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The title compound, (C4H12N5)[TlBr4], was crystallized from an aqueous solution containing [Tl(DMSO)6](ClO4)3, N,N-di­methyl­biguanide hydro­chloride and NaBr in a 1:1:3 molar ratio (DMSO is di­methyl sulfoxide). The geometry of [TlBr4] is a slightly distorted tetrahedron. The cation is protonated at one of the imino groups, and through this an intramolecular N—H...N hydrogen bond is formed, which stabilizes the conformation of the cation in the structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017853/cf6213sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017853/cf6213Isup2.hkl
Contains datablock I

CCDC reference: 200730

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](Tl-Br) = 0.002 Å
  • R factor = 0.052
  • wR factor = 0.110
  • Data-to-parameter ratio = 19.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N(2) - H(2A) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1994-1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1999); software used to prepare material for publication: SHELXTL.

1,1-Dimethylbiguanidium Tetrabromide-thallium(III) top
Crystal data top
C4H12N5+·TlBr4F(000) = 1168
Mr = 654.20Dx = 2.991 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1370 reflections
a = 10.191 (2) Åθ = 2.3–21.1°
b = 6.9540 (14) ŵ = 22.10 mm1
c = 20.544 (4) ÅT = 293 K
β = 93.77 (3)°Block, colourless
V = 1452.8 (5) Å30.23 × 0.11 × 0.11 mm
Z = 4
Data collection top
Bruker SMART5.0 CCD area-detector
diffractometer
2478 independent reflections
Radiation source: fine-focus sealed tube1494 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.073
ω scansθmax = 24.8°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1211
Tmin = 0.036, Tmax = 0.088k = 87
6686 measured reflectionsl = 2412
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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0365P)2]
where P = (Fo2 + 2Fc2)/3
2478 reflections(Δ/σ)max < 0.001
129 parametersΔρmax = 1.97 e Å3
0 restraintsΔρmin = 1.70 e Å3
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
Tl10.70962 (6)0.49259 (8)0.07178 (3)0.0476 (2)
Br10.84605 (17)0.6428 (2)0.02330 (7)0.0569 (5)
Br20.48134 (17)0.6420 (3)0.07722 (9)0.0708 (6)
Br30.7919 (2)0.6133 (4)0.17925 (9)0.0999 (8)
Br40.72811 (19)0.1318 (2)0.06499 (9)0.0780 (6)
C10.0941 (14)0.6304 (19)0.3138 (7)0.038 (4)
C20.1360 (14)0.7379 (19)0.2084 (7)0.038 (3)
C30.0885 (16)0.873 (2)0.1035 (7)0.061 (5)
H3A0.17710.86500.09040.091*
H3B0.04720.98650.08540.091*
H3C0.04020.76140.08800.091*
C40.0206 (18)1.0435 (19)0.2050 (8)0.072 (6)
H4A0.02091.02150.25110.109*
H4B0.06851.05080.18680.109*
H4C0.06511.16210.19700.109*
N10.0140 (13)0.4890 (17)0.2967 (5)0.062 (4)
H1A0.01510.41470.32600.074*
H1B0.00960.47070.25620.074*
N20.1178 (11)0.6352 (15)0.3754 (5)0.047 (3)
H2A0.08230.55190.39970.056*
H2B0.16920.72180.39270.056*
N30.1430 (11)0.7555 (15)0.2729 (5)0.037 (3)
N40.0902 (11)0.8801 (15)0.1734 (5)0.038 (3)
N50.1841 (12)0.5868 (16)0.1763 (5)0.052 (3)
H5A0.18340.58830.13440.062*
H5B0.21560.48910.19770.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Tl10.0453 (4)0.0570 (4)0.0398 (4)0.0032 (3)0.0037 (2)0.0059 (3)
Br10.0626 (12)0.0646 (11)0.0420 (10)0.0041 (9)0.0080 (8)0.0074 (8)
Br20.0521 (12)0.0772 (13)0.0809 (13)0.0087 (9)0.0119 (9)0.0306 (10)
Br30.0772 (16)0.171 (2)0.0482 (12)0.0246 (15)0.0184 (10)0.0032 (12)
Br40.0807 (15)0.0556 (11)0.0993 (16)0.0131 (10)0.0172 (12)0.0223 (10)
C10.044 (10)0.033 (8)0.036 (9)0.002 (7)0.003 (7)0.002 (7)
C20.040 (10)0.028 (8)0.047 (10)0.011 (7)0.003 (7)0.007 (7)
C30.088 (14)0.058 (11)0.036 (10)0.014 (10)0.005 (9)0.016 (8)
C40.108 (17)0.041 (11)0.065 (12)0.010 (9)0.027 (11)0.001 (8)
N10.081 (11)0.073 (9)0.029 (7)0.032 (8)0.014 (6)0.009 (7)
N20.070 (10)0.053 (8)0.016 (6)0.021 (7)0.005 (6)0.003 (5)
N30.046 (8)0.038 (7)0.027 (7)0.009 (6)0.002 (6)0.007 (5)
N40.052 (9)0.033 (7)0.026 (7)0.003 (6)0.008 (6)0.004 (5)
N50.094 (11)0.046 (7)0.015 (6)0.008 (7)0.003 (6)0.001 (5)
Geometric parameters (Å, º) top
Tl1—Br32.457 (2)C3—H3B0.960
Tl1—Br42.5207 (19)C3—H3C0.960
Tl1—Br22.5570 (18)C4—N41.508 (17)
Tl1—Br12.6827 (17)C4—H4A0.960
C1—N21.272 (15)C4—H4B0.960
C1—N11.311 (16)C4—H4C0.960
C1—N31.329 (15)N1—H1A0.860
C2—N41.291 (16)N1—H1B0.860
C2—N31.329 (15)N2—H2A0.860
C2—N51.351 (15)N2—H2B0.860
C3—N41.436 (15)N5—H5A0.860
C3—H3A0.960N5—H5B0.860
Br3—Tl1—Br4111.55 (8)N4—C4—H4B109.5
Br3—Tl1—Br294.56 (8)H4A—C4—H4B109.5
Br4—Tl1—Br2118.58 (6)N4—C4—H4C109.5
Br3—Tl1—Br1111.02 (7)H4A—C4—H4C109.5
Br4—Tl1—Br1107.64 (6)H4B—C4—H4C109.5
Br2—Tl1—Br1112.97 (6)C1—N1—H1A120.0
N2—C1—N1111.1 (12)C1—N1—H1B120.0
N2—C1—N3123.8 (13)H1A—N1—H1B120.0
N1—C1—N3125.1 (13)C1—N2—H2A120.0
N4—C2—N3118.6 (12)C1—N2—H2B120.0
N4—C2—N5117.0 (13)H2A—N2—H2B120.0
N3—C2—N5124.2 (13)C2—N3—C1124.9 (11)
N4—C3—H3A109.5C2—N4—C3120.6 (11)
N4—C3—H3B109.5C2—N4—C4120.0 (12)
H3A—C3—H3B109.5C3—N4—C4118.8 (11)
N4—C3—H3C109.5C2—N5—H5A120.0
H3A—C3—H3C109.5C2—N5—H5B120.0
H3B—C3—H3C109.5H5A—N5—H5B120.0
N4—C4—H4A109.5
N4—C2—N3—C1127.9 (14)N3—C2—N4—C3176.0 (13)
N5—C2—N3—C158 (2)N5—C2—N4—C32 (2)
N2—C1—N3—C2169.6 (14)N3—C2—N4—C413 (2)
N1—C1—N3—C212 (2)N5—C2—N4—C4172.9 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N50.862.773.188 (16)112
N5—H5B···N3i0.862.233.042 (15)158
N5—H5A···Br1ii0.862.793.520 (11)143
N2—H2B···Br1iii0.862.593.390 (11)155
N2—H2A···Br2i0.862.973.723 (10)148
N1—H1B···Br3iv0.862.673.312 (12)132
N1—H1A···Br2i0.862.753.538 (11)153
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1, y+1, z; (iii) x1/2, y+3/2, z+1/2; (iv) x1, y, z.
 

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