Bis(diethyl­enetriamine)cobalt(II) tetra­thio­molybdate(VI) oxotrithia­molybdate(VI)

In the crystal structure of the title compound, [Co(C₄H₁₃N₃)₂]₂[MoS₄][MoS₃O], discrete [MoS₄]^2- and [MoS₃O]^2- anions, as well as [Co(C₄H₁₃N₃)₂]²⁺ cations are found. Both anions occupy the same crystallographic position and are therefore disordered. The Co atom is octa­hedrally coordinated by six N atoms of the diethyl­enetriamine ligand whereas the Mo atom shows a distorted tetra­hedral geometry.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• Disorder in main residue
• R factor = 0.041
• wR factor = 0.098
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.95

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C14
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mo1
PLAT301_ALERT_3_C Main Residue  Disorder .........................       5.00 Perc.
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          9

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

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

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Computing details

Data collection: IPDS Program Package (Stoe & Cie, 1998); cell refinement: IPDS Program Package; data reduction: IPDS Program Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: CIFTAB in SHELXTL.

Bis(diethylenetriamine)cobalt(II) tetrathiomolybdate(VI) oxotrithiamolybdate(VI)

Crystal data

[Co(C4H13N3)2]2[MoS4][MoOS3]	F(000) = 980
Mr = 962.86	Dx = 1.761 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8000 reflections
a = 7.4164 (5) Å	θ = 3–25°
b = 15.9171 (11) Å	µ = 2.01 mm^−1
c = 15.4070 (12) Å	T = 293 K
β = 93.063 (9)°	Block, red–orange
V = 1816.2 (2) Å^3	0.09 × 0.09 × 0.08 mm
Z = 2

Data collection

Stoe IPDS-1 diffractometer	2455 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.048
Graphite monochromator	θmax = 25.7°, θmin = 2.6°
φ scans	h = −8→8
11766 measured reflections	k = −19→19
3269 independent reflections	l = −18→18

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)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.099	w = 1/[σ^2(Fo^2) + (0.0458P)^2 + 2.2351P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
3269 reflections	Δρmax = 0.55 e Å^−3
191 parameters	Δρmin = −0.60 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0022 (6)

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)
Mo1	0.60412 (7)	0.39189 (3)	0.70067 (3)	0.04170 (17)
S1	0.5524 (2)	0.38725 (9)	0.84014 (8)	0.0521 (4)
S2	0.3463 (2)	0.38495 (10)	0.62577 (9)	0.0567 (4)
S3	0.7703 (3)	0.28540 (11)	0.66326 (12)	0.0715 (5)
S4	0.7172 (9)	0.5013 (4)	0.6591 (4)	0.0548 (11)	0.50
O1	0.720 (3)	0.4902 (11)	0.6917 (9)	0.068 (5)	0.50
Co1	0.22236 (9)	0.63196 (4)	0.74333 (4)	0.03327 (19)
N1	0.1203 (6)	0.5070 (3)	0.7743 (3)	0.0442 (10)
H1N	0.0255	0.4944	0.7377	0.053*
H2N	0.2071	0.4685	0.7669	0.053*
C1	0.0644 (9)	0.5033 (4)	0.8646 (4)	0.0558 (15)
H1A	0.1649	0.4847	0.9026	0.067*
H1B	−0.0332	0.4632	0.8687	0.067*
C2	0.0019 (9)	0.5897 (4)	0.8936 (4)	0.0611 (16)
H2A	−0.1160	0.6015	0.8660	0.073*
H2B	−0.0103	0.5891	0.9559	0.073*
N2	0.1289 (6)	0.6570 (3)	0.8715 (2)	0.0430 (10)
H3N	0.0661	0.7061	0.8687	0.052*
C3	0.2877 (8)	0.6695 (4)	0.9322 (3)	0.0554 (15)
H3A	0.2516	0.6616	0.9913	0.066*
H3B	0.3303	0.7268	0.9270	0.066*
C4	0.4408 (8)	0.6096 (4)	0.9153 (3)	0.0548 (15)
H4A	0.5496	0.6275	0.9478	0.066*
H4B	0.4104	0.5536	0.9347	0.066*
N3	0.4732 (6)	0.6078 (3)	0.8217 (2)	0.0410 (9)
H4N	0.5174	0.5572	0.8077	0.049*
H5N	0.5559	0.6469	0.8099	0.049*
N11	−0.0308 (6)	0.6593 (3)	0.6700 (3)	0.0499 (11)
H6N	−0.1153	0.6217	0.6836	0.060*
H7N	−0.0700	0.7108	0.6840	0.060*
C11	−0.0024 (9)	0.6554 (4)	0.5760 (3)	0.0620 (17)
H11A	0.0316	0.7105	0.5556	0.074*
H11B	−0.1142	0.6392	0.5449	0.074*
C12	0.1432 (9)	0.5930 (4)	0.5574 (3)	0.0613 (17)
H12A	0.0977	0.5365	0.5654	0.074*
H12B	0.1739	0.5985	0.4973	0.074*
N12	0.3083 (7)	0.6055 (3)	0.6149 (2)	0.0458 (11)
H8N	0.3702	0.5561	0.6173	0.055*
C13	0.4338 (10)	0.6720 (4)	0.5890 (4)	0.0671 (18)
H13A	0.5554	0.6562	0.6089	0.081*
H13B	0.4304	0.6746	0.5261	0.081*
C14	0.3953 (12)	0.7563 (4)	0.6228 (4)	0.079 (2)
H14A	0.5047	0.7897	0.6228	0.095*
H14B	0.3058	0.7832	0.5839	0.095*
N13	0.3297 (6)	0.7559 (3)	0.7104 (3)	0.0451 (10)
H9N	0.2423	0.7948	0.7141	0.054*
H10N	0.4206	0.7695	0.7488	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.0454 (3)	0.0449 (3)	0.0352 (2)	0.0073 (2)	0.00582 (17)	0.00884 (18)
S1	0.0716 (11)	0.0532 (8)	0.0309 (6)	−0.0082 (7)	−0.0022 (6)	0.0013 (5)
S2	0.0651 (11)	0.0626 (9)	0.0412 (7)	0.0178 (7)	−0.0094 (6)	−0.0065 (6)
S3	0.0705 (13)	0.0733 (10)	0.0714 (11)	0.0366 (9)	0.0095 (9)	0.0091 (8)
S4	0.050 (2)	0.043 (2)	0.072 (3)	−0.0133 (16)	0.005 (2)	0.007 (2)
O1	0.078 (8)	0.050 (6)	0.074 (10)	−0.024 (5)	−0.002 (8)	0.027 (7)
Co1	0.0396 (4)	0.0388 (3)	0.0212 (3)	0.0012 (3)	−0.0011 (2)	0.0013 (2)
N1	0.043 (3)	0.045 (2)	0.045 (2)	0.0012 (19)	0.0007 (19)	−0.0010 (18)
C1	0.064 (4)	0.055 (3)	0.048 (3)	−0.016 (3)	0.004 (3)	0.015 (3)
C2	0.061 (5)	0.079 (4)	0.046 (3)	−0.001 (3)	0.024 (3)	0.004 (3)
N2	0.049 (3)	0.053 (2)	0.0273 (19)	0.008 (2)	0.0023 (17)	0.0010 (17)
C3	0.070 (4)	0.069 (4)	0.026 (2)	0.001 (3)	−0.006 (2)	−0.011 (2)
C4	0.054 (4)	0.071 (4)	0.037 (3)	−0.003 (3)	−0.018 (2)	0.004 (3)
N3	0.044 (3)	0.044 (2)	0.034 (2)	−0.0037 (18)	−0.0061 (17)	−0.0032 (17)
N11	0.055 (3)	0.052 (3)	0.042 (2)	0.012 (2)	−0.006 (2)	−0.0017 (19)
C11	0.068 (5)	0.075 (4)	0.041 (3)	0.007 (3)	−0.020 (3)	0.008 (3)
C12	0.080 (5)	0.077 (4)	0.026 (2)	0.002 (3)	−0.008 (3)	−0.011 (2)
N12	0.062 (3)	0.046 (2)	0.031 (2)	0.008 (2)	0.0085 (19)	0.0017 (17)
C13	0.080 (5)	0.073 (4)	0.051 (3)	−0.003 (3)	0.033 (3)	−0.003 (3)
C14	0.107 (7)	0.069 (4)	0.065 (4)	−0.031 (4)	0.041 (4)	−0.009 (3)
N13	0.051 (3)	0.045 (2)	0.039 (2)	0.005 (2)	0.005 (2)	0.0051 (18)

Geometric parameters (Å, º)

Mo1—O1	1.796 (17)	C4—N3	1.474 (6)
Mo1—S4	2.050 (6)	C4—H4A	0.9700
Mo1—S2	2.1826 (16)	C4—H4B	0.9700
Mo1—S3	2.1908 (16)	N3—H4N	0.9000
Mo1—S1	2.2041 (14)	N3—H5N	0.9000
Co1—N12	2.152 (4)	N11—C11	1.476 (7)
Co1—N2	2.164 (4)	N11—H6N	0.9000
Co1—N11	2.182 (4)	N11—H7N	0.9000
Co1—N1	2.191 (4)	C11—C12	1.506 (9)
Co1—N13	2.196 (4)	C11—H11A	0.9700
Co1—N3	2.197 (4)	C11—H11B	0.9700
N1—C1	1.474 (7)	C12—N12	1.486 (7)
N1—H1N	0.9000	C12—H12A	0.9700
N1—H2N	0.9000	C12—H12B	0.9700
C1—C2	1.524 (8)	N12—C13	1.478 (7)
C1—H1A	0.9700	N12—H8N	0.9100
C1—H1B	0.9700	C13—C14	1.473 (9)
C2—N2	1.479 (7)	C13—H13A	0.9700
C2—H2A	0.9700	C13—H13B	0.9700
C2—H2B	0.9700	C14—N13	1.459 (7)
N2—C3	1.478 (7)	C14—H14A	0.9700
N2—H3N	0.9100	C14—H14B	0.9700
C3—C4	1.516 (8)	N13—H9N	0.9000
C3—H3A	0.9700	N13—H10N	0.9000
C3—H3B	0.9700
O1—Mo1—S4	14.0 (5)	N3—C4—C3	110.1 (4)
O1—Mo1—S2	114.5 (5)	N3—C4—H4A	109.6
S4—Mo1—S2	103.84 (19)	C3—C4—H4A	109.6
O1—Mo1—S3	112.0 (7)	N3—C4—H4B	109.6
S4—Mo1—S3	109.2 (2)	C3—C4—H4B	109.6
S2—Mo1—S3	108.11 (7)	H4A—C4—H4B	108.2
O1—Mo1—S1	102.3 (5)	C4—N3—Co1	110.9 (3)
S4—Mo1—S1	115.37 (18)	C4—N3—H4N	109.5
S2—Mo1—S1	108.71 (6)	Co1—N3—H4N	109.5
S3—Mo1—S1	111.11 (6)	C4—N3—H5N	109.5
N12—Co1—N2	178.43 (18)	Co1—N3—H5N	109.5
N12—Co1—N11	81.49 (17)	H4N—N3—H5N	108.1
N2—Co1—N11	97.29 (17)	C11—N11—Co1	109.6 (3)
N12—Co1—N1	98.35 (16)	C11—N11—H6N	109.7
N2—Co1—N1	80.64 (16)	Co1—N11—H6N	109.7
N11—Co1—N1	89.79 (18)	C11—N11—H7N	109.7
N12—Co1—N13	80.48 (16)	Co1—N11—H7N	109.7
N2—Co1—N13	100.55 (16)	H6N—N11—H7N	108.2
N11—Co1—N13	90.77 (18)	N11—C11—C12	110.9 (4)
N1—Co1—N13	178.61 (17)	N11—C11—H11A	109.5
N12—Co1—N3	100.80 (17)	C12—C11—H11A	109.5
N2—Co1—N3	80.43 (16)	N11—C11—H11B	109.5
N11—Co1—N3	177.54 (16)	C12—C11—H11B	109.5
N1—Co1—N3	90.75 (16)	H11A—C11—H11B	108.1
N13—Co1—N3	88.74 (16)	N12—C12—C11	112.0 (4)
C1—N1—Co1	111.1 (3)	N12—C12—H12A	109.2
C1—N1—H1N	109.4	C11—C12—H12A	109.2
Co1—N1—H1N	109.4	N12—C12—H12B	109.2
C1—N1—H2N	109.4	C11—C12—H12B	109.2
Co1—N1—H2N	109.4	H12A—C12—H12B	107.9
H1N—N1—H2N	108.0	C13—N12—C12	116.5 (5)
N1—C1—C2	110.3 (4)	C13—N12—Co1	109.2 (3)
N1—C1—H1A	109.6	C12—N12—Co1	107.4 (3)
C2—C1—H1A	109.6	C13—N12—H8N	107.8
N1—C1—H1B	109.6	C12—N12—H8N	107.8
C2—C1—H1B	109.6	Co1—N12—H8N	107.8
H1A—C1—H1B	108.1	C14—C13—N12	114.9 (5)
N2—C2—C1	112.3 (5)	C14—C13—H13A	108.6
N2—C2—H2A	109.2	N12—C13—H13A	108.6
C1—C2—H2A	109.2	C14—C13—H13B	108.6
N2—C2—H2B	109.2	N12—C13—H13B	108.6
C1—C2—H2B	109.2	H13A—C13—H13B	107.5
H2A—C2—H2B	107.9	N13—C14—C13	113.7 (5)
C3—N2—C2	116.6 (4)	N13—C14—H14A	108.8
C3—N2—Co1	108.6 (3)	C13—C14—H14A	108.8
C2—N2—Co1	108.4 (3)	N13—C14—H14B	108.8
C3—N2—H3N	107.6	C13—C14—H14B	108.8
C2—N2—H3N	107.6	H14A—C14—H14B	107.7
Co1—N2—H3N	107.6	C14—N13—Co1	111.2 (3)
N2—C3—C4	112.7 (4)	C14—N13—H9N	109.4
N2—C3—H3A	109.1	Co1—N13—H9N	109.4
C4—C3—H3A	109.1	C14—N13—H10N	109.4
N2—C3—H3B	109.1	Co1—N13—H10N	109.4
C4—C3—H3B	109.1	H9N—N13—H10N	108.0
H3A—C3—H3B	107.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S4^i	0.90	2.53	3.396 (8)	161
N1—H2N···S2	0.90	2.79	3.497 (5)	136
N2—H3N···S3^ii	0.91	2.82	3.613 (5)	147
N3—H4N···S1	0.90	2.76	3.567 (4)	150
N3—H5N···S3^iii	0.90	2.58	3.409 (4)	154
N11—H6N···S4^i	0.90	2.30	3.133 (8)	153
N11—H7N···S1^ii	0.90	2.84	3.635 (5)	149
N12—H8N···S2	0.91	2.73	3.525 (4)	146
N12—H8N···S4	0.91	2.76	3.491 (8)	138
N13—H9N···S1^ii	0.90	2.73	3.574 (5)	157
N13—H10N···S3^iii	0.90	2.61	3.493 (5)	166
N1—H1N···O1^i	0.90	2.34	3.18 (2)	155
N11—H6N···O1^i	0.90	2.43	3.290 (18)	161

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