Dimorpholinium penta­chloridoanti­monate(III)

Abstract

The asymmetric unit of the title compound, (C₄H₁₀NO)₂[SbCl₅], consists of two morpholinium cations in chair conformations, and a penta­chloridoanti­monate dianion with the Sb^III ion in a slightly distorted square-pyramidal coordination environment. The morpholinium cations are connected to each other by N—H⋯O hydrogen bonds, and they link the chloride anions and the anti­monate SbCl₃ group via N—H⋯Cl contacts.

Related literature

For a phase transition in bis­(ethyl­dimethyl­ammonium) penta­chlorido­anti­monate(III), see: Bujak & Zaleski (1999 ▶); for the structure of N-methyl­piperazinediium penta­chlorido­­anti­monate(III), see: Shen-Tu et al. (2008 ▶); for the low-temperature phase of morpholinium tetra­fluorido­borate, see: Owczarek et al. (2008 ▶).

Experimental

Crystal data

• (C₄H₁₀NO)₂[SbCl₅]

• M _r = 475.26

• Orthorhombic,

• a = 9.0562 (18) Å

• b = 10.273 (2) Å

• c = 18.032 (4) Å

• V = 1677.6 (6) ų

• Z = 4

• Mo Kα radiation

• μ = 2.44 mm⁻¹

• T = 298 K

• 0.25 × 0.20 × 0.20 mm

Data collection

• Rigaku Mercury2 (2× 2 bin mode) diffractometer

• Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.567, T _max = 0.616

• 17552 measured reflections

• 3845 independent reflections

• 3759 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.021

• wR(F ²) = 0.046

• S = 1.24

• 3845 reflections

• 163 parameters

• H-atom parameters constrained

• Δρ_max = 0.32 e Å⁻³

• Δρ_min = −0.66 e Å⁻³

• Absolute structure: Flack (1983 ▶)

• Flack parameter: −0.005 (15)

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: SHELXL97.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1D⋯Cl5i	0.90	2.35	3.180 (2)	154
C1—H1B⋯Cl3ii	0.97	2.82	3.548 (3)	132
N2—H2D⋯Cl5iii	0.90	2.73	3.394 (2)	131
N2—H2C⋯Cl1iv	0.90	2.45	3.306 (3)	159
N2—H2D⋯O1v	0.90	2.44	2.848 (3)	108
N1—H1C⋯Cl3	0.90	2.75	3.463 (3)	137
N1—H1C⋯Cl5	0.90	2.72	3.448 (3)	138

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

supplementary crystallographic information

Comment

Structural investigation of crystalline solids undergoing phase transformation has been one of the classical areas of research among both chemists and physicists. The morpholinium tetrafluoroborate undergoes two reversible phase transitions (Owczarek et al. 2008). In our laboratory, a compound containing two morpholinium cations and a pentachloridoantimonate dianion in the asymmetric unit has been synthesized (Fig. 1), with the Sb^III ion in a slightly distorted square-pyramidal coordination environment.

The Sb atom is coordinated by five Cl atoms, with Sb—Cl distances ranging from 2.4045 (8) to 2.9230 (9) Å. The Sb—Cl distances are similar to the values of 2.4110 (10) to 2.9112 (11) Å reported by Shen-Tu et al. (2008) and slightly different to the values of 2.499 (4)–2.768 (4) Å reported by Bujak & Zaleski (1999). In the title compound the difference between the longest bond (Sb1—Cl5) and shortest bond (Sb1—Cl4) is ca 0.50 Å. The six-membered ring morpholinium cations have chair conformation. The morpholinium cations are connected to each other by N—H···O hydrogen bonds, and they link the Cl^- anions and the antimonate group SbCl₃via N–H···Cl contacts (Table 1, Fig. 2).

Experimental

SbCl₃, morpholine and 20% aqueous HCl in a molar ratio of 1:1:1 were mixed and dissolved in sufficient ethanol by heating to 353 K forming a clear solution. The reaction mixture was cooled slowly to room temperature, crystals of the title compound were formed, collected and washed with dilute aqueous HCl.

Refinement

H atoms were included in calculated positions with N—H = 0.90 and C—H = 0.97 Å and included in the riding-model approximation with U_iso(H) = 1.2U_eq(C, N).

Figures

Fig. 1.

A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.

Fig. 2.

The packing viewed approximately along the b axis. Hydrogen bonds are drawn as dashed lines.

Crystal data

(C4H10NO)2[SbCl5]	F(000) = 936
Mr = 475.26	Dx = 1.882 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3845 reflections
a = 9.0562 (18) Å	θ = 3–27.5°
b = 10.273 (2) Å	µ = 2.44 mm−1
c = 18.032 (4) Å	T = 298 K
V = 1677.6 (6) Å3	Block, colourless
Z = 4	0.25 × 0.20 × 0.20 mm

Data collection

Rigaku Mercury2 (2× 2 bin mode) diffractometer	3845 independent reflections
Radiation source: fine-focus sealed tube	3759 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→13
Tmin = 0.567, Tmax = 0.616	l = −23→23
17552 measured reflections

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021	H-atom parameters constrained
wR(F2) = 0.046	w = 1/[σ2(Fo2) + (0.0201P)2] where P = (Fo2 + 2Fc2)/3
S = 1.24	(Δ/σ)max = 0.003
3845 reflections	Δρmax = 0.32 e Å−3
163 parameters	Δρmin = −0.66 e Å−3
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.005 (15)

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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
C1	0.7135 (3)	0.5818 (4)	0.95313 (17)	0.0425 (8)
H1A	0.7413	0.6730	0.9546	0.051*
H1B	0.7866	0.5329	0.9808	0.051*
C2	0.5653 (4)	0.5651 (3)	0.98887 (17)	0.0431 (7)
H2A	0.5395	0.4735	0.9906	0.052*
H2B	0.5680	0.5980	1.0393	0.052*
C3	0.4560 (3)	0.5973 (4)	0.86593 (18)	0.0459 (8)
H3A	0.3890	0.6514	0.8374	0.055*
H3B	0.4236	0.5076	0.8616	0.055*
C4	0.6092 (3)	0.6104 (3)	0.83609 (17)	0.0440 (8)
H4A	0.6114	0.5797	0.7852	0.053*
H4B	0.6372	0.7016	0.8361	0.053*
C5	0.8890 (4)	0.6967 (3)	0.68509 (19)	0.0461 (8)
H5A	0.7903	0.6605	0.6819	0.055*
H5B	0.9521	0.6478	0.6516	0.055*
C6	0.8854 (3)	0.8366 (3)	0.66122 (19)	0.0442 (8)
H6A	0.8495	0.8431	0.6107	0.053*
H6B	0.8196	0.8858	0.6931	0.053*
C7	1.0960 (3)	0.8730 (3)	0.74228 (15)	0.0376 (6)
H7A	1.0382	0.9243	0.7769	0.045*
H7B	1.1976	0.9028	0.7446	0.045*
C8	1.0880 (4)	0.7312 (3)	0.76295 (16)	0.0411 (7)
H8A	1.1510	0.6814	0.7299	0.049*
H8B	1.1247	0.7199	0.8131	0.049*
Cl1	0.82449 (9)	1.24256 (9)	0.98134 (4)	0.0472 (2)
Cl2	0.55039 (9)	1.24280 (7)	0.82480 (4)	0.04292 (19)
Cl3	0.39146 (8)	0.94495 (7)	0.87224 (4)	0.03967 (18)
Cl4	0.76734 (9)	0.96688 (8)	0.86621 (5)	0.04330 (19)
Cl5	0.60479 (7)	0.89292 (7)	1.04341 (4)	0.03298 (15)
N1	0.4534 (2)	0.6378 (2)	0.94513 (14)	0.0407 (6)
H1C	0.4718	0.7238	0.9483	0.049*
H1D	0.3631	0.6231	0.9641	0.049*
N2	1.0376 (3)	0.8903 (2)	0.66613 (14)	0.0365 (6)
H2C	1.0966	0.8490	0.6336	0.044*
H2D	1.0366	0.9754	0.6544	0.044*
O1	0.7123 (2)	0.5387 (2)	0.87871 (12)	0.0377 (5)
O2	0.9422 (2)	0.6830 (2)	0.75855 (11)	0.0430 (5)
Sb1	0.580748 (19)	1.092473 (15)	0.928491 (9)	0.02418 (5)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0334 (15)	0.054 (2)	0.0404 (17)	0.0040 (17)	−0.0037 (13)	−0.0141 (16)
C2	0.0470 (18)	0.0450 (18)	0.0374 (16)	−0.0036 (16)	0.0051 (15)	−0.0036 (13)
C3	0.0338 (16)	0.053 (2)	0.0507 (19)	0.0112 (17)	−0.0098 (13)	−0.0112 (17)
C4	0.0459 (18)	0.0497 (19)	0.0364 (16)	0.0138 (17)	0.0012 (13)	0.0029 (14)
C5	0.0397 (18)	0.0457 (18)	0.0531 (19)	−0.0173 (15)	−0.0041 (15)	0.0022 (15)
C6	0.0322 (16)	0.0501 (19)	0.0502 (19)	−0.0012 (15)	−0.0070 (14)	0.0157 (15)
C7	0.0376 (15)	0.0393 (15)	0.0360 (15)	−0.0078 (14)	0.0006 (13)	−0.0015 (12)
C8	0.0445 (17)	0.0466 (17)	0.0322 (15)	0.0030 (17)	−0.0056 (15)	0.0060 (12)
Cl1	0.0464 (4)	0.0481 (5)	0.0472 (5)	−0.0051 (4)	0.0000 (4)	−0.0024 (4)
Cl2	0.0547 (5)	0.0364 (4)	0.0377 (4)	−0.0036 (4)	−0.0052 (3)	0.0098 (3)
Cl3	0.0387 (4)	0.0398 (4)	0.0405 (4)	−0.0074 (3)	−0.0098 (3)	0.0001 (3)
Cl4	0.0394 (4)	0.0377 (4)	0.0529 (5)	0.0030 (4)	0.0191 (4)	−0.0080 (3)
Cl5	0.0284 (3)	0.0367 (4)	0.0338 (3)	0.0025 (3)	0.0000 (3)	0.0024 (3)
N1	0.0215 (11)	0.0392 (14)	0.0613 (18)	−0.0020 (10)	0.0108 (11)	−0.0130 (12)
N2	0.0381 (13)	0.0300 (13)	0.0413 (14)	−0.0037 (11)	0.0054 (10)	0.0085 (11)
O1	0.0298 (11)	0.0443 (13)	0.0389 (12)	0.0123 (9)	0.0013 (9)	−0.0074 (10)
O2	0.0443 (12)	0.0420 (11)	0.0427 (12)	−0.0127 (11)	0.0039 (10)	0.0146 (9)
Sb1	0.02303 (8)	0.02452 (8)	0.02498 (8)	−0.00036 (8)	0.00101 (7)	−0.00180 (7)

Geometric parameters (Å, °)

C1—O1	1.413 (4)	C6—N2	1.487 (4)
C1—C2	1.499 (4)	C6—H6A	0.9700
C1—H1A	0.9700	C6—H6B	0.9700
C1—H1B	0.9700	C7—N2	1.482 (4)
C2—N1	1.485 (4)	C7—C8	1.506 (4)
C2—H2A	0.9700	C7—H7A	0.9700
C2—H2B	0.9700	C7—H7B	0.9700
C3—N1	1.488 (4)	C8—O2	1.412 (4)
C3—C4	1.494 (4)	C8—H8A	0.9700
C3—H3A	0.9700	C8—H8B	0.9700
C3—H3B	0.9700	Cl1—Sb1	2.8562 (9)
C4—O1	1.416 (4)	Cl2—Sb1	2.4405 (8)
C4—H4A	0.9700	Cl3—Sb1	2.5028 (8)
C4—H4B	0.9700	Cl4—Sb1	2.4045 (8)
C5—O2	1.417 (4)	N1—H1C	0.9000
C5—C6	1.501 (4)	N1—H1D	0.9000
C5—H5A	0.9700	N2—H2C	0.9000
C5—H5B	0.9700	N2—H2D	0.9000
O1—C1—C2	111.4 (2)	C5—C6—H6B	110.0
O1—C1—H1A	109.3	H6A—C6—H6B	108.4
C2—C1—H1A	109.3	N2—C7—C8	109.1 (2)
O1—C1—H1B	109.3	N2—C7—H7A	109.9
C2—C1—H1B	109.3	C8—C7—H7A	109.9
H1A—C1—H1B	108.0	N2—C7—H7B	109.9
N1—C2—C1	109.0 (3)	C8—C7—H7B	109.9
N1—C2—H2A	109.9	H7A—C7—H7B	108.3
C1—C2—H2A	109.9	O2—C8—C7	111.7 (3)
N1—C2—H2B	109.9	O2—C8—H8A	109.3
C1—C2—H2B	109.9	C7—C8—H8A	109.3
H2A—C2—H2B	108.3	O2—C8—H8B	109.3
N1—C3—C4	109.6 (2)	C7—C8—H8B	109.3
N1—C3—H3A	109.8	H8A—C8—H8B	107.9
C4—C3—H3A	109.8	C2—N1—C3	111.0 (2)
N1—C3—H3B	109.8	C2—N1—H1C	109.4
C4—C3—H3B	109.8	C3—N1—H1C	109.4
H3A—C3—H3B	108.2	C2—N1—H1D	109.4
O1—C4—C3	111.7 (3)	C3—N1—H1D	109.4
O1—C4—H4A	109.3	H1C—N1—H1D	108.0
C3—C4—H4A	109.3	C7—N2—C6	110.0 (2)
O1—C4—H4B	109.3	C7—N2—H2C	109.7
C3—C4—H4B	109.3	C6—N2—H2C	109.7
H4A—C4—H4B	107.9	C7—N2—H2D	109.7
O2—C5—C6	111.7 (3)	C6—N2—H2D	109.7
O2—C5—H5A	109.3	H2C—N2—H2D	108.2
C6—C5—H5A	109.3	C1—O1—C4	111.0 (2)
O2—C5—H5B	109.3	C8—O2—C5	109.6 (2)
C6—C5—H5B	109.3	Cl4—Sb1—Cl2	93.49 (3)
H5A—C5—H5B	107.9	Cl4—Sb1—Cl3	88.12 (3)
N2—C6—C5	108.5 (2)	Cl2—Sb1—Cl3	89.74 (3)
N2—C6—H6A	110.0	Cl4—Sb1—Cl1	84.40 (3)
C5—C6—H6A	110.0	Cl2—Sb1—Cl1	90.06 (3)
N2—C6—H6B	110.0	Cl3—Sb1—Cl1	172.49 (3)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1D···Cl5i	0.90	2.35	3.180 (2)	154
C1—H1B···Cl3ii	0.97	2.82	3.548 (3)	132
N2—H2D···Cl5iii	0.90	2.73	3.394 (2)	131
N2—H2C···Cl1iv	0.90	2.45	3.306 (3)	159
N2—H2D···O1v	0.90	2.44	2.848 (3)	108
N1—H1C···Cl3	0.90	2.75	3.463 (3)	137
N1—H1C···Cl5	0.90	2.72	3.448 (3)	138

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