
Br6 | 0.49427 (7) | 0.24963 (6) | 0.10751 (3) | 0.02226 (15) | |
Br7 | 0.30660 (6) | −0.05229 (6) | 0.31752 (3) | 0.01964 (15) | |
O1 | 0.5235 (4) | −0.0491 (4) | 0.1763 (2) | 0.0189 (10) | |
H1W | 0.6001 | −0.0612 | 0.1932 | 0.023* | |
H2W | 0.5545 | −0.0555 | 0.1300 | 0.023* | |
O2 | 0.2755 (4) | 0.2512 (4) | 0.2478 (2) | 0.0202 (10) | |
Re1 | 0.0000 | 0.5000 | 0.5000 | 0.01419 (9) | |
Br1 | 0.07213 (6) | 0.68849 (6) | 0.40966 (3) | 0.01884 (15) | |
Br2 | 0.14274 (6) | 0.34007 (6) | 0.42001 (3) | 0.01800 (14) | |
Br3 | 0.19123 (6) | 0.50460 (6) | 0.56235 (3) | 0.02026 (15) | |
O3A | 0.6108 (4) | 0.8904 (4) | 0.0401 (2) | 0.0269 (11) | |
H3W | 0.6256 | 0.9008 | −0.0073 | 0.032* | |
H4W | 0.6422 | 0.8045 | 0.0481 | 0.032* | |
Br8 | 0.82755 (6) | 0.83705 (6) | 0.21020 (3) | 0.01960 (15) | |
Br9 | 0.73144 (6) | 0.56873 (6) | 0.05088 (3) | 0.01989 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.022 (3) | 0.015 (3) | 0.020 (3) | −0.003 (2) | −0.005 (2) | −0.012 (2) |
N2 | 0.019 (3) | 0.012 (3) | 0.019 (3) | 0.001 (2) | −0.004 (2) | 0.004 (2) |
N3 | 0.023 (3) | 0.016 (3) | 0.018 (3) | −0.004 (2) | −0.003 (2) | −0.004 (2) |
C1 | 0.028 (4) | 0.029 (4) | 0.020 (4) | 0.003 (3) | −0.010 (3) | −0.001 (3) |
C2 | 0.022 (4) | 0.016 (3) | 0.025 (4) | −0.002 (3) | −0.006 (3) | 0.000 (3) |
C3 | 0.021 (4) | 0.024 (4) | 0.033 (4) | 0.004 (3) | −0.006 (3) | −0.011 (3) |
C4 | 0.020 (4) | 0.025 (4) | 0.015 (3) | 0.001 (3) | −0.005 (3) | −0.010 (3) |
C5 | 0.022 (4) | 0.009 (3) | 0.016 (3) | 0.003 (3) | −0.007 (3) | −0.003 (3) |
C6 | 0.016 (3) | 0.009 (3) | 0.017 (3) | 0.004 (2) | −0.002 (3) | −0.003 (3) |
C7 | 0.025 (4) | 0.021 (4) | 0.016 (3) | 0.007 (3) | −0.009 (3) | −0.004 (3) |
C8 | 0.030 (4) | 0.021 (4) | 0.013 (3) | −0.004 (3) | −0.002 (3) | −0.005 (3) |
C9 | 0.020 (4) | 0.020 (3) | 0.016 (3) | −0.002 (3) | 0.000 (3) | −0.002 (3) |
C10 | 0.021 (4) | 0.013 (3) | 0.014 (3) | −0.001 (3) | −0.008 (3) | 0.000 (3) |
C11 | 0.016 (3) | 0.017 (3) | 0.018 (3) | 0.001 (3) | −0.002 (3) | −0.005 (3) |
C12 | 0.009 (3) | 0.026 (4) | 0.025 (4) | −0.002 (3) | −0.001 (3) | −0.001 (3) |
C13 | 0.024 (4) | 0.017 (3) | 0.022 (4) | −0.008 (3) | −0.004 (3) | −0.005 (3) |
C14 | 0.026 (4) | 0.015 (3) | 0.025 (4) | −0.005 (3) | −0.002 (3) | −0.010 (3) |
C15 | 0.021 (4) | 0.021 (4) | 0.020 (4) | 0.000 (3) | −0.007 (3) | −0.002 (3) |
N4 | 0.020 (3) | 0.017 (3) | 0.018 (3) | −0.002 (2) | −0.001 (2) | −0.003 (2) |
N5 | 0.018 (3) | 0.015 (3) | 0.012 (3) | 0.002 (2) | −0.002 (2) | 0.002 (2) |
N6 | 0.021 (3) | 0.023 (3) | 0.023 (3) | −0.008 (2) | −0.004 (3) | 0.000 (3) |
C21 | 0.021 (4) | 0.024 (4) | 0.026 (4) | −0.006 (3) | 0.001 (3) | −0.007 (3) |
C22 | 0.022 (4) | 0.020 (4) | 0.035 (4) | −0.010 (3) | −0.006 (3) | 0.003 (3) |
C23 | 0.032 (4) | 0.011 (3) | 0.033 (4) | −0.001 (3) | −0.015 (3) | −0.002 (3) |
C24 | 0.023 (4) | 0.024 (4) | 0.017 (3) | −0.001 (3) | −0.003 (3) | −0.001 (3) |
C25 | 0.022 (4) | 0.017 (3) | 0.016 (3) | −0.004 (3) | −0.008 (3) | 0.003 (3) |
C26 | 0.019 (4) | 0.015 (3) | 0.018 (3) | 0.002 (3) | −0.008 (3) | 0.000 (3) |
C27 | 0.024 (4) | 0.020 (4) | 0.017 (3) | −0.001 (3) | −0.005 (3) | −0.007 (3) |
C28 | 0.027 (4) | 0.022 (4) | 0.016 (3) | 0.003 (3) | 0.007 (3) | 0.002 (3) |
C29 | 0.026 (4) | 0.016 (3) | 0.018 (3) | −0.006 (3) | −0.006 (3) | 0.008 (3) |
C30 | 0.019 (4) | 0.013 (3) | 0.023 (4) | −0.003 (3) | −0.004 (3) | 0.002 (3) |
C31 | 0.019 (4) | 0.021 (3) | 0.016 (3) | −0.005 (3) | −0.004 (3) | 0.000 (3) |
C32 | 0.022 (4) | 0.031 (4) | 0.024 (4) | −0.004 (3) | −0.005 (3) | 0.003 (3) |
C33 | 0.026 (4) | 0.022 (4) | 0.029 (4) | −0.003 (3) | −0.012 (3) | −0.007 (3) |
C34 | 0.027 (4) | 0.022 (4) | 0.031 (4) | −0.004 (3) | −0.012 (3) | −0.003 (3) |
C35 | 0.023 (4) | 0.025 (4) | 0.017 (3) | 0.002 (3) | −0.001 (3) | −0.010 (3) |
Re2 | 0.01566 (15) | 0.01453 (14) | 0.01316 (14) | −0.00219 (11) | −0.00329 (11) | −0.00269 (11) |
Br4 | 0.0190 (4) | 0.0191 (3) | 0.0172 (3) | −0.0046 (3) | −0.0060 (3) | −0.0042 (3) |
Br5 | 0.0228 (4) | 0.0224 (4) | 0.0227 (4) | −0.0037 (3) | −0.0104 (3) | −0.0050 (3) |
Br6 | 0.0269 (4) | 0.0208 (4) | 0.0179 (3) | −0.0054 (3) | −0.0030 (3) | 0.0028 (3) |
Br7 | 0.0213 (4) | 0.0215 (4) | 0.0153 (3) | −0.0064 (3) | 0.0005 (3) | −0.0007 (3) |
O1 | 0.021 (2) | 0.017 (2) | 0.019 (2) | −0.0025 (18) | −0.0044 (19) | −0.0049 (19) |
O2 | 0.023 (2) | 0.018 (2) | 0.021 (2) | 0.0033 (18) | −0.009 (2) | −0.0073 (19) |
Re1 | 0.0168 (2) | 0.01280 (19) | 0.01210 (19) | −0.00249 (15) | −0.00024 (16) | −0.00106 (15) |
Br1 | 0.0234 (4) | 0.0151 (3) | 0.0161 (3) | −0.0048 (3) | 0.0003 (3) | 0.0017 (3) |
Br2 | 0.0175 (3) | 0.0175 (3) | 0.0183 (3) | −0.0012 (3) | −0.0004 (3) | −0.0051 (3) |
Br3 | 0.0178 (3) | 0.0245 (4) | 0.0190 (3) | −0.0031 (3) | −0.0045 (3) | −0.0027 (3) |
O3A | 0.038 (3) | 0.023 (3) | 0.019 (2) | −0.004 (2) | 0.003 (2) | −0.010 (2) |
Br8 | 0.0198 (3) | 0.0238 (4) | 0.0159 (3) | −0.0051 (3) | −0.0010 (3) | −0.0052 (3) |
Br9 | 0.0225 (4) | 0.0212 (4) | 0.0155 (3) | −0.0050 (3) | 0.0005 (3) | −0.0033 (3) |
N1—C1 | 1.329 (8) | C21—C22 | 1.368 (8) |
N1—C5 | 1.354 (7) | C21—H21 | 0.9300 |
N1—H1N | 0.8600 | C22—C23 | 1.391 (9) |
N2—C6 | 1.340 (7) | C22—H22 | 0.9300 |
N2—C10 | 1.348 (7) | C23—C24 | 1.388 (8) |
N3—C15 | 1.341 (7) | C23—H23 | 0.9299 |
N3—C11 | 1.345 (7) | C24—C25 | 1.376 (8) |
N3—H3N | 0.8600 | C24—H24 | 0.9301 |
C1—C2 | 1.382 (8) | C25—C26 | 1.479 (8) |
C1—H1 | 0.9298 | C26—C27 | 1.405 (8) |
C2—C3 | 1.380 (9) | C27—C28 | 1.389 (8) |
C2—H2 | 0.9300 | C27—H27 | 0.9300 |
C3—C4 | 1.390 (8) | C28—C29 | 1.380 (8) |
C3—H3 | 0.9301 | C28—H28 | 0.9300 |
C4—C5 | 1.405 (8) | C29—C30 | 1.388 (8) |
C4—H4 | 0.9300 | C29—H29 | 0.9299 |
C5—C6 | 1.472 (8) | C30—C31 | 1.460 (8) |
C6—C7 | 1.412 (8) | C31—C32 | 1.404 (8) |
C7—C8 | 1.372 (8) | C32—C33 | 1.391 (8) |
C7—H7 | 0.9299 | C32—H32 | 0.9300 |
C8—C9 | 1.383 (8) | C33—C34 | 1.390 (9) |
C8—H8 | 0.9301 | C33—H33 | 0.9299 |
C9—C10 | 1.382 (8) | C34—C35 | 1.365 (8) |
C9—H9 | 0.9300 | C34—H34 | 0.9299 |
C10—C11 | 1.476 (8) | C35—H35 | 0.9300 |
C11—C12 | 1.390 (8) | Re1—Br3i | 2.5043 (6) |
C12—C13 | 1.390 (8) | Re1—Br3 | 2.5044 (6) |
C12—H12 | 0.9301 | Re1—Br2 | 2.5099 (6) |
C13—C14 | 1.384 (8) | Re1—Br2i | 2.5100 (6) |
C13—H13 | 0.9300 | Re1—Br1 | 2.5179 (6) |
C14—C15 | 1.374 (8) | Re1—Br1i | 2.5180 (6) |
C14—H14 | 0.9299 | Re2—O2 | 1.663 (4) |
C15—H15 | 0.9299 | Re2—O1 | 2.246 (4) |
N4—C21 | 1.321 (7) | Re2—Br7 | 2.5108 (7) |
N4—C25 | 1.359 (7) | Re2—Br4 | 2.5123 (7) |
N4—H4N | 0.8600 | Re2—Br5 | 2.5182 (7) |
N5—C26 | 1.340 (7) | Re2—Br6 | 2.5239 (7) |
N5—C30 | 1.343 (7) | O1—H1W | 0.8929 |
N6—C35 | 1.318 (7) | O1—H2W | 0.8879 |
N6—C31 | 1.357 (7) | O3A—H3W | 0.8787 |
N6—H6N | 0.8600 | O3A—H4W | 0.8932 |
C1—N1—C5 | 123.5 (5) | C25—C24—H24 | 120.3 |
C1—N1—H1N | 118.2 | C23—C24—H24 | 120.2 |
C5—N1—H1N | 118.2 | N4—C25—C24 | 118.2 (6) |
C6—N2—C10 | 118.4 (5) | N4—C25—C26 | 116.5 (5) |
C15—N3—C11 | 124.0 (5) | C24—C25—C26 | 125.3 (6) |
C15—N3—H3N | 118.0 | N5—C26—C27 | 123.4 (6) |
C11—N3—H3N | 118.0 | N5—C26—C25 | 115.5 (5) |
N1—C1—C2 | 120.7 (6) | C27—C26—C25 | 121.1 (6) |
N1—C1—H1 | 119.6 | C28—C27—C26 | 116.7 (6) |
C2—C1—H1 | 119.6 | C28—C27—H27 | 121.7 |
C3—C2—C1 | 118.0 (6) | C26—C27—H27 | 121.6 |
C3—C2—H2 | 121.0 | C29—C28—C27 | 120.7 (6) |
C1—C2—H2 | 121.0 | C29—C28—H28 | 119.7 |
C2—C3—C4 | 120.8 (6) | C27—C28—H28 | 119.6 |
C2—C3—H3 | 119.6 | C28—C29—C30 | 118.2 (6) |
C4—C3—H3 | 119.6 | C28—C29—H29 | 120.9 |
C3—C4—C5 | 119.2 (6) | C30—C29—H29 | 120.8 |
C3—C4—H4 | 120.4 | N5—C30—C29 | 122.8 (6) |
C5—C4—H4 | 120.4 | N5—C30—C31 | 115.5 (5) |
N1—C5—C4 | 117.6 (6) | C29—C30—C31 | 121.7 (6) |
N1—C5—C6 | 116.5 (5) | N6—C31—C32 | 116.3 (6) |
C4—C5—C6 | 125.9 (6) | N6—C31—C30 | 117.9 (5) |
N2—C6—C7 | 122.0 (6) | C32—C31—C30 | 125.7 (6) |
N2—C6—C5 | 116.3 (5) | C33—C32—C31 | 119.8 (6) |
C7—C6—C5 | 121.7 (6) | C33—C32—H32 | 120.1 |
C8—C7—C6 | 118.2 (6) | C31—C32—H32 | 120.1 |
C8—C7—H7 | 120.9 | C34—C33—C32 | 120.4 (6) |
C6—C7—H7 | 120.9 | C34—C33—H33 | 119.8 |
C7—C8—C9 | 120.1 (6) | C32—C33—H33 | 119.8 |
C7—C8—H8 | 119.9 | C35—C34—C33 | 117.8 (6) |
C9—C8—H8 | 120.0 | C35—C34—H34 | 121.1 |
C10—C9—C8 | 118.5 (6) | C33—C34—H34 | 121.1 |
C10—C9—H9 | 120.7 | N6—C35—C34 | 121.2 (6) |
C8—C9—H9 | 120.8 | N6—C35—H35 | 119.4 |
N2—C10—C9 | 122.7 (6) | C34—C35—H35 | 119.4 |
N2—C10—C11 | 115.4 (5) | O2—Re2—O1 | 178.43 (18) |
C9—C10—C11 | 121.8 (5) | O2—Re2—Br7 | 98.52 (14) |
N3—C11—C12 | 117.9 (6) | O1—Re2—Br7 | 83.05 (10) |
N3—C11—C10 | 117.1 (5) | O2—Re2—Br4 | 98.19 (13) |
C12—C11—C10 | 125.0 (6) | O1—Re2—Br4 | 81.84 (10) |
C11—C12—C13 | 119.5 (6) | Br7—Re2—Br4 | 87.55 (2) |
C11—C12—H12 | 120.2 | O2—Re2—Br5 | 97.92 (13) |
C13—C12—H12 | 120.3 | O1—Re2—Br5 | 82.07 (10) |
C14—C13—C12 | 120.1 (6) | Br7—Re2—Br5 | 89.73 (2) |
C14—C13—H13 | 119.9 | Br4—Re2—Br5 | 163.89 (2) |
C12—C13—H13 | 119.9 | O2—Re2—Br6 | 95.66 (14) |
C15—C14—C13 | 119.0 (6) | O1—Re2—Br6 | 82.77 (10) |
C15—C14—H14 | 120.5 | Br7—Re2—Br6 | 165.81 (2) |
C13—C14—H14 | 120.5 | Br4—Re2—Br6 | 90.20 (2) |
N3—C15—C14 | 119.5 (6) | Br5—Re2—Br6 | 88.55 (2) |
N3—C15—H15 | 120.3 | Re2—O1—H1W | 112.3 |
C14—C15—H15 | 120.3 | Re2—O1—H2W | 124.6 |
C21—N4—C25 | 123.1 (5) | H1W—O1—H2W | 99.9 |
C21—N4—H4N | 118.4 | Br3i—Re1—Br3 | 180.0 |
C25—N4—H4N | 118.4 | Br3i—Re1—Br2 | 89.34 (2) |
C26—N5—C30 | 118.1 (5) | Br3—Re1—Br2 | 90.66 (2) |
C35—N6—C31 | 124.4 (5) | Br3i—Re1—Br2i | 90.66 (2) |
C35—N6—H6N | 117.8 | Br3—Re1—Br2i | 89.34 (2) |
C31—N6—H6N | 117.8 | Br2—Re1—Br2i | 180.0 |
N4—C21—C22 | 120.9 (6) | Br3i—Re1—Br1 | 90.53 (2) |
N4—C21—H21 | 119.5 | Br3—Re1—Br1 | 89.47 (2) |
C22—C21—H21 | 119.6 | Br2—Re1—Br1 | 89.44 (2) |
C21—C22—C23 | 118.0 (6) | Br2i—Re1—Br1 | 90.56 (2) |
C21—C22—H22 | 121.0 | Br3i—Re1—Br1i | 89.47 (2) |
C23—C22—H22 | 121.0 | Br3—Re1—Br1i | 90.53 (2) |
C24—C23—C22 | 120.3 (6) | Br2—Re1—Br1i | 90.56 (2) |
C24—C23—H23 | 119.9 | Br2i—Re1—Br1i | 89.44 (2) |
C22—C23—H23 | 119.9 | Br1—Re1—Br1i | 180.0 |
C25—C24—C23 | 119.5 (6) | H3W—O3A—H4W | 99.5 |
C5—N1—C1—C2 | 1.3 (9) | C25—N4—C21—C22 | 1.2 (9) |
N1—C1—C2—C3 | 0.2 (9) | N4—C21—C22—C23 | −0.8 (9) |
C1—C2—C3—C4 | −2.6 (9) | C21—C22—C23—C24 | 1.0 (9) |
C2—C3—C4—C5 | 3.6 (9) | C22—C23—C24—C25 | −1.6 (9) |
C1—N1—C5—C4 | −0.3 (8) | C21—N4—C25—C24 | −1.7 (9) |
C1—N1—C5—C6 | 179.8 (5) | C21—N4—C25—C26 | 179.4 (6) |
C3—C4—C5—N1 | −2.1 (8) | C23—C24—C25—N4 | 1.9 (9) |
C3—C4—C5—C6 | 177.7 (6) | C23—C24—C25—C26 | −179.3 (6) |
C10—N2—C6—C7 | 0.4 (8) | C30—N5—C26—C27 | −0.6 (9) |
C10—N2—C6—C5 | −179.2 (5) | C30—N5—C26—C25 | −178.9 (5) |
N1—C5—C6—N2 | 0.6 (7) | N4—C25—C26—N5 | −10.8 (8) |
C4—C5—C6—N2 | −179.2 (5) | C24—C25—C26—N5 | 170.4 (5) |
N1—C5—C6—C7 | −178.9 (5) | N4—C25—C26—C27 | 170.9 (5) |
C4—C5—C6—C7 | 1.2 (9) | C24—C25—C26—C27 | −7.9 (9) |
N2—C6—C7—C8 | 0.6 (9) | N5—C26—C27—C28 | 1.8 (9) |
C5—C6—C7—C8 | −179.9 (5) | C25—C26—C27—C28 | 180.0 (5) |
C6—C7—C8—C9 | −0.1 (9) | C26—C27—C28—C29 | −2.2 (9) |
C7—C8—C9—C10 | −1.4 (9) | C27—C28—C29—C30 | 1.5 (9) |
C6—N2—C10—C9 | −1.9 (8) | C26—N5—C30—C29 | −0.2 (9) |
C6—N2—C10—C11 | 174.9 (5) | C26—N5—C30—C31 | 178.5 (5) |
C8—C9—C10—N2 | 2.4 (9) | C28—C29—C30—N5 | −0.3 (9) |
C8—C9—C10—C11 | −174.2 (5) | C28—C29—C30—C31 | −178.9 (5) |
C15—N3—C11—C12 | 1.4 (9) | C35—N6—C31—C32 | 2.2 (9) |
C15—N3—C11—C10 | −176.9 (5) | C35—N6—C31—C30 | −177.6 (6) |
N2—C10—C11—N3 | 1.1 (8) | N5—C30—C31—N6 | −2.1 (8) |
C9—C10—C11—N3 | 177.9 (5) | C29—C30—C31—N6 | 176.7 (5) |
N2—C10—C11—C12 | −177.1 (6) | N5—C30—C31—C32 | 178.1 (6) |
C9—C10—C11—C12 | −0.2 (9) | C29—C30—C31—C32 | −3.1 (10) |
N3—C11—C12—C13 | −1.8 (9) | N6—C31—C32—C33 | −2.2 (9) |
C10—C11—C12—C13 | 176.3 (5) | C30—C31—C32—C33 | 177.7 (6) |
C11—C12—C13—C14 | 0.8 (9) | C31—C32—C33—C34 | 0.7 (10) |
C12—C13—C14—C15 | 0.8 (9) | C32—C33—C34—C35 | 1.0 (9) |
C11—N3—C15—C14 | 0.2 (9) | C31—N6—C35—C34 | −0.7 (10) |
C13—C14—C15—N3 | −1.3 (9) | C33—C34—C35—N6 | −1.0 (9) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br8ii | 0.86 | 2.47 | 3.228 (6) | 146 |
O1—H1W···Br8iii | 0.89 | 2.46 | 3.310 (4) | 157 |
O1—H2W···O3Aiii | 0.88 | 1.83 | 2.710 (5) | 166 |
N3—H3N···Br8ii | 0.85 | 2.48 | 3.236 (5) | 147 |
O3A—H3W···Br5iv | 0.88 | 2.68 | 3.517 (4) | 157 |
N4—H4N···Br9iv | 0.86 | 2.51 | 3.247 (6) | 143 |
O3A—H4W···Br9 | 0.89 | 2.45 | 3.338 (4) | 171 |
N6—H6N···Br9iv | 0.85 | 2.48 | 3.245 (5) | 147 |
C9—H9···Br3ii | 0.93 | 2.76 | 3.664 (6) | 162 |
C15—H15···Br9ii | 0.92 | 2.81 | 3.598 (6) | 142 |
C22—H22···O3A | 0.92 | 2.58 | 3.504 (8) | 170 |
C23—H23···Br7v | 0.92 | 2.88 | 3.810 (7) | 172 |
C29—H29···Br4vi | 0.93 | 2.85 | 3.738 (6) | 158 |
C35—H35···Br8iv | 0.92 | 2.73 | 3.474 (6) | 137 |
Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+1, −y+1, −z; (v) x, y+1, z; (vi) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | (C15H13N3)4[ReBr6][ReBr4O(H2O)]2Br4·2H2O |
Mr | 3042.03 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 10.3458 (6), 10.3563 (6), 19.0582 (14) |
α, β, γ (°) | 81.361 (6), 79.041 (6), 79.987 (5) |
V (Å3) | 1959.7 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 13.85 |
Crystal size (mm) | 0.10 × 0.10 × 0.05 |
Data collection | |
Diffractometer | Oxford Diffraction KM-4-CCD |
Absorption correction | Numerical (CrysAlis RED; Oxford Diffraction, 2003) |
Tmin, Tmax | 0.456, 0.794 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 24231, 9275, 5991 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.672 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.062, 0.94 |
No. of reflections | 9275 |
No. of parameters | 448 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.24, −0.94 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and XP (Bruker, 1999), SHELXL97.
Re1—Br3 | 2.5044 (6) | Re2—Br7 | 2.5108 (7) |
Re1—Br2 | 2.5099 (6) | Re2—Br4 | 2.5123 (7) |
Re1—Br1 | 2.5179 (6) | Re2—Br5 | 2.5182 (7) |
Re2—O2 | 1.663 (4) | Re2—Br6 | 2.5239 (7) |
Re2—O1 | 2.246 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br8i | 0.86 | 2.47 | 3.228 (6) | 146 |
O1—H1W···Br8ii | 0.89 | 2.46 | 3.310 (4) | 157 |
O1—H2W···O3Aii | 0.88 | 1.83 | 2.710 (5) | 166 |
N3—H3N···Br8i | 0.85 | 2.48 | 3.236 (5) | 147 |
O3A—H3W···Br5iii | 0.88 | 2.68 | 3.517 (4) | 157 |
N4—H4N···Br9iii | 0.86 | 2.51 | 3.247 (6) | 143 |
O3A—H4W···Br9 | 0.89 | 2.45 | 3.338 (4) | 171 |
N6—H6N···Br9iii | 0.85 | 2.48 | 3.245 (5) | 147 |
C9—H9···Br3i | 0.93 | 2.76 | 3.664 (6) | 162 |
C15—H15···Br9i | 0.92 | 2.81 | 3.598 (6) | 142 |
C22—H22···O3A | 0.92 | 2.58 | 3.504 (8) | 170 |
C23—H23···Br7iv | 0.92 | 2.88 | 3.810 (7) | 172 |
C29—H29···Br4v | 0.93 | 2.85 | 3.738 (6) | 158 |
C35—H35···Br8iii | 0.92 | 2.73 | 3.474 (6) | 137 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z; (iii) −x+1, −y+1, −z; (iv) x, y+1, z; (v) x−1, y, z. |
This paper reports the crystal structure of the title mixed valence rhenium compound, (I). One of rhenium atoms lies on a centre of symmetry and other one in general position.
Compound (I) (Fig. 1) and some of its derivatives show interesting magnetic properties (Rose et al., 1996). Several papers describing the crystal structures of bromorhenates are available in the literature (Preetz & Struess, 1988, Chiozzone et al., 2006) but surprisingly the crystal structure of (I) has not been determined yet.
The [ReO(H2O)Br4]- units in (I) shows a distorted octahedral geometry about the Re(V) site defined by the terminal oxo ligand, the trans aqua ligand, and four bromide ions (Table 1). The Re—Br bond lengths in (I) agree with those in related crystal structures (Kochel, 2007; Abram et al., 1996).
In the crystal packing of (I), layers of rhenate anions and terpyridinium cations could be distinguished. However, the anion layer is additionally filled with the water molecules and bromide anions. The crystal structure is consolidated by a complex hydrogen bond system including various C—H···O links (Table 2).