catena-Poly[4-methyl­morpholin-4-ium [[di­chloridobismuth(III)]-di-μ-chlorido]]

The asymmetric unit of the title complex, {(C₅H₁₂NO)[BiCl₄]}_n, contains two bridging and two cis non-bridging chloride ligands coordinated to a central Bi^III atom, and one 4-methyl­morpholin-4-ium cation. The Bi^III atoms are linked by the bridging chloride ligands into linear chains parallel to the c axis. The chloride ions create a pseudo-octa­hedral geometry about each Bi^III atom. Bifurcated N—H⋯Cl hydrogen bonds link the cations to the anionic chains.

Related literature

For the structures of related amino compounds, see: Turnbull (2007). For the ferroelectric properties of related amino derivatives, see: Fu et al. (2011a,b,c).

Experimental

Crystal data

• (C₅H₁₂NO)[BiCl₄]

• M_r = 452.94

• Monoclinic, C 2/c

• a = 18.166 (4) Å

• b = 9.801 (2) Å

• c = 13.915 (3) Å

• β = 93.36 (3)°

• V = 2473.2 (9) ų

• Z = 8

• Mo Kα radiation

• μ = 15.08 mm⁻¹

• T = 298 K

• 0.10 × 0.05 × 0.05 mm

Data collection

• Rigaku Mercury2 diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) T_min = 0.428, T_max = 0.470

• 12468 measured reflections

• 2830 independent reflections

• 2437 reflections with I > 2σ(I)

• R_int = 0.090

Refinement

• R[F² > 2σ(F²)] = 0.037

• wR(F²) = 0.088

• S = 1.14

• 2830 reflections

• 111 parameters

• H-atom parameters constrained

• Δρ_max = 2.45 e Å⁻³

• Δρ_min = −1.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl3^i	0.90	2.76	3.434 (6)	133
N1—H1⋯Cl2^i	0.90	2.85	3.410 (6)	122
Symmetry code: (i) -x, -y+1, -z.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

S1. Comment

Simple organic salts containing amino cations have attracted attention as materials that display ferroelectric-paraelectric phase transitions (Fu et al., 2011a,b,c). In this study, we describe the crystal structure of the title compound, N-methylmorpholinium catena-Poly[(di-µ₂-chloro)-dichloro Bi^III]

The asymmetric unit contains four independent Cl atoms, one Bi^III atom and one organic cation (Fig. 1). All bond lengths and angles are normal and comparable with those reported for the cation in a related Ni(III) compound (Turnbull, 2007). The non-bridging (Cl1 & Cl2) and bridging Cl (Cl3 & Cl4) atoms create a pseudo-octahedral geometry about each Bi (III) atom. The Bi^III atoms are linked via bridging Cl ions into linear chains that propagate parallel to the c axis.

In the crystal structure, the amino N1 atom is involved in hydrogen bonds with the Cl atoms (Cl2 and Cl3) with the N—H···Cl distance of 3.434 (6) and 3.410 (6) Å, respectively. The bifurcated N—H···Cl H-bonds link the cations to the inorganic anion chain. (Fig. 2, Table 1).

Related literature

For the structures of related amino compounds, see: Turnbull (2007). For the ferroelectric properties of related amino derivatives, see: Fu et al. (2011a,b,c)

S2. Experimental

A mixture of N-methylmorpholine (0.4 mmol), BiCl₃ (0.4 mmol) and HCl/distilled water (10ml, 1:4) sealed in a Teflon-lined stainless steel vessel was maintained at 100 °C. Colorless block crystals suitable for X-ray analysis were obtained after 3 days.

S3. Refinement

All H atoms attached to C atoms were fixed geometrically and treated as riding with C-H = 0.97 Å (methylene) and C-H = 0.96 Å (methyl) with U_iso(H) = 1.2U_eq (methylene) and U_iso(H) = 1.5U_eq (methyl). Positional parameters of the N-bound H atom were intially refined freely, but subsequently restrained using a distance of 0.90 Å and, in the final refinements treated as riding on their parent nitrogen atoms with U_iso(H)=1.2U_eq(N).

Computing details

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A view of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of the title compound showing the one-dimensional chain. Hydrogen atoms not involved in hydrogen bonding have been omitted for clarity.

catena-Poly[4-methylmorpholin-4-ium [[dichloridobismuth(III)]-di-µ-chlorido]]

Crystal data

(C5H12NO)[BiCl4]	F(000) = 1664
Mr = 452.94	Dx = 2.433 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2830 reflections
a = 18.166 (4) Å	θ = 3.6–27.5°
b = 9.801 (2) Å	µ = 15.08 mm^−1
c = 13.915 (3) Å	T = 298 K
β = 93.36 (3)°	Block, colorless
V = 2473.2 (9) Å^3	0.10 × 0.05 × 0.05 mm
Z = 8

Data collection

Rigaku Mercury2 diffractometer	2830 independent reflections
Radiation source: fine-focus sealed tube	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.090
Detector resolution: 13.7 pixels mm^-1	θmax = 27.5°, θmin = 3.6°
CCD profile fitting scans	h = −23→23
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.428, Tmax = 0.470	l = −18→18
12468 measured reflections

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)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.088	w = 1/[σ^2(Fo^2) + (0.015P)^2 + 5.1391P] where P = (Fo^2 + 2Fc^2)/3
S = 1.14	(Δ/σ)max < 0.001
2830 reflections	Δρmax = 2.45 e Å^−3
111 parameters	Δρmin = −1.44 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0095 (2)

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
Bi1	0.038523 (12)	0.36337 (2)	−0.101352 (17)	0.02581 (15)
Cl4	−0.02461 (14)	0.3417 (2)	0.06880 (17)	0.0494 (6)
Cl3	−0.10115 (11)	0.3718 (2)	−0.22296 (15)	0.0407 (5)
Cl2	0.02635 (11)	0.1057 (2)	−0.11236 (16)	0.0438 (5)
Cl1	0.16693 (12)	0.3571 (2)	−0.02381 (18)	0.0568 (7)
N1	0.1587 (3)	0.9444 (6)	0.1521 (4)	0.0342 (14)
H1	0.1239	0.9003	0.1835	0.041*
O1	0.1918 (3)	1.1380 (6)	0.3004 (5)	0.0564 (18)
C2	0.2251 (4)	0.9334 (8)	0.2192 (6)	0.045 (2)
H2A	0.2371	0.8380	0.2299	0.054*
H2B	0.2667	0.9766	0.1907	0.054*
C1	0.2122 (4)	0.9995 (9)	0.3123 (5)	0.046 (2)
H1B	0.1735	0.9510	0.3432	0.055*
H1C	0.2568	0.9938	0.3540	0.055*
C4	0.1376 (5)	1.0896 (9)	0.1428 (6)	0.049 (2)
H4A	0.1754	1.1389	0.1106	0.058*
H4B	0.0917	1.0974	0.1040	0.058*
C5	0.1287 (5)	1.1502 (9)	0.2384 (8)	0.059 (3)
H5A	0.1166	1.2461	0.2305	0.070*
H5B	0.0878	1.1060	0.2675	0.070*
C3	0.1707 (6)	0.8803 (10)	0.0586 (8)	0.075 (3)
H3A	0.1258	0.8837	0.0185	0.113*
H3B	0.1852	0.7869	0.0685	0.113*
H3C	0.2088	0.9284	0.0277	0.113*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0243 (2)	0.0229 (2)	0.0303 (2)	0.00046 (9)	0.00217 (12)	−0.00330 (11)
Cl4	0.0746 (15)	0.0284 (11)	0.0480 (12)	−0.0059 (9)	0.0276 (11)	−0.0025 (9)
Cl3	0.0254 (10)	0.0589 (15)	0.0384 (11)	0.0057 (7)	0.0067 (8)	0.0025 (9)
Cl2	0.0409 (11)	0.0212 (10)	0.0692 (15)	0.0001 (8)	0.0033 (10)	−0.0040 (10)
Cl1	0.0340 (12)	0.0697 (18)	0.0647 (15)	−0.0136 (9)	−0.0135 (10)	0.0200 (11)
N1	0.035 (3)	0.036 (4)	0.033 (3)	−0.012 (3)	0.010 (2)	0.003 (3)
O1	0.052 (4)	0.049 (4)	0.068 (4)	−0.010 (3)	−0.003 (3)	−0.010 (3)
C2	0.029 (4)	0.033 (5)	0.071 (6)	0.001 (3)	−0.002 (4)	0.006 (4)
C1	0.040 (5)	0.058 (6)	0.040 (5)	−0.011 (4)	0.002 (3)	0.007 (4)
C4	0.050 (5)	0.037 (5)	0.058 (6)	−0.003 (4)	−0.004 (4)	0.021 (5)
C5	0.043 (6)	0.046 (6)	0.088 (8)	0.005 (4)	0.009 (5)	0.018 (5)
C3	0.080 (8)	0.070 (8)	0.078 (8)	−0.035 (5)	0.018 (6)	−0.012 (6)

Geometric parameters (Å, º)

Bi1—Cl1	2.513 (2)	C2—C1	1.480 (11)
Bi1—Cl2	2.539 (2)	C2—H2A	0.9700
Bi1—Cl4	2.699 (2)	C2—H2B	0.9700
Bi1—Cl3^i	2.758 (2)	C1—H1B	0.9700
Bi1—Cl4^ii	2.939 (2)	C1—H1C	0.9700
Bi1—Cl3	2.967 (2)	C4—C5	1.475 (13)
Cl4—Bi1^ii	2.939 (2)	C4—H4A	0.9700
Cl3—Bi1^i	2.758 (2)	C4—H4B	0.9700
N1—C3	1.473 (12)	C5—H5A	0.9700
N1—C4	1.476 (9)	C5—H5B	0.9700
N1—C2	1.486 (9)	C3—H3A	0.9600
N1—H1	0.9000	C3—H3B	0.9600
O1—C5	1.399 (11)	C3—H3C	0.9600
O1—C1	1.415 (10)
Cl1—Bi1—Cl2	94.42 (7)	C1—C2—H2B	109.5
Cl1—Bi1—Cl4	93.03 (9)	N1—C2—H2B	109.5
Cl2—Bi1—Cl4	86.25 (6)	H2A—C2—H2B	108.1
Cl1—Bi1—Cl3^i	87.74 (8)	O1—C1—C2	111.8 (7)
Cl2—Bi1—Cl3^i	90.88 (6)	O1—C1—H1B	109.3
Cl4—Bi1—Cl3^i	177.08 (6)	C2—C1—H1B	109.3
Cl1—Bi1—Cl4^ii	92.51 (7)	O1—C1—H1C	109.3
Cl2—Bi1—Cl4^ii	168.41 (7)	C2—C1—H1C	109.3
Cl4—Bi1—Cl4^ii	84.11 (6)	H1B—C1—H1C	107.9
Cl3^i—Bi1—Cl4^ii	98.68 (6)	C5—C4—N1	110.5 (7)
Cl1—Bi1—Cl3	170.68 (7)	C5—C4—H4A	109.5
Cl2—Bi1—Cl3	85.68 (6)	N1—C4—H4A	109.5
Cl4—Bi1—Cl3	96.28 (7)	C5—C4—H4B	109.5
Cl3^i—Bi1—Cl3	82.94 (6)	N1—C4—H4B	109.5
Cl4^ii—Bi1—Cl3	88.98 (6)	H4A—C4—H4B	108.1
Bi1—Cl4—Bi1^ii	95.89 (6)	O1—C5—C4	113.1 (7)
Bi1^i—Cl3—Bi1	96.97 (6)	O1—C5—H5A	109.0
C3—N1—C4	112.6 (7)	C4—C5—H5A	109.0
C3—N1—C2	111.5 (7)	O1—C5—H5B	109.0
C4—N1—C2	108.8 (6)	C4—C5—H5B	109.0
C3—N1—H1	111.6	H5A—C5—H5B	107.8
C4—N1—H1	108.7	N1—C3—H3A	109.5
C2—N1—H1	103.1	N1—C3—H3B	109.5
C5—O1—C1	110.7 (6)	H3A—C3—H3B	109.5
C1—C2—N1	110.7 (6)	N1—C3—H3C	109.5
C1—C2—H2A	109.5	H3A—C3—H3C	109.5
N1—C2—H2A	109.5	H3B—C3—H3C	109.5

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl3^ii	0.90	2.76	3.434 (6)	133
N1—H1···Cl2^ii	0.90	2.85	3.410 (6)	122

Symmetry code: (ii) −x, −y+1, −z.