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In the title compound, (C15H12N3)[ReO4], the cations exhibit a cistrans conformation of the pyridine rings. The crystal structure is stabilized by a three-dimensional network of C—H...O hydrogen-bond inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805039802/rz6139sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805039802/rz6139Isup2.hkl
Contains datablock I

CCDC reference: 296637

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.015 Å
  • R factor = 0.061
  • wR factor = 0.156
  • Data-to-parameter ratio = 16.4

checkCIF/PLATON results

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Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.124 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.12 PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 15
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

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).

Experimental top

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%.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the intramolecular N—H···N hydrogen bond (dashed line). Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. Crystal packing of the title compound viewed along the [010] direction. Displacement ellipsoids are drawn at the 50% probability level.
2,2':6',2''-Terpyridinium perrhenate top
Crystal data top
(C15H12N3)[ReO4]Z = 2
Mr = 484.48F(000) = 460
Triclinic, P1Dx = 2.211 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.112 (4) ÅCell parameters from 3150 reflections
b = 10.796 (2) Åθ = 3.5–28.4°
c = 11.806 (2) ŵ = 8.38 mm1
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
Data collection top
Kuma KM-4 CCD
diffractometer
3403 independent reflections
Radiation source: fine-focus sealed tube2853 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.124
Detector resolution: 0 pixels mm-1θmax = 28.4°, θmin = 3.5°
ω scansh = 87
Absorption correction: numerical
(CrysAlis RED in KM-4 CCD Software; Oxford Diffraction, 2004)
k = 1414
Tmin = 0.567, Tmax = 0.897l = 1515
10097 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-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 parametersΔρmax = 3.10 e Å3
0 restraintsΔρmin = 3.64 e Å3
Crystal data top
(C15H12N3)[ReO4]γ = 74.16 (3)°
Mr = 484.48V = 727.7 (5) Å3
Triclinic, P1Z = 2
a = 6.112 (4) ÅMo Kα radiation
b = 10.796 (2) ŵ = 8.38 mm1
c = 11.806 (2) ÅT = 100 K
α = 76.18 (3)°0.12 × 0.05 × 0.05 mm
β = 87.12 (3)°
Data collection top
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 = 0.897Rint = 0.124
10097 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0610 restraints
wR(F2) = 0.157H-atom parameters constrained
S = 1.02Δρmax = 3.10 e Å3
3403 reflectionsΔρmin = 3.64 e Å3
208 parameters
Special details top

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
xyzUiso*/Ueq
Re10.97030 (6)0.38090 (4)0.29653 (3)0.02163 (17)
O11.0169 (14)0.5163 (7)0.3344 (7)0.0348 (18)
O21.1068 (12)0.2368 (7)0.3946 (6)0.0263 (15)
O31.0768 (14)0.3743 (9)0.1603 (7)0.0380 (19)
O40.6827 (13)0.3924 (8)0.2968 (6)0.0286 (16)
N10.1762 (13)0.2701 (8)0.6562 (6)0.0199 (16)
H1A0.08900.30260.68860.024*
N20.2162 (13)0.1363 (8)0.7641 (6)0.0178 (15)
N30.7305 (13)0.0993 (8)0.9170 (7)0.0216 (17)
C10.3794 (17)0.3509 (10)0.6144 (8)0.0213 (19)
H10.42530.43720.62410.026*
C20.5177 (17)0.3040 (10)0.5573 (8)0.0208 (19)
H20.65970.35720.52830.025*
C30.4398 (17)0.1744 (10)0.5440 (7)0.0197 (18)
H30.52780.14210.50220.024*
C40.2337 (17)0.0934 (10)0.5918 (7)0.0196 (18)
H40.18480.00630.58460.023*
C50.1001 (15)0.1438 (9)0.6512 (7)0.0152 (17)
C60.1237 (15)0.0663 (10)0.7083 (7)0.0173 (18)
C70.2207 (16)0.0645 (9)0.7075 (8)0.0188 (18)
H70.15010.10980.66950.023*
C80.4299 (18)0.1269 (10)0.7659 (8)0.0207 (19)
H80.50270.21420.76450.025*
C90.5275 (17)0.0615 (10)0.8245 (8)0.022 (2)
H90.66300.10420.86620.027*
C100.4189 (15)0.0725 (10)0.8207 (8)0.0176 (18)
C110.5179 (17)0.1544 (10)0.8773 (8)0.0204 (19)
C120.3941 (16)0.2812 (9)0.8856 (8)0.0201 (18)
H120.24380.31500.85940.024*
C130.4995 (19)0.3557 (11)0.9336 (9)0.029 (2)
H130.42080.44030.94070.034*
C140.7289 (17)0.3008 (11)0.9717 (8)0.026 (2)
H140.80670.34951.00120.031*
C150.8351 (17)0.1711 (11)0.9635 (7)0.023 (2)
H150.98380.13270.99130.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Re10.0216 (2)0.0218 (2)0.0213 (2)0.00492 (16)0.00235 (14)0.00523 (15)
O10.034 (4)0.021 (4)0.051 (5)0.010 (3)0.012 (4)0.007 (3)
O20.030 (4)0.019 (3)0.030 (4)0.006 (3)0.000 (3)0.005 (3)
O30.031 (4)0.054 (5)0.026 (4)0.007 (4)0.002 (3)0.008 (4)
O40.027 (4)0.032 (4)0.027 (4)0.010 (3)0.002 (3)0.005 (3)
N10.017 (4)0.027 (4)0.016 (4)0.005 (3)0.002 (3)0.006 (3)
N20.020 (4)0.018 (4)0.015 (3)0.006 (3)0.001 (3)0.003 (3)
N30.015 (4)0.024 (4)0.023 (4)0.001 (3)0.002 (3)0.005 (3)
C10.023 (5)0.018 (5)0.021 (4)0.009 (4)0.000 (4)0.003 (4)
C20.022 (5)0.023 (5)0.014 (4)0.006 (4)0.004 (3)0.002 (3)
C30.026 (5)0.023 (5)0.011 (4)0.011 (4)0.003 (3)0.002 (3)
C40.027 (5)0.022 (5)0.012 (4)0.009 (4)0.000 (3)0.006 (3)
C50.013 (4)0.023 (5)0.008 (3)0.007 (3)0.003 (3)0.000 (3)
C60.012 (4)0.029 (5)0.012 (4)0.007 (4)0.002 (3)0.005 (4)
C70.022 (5)0.022 (5)0.015 (4)0.011 (4)0.002 (3)0.005 (3)
C80.030 (5)0.018 (5)0.016 (4)0.015 (4)0.005 (4)0.002 (3)
C90.017 (5)0.031 (5)0.015 (4)0.000 (4)0.003 (3)0.008 (4)
C100.015 (4)0.024 (5)0.016 (4)0.009 (4)0.005 (3)0.005 (3)
C110.026 (5)0.023 (5)0.010 (4)0.010 (4)0.003 (3)0.003 (3)
C120.016 (4)0.019 (5)0.022 (4)0.000 (4)0.006 (3)0.002 (4)
C130.029 (6)0.030 (6)0.029 (5)0.002 (4)0.011 (4)0.014 (4)
C140.022 (5)0.040 (6)0.020 (4)0.012 (4)0.004 (4)0.010 (4)
C150.021 (5)0.036 (6)0.011 (4)0.008 (4)0.000 (3)0.005 (4)
Geometric parameters (Å, º) top
Re1—O31.715 (8)C4—H40.9300
Re1—O11.723 (7)C5—C61.492 (12)
Re1—O21.727 (7)C6—C71.377 (13)
Re1—O41.728 (7)C7—C81.400 (14)
N1—C51.330 (12)C7—H70.9300
N1—C11.346 (13)C8—C91.355 (14)
N1—H1A0.8600C8—H80.9300
N2—C61.354 (11)C9—C101.408 (14)
N2—C101.362 (12)C9—H90.9300
N3—C111.329 (13)C10—C111.487 (13)
N3—C151.349 (13)C11—C121.395 (13)
C1—C21.371 (14)C12—C131.386 (13)
C1—H10.9300C12—H120.9300
C2—C31.394 (14)C13—C141.415 (14)
C2—H20.9300C13—H130.9300
C3—C41.380 (14)C14—C151.398 (15)
C3—H30.9300C14—H140.9300
C4—C51.391 (12)C15—H150.9300
O3—Re1—O1109.0 (4)C7—C6—C5123.0 (8)
O3—Re1—O2108.7 (4)C6—C7—C8117.5 (8)
O1—Re1—O2110.3 (4)C6—C7—H7121.3
O3—Re1—O4109.9 (4)C8—C7—H7121.3
O1—Re1—O4110.3 (4)C9—C8—C7120.8 (10)
O2—Re1—O4108.6 (4)C9—C8—H8119.6
C5—N1—C1124.9 (8)C7—C8—H8119.6
C5—N1—H1A117.6C8—C9—C10118.4 (9)
C1—N1—H1A117.6C8—C9—H9120.8
C6—N2—C10117.1 (8)C10—C9—H9120.8
C11—N3—C15118.5 (9)N2—C10—C9122.2 (8)
N1—C1—C2119.0 (9)N2—C10—C11115.3 (8)
N1—C1—H1120.5C9—C10—C11122.5 (9)
C2—C1—H1120.5N3—C11—C12123.2 (9)
C1—C2—C3118.2 (9)N3—C11—C10115.5 (9)
C1—C2—H2120.9C12—C11—C10121.3 (9)
C3—C2—H2120.9C13—C12—C11118.7 (9)
C4—C3—C2120.8 (9)C13—C12—H12120.6
C4—C3—H3119.6C11—C12—H12120.6
C2—C3—H3119.6C12—C13—C14118.8 (10)
C3—C4—C5119.2 (9)C12—C13—H13120.6
C3—C4—H4120.4C14—C13—H13120.6
C5—C4—H4120.4C15—C14—C13117.9 (9)
N1—C5—C4117.7 (8)C15—C14—H14121.0
N1—C5—C6117.8 (8)C13—C14—H14121.0
C4—C5—C6124.4 (9)N3—C15—C14122.6 (9)
N2—C6—C7123.9 (8)N3—C15—H15118.7
N2—C6—C5113.1 (8)C14—C15—H15118.7
C5—N1—C1—C23.1 (14)C7—C8—C9—C102.9 (14)
N1—C1—C2—C30.7 (13)C6—N2—C10—C91.5 (13)
C1—C2—C3—C43.1 (13)C6—N2—C10—C11178.1 (8)
C2—C3—C4—C51.9 (13)C8—C9—C10—N22.5 (14)
C1—N1—C5—C44.3 (13)C8—C9—C10—C11177.0 (8)
C1—N1—C5—C6176.3 (8)C15—N3—C11—C122.6 (14)
C3—C4—C5—N11.7 (13)C15—N3—C11—C10176.4 (8)
C3—C4—C5—C6179.0 (8)N2—C10—C11—N3170.0 (8)
C10—N2—C6—C71.0 (13)C9—C10—C11—N39.5 (12)
C10—N2—C6—C5178.8 (8)N2—C10—C11—C129.0 (12)
N1—C5—C6—N23.0 (11)C9—C10—C11—C12171.5 (9)
C4—C5—C6—N2177.7 (8)N3—C11—C12—C132.4 (15)
N1—C5—C6—C7179.1 (8)C10—C11—C12—C13176.5 (9)
C4—C5—C6—C70.2 (14)C11—C12—C13—C140.4 (15)
N2—C6—C7—C81.4 (13)C12—C13—C14—C152.8 (15)
C5—C6—C7—C8179.0 (8)C11—N3—C15—C140.0 (14)
C6—C7—C8—C92.4 (13)C13—C14—C15—N32.7 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N20.862.262.645 (11)108
N1—H1A···O1i0.862.072.763 (12)137
C1—H1···O4ii0.932.413.258 (14)151
C3—H3···O2iii0.932.463.185 (13)134
C4—H4···O2iv0.932.493.399 (13)166
C7—H7···O2iv0.932.603.505 (13)166
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x2, y, z; (iv) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula(C15H12N3)[ReO4]
Mr484.48
Crystal system, space groupTriclinic, 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)
V3)727.7 (5)
Z2
Radiation typeMo Kα
µ (mm1)8.38
Crystal size (mm)0.12 × 0.05 × 0.05
Data collection
DiffractometerKuma KM-4 CCD
diffractometer
Absorption correctionNumerical
(CrysAlis RED in KM-4 CCD Software; Oxford Diffraction, 2004)
Tmin, Tmax0.567, 0.897
No. of measured, independent and
observed [I > 2σ(I)] reflections
10097, 3403, 2853
Rint0.124
(sin θ/λ)max1)0.669
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.061, 0.157, 1.02
No. of reflections3403
No. of parameters208
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Re1—O31.715 (8)Re1—O21.727 (7)
Re1—O11.723 (7)Re1—O41.728 (7)
O3—Re1—O1109.0 (4)O3—Re1—O4109.9 (4)
O3—Re1—O2108.7 (4)O1—Re1—O4110.3 (4)
O1—Re1—O2110.3 (4)O2—Re1—O4108.6 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···N20.862.262.645 (11)108
N1—H1A···O1i0.862.072.763 (12)137
C1—H1···O4ii0.932.413.258 (14)151
C3—H3···O2iii0.932.463.185 (13)134
C4—H4···O2iv0.932.493.399 (13)166
C7—H7···O2iv0.932.603.505 (13)166
Symmetry codes: (i) x+1, y+1, z+1; (ii) x, y+1, z+1; (iii) x2, y, z; (iv) x+1, y, z+1.
 

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