Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030424/rn6062sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030424/rn6062Isup2.hkl |
CCDC reference: 287694
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.
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.
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.
(C4H12N2)2[Bi2Cl7I3]·4H2O | Z = 1 |
Mr = 1295.19 | F(000) = 584 |
Triclinic, P1 | Dx = 2.725 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2076 (8) Å | Cell parameters from 1080 reflections |
b = 10.4721 (11) Å | θ = 2.5–26.0° |
c = 10.7474 (11) Å | µ = 14.68 mm−1 |
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 |
Bruker APEX CCD area detector diffractometer | 3026 independent reflections |
Radiation source: fine-focus sealed tube | 2828 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
Detector resolution: 1.47 X 0.47 mm pixels mm-1 | θmax = 26.0°, θmin = 2.1° |
ϕ and ω scans | h = −10→10 |
Absorption correction: multi-scan (SADABS; Sheldrick 1996) | k = −12→10 |
Tmin = 0.032, Tmax = 0.053 | l = −12→13 |
4283 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-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 parameters | Δρmax = 2.61 e Å−3 |
0 restraints | Δρmin = −1.82 e Å−3 |
(C4H12N2)2[Bi2Cl7I3]·4H2O | γ = 110.504 (2)° |
Mr = 1295.19 | V = 789.18 (14) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.2076 (8) Å | Mo Kα radiation |
b = 10.4721 (11) Å | µ = 14.68 mm−1 |
c = 10.7474 (11) Å | T = 292 K |
α = 97.328 (2)° | 0.30 × 0.20 × 0.20 mm |
β = 108.678 (2)° |
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 = 0.053 | Rint = 0.027 |
4283 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.06 | Δρmax = 2.61 e Å−3 |
3026 reflections | Δρmin = −1.82 e Å−3 |
132 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Bi1 | 0.64627 (5) | 0.70527 (4) | 0.66232 (3) | 0.03354 (16) | |
Cl1 | 0.2593 (4) | 0.5023 (3) | 0.4817 (3) | 0.0384 (5) | |
Cl2 | 1.02800 (19) | 0.86963 (16) | 0.8387 (2) | 0.0786 (5) | 0.50 |
Cl3 | 0.6167 (4) | 0.5363 (3) | 0.8371 (3) | 0.0470 (6) | |
Cl4 | 0.6639 (4) | 0.8372 (3) | 0.4599 (3) | 0.0390 (5) | |
I1 | 0.48479 (13) | 0.87392 (9) | 0.77081 (9) | 0.0586 (3) | |
I2 | 1.02800 (19) | 0.86963 (16) | 0.8387 (2) | 0.0786 (5) | 0.50 |
O1 | 0.3254 (15) | 0.7406 (11) | 0.0595 (11) | 0.069 (3) | |
H1O1 | 0.4375 | 0.7515 | 0.0715 | 0.104* | |
H2O1 | 0.3107 | 0.8130 | 0.0396 | 0.104* | |
O2 | 0.7026 (15) | 0.7728 (12) | 0.0940 (10) | 0.072 (3) | |
H1O2 | 0.6974 | 0.7267 | 0.0206 | 0.107* | |
H2O2 | 0.7736 | 0.8594 | 0.1085 | 0.107* | |
C1 | 0.1766 (16) | 0.8149 (12) | 0.3323 (13) | 0.047 (3) | |
H1A | 0.3009 | 0.8804 | 0.3989 | 0.057* | |
H1B | 0.1340 | 0.8626 | 0.2655 | 0.057* | |
C2 | 0.0430 (16) | 0.7745 (13) | 0.4017 (13) | 0.050 (3) | |
H2A | 0.0294 | 0.8575 | 0.4397 | 0.060* | |
H2B | 0.0928 | 0.7371 | 0.4760 | 0.060* | |
N2 | −0.1453 (12) | 0.6656 (10) | 0.3027 (9) | 0.0398 (19) | |
H2C | −0.2232 | 0.6407 | 0.3468 | 0.048* | |
H2D | −0.1949 | 0.7039 | 0.2383 | 0.048* | |
C3 | −0.1365 (16) | 0.5366 (13) | 0.2353 (13) | 0.051 (3) | |
H4A | −0.2611 | 0.4719 | 0.1685 | 0.061* | |
H4B | −0.0955 | 0.4889 | 0.3027 | 0.061* | |
C4 | −0.0001 (16) | 0.5773 (13) | 0.1664 (11) | 0.047 (3) | |
H5A | 0.0130 | 0.4938 | 0.1291 | 0.056* | |
H5B | −0.0507 | 0.6134 | 0.0912 | 0.056* | |
N1 | 0.1902 (12) | 0.6870 (10) | 0.2621 (9) | 0.0396 (19) | |
H1C | 0.2642 | 0.7138 | 0.2155 | 0.047* | |
H1D | 0.2445 | 0.6495 | 0.3253 | 0.047* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Bi1 | 0.0389 (2) | 0.0324 (2) | 0.0303 (2) | 0.01495 (17) | 0.01440 (16) | 0.00883 (15) |
Cl1 | 0.0442 (13) | 0.0433 (13) | 0.0367 (13) | 0.0215 (11) | 0.0214 (11) | 0.0154 (11) |
Cl2 | 0.0363 (7) | 0.0550 (8) | 0.1035 (13) | 0.0072 (6) | −0.0054 (7) | 0.0102 (8) |
Cl3 | 0.0520 (15) | 0.0534 (16) | 0.0434 (14) | 0.0255 (13) | 0.0201 (12) | 0.0243 (12) |
Cl4 | 0.0460 (13) | 0.0433 (13) | 0.0348 (12) | 0.0227 (11) | 0.0198 (11) | 0.0109 (10) |
I1 | 0.0757 (6) | 0.0577 (5) | 0.0579 (5) | 0.0364 (4) | 0.0351 (4) | 0.0173 (4) |
I2 | 0.0363 (7) | 0.0550 (8) | 0.1035 (13) | 0.0072 (6) | −0.0054 (7) | 0.0102 (8) |
O1 | 0.078 (7) | 0.073 (6) | 0.086 (7) | 0.039 (5) | 0.054 (6) | 0.038 (6) |
O2 | 0.086 (7) | 0.091 (7) | 0.053 (5) | 0.044 (6) | 0.032 (5) | 0.033 (5) |
C1 | 0.039 (6) | 0.039 (6) | 0.061 (7) | 0.010 (5) | 0.023 (5) | 0.013 (5) |
C2 | 0.044 (6) | 0.051 (7) | 0.047 (7) | 0.015 (5) | 0.020 (5) | −0.002 (5) |
N2 | 0.036 (4) | 0.054 (5) | 0.033 (4) | 0.018 (4) | 0.017 (4) | 0.014 (4) |
C3 | 0.041 (6) | 0.057 (7) | 0.050 (7) | 0.018 (5) | 0.019 (5) | 0.009 (6) |
C4 | 0.045 (6) | 0.064 (7) | 0.033 (5) | 0.027 (5) | 0.014 (5) | 0.005 (5) |
N1 | 0.038 (4) | 0.053 (5) | 0.033 (4) | 0.020 (4) | 0.018 (4) | 0.014 (4) |
Bi1—Cl4 | 2.737 (3) | C2—N2 | 1.491 (14) |
Bi1—Cl3 | 2.749 (3) | C2—H2A | 0.9700 |
Bi1—Cl2 | 2.8210 (14) | C2—H2B | 0.9700 |
Bi1—I1 | 2.8879 (9) | N2—C3 | 1.486 (15) |
Bi1—Cl1 | 2.940 (3) | N2—H2C | 0.9000 |
Bi1—Cl1i | 2.969 (2) | N2—H2D | 0.9000 |
Cl1—Bi1i | 2.969 (2) | C3—C4 | 1.504 (16) |
O1—H1O1 | 0.8500 | C3—H4A | 0.9700 |
O1—H2O1 | 0.8500 | C3—H4B | 0.9700 |
O2—H1O2 | 0.8500 | C4—N1 | 1.493 (14) |
O2—H2O2 | 0.8500 | C4—H5A | 0.9700 |
C1—C2 | 1.489 (16) | C4—H5B | 0.9700 |
C1—N1 | 1.508 (14) | N1—H1C | 0.9000 |
C1—H1A | 0.9700 | N1—H1D | 0.9000 |
C1—H1B | 0.9700 | ||
Cl4—Bi1—Cl3 | 171.31 (8) | C1—C2—H2B | 109.6 |
Cl4—Bi1—Cl2 | 94.89 (7) | N2—C2—H2B | 109.6 |
Cl3—Bi1—Cl2 | 89.10 (7) | H2A—C2—H2B | 108.2 |
Cl4—Bi1—I1 | 93.11 (5) | C3—N2—C2 | 113.3 (9) |
Cl3—Bi1—I1 | 94.00 (6) | C3—N2—H2C | 108.9 |
Cl2—Bi1—I1 | 97.69 (4) | C2—N2—H2C | 108.9 |
Cl4—Bi1—Cl1 | 89.27 (7) | C3—N2—H2D | 108.9 |
Cl3—Bi1—Cl1 | 85.99 (8) | C2—N2—H2D | 108.9 |
Cl2—Bi1—Cl1 | 172.69 (6) | H2C—N2—H2D | 107.7 |
I1—Bi1—Cl1 | 88.07 (5) | N2—C3—C4 | 109.6 (10) |
Cl4—Bi1—Cl1i | 86.54 (7) | N2—C3—H4A | 109.8 |
Cl3—Bi1—Cl1i | 85.57 (8) | C4—C3—H4A | 109.8 |
Cl2—Bi1—Cl1i | 92.61 (7) | N2—C3—H4B | 109.8 |
I1—Bi1—Cl1i | 169.69 (6) | C4—C3—H4B | 109.8 |
Cl1—Bi1—Cl1i | 81.62 (7) | H4A—C3—H4B | 108.2 |
Bi1—Cl1—Bi1i | 98.38 (7) | N1—C4—C3 | 112.1 (9) |
H1O1—O1—H2O1 | 108.8 | N1—C4—H5A | 109.2 |
H1O2—O2—H2O2 | 108.1 | C3—C4—H5A | 109.2 |
C2—C1—N1 | 111.5 (9) | N1—C4—H5B | 109.2 |
C2—C1—H1A | 109.3 | C3—C4—H5B | 109.2 |
N1—C1—H1A | 109.3 | H5A—C4—H5B | 107.9 |
C2—C1—H1B | 109.3 | C4—N1—C1 | 111.5 (8) |
N1—C1—H1B | 109.3 | C4—N1—H1C | 109.3 |
H1A—C1—H1B | 108.0 | C1—N1—H1C | 109.3 |
C1—C2—N2 | 110.1 (9) | C4—N1—H1D | 109.3 |
C1—C2—H2A | 109.6 | C1—N1—H1D | 109.3 |
N2—C2—H2A | 109.6 | H1C—N1—H1D | 108.0 |
Cl4—Bi1—Cl1—Bi1i | 86.61 (7) | C1—C2—N2—C3 | 57.0 (13) |
Cl3—Bi1—Cl1—Bi1i | −86.10 (8) | C2—N2—C3—C4 | −56.1 (13) |
Cl2—Bi1—Cl1—Bi1i | −38.2 (5) | N2—C3—C4—N1 | 54.2 (13) |
I1—Bi1—Cl1—Bi1i | 179.75 (6) | C3—C4—N1—C1 | −54.1 (13) |
Cl1i—Bi1—Cl1—Bi1i | 0.0 | C2—C1—N1—C4 | 54.4 (13) |
N1—C1—C2—N2 | −54.8 (13) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···O2 | 0.85 | 2.04 | 2.888 (14) | 178 |
O1—H2O1···I2ii | 0.85 | 2.91 | 3.582 (10) | 137 |
O2—H1O2···Cl3iii | 0.85 | 2.35 | 3.167 (11) | 161 |
O2—H2O2···Cl2iv | 0.85 | 2.60 | 3.453 (11) | 175 |
N2—H2C···Cl1v | 0.90 | 2.54 | 3.258 (9) | 137 |
N2—H2D···O2vi | 0.90 | 1.87 | 2.771 (13) | 175 |
N1—H1C···O1 | 0.90 | 1.92 | 2.777 (13) | 158 |
N1—H1D···Cl1 | 0.90 | 2.42 | 3.272 (9) | 157 |
Symmetry codes: (ii) x−1, y, z−1; (iii) x, y, z−1; (iv) −x+2, −y+2, −z+1; (v) −x, −y+1, −z+1; (vi) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | (C4H12N2)2[Bi2Cl7I3]·4H2O |
Mr | 1295.19 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 789.18 (14) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 14.68 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker APEX CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick 1996) |
Tmin, Tmax | 0.032, 0.053 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4283, 3026, 2828 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.132, 1.06 |
No. of reflections | 3026 |
No. of parameters | 132 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.61, −1.82 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2003), SHELXTL.
Bi1—Cl4 | 2.737 (3) | Bi1—I1 | 2.8879 (9) |
Bi1—Cl3 | 2.749 (3) | Bi1—Cl1i | 2.969 (2) |
Bi1—Cl2 | 2.8210 (14) | ||
Cl4—Bi1—Cl3 | 171.31 (8) | Cl2—Bi1—Cl1 | 172.69 (6) |
Cl4—Bi1—Cl2 | 94.89 (7) | I1—Bi1—Cl1 | 88.07 (5) |
Cl3—Bi1—Cl2 | 89.10 (7) | Cl4—Bi1—Cl1i | 86.54 (7) |
Cl4—Bi1—I1 | 93.11 (5) | Cl3—Bi1—Cl1i | 85.57 (8) |
Cl3—Bi1—I1 | 94.00 (6) | Cl2—Bi1—Cl1i | 92.61 (7) |
Cl2—Bi1—I1 | 97.69 (4) | I1—Bi1—Cl1i | 169.69 (6) |
Cl4—Bi1—Cl1 | 89.27 (7) | Cl1—Bi1—Cl1i | 81.62 (7) |
Cl3—Bi1—Cl1 | 85.99 (8) | Bi1—Cl1—Bi1i | 98.38 (7) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O1···O2 | 0.85 | 2.04 | 2.888 (14) | 178.1 |
O1—H2O1···I2ii | 0.85 | 2.91 | 3.582 (10) | 137.1 |
O2—H1O2···Cl3iii | 0.85 | 2.35 | 3.167 (11) | 160.6 |
O2—H2O2···Cl2iv | 0.85 | 2.60 | 3.453 (11) | 175.1 |
N2—H2C···Cl1v | 0.90 | 2.54 | 3.258 (9) | 136.7 |
N2—H2D···O2vi | 0.90 | 1.87 | 2.771 (13) | 175.4 |
N1—H1C···O1 | 0.90 | 1.92 | 2.777 (13) | 157.5 |
N1—H1D···Cl1 | 0.90 | 2.42 | 3.272 (9) | 157.0 |
Symmetry codes: (ii) x−1, y, z−1; (iii) x, y, z−1; (iv) −x+2, −y+2, −z+1; (v) −x, −y+1, −z+1; (vi) x−1, y, z. |
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.