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Acta Cryst. (2007). E63, m2533    [ doi:10.1107/S1600536807044133 ]

Bis(2-Amino-6-methylpyridinium) aquatetrabromidooxidorhenate(V) bromide

A. Kochel

Abstract top

The title compound, (C6H9N2)2·[ReO(H2O)Br4]·Br, is a molecular salt incorporating rhenium(V)-containing oxoanions. The oxoanion shows a distorted trans-ReO2Br4 geometry. In the crystal structure, the component species are connected via N-H...Br and O-H...Br interactions.

Comment top

This paper reports the crystal structure of a molecular salt containing the [ReVO(H2O)Br4]− anion. All atoms lie on general positions (Fig. 1). The [ReO(H2O)Br4]− anion in (I) shows a distorted trans-ReO2Br4 octahedral geometry about the central Re(V) ion (Table 1). The water molecule is weakly coordinated to rhenium at the base of octahedron with a Re—O distance of 2.206 (3) Å. The Re—Br bond lengths in (I) agree with those in related crystal structures (Abram et al., 1996; Chiozzone et al., 2006; Kochel, 2007).

In the crystal, the component species interact via N—H···Br and O—H···Br hydrogen bonds (Table 2), resulting in alternating layers of anions and cations perpendicular to [010] The shortest Re···Re distances in (I) are 6.819 (3) Å for Re1···Re1i (i = −x, −y + 2, −z + 1) and 8.546 (4) Å for Re1···Re2i (i = −x − 1, −y + 2, −z).

Related literature top

For related structures, see: Abram et al. (1996); Chiozzone et al. (2006); Kochel (2007). For synthetic background, see: Watt & Thompson (1963).

Experimental top

(NH4)2ReBr6 was obtained by the method of Watt & Thompson (1963). A mixture of (NH4)2ReBr6 (0.33 g) and 2-amino-6-methylpyridine (0.80 g) was dissolved in 50- ml of ethanol solution, which was heated at 323 K for 10 h followed by slow cooling. After the reaction the mixture colour was yellow–orange. The solution was filtered and the filtrate was left standing for evaporation. After five days, orange plates of (I) appeared. Anal. Calc for C12H20Br5N4O2Re: C 17.19, H 2.57, N 6.68%; found C 16.34, H 2.30, N 6.54%. IR (KBr): 1195(versus), 1200(s), 990(m), 950(s), 1054(m), 980(s), 873(m), 810(s), 730(m), 310(s), 174(m), 159(m).

Refinement top

The N– and O-bound H atoms were located in difference maps and their positions were freely refined with Uiso(H) = 1.2Ueq(carrier). The C-bound H atoms were placed in idealized positions (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C).

The highest difference peak is 0.59Å from Re1. The deepest difference hole is 0.68Å from Re1.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); XP (Bruker, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. The crystal packing in (I).
Bis(2-Amino-6-methylpyridinium) aquatetrabromidooxidorhenate(V) bromide top
Crystal data top
(C6H9N2)2·[ReO(H2O)Br4]·BrF000 = 1544
Mr = 838.07Dx = 2.574 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5614 reflections
a = 11.996 (2) Åθ = 2.7–36.7º
b = 12.154 (3) ŵ = 14.87 mm−1
c = 18.206 (3) ÅT = 100 (2) K
β = 125.43 (2)ºPrism, orange
V = 2162.9 (7) Å30.08 × 0.08 × 0.07 mm
Z = 4
Data collection top
Kuma KM4 CCD
diffractometer		10288 independent reflections
Radiation source: fine-focus sealed tube5873 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.080
T = 100(2) Kθmax = 36.7º
ω scansθmin = 2.7º
Absorption correction: numerical
(CrysAlis [CrysAlis RED?]; Oxford Diffraction, 2003)		h = −19→19
Tmin = 0.340, Tmax = 0.563k = −18→20
40507 measured reflectionsl = −30→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.069  w = 1/[σ2(Fo2) + (0.0236P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.92(Δ/σ)max = 0.001
10288 reflectionsΔρmax = 2.13 e Å−3
243 parametersΔρmin = −2.32 e Å−3
8 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
(C6H9N2)2·[ReO(H2O)Br4]·BrV = 2162.9 (7) Å3
Mr = 838.07Z = 4
Monoclinic, P21/cMo Kα
a = 11.996 (2) ŵ = 14.87 mm−1
b = 12.154 (3) ÅT = 100 (2) K
c = 18.206 (3) Å0.08 × 0.08 × 0.07 mm
β = 125.43 (2)º
Data collection top
Kuma KM4 CCD
diffractometer		10288 independent reflections
Absorption correction: numerical
(CrysAlis [CrysAlis RED?]; Oxford Diffraction, 2003)		5873 reflections with I > 2σ(I)
Tmin = 0.340, Tmax = 0.563Rint = 0.080
40507 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0398 restraints
wR(F2) = 0.069H atoms treated by a mixture of
independent and constrained refinement
S = 0.92Δρmax = 2.13 e Å−3
10288 reflectionsΔρmin = −2.32 e Å−3
243 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 > 2sigma(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
N10.4220 (4)0.6746 (3)0.9044 (2)0.0208 (7)
H1N0.409 (5)0.7471 (18)0.911 (3)0.025*
N20.1884 (4)0.6673 (3)0.8315 (3)0.0324 (9)
H2N0.104 (3)0.634 (4)0.797 (3)0.039*
H3N0.193 (5)0.7408 (18)0.844 (3)0.039*
C20.3048 (4)0.6156 (3)0.8599 (3)0.0229 (9)
C30.3142 (5)0.5033 (3)0.8462 (3)0.0271 (10)
H30.23660.45910.81730.033*
C40.4377 (5)0.4602 (4)0.8757 (3)0.0310 (11)
H40.44400.38610.86580.037*
C50.5566 (5)0.5257 (4)0.9212 (3)0.0318 (11)
H50.64060.49530.94060.038*
C60.5479 (4)0.6329 (4)0.9365 (3)0.0261 (9)
C70.6656 (5)0.7116 (5)0.9858 (4)0.0397 (13)
H7A0.67610.73641.03960.060*
H7B0.64820.77360.94780.060*
H7C0.74780.67531.00160.060*
N30.1990 (3)0.6251 (3)0.5887 (2)0.0182 (7)
H4N0.265 (3)0.621 (4)0.578 (3)0.022*
N40.2592 (4)0.4446 (3)0.6379 (3)0.0278 (8)
H5N0.334 (3)0.457 (4)0.639 (3)0.033*
H6N0.239 (5)0.379 (2)0.653 (3)0.033*
C110.1736 (4)0.5308 (3)0.6153 (3)0.0205 (8)
C120.0562 (5)0.5275 (4)0.6155 (3)0.0275 (10)
H120.03240.46320.63110.033*
C13−0.0216 (5)0.6198 (4)0.5926 (3)0.0321 (11)
H13−0.09800.61870.59380.039*
C140.0113 (5)0.7163 (4)0.5672 (3)0.0288 (10)
H14−0.04210.77910.55270.035*
C150.1211 (4)0.7179 (3)0.5638 (3)0.0212 (8)
C160.1635 (4)0.8130 (3)0.5331 (3)0.0250 (9)
H16A0.15120.79430.47760.038*
H16B0.25810.82960.57810.038*
H16C0.10860.87600.52390.038*
Re1−0.237586 (16)0.926025 (12)0.281334 (11)0.01677 (4)
Br1−0.06351 (4)1.03636 (3)0.27687 (3)0.02292 (9)
Br2−0.38484 (4)1.09524 (3)0.23272 (3)0.02134 (9)
Br3−0.44110 (4)0.81224 (3)0.23999 (3)0.02152 (9)
Br4−0.12108 (4)0.75203 (3)0.28299 (3)0.02382 (9)
O1−0.3328 (3)0.9120 (2)0.1355 (2)0.0197 (6)
O2−0.1646 (3)0.9336 (2)0.3918 (2)0.0248 (6)
Br50.34325 (4)0.88956 (3)0.98187 (3)0.02261 (9)
H1W−0.324 (5)0.978 (2)0.111 (3)0.027*
H2W−0.426 (2)0.897 (4)0.088 (2)0.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0184 (17)0.0190 (16)0.027 (2)−0.0032 (14)0.0139 (16)−0.0034 (14)
N20.0181 (19)0.029 (2)0.041 (3)−0.0060 (17)0.0119 (19)−0.0156 (18)
C20.024 (2)0.025 (2)0.020 (2)−0.0060 (18)0.0128 (19)−0.0040 (17)
C30.035 (3)0.023 (2)0.029 (3)−0.0080 (19)0.021 (2)−0.0075 (18)
C40.045 (3)0.022 (2)0.026 (2)0.008 (2)0.021 (2)−0.0002 (18)
C50.026 (2)0.039 (3)0.029 (3)0.014 (2)0.015 (2)−0.001 (2)
C60.021 (2)0.037 (2)0.024 (2)−0.0022 (19)0.015 (2)−0.0027 (19)
C70.021 (2)0.054 (3)0.047 (3)−0.012 (2)0.021 (2)−0.015 (3)
N30.0143 (16)0.0228 (17)0.0180 (17)0.0015 (14)0.0096 (15)−0.0032 (13)
N40.031 (2)0.0208 (19)0.035 (2)0.0061 (17)0.0214 (19)0.0049 (16)
C110.024 (2)0.0206 (19)0.014 (2)−0.0007 (17)0.0095 (18)0.0008 (15)
C120.024 (2)0.034 (2)0.028 (3)−0.0007 (19)0.017 (2)0.0030 (19)
C130.022 (2)0.045 (3)0.037 (3)0.004 (2)0.021 (2)0.006 (2)
C140.021 (2)0.029 (2)0.034 (3)0.0073 (19)0.015 (2)0.004 (2)
C150.022 (2)0.0206 (19)0.018 (2)0.0020 (17)0.0097 (18)0.0008 (16)
C160.022 (2)0.0187 (19)0.027 (2)0.0003 (17)0.010 (2)0.0014 (17)
Re10.01591 (7)0.01429 (7)0.01882 (8)0.00079 (6)0.00933 (6)0.00002 (6)
Br10.0185 (2)0.01779 (18)0.0319 (2)−0.00143 (16)0.01433 (19)−0.00067 (16)
Br20.0206 (2)0.01803 (18)0.0250 (2)0.00517 (15)0.01295 (18)0.00171 (15)
Br30.0198 (2)0.02158 (19)0.0243 (2)−0.00228 (16)0.01344 (18)0.00220 (16)
Br40.0198 (2)0.01426 (18)0.0349 (3)0.00186 (15)0.01442 (19)−0.00040 (16)
O10.0256 (15)0.0159 (13)0.0201 (15)0.0004 (12)0.0147 (13)0.0013 (11)
O20.0258 (15)0.0221 (14)0.0218 (16)0.0022 (13)0.0111 (13)0.0022 (12)
Br50.0247 (2)0.02478 (19)0.0205 (2)−0.00570 (17)0.01438 (18)−0.00151 (16)
Geometric parameters (Å, °) top
N1—C21.352 (5)N4—H5N0.903 (19)
N1—C61.363 (5)N4—H6N0.920 (19)
N1—H1N0.913 (19)C11—C121.411 (6)
N2—C21.331 (6)C12—C131.361 (6)
N2—H2N0.922 (19)C12—H120.9300
N2—H3N0.915 (19)C13—C141.399 (6)
C2—C31.404 (6)C13—H130.9300
C3—C41.354 (6)C14—C151.354 (6)
C3—H30.9300C14—H140.9300
C4—C51.410 (7)C15—C161.496 (6)
C4—H40.9300C16—H16A0.9600
C5—C61.349 (6)C16—H16B0.9600
C5—H50.9300C16—H16C0.9600
C6—C71.498 (6)Re1—O21.667 (3)
C7—H7A0.9600Re1—O12.206 (3)
C7—H7B0.9600Re1—Br32.5117 (6)
C7—H7C0.9600Re1—Br22.5141 (6)
N3—C111.347 (5)Re1—Br12.5223 (5)
N3—C151.363 (5)Re1—Br42.5254 (6)
N3—H4N0.920 (19)O1—H1W0.948 (19)
N4—C111.354 (5)O1—H2W0.955 (19)
C2—N1—C6124.7 (4)C13—C12—C11118.9 (4)
C2—N1—H1N113 (3)C13—C12—H12120.6
C6—N1—H1N122 (3)C11—C12—H12120.6
C2—N2—H2N124 (3)C12—C13—C14121.2 (4)
C2—N2—H3N118 (3)C12—C13—H13119.4
H2N—N2—H3N118 (4)C14—C13—H13119.4
N2—C2—N1118.4 (4)C15—C14—C13119.7 (4)
N2—C2—C3124.3 (4)C15—C14—H14120.2
N1—C2—C3117.3 (4)C13—C14—H14120.2
C4—C3—C2119.2 (4)C14—C15—N3118.1 (4)
C4—C3—H3120.4C14—C15—C16125.4 (4)
C2—C3—H3120.4N3—C15—C16116.5 (4)
C3—C4—C5121.1 (4)C15—C16—H16A109.5
C3—C4—H4119.5C15—C16—H16B109.5
C5—C4—H4119.5H16A—C16—H16B109.5
C6—C5—C4119.6 (4)C15—C16—H16C109.5
C6—C5—H5120.2H16A—C16—H16C109.5
C4—C5—H5120.2H16B—C16—H16C109.5
C5—C6—N1118.1 (4)O2—Re1—O1178.68 (12)
C5—C6—C7125.6 (4)O2—Re1—Br397.54 (10)
N1—C6—C7116.4 (4)O1—Re1—Br382.06 (8)
C6—C7—H7A109.5O2—Re1—Br298.64 (10)
C6—C7—H7B109.5O1—Re1—Br282.62 (7)
H7A—C7—H7B109.5Br3—Re1—Br288.99 (2)
C6—C7—H7C109.5O2—Re1—Br198.28 (10)
H7A—C7—H7C109.5O1—Re1—Br182.12 (8)
H7B—C7—H7C109.5Br3—Re1—Br1164.174 (16)
C11—N3—C15124.7 (3)Br2—Re1—Br188.83 (2)
C11—N3—H4N116 (3)O2—Re1—Br497.56 (10)
C15—N3—H4N119 (3)O1—Re1—Br481.18 (7)
C11—N4—H5N116 (3)Br3—Re1—Br488.71 (2)
C11—N4—H6N118 (3)Br2—Re1—Br4163.793 (16)
H5N—N4—H6N125 (4)Br1—Re1—Br489.02 (2)
N3—C11—N4118.5 (4)Re1—O1—H1W112 (3)
N3—C11—C12117.4 (4)Re1—O1—H2W129 (3)
N4—C11—C12124.1 (4)H1W—O1—H2W97 (4)
C6—N1—C2—N2−179.4 (4)C15—N3—C11—N4179.7 (4)
C6—N1—C2—C30.2 (6)C15—N3—C11—C121.5 (6)
N2—C2—C3—C4178.0 (4)N3—C11—C12—C13−2.6 (6)
N1—C2—C3—C4−1.6 (6)N4—C11—C12—C13179.2 (4)
C2—C3—C4—C51.2 (7)C11—C12—C13—C141.4 (7)
C3—C4—C5—C60.6 (7)C12—C13—C14—C151.1 (7)
C4—C5—C6—N1−2.0 (7)C13—C14—C15—N3−2.2 (7)
C4—C5—C6—C7178.3 (5)C13—C14—C15—C16176.5 (4)
C2—N1—C6—C51.6 (6)C11—N3—C15—C141.0 (6)
C2—N1—C6—C7−178.7 (4)C11—N3—C15—C16−177.8 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Br50.92 (3)2.54 (5)3.354 (4)148 (5)
O1—H1W···Br5i0.95 (4)2.25 (4)3.176 (3)165 (4)
N2—H2N···Br1ii0.92 (5)2.76 (5)3.573 (5)148 (4)
N2—H2N···Br4ii0.92 (5)2.91 (5)3.424 (6)117 (4)
O1—H2W···Br5iii0.95 (3)2.28 (3)3.225 (4)170 (4)
N2—H3N···Br50.92 (2)2.75 (4)3.514 (4)141 (3)
N3—H4N···Br5iv0.92 (5)2.42 (5)3.273 (4)154 (4)
N4—H5N···Br2v0.90 (5)2.83 (5)3.592 (6)143 (4)
N4—H6N···Br4vi0.92 (4)2.79 (5)3.647 (5)155 (5)
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x−1, y, z−1; (iv) x, −y+3/2, z−1/2; (v) x+1, −y+3/2, z+1/2; (vi) −x, −y+1, −z+1.
Selected geometric parameters (Å) top
Re1—O21.667 (3)Re1—Br22.5141 (6)
Re1—O12.206 (3)Re1—Br12.5223 (5)
Re1—Br32.5117 (6)Re1—Br42.5254 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···Br50.92 (3)2.54 (5)3.354 (4)148 (5)
O1—H1W···Br5i0.95 (4)2.25 (4)3.176 (3)165 (4)
N2—H2N···Br1ii0.92 (5)2.76 (5)3.573 (5)148 (4)
N2—H2N···Br4ii0.92 (5)2.91 (5)3.424 (6)117 (4)
O1—H2W···Br5iii0.95 (3)2.28 (3)3.225 (4)170 (4)
N2—H3N···Br50.92 (2)2.75 (4)3.514 (4)141 (3)
N3—H4N···Br5iv0.92 (5)2.42 (5)3.273 (4)154 (4)
N4—H5N···Br2v0.90 (5)2.83 (5)3.592 (6)143 (4)
N4—H6N···Br4vi0.92 (4)2.79 (5)3.647 (5)155 (5)
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x−1, y, z−1; (iv) x, −y+3/2, z−1/2; (v) x+1, −y+3/2, z+1/2; (vi) −x, −y+1, −z+1.
references
References top

Abram, U., Hubener, R., Alberta, R. & Schibili, R. (1996). Z. Anorg. Allg. Chem. 622, 813–818.

Bruker (1999). XP. Bruker AXS Inc., Madison, Wisconsin, USA. [Please provide full details for missing reference]

Chiozzone, R., Cuevas, A., Gonzales, R., Kremer, C., Armentano, D., De Munno, G. & Faus, J. (2006). Inorg. Chim. Acta, 359, 2194–2200.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?. [Reference not cited - may it be removed?]

Kochel, A. (2007). Acta Cryst. E63, m1968–?.

Oxford Diffraction (2003). CrysAlis CCD and CrysAlis RED. Versions 1.171.30. Oxford Diffraction Poland, Wrocław, Poland.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.

Watt, G. W. & Thompson, R. J. (1963). Inorg. Synth. 7, 190–192.