Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039802/rz6139sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039802/rz6139Isup2.hkl |
CCDC reference: 296637
A mixture of (NH4)2ReI6 (0.02 g) and 2,2':6',2''terpirydine (0.04 g) was dissolved in water (50 ml) and heated at 340 K for 10 h. The solution changed colour from black to light brown. After completion of the reaction, the solution was left to evaporate slowly at room temperature. After five days, yellow crystals of the title compound were obtained (yield 60%). The compound is stable in air, and dissolves easly in hot water, methanol and ethanol. IR (KBr, cm−1): ν 3090, 1620, 1604, 1581, 1562, 1528, 1455, 1427, 1407, 1298, 1063, 920, 904, 874, 1455, 1427, 1407, 1298, 1063, 920, 904, 874, 774, 736, 648, 620, 398, 340, 320, 298, 257, 238, 191, 135, 108, 85, 71. Analysis calculated for C15H12N3O4Re: C 37.18, H 2.49, N 8.67, O 13.20, Re 26.00%; found: C 33.34, H 2.01, N 9.10%.
All H atoms were placed in calculated positions (C—H = 0.93 Å and N—H = 0.86 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C,N). The highest and deepest residual peaks in the final difference Fourier synthesis are located 0.95 and 0.84 Å, respectively, from atom Re1. The relatively small size and poor diffraction quality of the crystals selected for the X-ray analysis could account for the rather high Rint value (0.124).
Data collection: KM-4 CCD Software (Oxford Diffraction, 2004); cell refinement: KM-4 CCD Software; data reduction: KM-4 CCD Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
(C15H12N3)[ReO4] | Z = 2 |
Mr = 484.48 | F(000) = 460 |
Triclinic, P1 | Dx = 2.211 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.112 (4) Å | Cell parameters from 3150 reflections |
b = 10.796 (2) Å | θ = 3.5–28.4° |
c = 11.806 (2) Å | µ = 8.38 mm−1 |
α = 76.18 (3)° | T = 100 K |
β = 87.12 (3)° | Plate, yellow |
γ = 74.16 (3)° | 0.12 × 0.05 × 0.05 mm |
V = 727.7 (5) Å3 |
Kuma KM-4 CCD diffractometer | 3403 independent reflections |
Radiation source: fine-focus sealed tube | 2853 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.124 |
Detector resolution: 0 pixels mm-1 | θmax = 28.4°, θmin = 3.5° |
ω scans | h = −8→7 |
Absorption correction: numerical (CrysAlis RED in KM-4 CCD Software; Oxford Diffraction, 2004) | k = −14→14 |
Tmin = 0.567, Tmax = 0.897 | l = −15→15 |
10097 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)] = 0.061 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1028P)2] where P = (Fo2 + 2Fc2)/3 |
3403 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 3.10 e Å−3 |
0 restraints | Δρmin = −3.64 e Å−3 |
(C15H12N3)[ReO4] | γ = 74.16 (3)° |
Mr = 484.48 | V = 727.7 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.112 (4) Å | Mo Kα radiation |
b = 10.796 (2) Å | µ = 8.38 mm−1 |
c = 11.806 (2) Å | T = 100 K |
α = 76.18 (3)° | 0.12 × 0.05 × 0.05 mm |
β = 87.12 (3)° |
Kuma KM-4 CCD diffractometer | 3403 independent reflections |
Absorption correction: numerical (CrysAlis RED in KM-4 CCD Software; Oxford Diffraction, 2004) | 2853 reflections with I > 2σ(I) |
Tmin = 0.567, Tmax = 0.897 | Rint = 0.124 |
10097 measured reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.157 | H-atom parameters constrained |
S = 1.02 | Δρmax = 3.10 e Å−3 |
3403 reflections | Δρmin = −3.64 e Å−3 |
208 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 | ||
Re1 | 0.97030 (6) | 0.38090 (4) | 0.29653 (3) | 0.02163 (17) | |
O1 | 1.0169 (14) | 0.5163 (7) | 0.3344 (7) | 0.0348 (18) | |
O2 | 1.1068 (12) | 0.2368 (7) | 0.3946 (6) | 0.0263 (15) | |
O3 | 1.0768 (14) | 0.3743 (9) | 0.1603 (7) | 0.0380 (19) | |
O4 | 0.6827 (13) | 0.3924 (8) | 0.2968 (6) | 0.0286 (16) | |
N1 | −0.1762 (13) | 0.2701 (8) | 0.6562 (6) | 0.0199 (16) | |
H1A | −0.0890 | 0.3026 | 0.6886 | 0.024* | |
N2 | 0.2162 (13) | 0.1363 (8) | 0.7641 (6) | 0.0178 (15) | |
N3 | 0.7305 (13) | 0.0993 (8) | 0.9170 (7) | 0.0216 (17) | |
C1 | −0.3794 (17) | 0.3509 (10) | 0.6144 (8) | 0.0213 (19) | |
H1 | −0.4253 | 0.4372 | 0.6241 | 0.026* | |
C2 | −0.5177 (17) | 0.3040 (10) | 0.5573 (8) | 0.0208 (19) | |
H2 | −0.6597 | 0.3572 | 0.5283 | 0.025* | |
C3 | −0.4398 (17) | 0.1744 (10) | 0.5440 (7) | 0.0197 (18) | |
H3 | −0.5278 | 0.1421 | 0.5022 | 0.024* | |
C4 | −0.2337 (17) | 0.0934 (10) | 0.5918 (7) | 0.0196 (18) | |
H4 | −0.1848 | 0.0063 | 0.5846 | 0.023* | |
C5 | −0.1001 (15) | 0.1438 (9) | 0.6512 (7) | 0.0152 (17) | |
C6 | 0.1237 (15) | 0.0663 (10) | 0.7083 (7) | 0.0173 (18) | |
C7 | 0.2207 (16) | −0.0645 (9) | 0.7075 (8) | 0.0188 (18) | |
H7 | 0.1501 | −0.1098 | 0.6695 | 0.023* | |
C8 | 0.4299 (18) | −0.1269 (10) | 0.7659 (8) | 0.0207 (19) | |
H8 | 0.5027 | −0.2142 | 0.7645 | 0.025* | |
C9 | 0.5275 (17) | −0.0615 (10) | 0.8245 (8) | 0.022 (2) | |
H9 | 0.6630 | −0.1042 | 0.8662 | 0.027* | |
C10 | 0.4189 (15) | 0.0725 (10) | 0.8207 (8) | 0.0176 (18) | |
C11 | 0.5179 (17) | 0.1544 (10) | 0.8773 (8) | 0.0204 (19) | |
C12 | 0.3941 (16) | 0.2812 (9) | 0.8856 (8) | 0.0201 (18) | |
H12 | 0.2438 | 0.3150 | 0.8594 | 0.024* | |
C13 | 0.4995 (19) | 0.3557 (11) | 0.9336 (9) | 0.029 (2) | |
H13 | 0.4208 | 0.4403 | 0.9407 | 0.034* | |
C14 | 0.7289 (17) | 0.3008 (11) | 0.9717 (8) | 0.026 (2) | |
H14 | 0.8067 | 0.3495 | 1.0012 | 0.031* | |
C15 | 0.8351 (17) | 0.1711 (11) | 0.9635 (7) | 0.023 (2) | |
H15 | 0.9838 | 0.1327 | 0.9913 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Re1 | 0.0216 (2) | 0.0218 (2) | 0.0213 (2) | −0.00492 (16) | −0.00235 (14) | −0.00523 (15) |
O1 | 0.034 (4) | 0.021 (4) | 0.051 (5) | −0.010 (3) | −0.012 (4) | −0.007 (3) |
O2 | 0.030 (4) | 0.019 (3) | 0.030 (4) | −0.006 (3) | 0.000 (3) | −0.005 (3) |
O3 | 0.031 (4) | 0.054 (5) | 0.026 (4) | −0.007 (4) | −0.002 (3) | −0.008 (4) |
O4 | 0.027 (4) | 0.032 (4) | 0.027 (4) | −0.010 (3) | 0.002 (3) | −0.005 (3) |
N1 | 0.017 (4) | 0.027 (4) | 0.016 (4) | −0.005 (3) | −0.002 (3) | −0.006 (3) |
N2 | 0.020 (4) | 0.018 (4) | 0.015 (3) | −0.006 (3) | 0.001 (3) | −0.003 (3) |
N3 | 0.015 (4) | 0.024 (4) | 0.023 (4) | 0.001 (3) | 0.002 (3) | −0.005 (3) |
C1 | 0.023 (5) | 0.018 (5) | 0.021 (4) | −0.009 (4) | 0.000 (4) | 0.003 (4) |
C2 | 0.022 (5) | 0.023 (5) | 0.014 (4) | −0.006 (4) | 0.004 (3) | 0.002 (3) |
C3 | 0.026 (5) | 0.023 (5) | 0.011 (4) | −0.011 (4) | 0.003 (3) | −0.002 (3) |
C4 | 0.027 (5) | 0.022 (5) | 0.012 (4) | −0.009 (4) | 0.000 (3) | −0.006 (3) |
C5 | 0.013 (4) | 0.023 (5) | 0.008 (3) | −0.007 (3) | 0.003 (3) | 0.000 (3) |
C6 | 0.012 (4) | 0.029 (5) | 0.012 (4) | −0.007 (4) | −0.002 (3) | −0.005 (4) |
C7 | 0.022 (5) | 0.022 (5) | 0.015 (4) | −0.011 (4) | 0.002 (3) | −0.005 (3) |
C8 | 0.030 (5) | 0.018 (5) | 0.016 (4) | −0.015 (4) | 0.005 (4) | 0.002 (3) |
C9 | 0.017 (5) | 0.031 (5) | 0.015 (4) | 0.000 (4) | 0.003 (3) | −0.008 (4) |
C10 | 0.015 (4) | 0.024 (5) | 0.016 (4) | −0.009 (4) | 0.005 (3) | −0.005 (3) |
C11 | 0.026 (5) | 0.023 (5) | 0.010 (4) | −0.010 (4) | 0.003 (3) | 0.003 (3) |
C12 | 0.016 (4) | 0.019 (5) | 0.022 (4) | 0.000 (4) | −0.006 (3) | −0.002 (4) |
C13 | 0.029 (6) | 0.030 (6) | 0.029 (5) | −0.002 (4) | −0.011 (4) | −0.014 (4) |
C14 | 0.022 (5) | 0.040 (6) | 0.020 (4) | −0.012 (4) | −0.004 (4) | −0.010 (4) |
C15 | 0.021 (5) | 0.036 (6) | 0.011 (4) | −0.008 (4) | 0.000 (3) | −0.005 (4) |
Re1—O3 | 1.715 (8) | C4—H4 | 0.9300 |
Re1—O1 | 1.723 (7) | C5—C6 | 1.492 (12) |
Re1—O2 | 1.727 (7) | C6—C7 | 1.377 (13) |
Re1—O4 | 1.728 (7) | C7—C8 | 1.400 (14) |
N1—C5 | 1.330 (12) | C7—H7 | 0.9300 |
N1—C1 | 1.346 (13) | C8—C9 | 1.355 (14) |
N1—H1A | 0.8600 | C8—H8 | 0.9300 |
N2—C6 | 1.354 (11) | C9—C10 | 1.408 (14) |
N2—C10 | 1.362 (12) | C9—H9 | 0.9300 |
N3—C11 | 1.329 (13) | C10—C11 | 1.487 (13) |
N3—C15 | 1.349 (13) | C11—C12 | 1.395 (13) |
C1—C2 | 1.371 (14) | C12—C13 | 1.386 (13) |
C1—H1 | 0.9300 | C12—H12 | 0.9300 |
C2—C3 | 1.394 (14) | C13—C14 | 1.415 (14) |
C2—H2 | 0.9300 | C13—H13 | 0.9300 |
C3—C4 | 1.380 (14) | C14—C15 | 1.398 (15) |
C3—H3 | 0.9300 | C14—H14 | 0.9300 |
C4—C5 | 1.391 (12) | C15—H15 | 0.9300 |
O3—Re1—O1 | 109.0 (4) | C7—C6—C5 | 123.0 (8) |
O3—Re1—O2 | 108.7 (4) | C6—C7—C8 | 117.5 (8) |
O1—Re1—O2 | 110.3 (4) | C6—C7—H7 | 121.3 |
O3—Re1—O4 | 109.9 (4) | C8—C7—H7 | 121.3 |
O1—Re1—O4 | 110.3 (4) | C9—C8—C7 | 120.8 (10) |
O2—Re1—O4 | 108.6 (4) | C9—C8—H8 | 119.6 |
C5—N1—C1 | 124.9 (8) | C7—C8—H8 | 119.6 |
C5—N1—H1A | 117.6 | C8—C9—C10 | 118.4 (9) |
C1—N1—H1A | 117.6 | C8—C9—H9 | 120.8 |
C6—N2—C10 | 117.1 (8) | C10—C9—H9 | 120.8 |
C11—N3—C15 | 118.5 (9) | N2—C10—C9 | 122.2 (8) |
N1—C1—C2 | 119.0 (9) | N2—C10—C11 | 115.3 (8) |
N1—C1—H1 | 120.5 | C9—C10—C11 | 122.5 (9) |
C2—C1—H1 | 120.5 | N3—C11—C12 | 123.2 (9) |
C1—C2—C3 | 118.2 (9) | N3—C11—C10 | 115.5 (9) |
C1—C2—H2 | 120.9 | C12—C11—C10 | 121.3 (9) |
C3—C2—H2 | 120.9 | C13—C12—C11 | 118.7 (9) |
C4—C3—C2 | 120.8 (9) | C13—C12—H12 | 120.6 |
C4—C3—H3 | 119.6 | C11—C12—H12 | 120.6 |
C2—C3—H3 | 119.6 | C12—C13—C14 | 118.8 (10) |
C3—C4—C5 | 119.2 (9) | C12—C13—H13 | 120.6 |
C3—C4—H4 | 120.4 | C14—C13—H13 | 120.6 |
C5—C4—H4 | 120.4 | C15—C14—C13 | 117.9 (9) |
N1—C5—C4 | 117.7 (8) | C15—C14—H14 | 121.0 |
N1—C5—C6 | 117.8 (8) | C13—C14—H14 | 121.0 |
C4—C5—C6 | 124.4 (9) | N3—C15—C14 | 122.6 (9) |
N2—C6—C7 | 123.9 (8) | N3—C15—H15 | 118.7 |
N2—C6—C5 | 113.1 (8) | C14—C15—H15 | 118.7 |
C5—N1—C1—C2 | −3.1 (14) | C7—C8—C9—C10 | −2.9 (14) |
N1—C1—C2—C3 | −0.7 (13) | C6—N2—C10—C9 | −1.5 (13) |
C1—C2—C3—C4 | 3.1 (13) | C6—N2—C10—C11 | 178.1 (8) |
C2—C3—C4—C5 | −1.9 (13) | C8—C9—C10—N2 | 2.5 (14) |
C1—N1—C5—C4 | 4.3 (13) | C8—C9—C10—C11 | −177.0 (8) |
C1—N1—C5—C6 | −176.3 (8) | C15—N3—C11—C12 | −2.6 (14) |
C3—C4—C5—N1 | −1.7 (13) | C15—N3—C11—C10 | 176.4 (8) |
C3—C4—C5—C6 | 179.0 (8) | N2—C10—C11—N3 | −170.0 (8) |
C10—N2—C6—C7 | 1.0 (13) | C9—C10—C11—N3 | 9.5 (12) |
C10—N2—C6—C5 | 178.8 (8) | N2—C10—C11—C12 | 9.0 (12) |
N1—C5—C6—N2 | 3.0 (11) | C9—C10—C11—C12 | −171.5 (9) |
C4—C5—C6—N2 | −177.7 (8) | N3—C11—C12—C13 | 2.4 (15) |
N1—C5—C6—C7 | −179.1 (8) | C10—C11—C12—C13 | −176.5 (9) |
C4—C5—C6—C7 | 0.2 (14) | C11—C12—C13—C14 | 0.4 (15) |
N2—C6—C7—C8 | −1.4 (13) | C12—C13—C14—C15 | −2.8 (15) |
C5—C6—C7—C8 | −179.0 (8) | C11—N3—C15—C14 | 0.0 (14) |
C6—C7—C8—C9 | 2.4 (13) | C13—C14—C15—N3 | 2.7 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2 | 0.86 | 2.26 | 2.645 (11) | 108 |
N1—H1A···O1i | 0.86 | 2.07 | 2.763 (12) | 137 |
C1—H1···O4ii | 0.93 | 2.41 | 3.258 (14) | 151 |
C3—H3···O2iii | 0.93 | 2.46 | 3.185 (13) | 134 |
C4—H4···O2iv | 0.93 | 2.49 | 3.399 (13) | 166 |
C7—H7···O2iv | 0.93 | 2.60 | 3.505 (13) | 166 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x−2, y, z; (iv) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C15H12N3)[ReO4] |
Mr | 484.48 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 6.112 (4), 10.796 (2), 11.806 (2) |
α, β, γ (°) | 76.18 (3), 87.12 (3), 74.16 (3) |
V (Å3) | 727.7 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 8.38 |
Crystal size (mm) | 0.12 × 0.05 × 0.05 |
Data collection | |
Diffractometer | Kuma KM-4 CCD diffractometer |
Absorption correction | Numerical (CrysAlis RED in KM-4 CCD Software; Oxford Diffraction, 2004) |
Tmin, Tmax | 0.567, 0.897 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10097, 3403, 2853 |
Rint | 0.124 |
(sin θ/λ)max (Å−1) | 0.669 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.157, 1.02 |
No. of reflections | 3403 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 3.10, −3.64 |
Computer programs: KM-4 CCD Software (Oxford Diffraction, 2004), KM-4 CCD Software, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Re1—O3 | 1.715 (8) | Re1—O2 | 1.727 (7) |
Re1—O1 | 1.723 (7) | Re1—O4 | 1.728 (7) |
O3—Re1—O1 | 109.0 (4) | O3—Re1—O4 | 109.9 (4) |
O3—Re1—O2 | 108.7 (4) | O1—Re1—O4 | 110.3 (4) |
O1—Re1—O2 | 110.3 (4) | O2—Re1—O4 | 108.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2 | 0.86 | 2.26 | 2.645 (11) | 108 |
N1—H1A···O1i | 0.86 | 2.07 | 2.763 (12) | 137 |
C1—H1···O4ii | 0.93 | 2.41 | 3.258 (14) | 151 |
C3—H3···O2iii | 0.93 | 2.46 | 3.185 (13) | 134 |
C4—H4···O2iv | 0.93 | 2.49 | 3.399 (13) | 166 |
C7—H7···O2iv | 0.93 | 2.60 | 3.505 (13) | 166 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+1; (iii) x−2, y, z; (iv) −x+1, −y, −z+1. |
The title compound is the product of the hydrolysis of (NH4)2ReI6 in the presence of 2,2':6,2''-terpyridine. The structure consists of terpyridinium cations (terpyH) protonated at atom N1 and perrhenate anions (Fig. 1). The pyridine rings of the cation show a cis--trans conformation closely resembling that observed in [terpyH](CF3SO)3 (Hergold-Brundić et al., 1996). In this conformation, atom H1A is involved in a bifurcated hydrogen interaction with atoms N2 and O1 as acceptors (Table 2.). The Re—O bond lengths in the perrhenate anion (Table 1) are in agreement with the literature data (Herrman et al., 1990; Kochel, 2005). In the crystal structure, cations and anions are packed in stacks extending along [010] linked by C—H···O hydrogen interactions (Table 2).