Bromidobis(morpholine-4-dithio­carboxyl­ato-κ²S,S′)anti­mony(III)

In the title compound, [SbBr(C₄₅H₈NOS₂)₂], both organic ligands bond to Sb in an S,S′-bidentate mode, although one of the Sb—S bond lengths is much longer than the other three. A bromide ion completes the very distorted trigonal–bipyramidal geometry about the Sb atom.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.015 Å
• R factor = 0.052
• wR factor = 0.160
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.60
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         16

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.601
            Tmax scaled      0.155 Tmin scaled      0.138
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Dialkyl-substituted dithiocarbamate anions have proved to be highly versatile chelating agents for the separation of metals as metal chelates using gas chromatography. Some dialkyl-substituted dithiocarbamate salts have also shown interesting biological effects which include anti-alkylation or anti-HIV properties (Sheng et al., 1999). Here, we report the synthesis and structure of the title compound, (I).

The Sb atom is five-coordinated with a distorted trigonal bipyramidal geometry (Table 1, Fig. 1). Around the central Sb atom, atoms S1, S3, S4 occupy the equatorial plane, while Br1 and S2 lie in axial sites. The axial bond angle [150.27 (6)°] deviates from linearity by over 29°. The sum of the S3—Sb1—S4 [66.17 (7)°], S3—Sb1—S1 [89.32 (8)°] and S1—Sb1—S4 [139.75 (7)°] bond angles is 295.2°, which shows that these atoms have large deviations from ideal trigonal bipyramidal geometry. The C—S bonds associated with the strong Sb—S bonds are significantly longer than that associated with the weak Sb—S bonds, suggesting some delocation in the system.

In the crystal, a two-dimensional chain network arises from intermolecular weak Sb···S and S···S contacts (Fig. 2).

Related literature

For background, see: Sheng et al. (1999).

S2. Experimental

Morpholinyldithiocarbamate (371 mg, 2 mmol) was added to a stirring solution containing tribromoantimony (362 mg, 1 mmol) in ethanol (80 ml). After stirring for 8 h at room temperature, a yellow solution was obtained and then filtered. The resulting solution was evaporated under vacuum until the title compound was obtaibed as a yellow solid, which was recrystallized from methanol/dichloromethane (2:1 v/v) to give yellow blocks of (I); yield 76%, m.p. 507 K. Anal. Calcd (%) for C₁₀H₁₆BrN₂O₂S₄Sb: C 22.83; H 3.06; N 5.32; Found: C 22.71; H 3.19; N 5.49.

S3. Refinement

The H atoms were positioned geometrically (C—H = 0.97 Å) and refined as riding with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker 1998); cell refinement: SAINT (Bruker 1998); data reduction: SAINT (Bruker 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 1998); software used to prepare material for publication: SHELXL97 (Bruker 1998).

Figures

	Fig. 1. The molecular structure of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 30% probability level.
	Fig. 2. A packing diagram for (I). H atoms have been omitted for clarity.

Bromidobis(morpholine-4-dithiocarboxylato-κ²S,S')antimony(III)

Crystal data

[SbBr(C5H8NOS2)2]	Z = 2
Mr = 526.15	F(000) = 512
Triclinic, P1	Dx = 2.000 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.428 (2) Å	Cell parameters from 2859 reflections
b = 11.175 (4) Å	θ = 2.9–28.0°
c = 13.241 (4) Å	µ = 4.34 mm^−1
α = 71.060 (4)°	T = 293 K
β = 81.796 (4)°	Block, yellow
γ = 76.924 (3)°	0.48 × 0.46 × 0.43 mm
V = 873.8 (5) Å^3

Data collection

Bruker SMART CCD diffractometer	3044 independent reflections
Radiation source: fine-focus sealed tube	2616 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→7
Tmin = 0.230, Tmax = 0.257	k = −13→13
4592 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0961P)^2 + 5.9643P] where P = (Fo^2 + 2Fc^2)/3
3044 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 2.02 e Å^−3
0 restraints	Δρmin = −1.04 e Å^−3

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
Sb1	−0.00045 (9)	0.46615 (5)	0.32671 (4)	0.0291 (2)
Br1	0.16432 (17)	0.69319 (9)	0.27216 (8)	0.0455 (3)
N1	0.2808 (12)	0.1526 (7)	0.5928 (6)	0.0327 (16)
N2	0.2041 (11)	0.3082 (7)	0.0529 (6)	0.0326 (16)
O1	0.5164 (13)	−0.0596 (7)	0.7403 (6)	0.0519 (18)
O2	0.3961 (12)	0.1478 (7)	−0.0739 (5)	0.0477 (17)
S1	0.2747 (4)	0.3940 (2)	0.46525 (18)	0.0347 (5)
S2	0.0126 (4)	0.2235 (2)	0.43813 (19)	0.0402 (6)
S3	0.2845 (3)	0.4096 (2)	0.19460 (18)	0.0336 (5)
S4	−0.1470 (3)	0.3730 (2)	0.17329 (19)	0.0375 (5)
C1	0.1961 (13)	0.2443 (8)	0.5102 (7)	0.0299 (18)
C2	0.4261 (16)	0.1714 (9)	0.6596 (8)	0.041 (2)
H2A	0.3463	0.1874	0.7234	0.049*
H2B	0.4890	0.2461	0.6204	0.049*
C3	0.6012 (17)	0.0538 (9)	0.6913 (9)	0.047 (2)
H3A	0.6928	0.0451	0.6282	0.056*
H3B	0.6882	0.0647	0.7406	0.056*
C4	0.3955 (18)	−0.0798 (9)	0.6673 (9)	0.048 (3)
H4A	0.3447	−0.1602	0.6996	0.057*
H4B	0.4857	−0.0857	0.6031	0.057*
C5	0.2063 (16)	0.0308 (9)	0.6381 (8)	0.042 (2)
H5A	0.1272	0.0182	0.5864	0.050*
H5B	0.1108	0.0329	0.7015	0.050*
C6	0.1182 (13)	0.3570 (7)	0.1320 (6)	0.0270 (17)
C7	0.4269 (14)	0.3060 (9)	0.0091 (8)	0.038 (2)
H7A	0.5094	0.3198	0.0588	0.046*
H7B	0.4328	0.3750	−0.0579	0.046*
C8	0.5227 (16)	0.1772 (9)	−0.0101 (8)	0.041 (2)
H8A	0.6655	0.1798	−0.0452	0.049*
H8B	0.5349	0.1099	0.0582	0.049*
C9	0.1872 (17)	0.1407 (10)	−0.0235 (8)	0.046 (2)
H9A	0.1969	0.0745	0.0455	0.055*
H9B	0.1049	0.1163	−0.0670	0.055*
C10	0.0739 (17)	0.2665 (11)	−0.0077 (9)	0.049 (3)
H10A	0.0500	0.3311	−0.0767	0.059*
H10B	−0.0643	0.2572	0.0311	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Sb1	0.0306 (3)	0.0284 (3)	0.0290 (3)	−0.0039 (2)	−0.0028 (2)	−0.0107 (2)
Br1	0.0604 (7)	0.0351 (5)	0.0466 (6)	−0.0170 (5)	−0.0012 (5)	−0.0156 (4)
N1	0.035 (4)	0.030 (4)	0.032 (4)	−0.009 (3)	−0.007 (3)	−0.004 (3)
N2	0.027 (4)	0.036 (4)	0.042 (4)	−0.005 (3)	−0.006 (3)	−0.020 (3)
O1	0.069 (5)	0.037 (4)	0.047 (4)	−0.010 (3)	−0.025 (4)	0.000 (3)
O2	0.058 (4)	0.050 (4)	0.043 (4)	−0.010 (3)	0.000 (3)	−0.026 (3)
S1	0.0436 (13)	0.0311 (11)	0.0342 (11)	−0.0125 (9)	−0.0104 (9)	−0.0099 (9)
S2	0.0489 (14)	0.0360 (12)	0.0401 (13)	−0.0165 (10)	−0.0160 (10)	−0.0067 (10)
S3	0.0260 (11)	0.0441 (12)	0.0407 (12)	−0.0111 (9)	−0.0009 (9)	−0.0243 (10)
S4	0.0253 (11)	0.0490 (13)	0.0432 (13)	−0.0070 (10)	−0.0045 (9)	−0.0200 (11)
C1	0.027 (4)	0.033 (4)	0.032 (4)	−0.009 (3)	−0.001 (3)	−0.011 (4)
C2	0.053 (6)	0.034 (5)	0.039 (5)	−0.005 (4)	−0.015 (4)	−0.013 (4)
C3	0.047 (6)	0.043 (5)	0.053 (6)	−0.010 (5)	−0.023 (5)	−0.009 (5)
C4	0.065 (7)	0.033 (5)	0.045 (6)	−0.014 (5)	−0.021 (5)	−0.001 (4)
C5	0.046 (6)	0.034 (5)	0.044 (5)	−0.017 (4)	−0.005 (4)	−0.002 (4)
C6	0.028 (4)	0.023 (4)	0.031 (4)	−0.008 (3)	−0.008 (3)	−0.007 (3)
C7	0.035 (5)	0.041 (5)	0.042 (5)	−0.011 (4)	−0.004 (4)	−0.016 (4)
C8	0.044 (5)	0.045 (5)	0.035 (5)	−0.004 (4)	−0.003 (4)	−0.017 (4)
C9	0.055 (6)	0.045 (6)	0.050 (6)	−0.011 (5)	−0.011 (5)	−0.025 (5)
C10	0.044 (6)	0.063 (7)	0.055 (6)	−0.007 (5)	−0.013 (5)	−0.036 (5)

Geometric parameters (Å, º)

Sb1—S3	2.469 (2)	C2—H2A	0.9700
Sb1—S1	2.542 (2)	C2—H2B	0.9700
Sb1—S2	2.621 (2)	C3—H3A	0.9700
Sb1—S4	2.909 (2)	C3—H3B	0.9700
Sb1—Br1	2.8087 (14)	C4—C5	1.517 (14)
N1—C1	1.317 (11)	C4—H4A	0.9700
N1—C5	1.458 (11)	C4—H4B	0.9700
N1—C2	1.464 (12)	C5—H5A	0.9700
N2—C6	1.330 (11)	C5—H5B	0.9700
N2—C7	1.464 (11)	C7—C8	1.518 (13)
N2—C10	1.474 (12)	C7—H7A	0.9700
O1—C3	1.414 (12)	C7—H7B	0.9700
O1—C4	1.423 (12)	C8—H8A	0.9700
O2—C8	1.408 (12)	C8—H8B	0.9700
O2—C9	1.419 (12)	C9—C10	1.495 (14)
S1—C1	1.748 (9)	C9—H9A	0.9700
S2—C1	1.716 (9)	C9—H9B	0.9700
S3—C6	1.740 (8)	C10—H10A	0.9700
S4—C6	1.702 (8)	C10—H10B	0.9700
C2—C3	1.510 (13)
S3—Sb1—S1	89.32 (8)	O1—C4—H4A	109.7
S3—Sb1—S2	92.18 (8)	C5—C4—H4A	109.7
S1—Sb1—S2	69.49 (7)	O1—C4—H4B	109.7
S3—Sb1—Br1	83.76 (6)	C5—C4—H4B	109.7
S1—Sb1—Br1	80.99 (6)	H4A—C4—H4B	108.2
S2—Sb1—Br1	150.27 (6)	N1—C5—C4	110.0 (8)
S3—Sb1—S4	66.17 (7)	N1—C5—H5A	109.7
S1—Sb1—S4	139.75 (7)	C4—C5—H5A	109.7
S2—Sb1—S4	79.63 (7)	N1—C5—H5B	109.7
Br1—Sb1—S4	124.28 (6)	C4—C5—H5B	109.7
C1—N1—C5	122.2 (8)	H5A—C5—H5B	108.2
C1—N1—C2	123.5 (7)	N2—C6—S4	123.2 (6)
C5—N1—C2	113.3 (7)	N2—C6—S3	118.3 (6)
C6—N2—C7	123.8 (7)	S4—C6—S3	118.5 (5)
C6—N2—C10	122.0 (7)	N2—C7—C8	110.1 (7)
C7—N2—C10	113.7 (7)	N2—C7—H7A	109.6
C3—O1—C4	110.0 (7)	C8—C7—H7A	109.6
C8—O2—C9	110.7 (7)	N2—C7—H7B	109.6
C1—S1—Sb1	87.9 (3)	C8—C7—H7B	109.6
C1—S2—Sb1	86.0 (3)	H7A—C7—H7B	108.1
C6—S3—Sb1	94.4 (3)	O2—C8—C7	111.4 (8)
C6—S4—Sb1	80.8 (3)	O2—C8—H8A	109.3
N1—C1—S2	122.9 (6)	C7—C8—H8A	109.3
N1—C1—S1	120.7 (6)	O2—C8—H8B	109.3
S2—C1—S1	116.3 (5)	C7—C8—H8B	109.3
N1—C2—C3	110.4 (7)	H8A—C8—H8B	108.0
N1—C2—H2A	109.6	O2—C9—C10	111.6 (9)
C3—C2—H2A	109.6	O2—C9—H9A	109.3
N1—C2—H2B	109.6	C10—C9—H9A	109.3
C3—C2—H2B	109.6	O2—C9—H9B	109.3
H2A—C2—H2B	108.1	C10—C9—H9B	109.3
O1—C3—C2	111.6 (8)	H9A—C9—H9B	108.0
O1—C3—H3A	109.3	N2—C10—C9	109.7 (8)
C2—C3—H3A	109.3	N2—C10—H10A	109.7
O1—C3—H3B	109.3	C9—C10—H10A	109.7
C2—C3—H3B	109.3	N2—C10—H10B	109.7
H3A—C3—H3B	108.0	C9—C10—H10B	109.7
O1—C4—C5	109.9 (9)	H10A—C10—H10B	108.2