Bis(morpholinium) tetra­iodo­(morpholine-4-carbodithio­ato-κ²S,S′)bis­muth(III)

The crystal structure of the title compound, (C₄H₁₀NO)₂[Bi(C₅H₈NOS₂)I₄], the Bi^III complex anions and morpholinium cations. The Bi^III ion is coordinated by four I⁻ anions and two S atoms from a morpholine-4-carbodithio­ate (mcda) dianion with a distorted octa­hedral coordination geometry. In the anion, Bi, the CS₂ atoms, N, O and two I atoms are located on a mirror plane; the morpholine C atoms of the mcda ligand are disordered on both sides of the mirror plane. N—H...I hydrogen bonding between the morpholinium cation and the Bi^III complex stabilize the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.020 Å
• Disorder in main residue
• R factor = 0.049
• wR factor = 0.128
• Data-to-parameter ratio = 16.5

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.111
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT076_ALERT_1_C Occupancy       0.50 less than 1.0 for Sp.pos  .        H3B
PLAT301_ALERT_3_C Main Residue  Disorder .........................      22.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         20
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.24 Ratio

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

   5 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
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Bis(morpholinium) tetraiodo(morpholine-4-carbodithioato-κ²S,S')bismuth(III)

Crystal data

(C4H10NO)2[Bi(C5H8NOS2)I4]	F(000) = 1912
Mr = 1055.08	Dx = 2.592 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3265 reflections
a = 9.3320 (19) Å	θ = 2.4–24.4°
b = 14.561 (3) Å	µ = 11.26 mm^−1
c = 19.901 (4) Å	T = 298 K
V = 2704.2 (10) Å^3	Block, orange–red
Z = 4	0.25 × 0.24 × 0.23 mm

Data collection

Siemens SMART CCD area-detector diffractometer	2449 independent reflections
Radiation source: fine-focus sealed tube	1731 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.111
φ and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
Tmin = 0.068, Tmax = 0.075	k = −13→17
13326 measured reflections	l = −23→23

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0326P)^2 + 20.8113P] where P = (Fo^2 + 2Fc^2)/3
2449 reflections	(Δ/σ)max < 0.001
148 parameters	Δρmax = 2.09 e Å^−3
109 restraints	Δρmin = −2.09 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	Occ. (<1)
Bi1	0.65083 (6)	0.2500	0.59690 (3)	0.0434 (2)
I1	0.63745 (10)	0.46001 (6)	0.60328 (5)	0.0593 (3)
I2	0.99251 (11)	0.2500	0.56430 (6)	0.0516 (3)
I3	0.43808 (13)	0.2500	0.72364 (6)	0.0540 (4)
N1	0.4030 (16)	0.2500	0.4035 (8)	0.076 (4)
N2	0.2311 (11)	0.4240 (8)	0.6326 (5)	0.063 (3)
H2A	0.3208	0.4014	0.6344	0.076*
H2B	0.1717	0.3777	0.6216	0.076*
O1	0.2440 (16)	0.2500	0.2880 (8)	0.093 (4)
O2	0.0526 (12)	0.5771 (7)	0.6466 (7)	0.090 (3)
S1	0.3965 (4)	0.2500	0.5379 (2)	0.0483 (11)
S2	0.6656 (4)	0.2500	0.4614 (3)	0.0531 (12)
C1	0.4835 (16)	0.2500	0.4632 (8)	0.052 (4)
C2	0.254 (2)	0.2856 (17)	0.4059 (13)	0.067 (5)	0.50
H2C	0.2497	0.3507	0.3959	0.081*	0.50
H2D	0.2102	0.2747	0.4495	0.081*	0.50
C3	0.178 (2)	0.231 (2)	0.3514 (10)	0.078 (6)	0.50
H3A	0.1850	0.1660	0.3612	0.094*	0.50
H3B	0.0779	0.2479	0.3499	0.094*	0.50
C4	0.391 (2)	0.225 (2)	0.2878 (14)	0.083 (6)	0.50
H4A	0.4306	0.2385	0.2437	0.100*	0.50
H4B	0.4042	0.1601	0.2964	0.100*	0.50
C5	0.473 (3)	0.2844 (18)	0.3388 (13)	0.070 (5)	0.50
H5A	0.4578	0.3498	0.3329	0.084*	0.50
H5B	0.5745	0.2712	0.3381	0.084*	0.50
C6	0.0808 (15)	0.5420 (11)	0.5821 (8)	0.081 (5)
H6A	0.0798	0.5916	0.5496	0.098*
H6B	0.0064	0.4985	0.5698	0.098*
C7	0.2240 (16)	0.4950 (12)	0.5806 (8)	0.084 (5)
H7A	0.2390	0.4674	0.5368	0.101*
H7B	0.2992	0.5399	0.5880	0.101*
C8	0.1912 (14)	0.4601 (10)	0.6989 (7)	0.069 (4)
H8A	0.2629	0.5037	0.7139	0.082*
H8B	0.1874	0.4102	0.7312	0.082*
C9	0.0485 (15)	0.5061 (12)	0.6952 (7)	0.084 (5)
H9A	−0.0243	0.4616	0.6831	0.101*
H9B	0.0241	0.5316	0.7388	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.0342 (3)	0.0467 (4)	0.0493 (5)	0.000	0.0029 (3)	0.000
I1	0.0666 (6)	0.0474 (5)	0.0639 (7)	−0.0041 (4)	0.0074 (4)	0.0011 (4)
I2	0.0327 (6)	0.0642 (8)	0.0580 (8)	0.000	0.0022 (5)	0.000
I3	0.0602 (7)	0.0567 (7)	0.0450 (8)	0.000	0.0023 (5)	0.000
N1	0.051 (7)	0.115 (10)	0.063 (9)	0.000	0.010 (6)	0.000
N2	0.054 (6)	0.069 (8)	0.066 (9)	0.019 (6)	−0.007 (6)	−0.008 (6)
O1	0.074 (7)	0.128 (10)	0.077 (8)	0.000	−0.006 (6)	0.000
O2	0.103 (9)	0.065 (7)	0.102 (10)	0.032 (6)	−0.002 (7)	0.003 (7)
S1	0.033 (2)	0.068 (3)	0.044 (3)	0.000	0.0070 (17)	0.000
S2	0.033 (2)	0.071 (3)	0.056 (3)	0.000	0.0110 (19)	0.000
C1	0.034 (7)	0.071 (10)	0.051 (9)	0.000	0.004 (6)	0.000
C2	0.044 (8)	0.092 (11)	0.066 (10)	0.016 (7)	−0.002 (8)	−0.002 (8)
C3	0.057 (9)	0.109 (13)	0.068 (10)	−0.001 (9)	−0.007 (8)	−0.007 (9)
C4	0.068 (9)	0.114 (13)	0.067 (11)	0.005 (9)	0.011 (8)	−0.009 (9)
C5	0.052 (9)	0.097 (11)	0.060 (10)	0.001 (8)	0.008 (8)	−0.005 (8)
C6	0.075 (11)	0.097 (13)	0.071 (13)	0.005 (9)	−0.009 (9)	0.034 (10)
C7	0.078 (11)	0.125 (15)	0.050 (10)	0.005 (10)	0.019 (8)	0.013 (10)
C8	0.079 (10)	0.081 (11)	0.046 (10)	0.006 (8)	−0.009 (7)	0.007 (8)
C9	0.083 (11)	0.120 (14)	0.049 (10)	0.028 (10)	0.013 (8)	−0.010 (10)

Geometric parameters (Å, º)

Bi1—I1^i	3.0631 (11)	C2—C3	1.516 (18)
Bi1—I1	3.0631 (11)	C2—H2C	0.9700
Bi1—I2	3.2539 (13)	C2—H2D	0.9700
Bi1—I3	3.2099 (15)	C3—H3A	0.9700
Bi1—S1	2.648 (4)	C3—H3B	0.9700
Bi1—S2	2.701 (5)	C4—C4^i	0.72 (6)
N1—C1	1.405 (15)	C4—C5^i	1.27 (3)
N1—C2^i	1.488 (17)	C4—C5	1.533 (18)
N1—C2	1.488 (16)	C4—H4A	0.9700
N1—C5^i	1.53 (3)	C4—H4B	0.9700
N1—C5	1.53 (3)	C5—C5^i	1.00 (5)
N2—C7	1.464 (13)	C5—C4^i	1.27 (3)
N2—C8	1.469 (13)	C5—H5A	0.9700
N2—H2A	0.9000	C5—H5B	0.9700
N2—H2B	0.9000	C6—C7	1.501 (15)
O1—C4^i	1.421 (17)	C6—H6A	0.9700
O1—C4	1.421 (17)	C6—H6B	0.9700
O1—C3^i	1.429 (17)	C7—H7A	0.9700
O1—C3	1.429 (17)	C7—H7B	0.9700
O2—C6	1.406 (14)	C8—C9	1.492 (14)
O2—C9	1.417 (14)	C8—H8A	0.9700
S1—C1	1.694 (17)	C8—H8B	0.9700
S2—C1	1.700 (15)	C9—H9A	0.9700
C2—C2^i	1.04 (5)	C9—H9B	0.9700
C2—C3^i	1.31 (3)
I1^i—Bi1—I1	173.33 (4)	O1—C3—C2	109 (2)
S1—Bi1—S2	66.61 (13)	O1—C3—H3A	109.8
S1—Bi1—I1^i	88.96 (2)	C2—C3—H3A	109.8
S2—Bi1—I1^i	92.49 (2)	O1—C3—H3B	109.8
S1—Bi1—I1	88.96 (2)	C2—C3—H3B	109.8
S2—Bi1—I1	92.49 (2)	H3A—C3—H3B	108.2
S1—Bi1—I3	78.10 (10)	C5^i—C4—O1	127 (2)
S2—Bi1—I3	144.72 (9)	C4^i—C4—C5	55.8 (15)
I1^i—Bi1—I3	86.69 (2)	O1—C4—C5	109.4 (19)
I1—Bi1—I3	86.69 (2)	C5^i—C4—H4A	121.1
S1—Bi1—I2	142.19 (10)	O1—C4—H4A	108.5
S2—Bi1—I2	75.57 (9)	C5—C4—H4A	107.3
I1^i—Bi1—I2	92.76 (2)	C5^i—C4—H4B	71.3
I1—Bi1—I2	92.76 (2)	O1—C4—H4B	111.6
I2—Bi1—I3	139.71 (4)	C5—C4—H4B	111.7
C1—N1—C2^i	118.3 (15)	H4A—C4—H4B	108.1
C1—N1—C2	118.3 (15)	C4^i—C5—N1	113 (2)
C1—N1—C5^i	119.1 (15)	N1—C5—C4	99.4 (19)
C2^i—N1—C5^i	108.1 (16)	C4^i—C5—H5A	85.7
C2—N1—C5^i	122.6 (17)	N1—C5—H5A	111.3
C1—N1—C5	119.1 (15)	C4—C5—H5A	113.7
C2^i—N1—C5	122.6 (17)	C4^i—C5—H5B	123.5
C2—N1—C5	108.1 (16)	N1—C5—H5B	111.3
C7—N2—C8	111.7 (11)	C4—C5—H5B	111.4
C7—N2—H2A	109.3	H5A—C5—H5B	109.4
C8—N2—H2A	109.3	O2—C6—C7	110.5 (12)
C7—N2—H2B	109.3	O2—C6—H6A	109.6
C8—N2—H2B	109.3	C7—C6—H6A	109.6
H2A—N2—H2B	107.9	O2—C6—H6B	109.6
C4^i—O1—C3^i	111.6 (18)	C7—C6—H6B	109.6
C4—O1—C3^i	117.8 (17)	H6A—C6—H6B	108.1
C4^i—O1—C3	117.8 (17)	N2—C7—C6	110.4 (11)
C4—O1—C3	111.6 (18)	N2—C7—H7A	109.6
C6—O2—C9	111.3 (12)	C6—C7—H7A	109.6
C1—S1—Bi1	87.7 (5)	N2—C7—H7B	109.6
C1—S2—Bi1	85.8 (6)	C6—C7—H7B	109.6
N1—C1—S1	119.1 (12)	H7A—C7—H7B	108.1
N1—C1—S2	121.1 (13)	N2—C8—C9	110.0 (10)
S1—C1—S2	119.9 (10)	N2—C8—H8A	109.7
C2^i—C2—C3^i	79 (2)	C9—C8—H8A	109.7
C2^i—C2—N1	69.6 (10)	N2—C8—H8B	109.7
C3^i—C2—N1	114 (2)	C9—C8—H8B	109.7
N1—C2—C3	103.2 (17)	H8A—C8—H8B	108.2
C3^i—C2—H2C	89.4	O2—C9—C8	109.7 (12)
N1—C2—H2C	111.7	O2—C9—H9A	109.7
C3—C2—H2C	110.2	C8—C9—H9A	109.7
C3^i—C2—H2D	118.9	O2—C9—H9B	109.7
N1—C2—H2D	111.3	C8—C9—H9B	109.7
C3—C2—H2D	111.1	H9A—C9—H9B	108.2
H2C—C2—H2D	109.2

Symmetry code: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···I3	0.90	3.03	3.665 (10)	129
N2—H2B···I2^ii	0.90	2.75	3.636 (12)	169

Symmetry code: (ii) x−1, y, z.