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The Cd atom in the title compound, (C13H16N2)[CdBr2Cl2], is coordinated by four halogen atoms in a tetra­hedral geometry. The four halogen atoms are each disordered between Br and Cl, with the Br:Cl ratios being approximately 0.5:0.5, 0.6:0.4, 0.4:0.6 and 0.8:0.2.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025597/wn2142sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025597/wn2142Isup2.hkl
Contains datablock I

CCDC reference: 654685

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.012 Å
  • Disorder in main residue
  • R factor = 0.037
  • wR factor = 0.121
  • Data-to-parameter ratio = 16.0

checkCIF/PLATON results

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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 ..................... 0.95 PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 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 FORMU01_ALERT_1_G There is a discrepancy between the atom counts in the _chemical_formula_sum and _chemical_formula_moiety. This is usually due to the moiety formula being in the wrong format. Atom count from _chemical_formula_sum: C13 H16 Br2.25 Cd1 Cl1.75 N Atom count from _chemical_formula_moiety: PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 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 paper reports the structure of the tetrahedral dibromidodichloridocadmate(II), which has been isolated as the 1,2-ethanedipyridinium salt (Liu et al., 2007). The structure of propyl-1,3-di(4-pyridinium) tetrabromidocadmate(II) has been reported in the non-centrosymmetric space group Cc (Kao & Chen, 2004). The title compound, [C13H16N2][CdBr2Cl2] is not, however, isostructural. The cadmium atom in the centrosymmetric structure is coordinated by four halogen atoms in a tetrahedral geometry; the halogen atoms are disordered (Fig. 1). The cations and anions do not have signification interactions with each other.

Related literature top

For related literature, see: Kao & Chen (2004); Liu et al. (2007).

Experimental top

The salt was synthesized from the reaction of 1,3-propanedipyridinium dibromide (0.036 g, 0.1 mmol) in methanol (5 ml) and cadmium dichloride (0.037 g, 0.2 mmol) in DMF (10 ml). The mixture was set aside for the formation of colourless crystals in 30% yield after several days.

Refinement top

The halogens lie in general positions; initial attempts to refine the structure with either four chlorines or four bromines gave unacceptably high R-indices (and large peaks/holes). The four halogen atoms were then refined as four (Br+Cl) mixtures; one attempt allowed the mixtures to have the same displacement parameters as well as to share the same site. A second attempt had the components having only the same displacement parameters. The second led to a formulation consisting of approximately 2.25 Br and 1.75 Cl atoms for the anion. A special restraint was used that fixed the total number of Br and Cl atoms as exactly 2.25 Br and 1.75 Cl. In the best disorder model, the site occupancy factors for the (Br+Cl) mixtures refined to 0.486 (2):0.514 (2), 0.561 (2):0.439 (2), 0.431 (2):0.569 (2) and 0.771 (2):0.229 (2).

The compound is [C13H16N2] [CdBr2.25Cl1.75] but because it has nearly equal numbers of bromine and chlorine atoms, it is regarded as [C13H16N2] [CdBr2Cl2] for the purpose of naming the compound. The CH&N elemental percentages are in fair agreement with the [C13H16N2] [CdBr2.25Cl1.75] formulation.

The disorder in the anion did not affect the cation. Carbon-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).

Structure description top

The preceding paper reports the structure of the tetrahedral dibromidodichloridocadmate(II), which has been isolated as the 1,2-ethanedipyridinium salt (Liu et al., 2007). The structure of propyl-1,3-di(4-pyridinium) tetrabromidocadmate(II) has been reported in the non-centrosymmetric space group Cc (Kao & Chen, 2004). The title compound, [C13H16N2][CdBr2Cl2] is not, however, isostructural. The cadmium atom in the centrosymmetric structure is coordinated by four halogen atoms in a tetrahedral geometry; the halogen atoms are disordered (Fig. 1). The cations and anions do not have signification interactions with each other.

For related literature, see: Kao & Chen (2004); Liu 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 structure of [C13H16N2][CdBr2Cl2], with displacement ellipsoids drawn at the 50% probability level. The bromine and chlorine atoms are disordered; the figure depicts the anion as a [CdX4]2- species. Hydrogen atoms are drawn as spheres of arbitrary radius.
Propane-1,3-diyldipyridinium dibromidodichloridocadmate(II) top
Crystal data top
(C13H16N2)[CdBr2Cl2]F(000) = 1058
Mr = 554.51Dx = 2.003 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2441 reflections
a = 8.1159 (6) Åθ = 2.7–21.3°
b = 15.058 (1) ŵ = 6.32 mm1
c = 15.103 (1) ÅT = 295 K
β = 95.023 (1)°Block, colourless
V = 1838.6 (2) Å30.15 × 0.10 × 0.08 mm
Z = 4
Data collection top
Bruker APEX area-detector
diffractometer
3220 independent reflections
Radiation source: fine-focus sealed tube2287 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
φ and ω scansθmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.409, Tmax = 0.632k = 1717
10838 measured reflectionsl = 1717
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)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.121H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.0638P)2]
where P = (Fo2 + 2Fc2)/3
3220 reflections(Δ/σ)max = 0.001
201 parametersΔρmax = 0.82 e Å3
6 restraintsΔρmin = 0.63 e Å3
Crystal data top
(C13H16N2)[CdBr2Cl2]V = 1838.6 (2) Å3
Mr = 554.51Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.1159 (6) ŵ = 6.32 mm1
b = 15.058 (1) ÅT = 295 K
c = 15.103 (1) Å0.15 × 0.10 × 0.08 mm
β = 95.023 (1)°
Data collection top
Bruker APEX area-detector
diffractometer
3220 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2287 reflections with I > 2σ(I)
Tmin = 0.409, Tmax = 0.632Rint = 0.034
10838 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0376 restraints
wR(F2) = 0.121H-atom parameters constrained
S = 1.08Δρmax = 0.82 e Å3
3220 reflectionsΔρmin = 0.63 e Å3
201 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cd10.25358 (6)0.20461 (3)0.28984 (3)0.0586 (2)
Br10.4650 (9)0.3290 (3)0.2721 (6)0.0757 (10)0.4863 (18)
Cl10.485 (2)0.3078 (9)0.2754 (14)0.0757 (10)0.5137 (18)
Br20.3988 (7)0.0714 (3)0.3716 (4)0.0712 (8)0.561 (2)
Cl20.416 (2)0.0906 (10)0.3671 (15)0.0712 (8)0.439 (2)
Br30.1618 (15)0.1511 (12)0.1337 (11)0.0651 (15)0.431 (2)
Cl30.135 (3)0.145 (2)0.139 (2)0.0651 (15)0.569 (2)
Br40.0147 (3)0.27032 (12)0.36647 (16)0.0712 (5)0.771 (2)
Cl40.011 (3)0.2488 (14)0.3558 (16)0.0712 (5)0.229 (2)
N10.6152 (5)0.1612 (3)0.0464 (3)0.0528 (12)
C10.6960 (9)0.1278 (5)0.0181 (5)0.0695 (18)
H10.71190.16250.06760.083*
C20.7553 (10)0.0450 (6)0.0135 (6)0.095 (3)
H20.81480.02400.05900.114*
C30.7317 (11)0.0074 (6)0.0538 (8)0.098 (3)
H30.76910.06580.05510.118*
C40.6496 (10)0.0269 (6)0.1227 (7)0.096 (3)
H40.63390.00770.17230.115*
C50.5921 (8)0.1118 (5)0.1169 (5)0.073 (2)
H50.53620.13540.16280.088*
N20.9403 (6)0.3797 (3)0.1317 (3)0.0568 (13)
C61.0594 (8)0.3774 (5)0.0759 (4)0.0649 (17)
H61.06190.33150.03470.078*
C71.1779 (9)0.4426 (6)0.0793 (6)0.084 (2)
H71.26120.44160.04090.101*
C81.1712 (9)0.5093 (6)0.1404 (6)0.087 (2)
H81.25030.55410.14350.104*
C91.0487 (11)0.5103 (6)0.1970 (5)0.087 (2)
H91.04380.55550.23860.105*
C100.9341 (9)0.4443 (5)0.1915 (5)0.0731 (19)
H100.85050.44430.22990.088*
C110.5538 (8)0.2530 (4)0.0405 (5)0.0660 (18)
H11A0.48590.26400.08910.079*
H11B0.48470.26040.01470.079*
C120.6934 (8)0.3208 (4)0.0443 (5)0.0657 (18)
H12A0.75270.31490.00840.079*
H12B0.64700.38010.04460.079*
C130.8126 (8)0.3086 (5)0.1259 (5)0.073 (2)
H13A0.75240.31000.17860.087*
H13B0.86600.25110.12350.087*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.0570 (3)0.0650 (3)0.0539 (3)0.0085 (2)0.0050 (2)0.0107 (2)
Br10.077 (2)0.062 (3)0.0900 (11)0.0072 (19)0.0218 (13)0.022 (2)
Cl10.077 (2)0.062 (3)0.0900 (11)0.0072 (19)0.0218 (13)0.022 (2)
Br20.0635 (15)0.056 (2)0.0904 (11)0.0047 (14)0.0153 (10)0.0029 (17)
Cl20.0635 (15)0.056 (2)0.0904 (11)0.0047 (14)0.0153 (10)0.0029 (17)
Br30.067 (4)0.072 (3)0.056 (2)0.003 (3)0.004 (2)0.0156 (17)
Cl30.067 (4)0.072 (3)0.056 (2)0.003 (3)0.004 (2)0.0156 (17)
Br40.0762 (11)0.0748 (13)0.0660 (9)0.0202 (8)0.0252 (7)0.0008 (8)
Cl40.0762 (11)0.0748 (13)0.0660 (9)0.0202 (8)0.0252 (7)0.0008 (8)
N10.051 (3)0.056 (3)0.051 (3)0.005 (2)0.001 (2)0.006 (2)
C10.085 (5)0.064 (5)0.062 (4)0.008 (4)0.018 (4)0.010 (4)
C20.099 (7)0.077 (6)0.111 (7)0.005 (5)0.025 (5)0.025 (5)
C30.083 (6)0.056 (5)0.150 (9)0.001 (4)0.025 (6)0.015 (6)
C40.092 (6)0.076 (6)0.112 (7)0.019 (5)0.028 (5)0.043 (6)
C50.060 (4)0.092 (6)0.069 (5)0.013 (4)0.012 (3)0.009 (4)
N20.052 (3)0.060 (3)0.057 (3)0.010 (3)0.001 (2)0.005 (3)
C60.060 (4)0.071 (5)0.065 (4)0.007 (4)0.012 (3)0.006 (3)
C70.076 (5)0.094 (6)0.085 (6)0.001 (5)0.020 (4)0.009 (5)
C80.068 (5)0.075 (5)0.114 (7)0.008 (4)0.014 (5)0.011 (5)
C90.090 (6)0.075 (6)0.091 (6)0.017 (5)0.018 (5)0.018 (5)
C100.065 (4)0.088 (5)0.065 (4)0.020 (4)0.001 (3)0.006 (4)
C110.057 (4)0.063 (4)0.076 (5)0.002 (3)0.004 (3)0.009 (4)
C120.072 (4)0.052 (4)0.070 (4)0.004 (3)0.011 (3)0.005 (3)
C130.062 (4)0.073 (5)0.081 (5)0.006 (4)0.002 (4)0.015 (4)
Geometric parameters (Å, º) top
Cd1—Cl22.404 (19)N2—C101.331 (8)
Cd1—Cl12.46 (2)N2—C61.338 (8)
Cd1—Br32.540 (17)N2—C131.488 (8)
Cd1—Br42.544 (2)C6—C71.373 (10)
Cd1—Cl42.53 (2)C6—H60.9300
Cd1—Cl32.55 (3)C7—C81.368 (11)
Cd1—Br12.570 (8)C7—H70.9300
Cd1—Br22.585 (5)C8—C91.366 (11)
N1—C11.320 (8)C8—H80.9300
N1—C51.327 (8)C9—C101.358 (10)
N1—C111.469 (8)C9—H90.9300
C1—C21.336 (11)C10—H100.9300
C1—H10.9300C11—C121.522 (9)
C2—C31.314 (12)C11—H11A0.9700
C2—H20.9300C11—H11B0.9700
C3—C41.383 (12)C12—C131.511 (9)
C3—H30.9300C12—H12A0.9700
C4—C51.362 (11)C12—H12B0.9700
C4—H40.9300C13—H13A0.9700
C5—H50.9300C13—H13B0.9700
Cl2—Cd1—Cl195.9 (5)C5—C4—H4120.4
Cl2—Cd1—Br3109.1 (7)C3—C4—H4120.4
Cl1—Cd1—Br3106.4 (6)N1—C5—C4120.4 (7)
Cl2—Cd1—Br4117.7 (6)N1—C5—H5119.8
Cl1—Cd1—Br4114.4 (3)C4—C5—H5119.8
Br3—Cd1—Br4111.9 (3)C10—N2—C6121.3 (6)
Cl2—Cd1—Cl4116.4 (8)C10—N2—C13119.9 (6)
Cl1—Cd1—Cl4123.3 (6)C6—N2—C13118.8 (6)
Br3—Cd1—Cl4105.0 (6)N2—C6—C7119.9 (7)
Br4—Cd1—Cl49.3 (5)N2—C6—H6120.0
Cl2—Cd1—Cl3109.2 (9)C7—C6—H6120.0
Cl1—Cd1—Cl3112.1 (8)C8—C7—C6118.8 (7)
Br3—Cd1—Cl35.9 (7)C8—C7—H7120.6
Br4—Cd1—Cl3107.3 (6)C6—C7—H7120.6
Cl4—Cd1—Cl3100.1 (7)C7—C8—C9120.3 (8)
Cl2—Cd1—Br1103.2 (4)C7—C8—H8119.9
Cl1—Cd1—Br17.9 (4)C9—C8—H8119.9
Br3—Cd1—Br1106.2 (4)C10—C9—C8119.0 (8)
Br4—Cd1—Br1107.84 (13)C10—C9—H9120.5
Cl4—Cd1—Br1116.5 (5)C8—C9—H9120.5
Cl3—Cd1—Br1111.6 (6)N2—C10—C9120.6 (7)
Cl2—Cd1—Br26.4 (5)N2—C10—H10119.7
Cl1—Cd1—Br2102.2 (4)C9—C10—H10119.7
Br3—Cd1—Br2106.4 (4)N1—C11—C12112.4 (5)
Br4—Cd1—Br2114.72 (16)N1—C11—H11A109.1
Cl4—Cd1—Br2112.5 (6)C12—C11—H11A109.1
Cl3—Cd1—Br2105.8 (8)N1—C11—H11B109.1
Br1—Cd1—Br2109.55 (17)C12—C11—H11B109.1
C1—N1—C5119.6 (6)H11A—C11—H11B107.9
C1—N1—C11120.1 (5)C13—C12—C11111.8 (6)
C5—N1—C11120.3 (6)C13—C12—H12A109.3
N1—C1—C2121.1 (7)C11—C12—H12A109.3
N1—C1—H1119.4C13—C12—H12B109.3
C2—C1—H1119.4C11—C12—H12B109.3
C3—C2—C1121.7 (8)H12A—C12—H12B107.9
C3—C2—H2119.2N2—C13—C12110.7 (6)
C1—C2—H2119.2N2—C13—H13A109.5
C2—C3—C4118.0 (8)C12—C13—H13A109.5
C2—C3—H3121.0N2—C13—H13B109.5
C4—C3—H3121.0C12—C13—H13B109.5
C5—C4—C3119.2 (8)H13A—C13—H13B108.1
C5—N1—C1—C20.2 (10)C6—C7—C8—C90.2 (12)
C11—N1—C1—C2178.9 (7)C7—C8—C9—C100.0 (12)
N1—C1—C2—C32.1 (13)C6—N2—C10—C90.4 (10)
C1—C2—C3—C43.0 (13)C13—N2—C10—C9179.2 (6)
C2—C3—C4—C52.1 (12)C8—C9—C10—N20.3 (11)
C1—N1—C5—C40.7 (9)C1—N1—C11—C1266.1 (7)
C11—N1—C5—C4179.7 (6)C5—N1—C11—C12112.9 (7)
C3—C4—C5—N10.3 (11)N1—C11—C12—C1354.8 (8)
C10—N2—C6—C70.2 (10)C10—N2—C13—C12106.4 (7)
C13—N2—C6—C7179.4 (6)C6—N2—C13—C1273.3 (8)
N2—C6—C7—C80.1 (11)C11—C12—C13—N2175.6 (5)

Experimental details

Crystal data
Chemical formula(C13H16N2)[CdBr2Cl2]
Mr554.51
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.1159 (6), 15.058 (1), 15.103 (1)
β (°) 95.023 (1)
V3)1838.6 (2)
Z4
Radiation typeMo Kα
µ (mm1)6.32
Crystal size (mm)0.15 × 0.10 × 0.08
Data collection
DiffractometerBruker APEX area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.409, 0.632
No. of measured, independent and
observed [I > 2σ(I)] reflections
10838, 3220, 2287
Rint0.034
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.121, 1.08
No. of reflections3220
No. of parameters201
No. of restraints6
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.82, 0.63

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

 

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