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The Hg atom in the title compound, (C13H16N2)[HgBr2I2], is coordinated by four halogen atoms in a tetra­hedral geometry. The four halogen atoms are each disordered between I and Br, with the I:Br ratios being 0.228 (3):0.772 (3), 0.333 (6):0.667 (6), 0.346 (6):0.654 (6) and 0.843 (7):0.157 (7).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027456/ci2387sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027456/ci2387Isup2.hkl
Contains datablock I

CCDC reference: 622694

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.012 Å
  • Disorder in main residue
  • R factor = 0.039
  • wR factor = 0.100
  • Data-to-parameter ratio = 20.1

checkCIF/PLATON results

No syntax errors found



Alert level A ABSTM02_ALERT_3_A Crystal and compound unsuitable for non-numerical corrections. Product of mu and tmid > 3.0 Value of mu given = 15.022 tmid = 0.300
Author Response: Answer as given above. The crystal structure is one of a series of related tetrahalogenomercurates.
PLAT061_ALERT_3_A Tmax/Tmin Range Test RR' too Large .............       0.13
Author Response: The transmission range was given by SADABS, which was run by assuming the presence of heavy atoms. If the it was run by assuming no heavy atoms, then the range would be much smaller.
PLAT065_ALERT_3_A Crystal Requires Numerical Correction mu*tmid ..       4.51
Author Response: The crystals do not have well-formed faces for a numerical correction. The value is somewhat larger than the cutoff of 3.0, but as the structure seems to have refined smoothly, the correction is alright.

Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.25 Ratio PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.18 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C2 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1 PLAT301_ALERT_3_C Main Residue Disorder ......................... 17.00 Perc. PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 12
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 96
3 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 6 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The preceding study reports the structure of a tetrahedral dibromidodichloridomercurate(II), which has been isolated as the 1,2-ethanedipyridinium salt (Wang et al., 2007). Replacing the cation by 1,3-propanedipyridinium furnishes a similar tetrahalomercurate. The anion of the salt is composed 2.25 bromines and 1.75 iodines; the metal atom shows tetrahedral coordination (Fig. 1). Selected bond distances are given in Table 1.

Related literature top

For related tetrahalogenomercurates, see the preceding paper by Wang et al. (2007).

Experimental top

The salt was synthesized from the reaction of propane-1,3-dipyridinium dibromide (0.036 g, 0.1 mmol) in methanol (5 ml) and mercuric iodide (0.091 g, 0.2 mmol) in DMF (10 ml). The mixture was set aside for the formation of colorless crystals in 30% yield after several days.

Refinement top

The four halogens lie in general positions. Initial attempts to refine the structure with either four bromines or four iodines gave unacceptably high R-indices and large peaks/deep holes. The four halogen atoms were then refined as four (Br+I) mixtures; one attempt allowed the mixtures to have the same displacement parameters as well as sharing the same site. A second attempt had the components having the same displacement parameters only. The second led to a formulation consisting of approximately of 2.25 Br and 1.75 I atoms. The use of a restraint that fixed the number of Br and I atoms as exactly 2.25 Br and 1.75 I led to occupancies of 0.772 (3), 0.667 (6), 0.654 (6) and 0.157 (7), respectively, for Br1, Br2, Br3 and Br4, and 0.228 (3), 0.333 (6), 0.346 (6) and 0.843 (7), respectively, for I1, I2, I3 and I4.

The anion is [HgBr2.25I1.75]2-, but because it has nearly two bromine and two iodine atoms, it is regarded as [HgBr2I2] for the purpose of naming the compound. The formulation is in fair agreement with CH&N elemental analysis. The refinement for a [C13H16N2] [HgBr2.5I1.5] formulation is not significantly distinguishable in the R index, however.

Disorder also affected the cation; the pyridyl ring was refined as a rigid hexagon (C—C = C—N = 1.39 Å). The C(sp3)—C(sp3) distance was restrained to 1.50 (1) Å, and the N···C(sp3) distance to 2.45 (1) Å. The displacement parameters of atoms of the cation were restrained to be nearly isotropic. C-bound H atoms were positioned geometrically (C–H = 0.93 and 0.97 Å), and were included in the refinement in the riding model approximation, with Uiso(H) = 1.2Ueq(C).

The final difference Fourier map had a large peak at 0.93 Å from Hg1, but was otherwise featureless.

Structure description top

The preceding study reports the structure of a tetrahedral dibromidodichloridomercurate(II), which has been isolated as the 1,2-ethanedipyridinium salt (Wang et al., 2007). Replacing the cation by 1,3-propanedipyridinium furnishes a similar tetrahalomercurate. The anion of the salt is composed 2.25 bromines and 1.75 iodines; the metal atom shows tetrahedral coordination (Fig. 1). Selected bond distances are given in Table 1.

For related tetrahalogenomercurates, see the preceding paper by Wang et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. The molecular structure of [C13H16N2][HgBr2I2]. Displacement ellipsoids drawn at the 50% probability level. The bromine and iodine atoms are disordered; the figure depicts the anion as an [HgX4]2- species. Hydrogen atoms are drawn as spheres of arbitrary radius.
1,1'-(Propane-1,3-diyl)dipyridinium dibromidodiiodidomercurate(II) top
Crystal data top
(C13H16N2)[HgBr2I2]F(000) = 1438
Mr = 802.74Dx = 2.690 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3755 reflections
a = 8.297 (2) Åθ = 2.6–23.5°
b = 15.431 (4) ŵ = 15.02 mm1
c = 15.563 (4) ÅT = 295 K
β = 95.984 (5)°Block, colourless
V = 1981.8 (9) Å30.30 × 0.30 × 0.26 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer
3482 independent reflections
Radiation source: fine-focus sealed tube2630 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.011, Tmax = 0.111k = 1818
14070 measured reflectionsl = 1818
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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0445P)2 + 4.75P]
where P = (Fo2 + 2Fc2)/3
3482 reflections(Δ/σ)max = 0.001
173 parametersΔρmax = 1.19 e Å3
96 restraintsΔρmin = 0.75 e Å3
Crystal data top
(C13H16N2)[HgBr2I2]V = 1981.8 (9) Å3
Mr = 802.74Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.297 (2) ŵ = 15.02 mm1
b = 15.431 (4) ÅT = 295 K
c = 15.563 (4) Å0.30 × 0.30 × 0.26 mm
β = 95.984 (5)°
Data collection top
Bruker APEX area-detector
diffractometer
3482 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2630 reflections with I > 2σ(I)
Tmin = 0.011, Tmax = 0.111Rint = 0.046
14070 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03996 restraints
wR(F2) = 0.100H-atom parameters constrained
S = 1.01Δρmax = 1.19 e Å3
3482 reflectionsΔρmin = 0.75 e Å3
173 parameters
Special details top

Experimental. The crystals do not have well formed faces for a numerical correction. The value is somewhat larger than the cutoff of 3.0, but as the structure seems to have refined smoothly, the correction is alright.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Hg10.25202 (5)0.20536 (2)0.28986 (2)0.06365 (15)
I10.478 (3)0.3426 (13)0.2693 (18)0.0854 (11)0.228 (3)
I20.419 (2)0.0865 (8)0.3686 (12)0.0679 (12)0.333 (6)
I30.134 (3)0.1381 (19)0.1346 (19)0.0669 (17)0.346 (6)
I40.0046 (2)0.27339 (11)0.36694 (10)0.0720 (5)0.843 (7)
Br10.4644 (13)0.3249 (5)0.2738 (7)0.0854 (11)0.772 (3)
Br20.4084 (16)0.0665 (5)0.3778 (9)0.0679 (12)0.667 (6)
Br30.164 (2)0.1474 (15)0.1304 (15)0.0669 (17)0.654 (6)
Br40.0355 (19)0.2486 (10)0.3560 (10)0.0720 (5)0.157 (7)
N10.6071 (6)0.1678 (3)0.0538 (4)0.0562 (18)
C10.6774 (8)0.1293 (5)0.0139 (4)0.089 (3)
H10.68730.16030.06430.106*
C20.7330 (9)0.0444 (5)0.0062 (6)0.118 (5)
H20.78010.01860.05150.142*
C30.7182 (10)0.0020 (3)0.0691 (8)0.116 (5)
H30.75540.05880.07420.139*
C40.6479 (10)0.0366 (5)0.1368 (6)0.106 (4)
H40.63800.00550.18720.127*
C50.5923 (8)0.1215 (5)0.1292 (3)0.075 (3)
H50.54530.14720.17440.090*
N20.9334 (6)0.3771 (3)0.1315 (4)0.0609 (19)
C61.0535 (7)0.3751 (4)0.0756 (4)0.073 (3)
H61.05770.32950.03680.087*
C71.1673 (7)0.4414 (5)0.0775 (5)0.082 (3)
H71.24760.44010.04010.098*
C81.1611 (8)0.5096 (4)0.1354 (5)0.095 (4)
H81.23720.55390.13670.114*
C91.0410 (10)0.5116 (4)0.1913 (5)0.087 (3)
H91.03680.55720.23010.104*
C100.9272 (7)0.4453 (4)0.1894 (4)0.073 (3)
H100.84680.44660.22680.087*
C110.5536 (10)0.2563 (6)0.0483 (7)0.075 (3)
H11A0.49130.26840.09630.090*
H11B0.48230.26390.00460.090*
C120.6891 (10)0.3202 (5)0.0496 (6)0.068 (3)
H12A0.64500.37850.04880.081*
H12B0.74420.31280.00190.081*
C130.8085 (10)0.3095 (6)0.1278 (5)0.067 (3)
H13A0.75230.31250.17930.081*
H13B0.85930.25300.12630.081*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0598 (2)0.0770 (3)0.0551 (2)0.00921 (18)0.01045 (17)0.01326 (18)
I10.084 (2)0.079 (3)0.0980 (15)0.025 (2)0.0357 (12)0.027 (3)
I20.0654 (16)0.055 (4)0.080 (3)0.006 (3)0.0092 (15)0.007 (3)
I30.064 (5)0.081 (4)0.0569 (19)0.001 (3)0.011 (3)0.016 (2)
I40.0786 (10)0.0844 (10)0.0582 (6)0.0220 (6)0.0310 (6)0.0064 (6)
Br10.084 (2)0.079 (3)0.0980 (15)0.025 (2)0.0357 (12)0.027 (3)
Br20.0654 (16)0.055 (4)0.080 (3)0.006 (3)0.0092 (15)0.007 (3)
Br30.064 (5)0.081 (4)0.0569 (19)0.001 (3)0.011 (3)0.016 (2)
Br40.0786 (10)0.0844 (10)0.0582 (6)0.0220 (6)0.0310 (6)0.0064 (6)
N10.048 (4)0.070 (5)0.051 (4)0.007 (4)0.005 (3)0.002 (4)
C10.101 (9)0.105 (9)0.065 (7)0.037 (7)0.031 (6)0.015 (6)
C20.119 (11)0.089 (9)0.152 (14)0.017 (8)0.041 (10)0.057 (9)
C30.090 (9)0.069 (8)0.184 (16)0.016 (7)0.013 (10)0.020 (10)
C40.096 (9)0.088 (9)0.127 (12)0.025 (7)0.015 (9)0.029 (8)
C50.073 (7)0.094 (8)0.060 (7)0.007 (6)0.011 (5)0.013 (6)
N20.055 (5)0.071 (5)0.058 (5)0.005 (4)0.009 (4)0.002 (4)
C60.069 (7)0.080 (7)0.072 (7)0.007 (5)0.020 (5)0.002 (5)
C70.069 (7)0.098 (8)0.082 (8)0.004 (6)0.023 (6)0.019 (6)
C80.078 (8)0.098 (9)0.106 (10)0.010 (7)0.009 (7)0.004 (8)
C90.091 (8)0.078 (7)0.087 (8)0.006 (6)0.009 (7)0.027 (6)
C100.068 (7)0.095 (8)0.057 (6)0.022 (6)0.008 (5)0.004 (5)
C110.069 (7)0.076 (7)0.077 (7)0.005 (6)0.007 (6)0.008 (5)
C120.065 (6)0.063 (6)0.073 (7)0.001 (5)0.007 (5)0.010 (5)
C130.061 (6)0.083 (7)0.060 (6)0.001 (5)0.016 (5)0.007 (5)
Geometric parameters (Å, º) top
Hg1—I22.534 (14)N2—C61.39
Hg1—Br12.582 (6)N2—C101.39
Hg1—Br22.79 (1)N2—C131.467 (9)
Hg1—Br32.67 (2)C6—C71.39
Hg1—Br42.78 (1)C6—H60.93
Hg1—I42.6963 (14)C7—C81.39
Hg1—I32.72 (3)C7—H70.93
Hg1—I12.868 (16)C8—C91.39
N1—C11.39C8—H80.93
N1—C51.39C9—C101.39
N1—C111.435 (11)C9—H90.93
C1—C21.39C10—H100.93
C1—H10.93C11—C121.494 (7)
C2—C31.39C11—H11A0.97
C2—H20.93C11—H11B0.97
C3—C41.39C12—C131.495 (8)
C3—H30.93C12—H12A0.97
C4—C51.39C12—H12B0.97
C4—H40.93C13—H13A0.97
C5—H50.93C13—H13B0.97
I2—Hg1—Br1102.8 (4)C5—C4—C3120.0
I2—Hg1—Br3106.8 (7)C5—C4—H4120.0
Br1—Hg1—Br3105.8 (4)C3—C4—H4120.0
I2—Hg1—I4118.0 (4)C4—C5—N1120.0
Br1—Hg1—I4108.9 (2)C4—C5—H5120.0
Br3—Hg1—I4113.4 (4)N1—C5—H5120.0
I2—Hg1—I3106.3 (8)C6—N2—C10120.0
Br1—Hg1—I3111.9 (5)C6—N2—C13120.6 (6)
Br3—Hg1—I36.3 (6)C10—N2—C13119.3 (6)
I4—Hg1—I3108.9 (5)C7—C6—N2120.0
I2—Hg1—Br4116.2 (5)C7—C6—H6120.0
Br1—Hg1—Br4119.1 (4)N2—C6—H6120.0
Br3—Hg1—Br4105.3 (5)C6—C7—C8120.0
I4—Hg1—Br410.9 (3)C6—C7—H7120.0
I3—Hg1—Br4100.3 (6)C8—C7—H7120.0
I2—Hg1—Br25.3 (6)C9—C8—C7120.0
Br1—Hg1—Br2108.0 (4)C9—C8—H8120.0
Br3—Hg1—Br2105.5 (6)C7—C8—H8120.0
I4—Hg1—Br2114.7 (3)C8—C9—C10120.0
I3—Hg1—Br2104.4 (7)C8—C9—H9120.0
Br4—Hg1—Br2112.1 (4)C10—C9—H9120.0
I2—Hg1—I1105.0 (7)C9—C10—N2120.0
Br1—Hg1—I12.3 (9)C9—C10—H10120.0
Br3—Hg1—I1105.2 (6)N2—C10—H10120.0
I4—Hg1—I1107.4 (5)N1—C11—C12113.5 (7)
I3—Hg1—I1111.2 (7)N1—C11—H11A108.9
Br4—Hg1—I1117.4 (6)C12—C11—H11A108.9
Br2—Hg1—I1110.3 (6)N1—C11—H11B108.9
Br4—I4—Hg193.3 (16)C12—C11—H11B108.9
I4—Br4—Hg175.8 (16)H11A—C11—H11B107.7
C1—N1—C5120.0C11—C12—C13111.9 (6)
C1—N1—C11120.9 (6)C11—C12—H12A109.2
C5—N1—C11119.1 (6)C13—C12—H12A109.2
C2—C1—N1120.0C11—C12—H12B109.2
C2—C1—H1120.0C13—C12—H12B109.2
N1—C1—H1120.0H12A—C12—H12B107.9
C1—C2—C3120.0N2—C13—C12111.1 (6)
C1—C2—H2120.0N2—C13—H13A109.4
C3—C2—H2120.0C12—C13—H13A109.4
C2—C3—C4120.0N2—C13—H13B109.4
C2—C3—H3120.0C12—C13—H13B109.4
C4—C3—H3120.0H13A—C13—H13B108.0
I2—Hg1—I4—Br483.3 (19)I1—Hg1—Br4—I423 (2)
Br1—Hg1—I4—Br4160.2 (18)C11—N1—C1—C2178.0 (6)
Br3—Hg1—I4—Br442.6 (19)C11—N1—C5—C4178.0 (6)
I3—Hg1—I4—Br437.9 (19)C13—N2—C6—C7177.5 (6)
Br2—Hg1—I4—Br478.7 (19)C13—N2—C10—C9177.5 (6)
I1—Hg1—I4—Br4158.4 (19)C1—N1—C11—C1268.6 (9)
I2—Hg1—Br4—I4102.2 (18)C5—N1—C11—C12109.4 (8)
Br1—Hg1—Br4—I422 (2)N1—C11—C12—C1355.9 (12)
Br3—Hg1—Br4—I4139.9 (18)C6—N2—C13—C1273.2 (9)
I3—Hg1—Br4—I4143.8 (19)C10—N2—C13—C12104.3 (8)
Br2—Hg1—Br4—I4105.9 (18)C11—C12—C13—N2175.5 (8)

Experimental details

Crystal data
Chemical formula(C13H16N2)[HgBr2I2]
Mr802.74
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.297 (2), 15.431 (4), 15.563 (4)
β (°) 95.984 (5)
V3)1981.8 (9)
Z4
Radiation typeMo Kα
µ (mm1)15.02
Crystal size (mm)0.30 × 0.30 × 0.26
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.011, 0.111
No. of measured, independent and
observed [I > 2σ(I)] reflections
14070, 3482, 2630
Rint0.046
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.100, 1.01
No. of reflections3482
No. of parameters173
No. of restraints96
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.19, 0.75

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Selected bond lengths (Å) top
Hg1—I22.534 (14)Hg1—Br42.78 (1)
Hg1—Br12.582 (6)Hg1—I42.6963 (14)
Hg1—Br22.79 (1)Hg1—I32.72 (3)
Hg1—Br32.67 (2)Hg1—I12.868 (16)
 

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