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The title salt, (C4H12N2)2[Bi2Cl7I3]·4H2O, was prepared by the reaction of bis­muth trichloride, potassium iodide and piperazine in a hydro­chloric acid medium. It is composed of piperazinium dications and dimeric [Bi2Cl7I3]4− tetra­anions, together with water of crystallization. The halobismuthate(III) tetra­anion is located on a center of inversion. Hydrogen bonds, including N—H...O, N—H...Cl, N—H...I, O—H...O, O—H...Cl and O—H...I inter­actions, are present in the crystal structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030424/rn6062sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030424/rn6062Isup2.hkl
Contains datablock I

CCDC reference: 287694

Key indicators

  • Single-crystal X-ray study
  • T = 292 K
  • Mean [sigma](C-C) = 0.020 Å
  • Disorder in main residue
  • R factor = 0.046
  • wR factor = 0.132
  • Data-to-parameter ratio = 22.9

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Bi1 PLAT301_ALERT_3_C Main Residue Disorder ......................... 7.00 Perc. PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 20 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 3 CL2 -BI1 -CL1 -BI1 -38.20 0.50 1.555 1.555 1.555 2.666 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.18 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 3 ALERT type 3 Indicator that the structure quality may be low 3 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The chemistry and physics of halobismuthate(III) complexes have received considerable interest in recent years because of their anti-ulcer activity (Turel et al., 1998) and their unique optical and electronic properties, including nonlinear optical activity, luminescence and semiconductivity (Goforth et al., 2004). Therefore, we report the crystal structure of a novel mixed halobismuthate(III) complex, bis(piperazinium) di-µ-chloropentachlorotriiododibismuthate(III) tetrahydrate, (I). Complex (I) is made up of bisprotonated piperazine cations (2+) with a chair-like conformation and a dinuclear mixed haloanion of bismuth(III) (Fig. 1), [Bi2Cl7I3]4−, together with water molecules of crystallization. The [Bi2Cl7I3]4− anion is built up of two edge-sharing [BiX6] octahedral units, resulting in a centrosymmetric [Bi2X10]4− fragment, and is sited over a crystallographic inversion center. Although the [Bi2X10]4− fragment has been reported previously (Benetollo et al., 2001; Bigoli et al., 1984; Bowmaker et al., 1998; Chaabouni et al., 1998; Charmant et al., 2002; Wu et al., 2005), the mixed-halide [Bi2X10]4− anions are rarely mentioned in the literature (Goforth et al., 2004). In (I), one of the five crystallographically independent halide sites are affected by halide mixing. This site (Cl2/I2) and that of symmetry related by an inversion center (designated A) are equatorial ligand sites in relation to the Bi2Cl3I3 basal plane.

Within the basal plane, two chloride ligands bridge the bismuth centers; one bismuth center has a terminal iodide and two terminal chloride ligands, and the other has a terminal chloride and two terminal iodide ligands. Bond distances and angles for this anion are given in Table 1. There are complicated hydrogen bonding interactions among the [Bi2Cl7I3]4− anions, piperazinium cations and water molecules of crystallization, which result in various supramolecular assemblies. Two neighboring water molecules of crystallization aggregates into a dimer through O—H···O hydrogen bonds (Fig. 2). Such dimeric water molecules are linked by N—H···O hydrogen bonds with their neighboring piperazium cations to form a one-dimensional chain along the a axis (Fig. 2). Furthermore, such dimeric water molecules and the [Bi2Cl7I3]4− anions are assembled into two-dimensional layers parallel to the (011) plane through O—H···Cl and O—H···I hydrogen-bonding interactions (Fig. 3). In particular, the N—H···Cl and O—H···I hydrogen bonds between each of the [Bi2Cl7I3]4− anions and its four neighboring piperazium cations result in another chain, formed by one row of halobisthate anions sandwiched in two parallel rows of piperazium cations, along the a axis in the crystals (Fig. 4). These chains are then linked by hydrogen bonds involving water molecules forming a three-dimensional extended structure. Detailed hydrogen bond parameters are given in Table 2.

Experimental top

An aqueous solution of BiCl3 (0.39 g,1.2 mmol, dissolved in 2 ml of concentrated HCl) and piperazine hexahydrate (0.65 g, 3.3 mmol, dissolved in 15 ml of water) was refluxed for about 1 h, then KI (QUANTITY??) was added. The resulting solution was refluxed for another 1 h. After filtering, yellow crystals of the title compound suitable for single-crystal X-ray diffraction were deposited over a peroid of about four days on slow evaporation at room temperature. IR (KBr, cm−1): 3578 (m, O—H), 3493 (m, O—H), 3137 (m, N—H), 3003 (m, N—H), 2810 (m, C—H), 2360 (w), 2341 (w), 1613 (s, H2O), 1575 (s, NH2), 1453 (vs, CH2), 1441 (vs, CH2), 1318 (m), 1308 (m), 1200 (w), 1083 (s), 1053 (s), 1001 (m), 941 (vs), 864 (s), 682 (s). UV (in DMSO): 222, 322 nm.

Refinement top

The refinement of the Cl2/I2 site as single site fully occupied by either Cl or I alone resulted in a higher residual factor and unreasonably large or small, and also significantly elongated, displacement parameters. This site was successfully modeled as mixed Cl/I position. Initially, the occupancies of these atoms were allowed to refine freely. The resulting occupancies both approached 1/2, and correspondingly, their sum was close to unity, thereby supporting the assignment as a mixed Cl/I position. For the final cycles, the occupancies were constrained to 1/2, since the elemental analysis implies that the ratio of Bi to Cl and to I in the title compound is close to 2:7:3. No unusual problems were encountered for Cl1, I1, Cl3 or Cl4, and the final refined composition of the anion is then Bi2Cl7I3. H atoms attached to O atoms were located in a difference Fourier map and other H atoms were positioned geometrically. H atoms attached to N and C atoms were refined using a riding model, with C—H = 0.97 Å and N—H = 0.90 Å, and those attached to O atoms were refined in fixed positions, with O—H = 0.85 Å. For all H atoms, Uiso(H) = 1.2Ueq(parent atom). The locations of the maximum and minimum difference density peaks are 1.01 and 0.63 Å from Bi1 and I1, respectively.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2003); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A perspective view of the [Bi2Cl7I3]4− anion and the piperazium cation with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level [symmetry code: (A) 1 − x, 1 − y, 1 − z].
[Figure 2] Fig. 2. A view showing the chain propagated by water molecules via O—H···O hydrogen bonds and piperazium cations via N—H···O hydrogen bonds (hydrogen bonds shown as dashed lines).
[Figure 3] Fig. 3. A hydrogen bonded layer composed of water molecules and the [Bi2Cl7I3]4− anions via O—H···Cl and O—H···I hydrogen bonds (dashed lines).
[Figure 4] Fig. 4. A cation–anion alternating chain composed of piperazium cations and [Bi2Cl7I3]4− anions (dashed lines indicate hydrogen bonds).
Bis(piperazinium) di-µ-chloro-pentachloro-triiododibismuthate top
Crystal data top
(C4H12N2)2[Bi2Cl7I3]·4H2OZ = 1
Mr = 1295.19F(000) = 584
Triclinic, P1Dx = 2.725 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.2076 (8) ÅCell parameters from 1080 reflections
b = 10.4721 (11) Åθ = 2.5–26.0°
c = 10.7474 (11) ŵ = 14.68 mm1
α = 97.328 (2)°T = 292 K
β = 108.678 (2)°Block, yellow
γ = 110.504 (2)°0.30 × 0.20 × 0.20 mm
V = 789.18 (14) Å3
Data collection top
Bruker APEX CCD area detector
diffractometer
3026 independent reflections
Radiation source: fine-focus sealed tube2828 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
Detector resolution: 1.47 X 0.47 mm pixels mm-1θmax = 26.0°, θmin = 2.1°
ϕ and ω scansh = 1010
Absorption correction: multi-scan
(SADABS; Sheldrick 1996)
k = 1210
Tmin = 0.032, Tmax = 0.053l = 1213
4283 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)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0801P)2 + 3.4558P]
where P = (Fo2 + 2Fc2)/3
3026 reflections(Δ/σ)max = 0.001
132 parametersΔρmax = 2.61 e Å3
0 restraintsΔρmin = 1.82 e Å3
Crystal data top
(C4H12N2)2[Bi2Cl7I3]·4H2Oγ = 110.504 (2)°
Mr = 1295.19V = 789.18 (14) Å3
Triclinic, P1Z = 1
a = 8.2076 (8) ÅMo Kα radiation
b = 10.4721 (11) ŵ = 14.68 mm1
c = 10.7474 (11) ÅT = 292 K
α = 97.328 (2)°0.30 × 0.20 × 0.20 mm
β = 108.678 (2)°
Data collection top
Bruker APEX CCD area detector
diffractometer
3026 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick 1996)
2828 reflections with I > 2σ(I)
Tmin = 0.032, Tmax = 0.053Rint = 0.027
4283 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.132H-atom parameters constrained
S = 1.06Δρmax = 2.61 e Å3
3026 reflectionsΔρmin = 1.82 e Å3
132 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*/UeqOcc. (<1)
Bi10.64627 (5)0.70527 (4)0.66232 (3)0.03354 (16)
Cl10.2593 (4)0.5023 (3)0.4817 (3)0.0384 (5)
Cl21.02800 (19)0.86963 (16)0.8387 (2)0.0786 (5)0.50
Cl30.6167 (4)0.5363 (3)0.8371 (3)0.0470 (6)
Cl40.6639 (4)0.8372 (3)0.4599 (3)0.0390 (5)
I10.48479 (13)0.87392 (9)0.77081 (9)0.0586 (3)
I21.02800 (19)0.86963 (16)0.8387 (2)0.0786 (5)0.50
O10.3254 (15)0.7406 (11)0.0595 (11)0.069 (3)
H1O10.43750.75150.07150.104*
H2O10.31070.81300.03960.104*
O20.7026 (15)0.7728 (12)0.0940 (10)0.072 (3)
H1O20.69740.72670.02060.107*
H2O20.77360.85940.10850.107*
C10.1766 (16)0.8149 (12)0.3323 (13)0.047 (3)
H1A0.30090.88040.39890.057*
H1B0.13400.86260.26550.057*
C20.0430 (16)0.7745 (13)0.4017 (13)0.050 (3)
H2A0.02940.85750.43970.060*
H2B0.09280.73710.47600.060*
N20.1453 (12)0.6656 (10)0.3027 (9)0.0398 (19)
H2C0.22320.64070.34680.048*
H2D0.19490.70390.23830.048*
C30.1365 (16)0.5366 (13)0.2353 (13)0.051 (3)
H4A0.26110.47190.16850.061*
H4B0.09550.48890.30270.061*
C40.0001 (16)0.5773 (13)0.1664 (11)0.047 (3)
H5A0.01300.49380.12910.056*
H5B0.05070.61340.09120.056*
N10.1902 (12)0.6870 (10)0.2621 (9)0.0396 (19)
H1C0.26420.71380.21550.047*
H1D0.24450.64950.32530.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Bi10.0389 (2)0.0324 (2)0.0303 (2)0.01495 (17)0.01440 (16)0.00883 (15)
Cl10.0442 (13)0.0433 (13)0.0367 (13)0.0215 (11)0.0214 (11)0.0154 (11)
Cl20.0363 (7)0.0550 (8)0.1035 (13)0.0072 (6)0.0054 (7)0.0102 (8)
Cl30.0520 (15)0.0534 (16)0.0434 (14)0.0255 (13)0.0201 (12)0.0243 (12)
Cl40.0460 (13)0.0433 (13)0.0348 (12)0.0227 (11)0.0198 (11)0.0109 (10)
I10.0757 (6)0.0577 (5)0.0579 (5)0.0364 (4)0.0351 (4)0.0173 (4)
I20.0363 (7)0.0550 (8)0.1035 (13)0.0072 (6)0.0054 (7)0.0102 (8)
O10.078 (7)0.073 (6)0.086 (7)0.039 (5)0.054 (6)0.038 (6)
O20.086 (7)0.091 (7)0.053 (5)0.044 (6)0.032 (5)0.033 (5)
C10.039 (6)0.039 (6)0.061 (7)0.010 (5)0.023 (5)0.013 (5)
C20.044 (6)0.051 (7)0.047 (7)0.015 (5)0.020 (5)0.002 (5)
N20.036 (4)0.054 (5)0.033 (4)0.018 (4)0.017 (4)0.014 (4)
C30.041 (6)0.057 (7)0.050 (7)0.018 (5)0.019 (5)0.009 (6)
C40.045 (6)0.064 (7)0.033 (5)0.027 (5)0.014 (5)0.005 (5)
N10.038 (4)0.053 (5)0.033 (4)0.020 (4)0.018 (4)0.014 (4)
Geometric parameters (Å, º) top
Bi1—Cl42.737 (3)C2—N21.491 (14)
Bi1—Cl32.749 (3)C2—H2A0.9700
Bi1—Cl22.8210 (14)C2—H2B0.9700
Bi1—I12.8879 (9)N2—C31.486 (15)
Bi1—Cl12.940 (3)N2—H2C0.9000
Bi1—Cl1i2.969 (2)N2—H2D0.9000
Cl1—Bi1i2.969 (2)C3—C41.504 (16)
O1—H1O10.8500C3—H4A0.9700
O1—H2O10.8500C3—H4B0.9700
O2—H1O20.8500C4—N11.493 (14)
O2—H2O20.8500C4—H5A0.9700
C1—C21.489 (16)C4—H5B0.9700
C1—N11.508 (14)N1—H1C0.9000
C1—H1A0.9700N1—H1D0.9000
C1—H1B0.9700
Cl4—Bi1—Cl3171.31 (8)C1—C2—H2B109.6
Cl4—Bi1—Cl294.89 (7)N2—C2—H2B109.6
Cl3—Bi1—Cl289.10 (7)H2A—C2—H2B108.2
Cl4—Bi1—I193.11 (5)C3—N2—C2113.3 (9)
Cl3—Bi1—I194.00 (6)C3—N2—H2C108.9
Cl2—Bi1—I197.69 (4)C2—N2—H2C108.9
Cl4—Bi1—Cl189.27 (7)C3—N2—H2D108.9
Cl3—Bi1—Cl185.99 (8)C2—N2—H2D108.9
Cl2—Bi1—Cl1172.69 (6)H2C—N2—H2D107.7
I1—Bi1—Cl188.07 (5)N2—C3—C4109.6 (10)
Cl4—Bi1—Cl1i86.54 (7)N2—C3—H4A109.8
Cl3—Bi1—Cl1i85.57 (8)C4—C3—H4A109.8
Cl2—Bi1—Cl1i92.61 (7)N2—C3—H4B109.8
I1—Bi1—Cl1i169.69 (6)C4—C3—H4B109.8
Cl1—Bi1—Cl1i81.62 (7)H4A—C3—H4B108.2
Bi1—Cl1—Bi1i98.38 (7)N1—C4—C3112.1 (9)
H1O1—O1—H2O1108.8N1—C4—H5A109.2
H1O2—O2—H2O2108.1C3—C4—H5A109.2
C2—C1—N1111.5 (9)N1—C4—H5B109.2
C2—C1—H1A109.3C3—C4—H5B109.2
N1—C1—H1A109.3H5A—C4—H5B107.9
C2—C1—H1B109.3C4—N1—C1111.5 (8)
N1—C1—H1B109.3C4—N1—H1C109.3
H1A—C1—H1B108.0C1—N1—H1C109.3
C1—C2—N2110.1 (9)C4—N1—H1D109.3
C1—C2—H2A109.6C1—N1—H1D109.3
N2—C2—H2A109.6H1C—N1—H1D108.0
Cl4—Bi1—Cl1—Bi1i86.61 (7)C1—C2—N2—C357.0 (13)
Cl3—Bi1—Cl1—Bi1i86.10 (8)C2—N2—C3—C456.1 (13)
Cl2—Bi1—Cl1—Bi1i38.2 (5)N2—C3—C4—N154.2 (13)
I1—Bi1—Cl1—Bi1i179.75 (6)C3—C4—N1—C154.1 (13)
Cl1i—Bi1—Cl1—Bi1i0.0C2—C1—N1—C454.4 (13)
N1—C1—C2—N254.8 (13)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O20.852.042.888 (14)178
O1—H2O1···I2ii0.852.913.582 (10)137
O2—H1O2···Cl3iii0.852.353.167 (11)161
O2—H2O2···Cl2iv0.852.603.453 (11)175
N2—H2C···Cl1v0.902.543.258 (9)137
N2—H2D···O2vi0.901.872.771 (13)175
N1—H1C···O10.901.922.777 (13)158
N1—H1D···Cl10.902.423.272 (9)157
Symmetry codes: (ii) x1, y, z1; (iii) x, y, z1; (iv) x+2, y+2, z+1; (v) x, y+1, z+1; (vi) x1, y, z.

Experimental details

Crystal data
Chemical formula(C4H12N2)2[Bi2Cl7I3]·4H2O
Mr1295.19
Crystal system, space groupTriclinic, P1
Temperature (K)292
a, b, c (Å)8.2076 (8), 10.4721 (11), 10.7474 (11)
α, β, γ (°)97.328 (2), 108.678 (2), 110.504 (2)
V3)789.18 (14)
Z1
Radiation typeMo Kα
µ (mm1)14.68
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker APEX CCD area detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick 1996)
Tmin, Tmax0.032, 0.053
No. of measured, independent and
observed [I > 2σ(I)] reflections
4283, 3026, 2828
Rint0.027
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.132, 1.06
No. of reflections3026
No. of parameters132
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)2.61, 1.82

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003), SHELXTL.

Selected geometric parameters (Å, º) top
Bi1—Cl42.737 (3)Bi1—I12.8879 (9)
Bi1—Cl32.749 (3)Bi1—Cl1i2.969 (2)
Bi1—Cl22.8210 (14)
Cl4—Bi1—Cl3171.31 (8)Cl2—Bi1—Cl1172.69 (6)
Cl4—Bi1—Cl294.89 (7)I1—Bi1—Cl188.07 (5)
Cl3—Bi1—Cl289.10 (7)Cl4—Bi1—Cl1i86.54 (7)
Cl4—Bi1—I193.11 (5)Cl3—Bi1—Cl1i85.57 (8)
Cl3—Bi1—I194.00 (6)Cl2—Bi1—Cl1i92.61 (7)
Cl2—Bi1—I197.69 (4)I1—Bi1—Cl1i169.69 (6)
Cl4—Bi1—Cl189.27 (7)Cl1—Bi1—Cl1i81.62 (7)
Cl3—Bi1—Cl185.99 (8)Bi1—Cl1—Bi1i98.38 (7)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O1···O20.852.042.888 (14)178.1
O1—H2O1···I2ii0.852.913.582 (10)137.1
O2—H1O2···Cl3iii0.852.353.167 (11)160.6
O2—H2O2···Cl2iv0.852.603.453 (11)175.1
N2—H2C···Cl1v0.902.543.258 (9)136.7
N2—H2D···O2vi0.901.872.771 (13)175.4
N1—H1C···O10.901.922.777 (13)157.5
N1—H1D···Cl10.902.423.272 (9)157.0
Symmetry codes: (ii) x1, y, z1; (iii) x, y, z1; (iv) x+2, y+2, z+1; (v) x, y+1, z+1; (vi) x1, y, z.
 

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