Bis(1-methyl-piperazine-1,4-diium) di-μ-bromido-bis-[tetra-bromido-bismuthate(III)] dihydrate.

In the title hydrated salt, (C5H14N2)2[Bi2Br10]·2H2O, the com-plete [Bi2Br10](4-) biocta-hedron is generated by crystallographic inversion symmetry. The diprotonated piperazine ring adopts a chair conformation, with the methyl group occupying an equatorial position. In the crystal, the tetra-anions and water mol-ecules are linked by O-H⋯Br and O-H⋯(Br,Br) hydrogen bonds to generate [100] chains. The chains are crosslinked by N-H⋯Br, N-H⋯O and C-H⋯Br hydrogen bonds originating from the piperazinediium dications, thereby forming a three-dimensional network.

Related literature

For another deca­bromido­dibismuthate(III) compound, see: Li et al. (2006 ▶). For related methyl­piperazin-1,4-diium salts, see: Dutkiewicz et al. (2011 ▶); Essid et al. (2014 ▶). For related piperazine derivatives, see: Marouani et al. (2010 ▶); Essid et al. (2010 ▶).

Experimental

Crystal data

(C5H14N2)2[Bi2Br10]·2H2O

M = 1457.46

Monoclinic,

a = 7.9263 (3) Å

b = 19.0424 (7) Å

c = 12.5861 (4) Å

β = 125.770 (2)°

V = 1541.35 (9) Å3

Z = 2

Mo Kα radiation

μ = 24.38 mm−1

T = 150 K

0.15 × 0.12 × 0.07 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.071, T max = 0.182

23912 measured reflections

3525 independent reflections

3262 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.056

S = 1.09

3525 reflections

136 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.23 e Å−3

Δρmin = −1.52 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and CRYSCAL (T. Roisnel, local program).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814009805/hb7225sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009805/hb7225Isup2.hkl

CCDC reference: 1000442

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C5H14N2)2[Bi2Br10]·2H2O	F(000) = 1304
Mr = 1457.46	Dx = 3.140 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9944 reflections
a = 7.9263 (3) Å	θ = 2.8–27.5°
b = 19.0424 (7) Å	µ = 24.38 mm−1
c = 12.5861 (4) Å	T = 150 K
β = 125.770 (2)°	Prism, colourless
V = 1541.35 (9) Å3	0.15 × 0.12 × 0.07 mm
Z = 2

Bruker APEXII diffractometer	3262 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
CCD rotation images, thin slices scans	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −10→10
Tmin = 0.071, Tmax = 0.182	k = −22→24
23912 measured reflections	l = −13→12
3525 independent 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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0151P)2 + 6.909P] where P = (Fo2 + 2Fc2)/3
3525 reflections	(Δ/σ)max = 0.041
136 parameters	Δρmax = 1.23 e Å−3
3 restraints	Δρmin = −1.52 e Å−3

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
Bi	0.10118 (2)	−0.407806 (8)	0.622821 (15)	0.01138 (6)
Br1	0.27752 (7)	−0.49972 (2)	0.51922 (4)	0.01697 (10)
Br2	−0.00499 (8)	−0.31232 (3)	0.41496 (5)	0.02036 (11)
Br3	−0.12297 (8)	−0.32553 (3)	0.67787 (5)	0.02123 (11)
Br4	0.25521 (8)	−0.49702 (3)	0.83467 (5)	0.02381 (12)
Br5	0.46641 (7)	−0.33162 (2)	0.77789 (5)	0.02014 (11)
O	0.2175 (6)	0.02902 (19)	0.6937 (4)	0.0248 (8)
N1	0.3077 (6)	−0.1749 (2)	0.6194 (4)	0.0145 (8)
H1	0.2760	−0.2201	0.6249	0.017*
C1	0.4166 (8)	−0.1760 (3)	0.5543 (5)	0.0235 (11)
H1A	0.3234	−0.1933	0.4665	0.035*
H1B	0.5361	−0.2061	0.6025	0.035*
H1C	0.4600	−0.1292	0.5522	0.035*
C2	0.4472 (7)	−0.1466 (3)	0.7560 (4)	0.0167 (9)
H2A	0.4885	−0.0990	0.7534	0.020*
H2B	0.5718	−0.1751	0.8064	0.020*
C3	0.3371 (8)	−0.1467 (3)	0.8219 (5)	0.0195 (10)
H3A	0.3068	−0.1946	0.8317	0.023*
H3B	0.4269	−0.1261	0.9085	0.023*
N2	0.1400 (6)	−0.1059 (2)	0.7427 (4)	0.0168 (8)
H2C	0.1693	−0.0607	0.7387	0.020*
H2D	0.0746	−0.1073	0.7818	0.020*
C4	0.0000 (7)	−0.1347 (3)	0.6073 (5)	0.0184 (10)
H4A	−0.1254	−0.1065	0.5570	0.022*
H4B	−0.0397	−0.1824	0.6109	0.022*
C5	0.1080 (7)	−0.1344 (2)	0.5413 (5)	0.0177 (10)
H5A	0.0174	−0.1550	0.4548	0.021*
H5B	0.1368	−0.0863	0.5310	0.021*
H2	0.360 (4)	0.035 (4)	0.730 (7)	0.08 (3)*
H3	0.203 (10)	0.062 (3)	0.745 (6)	0.05 (2)*

	U11	U22	U33	U12	U13	U23
Bi	0.00972 (9)	0.01144 (9)	0.01281 (9)	−0.00006 (6)	0.00649 (7)	−0.00024 (6)
Br1	0.0124 (2)	0.0197 (2)	0.0184 (2)	0.00040 (17)	0.0087 (2)	−0.00129 (17)
Br2	0.0198 (3)	0.0218 (2)	0.0206 (2)	0.00041 (19)	0.0125 (2)	0.00260 (18)
Br3	0.0254 (3)	0.0199 (2)	0.0242 (2)	0.00474 (19)	0.0178 (2)	−0.00034 (18)
Br4	0.0202 (3)	0.0235 (3)	0.0190 (2)	−0.00190 (19)	0.0065 (2)	0.00602 (19)
Br5	0.0143 (2)	0.0189 (2)	0.0224 (2)	−0.00246 (18)	0.0080 (2)	−0.00086 (18)
O	0.0156 (18)	0.0231 (19)	0.028 (2)	−0.0021 (15)	0.0085 (16)	0.0002 (15)
N1	0.016 (2)	0.0114 (18)	0.018 (2)	−0.0006 (15)	0.0112 (17)	−0.0011 (15)
C1	0.026 (3)	0.026 (3)	0.029 (3)	−0.001 (2)	0.022 (2)	0.000 (2)
C2	0.010 (2)	0.021 (2)	0.015 (2)	−0.0014 (18)	0.0052 (19)	−0.0039 (18)
C3	0.019 (2)	0.024 (3)	0.016 (2)	0.001 (2)	0.010 (2)	0.0007 (19)
N2	0.018 (2)	0.017 (2)	0.018 (2)	0.0023 (16)	0.0122 (18)	−0.0001 (16)
C4	0.013 (2)	0.021 (2)	0.019 (2)	0.0005 (19)	0.008 (2)	−0.0023 (19)
C5	0.016 (2)	0.016 (2)	0.013 (2)	0.0031 (18)	0.0036 (19)	0.0008 (17)

Bi—Br3	2.7441 (5)	C1—H1C	0.9600
Bi—Br4	2.7714 (5)	C2—C3	1.515 (7)
Bi—Br5	2.7730 (5)	C2—H2A	0.9700
Bi—Br2	2.8784 (5)	C2—H2B	0.9700
Bi—Br1	2.9746 (5)	C3—N2	1.489 (6)
Bi—Br1i	3.0056 (5)	C3—H3A	0.9700
Br1—Bii	3.0056 (5)	C3—H3B	0.9700
O—H2	0.943 (10)	N2—C4	1.492 (6)
O—H3	0.945 (10)	N2—H2C	0.9000
N1—C1	1.497 (6)	N2—H2D	0.9000
N1—C2	1.500 (6)	C4—C5	1.501 (7)
N1—C5	1.500 (6)	C4—H4A	0.9700
N1—H1	0.9100	C4—H4B	0.9700
C1—H1A	0.9600	C5—H5A	0.9700
C1—H1B	0.9600	C5—H5B	0.9700
Br3—Bi—Br4	95.349 (16)	N1—C2—H2A	109.5
Br3—Bi—Br5	95.001 (16)	C3—C2—H2A	109.5
Br4—Bi—Br5	87.249 (15)	N1—C2—H2B	109.5
Br3—Bi—Br2	88.872 (15)	C3—C2—H2B	109.5
Br4—Bi—Br2	172.766 (16)	H2A—C2—H2B	108.1
Br5—Bi—Br2	86.531 (15)	N2—C3—C2	110.3 (4)
Br3—Bi—Br1	170.436 (15)	N2—C3—H3A	109.6
Br4—Bi—Br1	90.312 (15)	C2—C3—H3A	109.6
Br5—Bi—Br1	92.961 (15)	N2—C3—H3B	109.6
Br2—Bi—Br1	86.326 (14)	C2—C3—H3B	109.6
Br3—Bi—Br1i	85.170 (15)	H3A—C3—H3B	108.1
Br4—Bi—Br1i	86.460 (14)	C3—N2—C4	111.2 (4)
Br5—Bi—Br1i	173.695 (15)	C3—N2—H2C	109.4
Br2—Bi—Br1i	99.774 (14)	C4—N2—H2C	109.4
Br1—Bi—Br1i	87.498 (13)	C3—N2—H2D	109.4
Bi—Br1—Bii	92.502 (13)	C4—N2—H2D	109.4
H2—O—H3	100 (2)	H2C—N2—H2D	108.0
C1—N1—C2	111.0 (4)	N2—C4—C5	110.3 (4)
C1—N1—C5	111.9 (4)	N2—C4—H4A	109.6
C2—N1—C5	110.8 (3)	C5—C4—H4A	109.6
C1—N1—H1	107.7	N2—C4—H4B	109.6
C2—N1—H1	107.7	C5—C4—H4B	109.6
C5—N1—H1	107.7	H4A—C4—H4B	108.1
N1—C1—H1A	109.5	N1—C5—C4	111.1 (4)
N1—C1—H1B	109.5	N1—C5—H5A	109.4
H1A—C1—H1B	109.5	C4—C5—H5A	109.4
N1—C1—H1C	109.5	N1—C5—H5B	109.4
H1A—C1—H1C	109.5	C4—C5—H5B	109.4
H1B—C1—H1C	109.5	H5A—C5—H5B	108.0
N1—C2—C3	110.7 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Br5	0.91	2.66	3.396 (4)	138
N1—H1···Br2	0.91	2.85	3.486 (4)	128
N2—H2C···O	0.90	1.91	2.793 (6)	167
N2—H2D···Br2ii	0.90	2.60	3.371 (4)	143
O—H2···Br5iii	0.94 (1)	2.91 (7)	3.522 (4)	123 (6)
O—H2···Br1iii	0.94 (1)	2.84 (7)	3.531 (4)	131 (7)
O—H3···Br3iv	0.95 (1)	2.59 (2)	3.501 (4)	162 (6)
C2—H2B···Br2v	0.97	2.80	3.649 (5)	147

Table 1

Selected bond lengths (Å)

Bi—Br3	2.7441 (5)
Bi—Br4	2.7714 (5)
Bi—Br5	2.7730 (5)
Bi—Br2	2.8784 (5)
Bi—Br1	2.9746 (5)
Bi—Br1i	3.0056 (5)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Br5	0.91	2.66	3.396 (4)	138
N1—H1⋯Br2	0.91	2.85	3.486 (4)	128
N2—H2C⋯O	0.90	1.91	2.793 (6)	167
N2—H2D⋯Br2ii	0.90	2.60	3.371 (4)	143
O—H2⋯Br5iii	0.94 (1)	2.91 (7)	3.522 (4)	123 (6)
O—H2⋯Br1iii	0.94 (1)	2.84 (7)	3.531 (4)	131 (7)
O—H3⋯Br3iv	0.95 (1)	2.59 (2)	3.501 (4)	162 (6)
C2—H2B⋯Br2v	0.97	2.80	3.649 (5)	147

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) .