Bis(piperazinium) di-μ-chloro-bis­[tetra­chloro­bismuthate(III)] trihydrate

The title salt, (C₄H₁₂N₂)₂[Bi₂Cl₁₀]·3H₂O, was prepared by reaction of bismuth trichloride and piperazine in a hydro­chloric acid medium. It consists of piperazinium dications and dimeric [Bi₂Cl₁₀]⁴⁻ tetra­anions, the latter with twofold rotation symmetry, together with water of crystallization. Hydrogen-bond inter­actions, including N—H...O, N—H...Cl and O—H...Cl inter­actions, stabilize the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.036
• wR factor = 0.100
• Data-to-parameter ratio = 26.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Bi     -   Cl1     ..      10.41 su

Alert level C
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           28.25
           From the CIF: _diffrn_reflns_theta_full          28.25
           From the CIF: _reflns_number_total               3240
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         3424
           Completeness (_total/calc)             94.63%
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Bi     -   Cl2     ..       9.48 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Bi     -   Cl4     ..       5.72 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Bi     -   Cl1_a   ..       8.07 su
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         10
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          4
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          4
              H2 O

   0 ALERT level A = In general: serious problem
   2 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
   4 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SMART; data reduction: SAINT (Bruker, 2003); 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.

Bis(piperazinium) di-µ-chloro-bis[tetraochlorobismuthate(III)] trihydrate

Crystal data

(C4H12N2)[Bi2Cl10]·3H2O	F(000) = 1864
Mr = 1002.82	Dx = 2.405 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3992 reflections
a = 14.3223 (14) Å	θ = 2.9–28.2°
b = 15.7868 (14) Å	µ = 13.67 mm^−1
c = 13.5226 (13) Å	T = 291 K
β = 115.067 (2)°	Block, colourless
V = 2769.5 (5) Å^3	0.30 × 0.20 × 0.15 mm
Z = 4

Data collection

Bruker APEX CCD area-detector diffractometer	3240 independent reflections
Radiation source: fine-focus sealed tube	2631 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
φ and ω scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick 1996)	h = −17→18
Tmin = 0.053, Tmax = 0.132	k = −13→20
8270 measured reflections	l = −17→17

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.100	w = 1/[σ^2(Fo^2) + (0.0408P)^2 + 9.2258P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
3240 reflections	Δρmax = 2.20 e Å^−3
124 parameters	Δρmin = −3.00 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00346 (12)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Bi	0.432092 (15)	0.747593 (12)	0.862727 (16)	0.02081 (13)
Cl1	0.63347 (14)	0.74855 (8)	0.86902 (14)	0.0284 (4)
Cl2	0.42404 (10)	0.92415 (10)	0.83824 (13)	0.0280 (3)
Cl3	0.23849 (14)	0.73953 (11)	0.81864 (18)	0.0398 (4)
Cl4	0.46021 (12)	0.58336 (10)	0.89684 (14)	0.0356 (4)
Cl5	0.48871 (17)	0.77078 (13)	1.06923 (15)	0.0445 (4)
N1	0.6746 (4)	0.9537 (3)	0.9344 (4)	0.0270 (11)
H1NA	0.6139	0.9350	0.8834	0.032*
H1NB	0.7253	0.9321	0.9195	0.032*
N2	0.7876 (4)	1.0518 (3)	1.1272 (4)	0.0298 (11)
H2NA	0.8483	1.0703	1.1783	0.036*
H2NB	0.7371	1.0735	1.1427	0.036*
C1	0.6776 (6)	1.0474 (4)	0.9316 (5)	0.0390 (16)
H1A	0.6188	1.0701	0.9407	0.047*
H1B	0.6724	1.0656	0.8609	0.047*
C2	0.7746 (6)	1.0823 (6)	1.0191 (6)	0.0450 (18)
H2A	0.8332	1.0648	1.0058	0.054*
H2B	0.7718	1.1437	1.0175	0.054*
C3	0.6874 (4)	0.9257 (4)	1.0437 (5)	0.0295 (13)
H3A	0.6882	0.8642	1.0463	0.035*
H3B	0.6292	0.9451	1.0564	0.035*
C4	0.7844 (5)	0.9588 (4)	1.1316 (5)	0.0335 (14)
H4A	0.7889	0.9412	1.2021	0.040*
H4B	0.8432	0.9353	1.1230	0.040*
O1	0.8281 (3)	0.8958 (3)	0.8727 (3)	0.0406 (11)
H1	0.8864	0.8991	0.9272	0.049*
H2	0.8187	0.8447	0.8511	0.049*
O2	1.0000	1.1259 (4)	1.2500	0.0419 (16)
H3	1.0127	1.1575	1.2063	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi	0.01990 (17)	0.01774 (17)	0.02359 (18)	0.00193 (8)	0.00807 (11)	0.00356 (7)
Cl1	0.0247 (8)	0.0252 (9)	0.0293 (8)	0.0016 (5)	0.0056 (7)	−0.0006 (5)
Cl2	0.0254 (6)	0.0233 (7)	0.0357 (8)	0.0018 (6)	0.0135 (6)	−0.0010 (6)
Cl3	0.0238 (8)	0.0413 (10)	0.0535 (11)	0.0003 (7)	0.0155 (8)	0.0127 (8)
Cl4	0.0349 (7)	0.0214 (8)	0.0446 (9)	−0.0014 (7)	0.0112 (7)	0.0037 (7)
Cl5	0.0613 (12)	0.0415 (9)	0.0274 (8)	0.0086 (10)	0.0155 (8)	0.0019 (8)
N1	0.024 (2)	0.026 (3)	0.027 (2)	−0.003 (2)	0.007 (2)	−0.008 (2)
N2	0.028 (2)	0.028 (3)	0.034 (3)	−0.004 (2)	0.014 (2)	−0.013 (2)
C1	0.055 (4)	0.025 (3)	0.037 (4)	0.004 (3)	0.020 (3)	0.004 (3)
C2	0.063 (4)	0.037 (4)	0.041 (4)	−0.022 (4)	0.028 (3)	−0.012 (3)
C3	0.035 (3)	0.020 (3)	0.036 (3)	0.000 (3)	0.017 (3)	−0.001 (3)
C4	0.035 (3)	0.027 (3)	0.033 (3)	0.008 (3)	0.010 (3)	−0.002 (3)
O1	0.032 (2)	0.036 (3)	0.045 (3)	0.000 (2)	0.008 (2)	−0.015 (2)
O2	0.049 (4)	0.035 (4)	0.048 (4)	0.000	0.027 (3)	0.000

Geometric parameters (Å, º)

Bi—Cl3	2.5806 (18)	N2—H2NB	0.9000
Bi—Cl5	2.5828 (18)	C1—C2	1.496 (9)
Bi—Cl4	2.6344 (16)	C1—H1A	0.9700
Bi—Cl2	2.8034 (16)	C1—H1B	0.9700
Bi—Cl1	2.8493 (19)	C2—H2A	0.9700
Bi—Cl1^i	2.8652 (18)	C2—H2B	0.9700
Cl1—Bi^i	2.8652 (18)	C3—C4	1.488 (8)
N1—C3	1.479 (7)	C3—H3A	0.9700
N1—C1	1.481 (8)	C3—H3B	0.9700
N1—H1NA	0.9000	C4—H4A	0.9700
N1—H1NB	0.9000	C4—H4B	0.9700
N2—C4	1.471 (8)	O1—H1	0.8500
N2—C2	1.475 (8)	O1—H2	0.8500
N2—H2NA	0.9000	O2—H3	0.8500
Cl3—Bi—Cl5	94.08 (7)	H2NA—N2—H2NB	107.9
Cl3—Bi—Cl4	93.53 (5)	N1—C1—C2	112.1 (6)
Cl5—Bi—Cl4	89.74 (6)	N1—C1—H1A	109.2
Cl3—Bi—Cl2	92.02 (5)	C2—C1—H1A	109.2
Cl5—Bi—Cl2	88.00 (6)	N1—C1—H1B	109.2
Cl4—Bi—Cl2	174.15 (4)	C2—C1—H1B	109.2
Cl3—Bi—Cl1	169.16 (6)	H1A—C1—H1B	107.9
Cl5—Bi—Cl1	96.71 (6)	N2—C2—C1	110.4 (6)
Cl4—Bi—Cl1	85.54 (4)	N2—C2—H2A	109.6
Cl2—Bi—Cl1	89.35 (4)	C1—C2—H2A	109.6
Cl3—Bi—Cl1^i	85.72 (7)	N2—C2—H2B	109.6
Cl5—Bi—Cl1^i	171.53 (5)	C1—C2—H2B	109.6
Cl4—Bi—Cl1^i	98.72 (5)	H2A—C2—H2B	108.1
Cl2—Bi—Cl1^i	83.54 (4)	N1—C3—C4	111.8 (5)
Cl1—Bi—Cl1^i	83.75 (5)	N1—C3—H3A	109.3
Bi—Cl1—Bi^i	96.25 (5)	C4—C3—H3A	109.3
C3—N1—C1	109.4 (5)	N1—C3—H3B	109.3
C3—N1—H1NA	109.8	C4—C3—H3B	109.3
C1—N1—H1NA	109.8	H3A—C3—H3B	107.9
C3—N1—H1NB	109.8	N2—C4—C3	110.6 (5)
C1—N1—H1NB	109.8	N2—C4—H4A	109.5
H1NA—N1—H1NB	108.2	C3—C4—H4A	109.5
C4—N2—C2	111.9 (5)	N2—C4—H4B	109.5
C4—N2—H2NA	109.2	C3—C4—H4B	109.5
C2—N2—H2NA	109.2	H4A—C4—H4B	108.1
C4—N2—H2NB	109.2	H1—O1—H2	108.0
C2—N2—H2NB	109.2
Cl3—Bi—Cl1—Bi^i	13.2 (3)	C4—N2—C2—C1	55.0 (8)
Cl5—Bi—Cl1—Bi^i	−172.10 (5)	N1—C1—C2—N2	−55.7 (8)
Cl4—Bi—Cl1—Bi^i	98.69 (5)	C1—N1—C3—C4	−56.6 (6)
Cl2—Bi—Cl1—Bi^i	−84.18 (4)	C2—N2—C4—C3	−55.6 (7)
Cl1^i—Bi—Cl1—Bi^i	−0.61 (5)	N1—C3—C4—N2	56.7 (7)
C3—N1—C1—C2	56.2 (7)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NB···O1	0.90	1.92	2.814 (6)	173
N1—H1NA···Cl2	0.90	2.53	3.291 (5)	143
N2—H2NA···O2	0.90	2.16	3.017 (5)	160
N2—H2NB···Cl2^ii	0.90	2.43	3.278 (5)	157
O1—H1···Cl4^iii	0.85	2.48	3.318 (4)	170
O1—H2···Cl3^i	0.85	2.67	3.407 (5)	147
O2—H3···Cl5^iv	0.85	2.49	3.301 (5)	159

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, −y+2, −z+2; (iii) −x+3/2, −y+3/2, −z+2; (iv) x+1/2, y+1/2, z.