Crystal structure of tris­{N,N-diethyl-N′-[(4-nitro­phen­yl)(oxo)meth­yl]carbamimido­thio­ato}cobalt(III)

The synthesis, crystal structure and a Hirshfeld surface analysis of tris­{N,N-diethyl-N′-[(4-nitro­phen­yl)(oxo)meth­yl]carbamimido­thio­ato}cobalt(III) are described.

Computing details

Tris{N,N-diethyl-N'-[(4-nitrophenyl)(oxo)methyl]carbamimidothioato}cobalt(III)

Crystal data

[Co(C12H14N3O3S)3]	Dx = 1.356 Mg m^−3
Mr = 899.89	Cu Kα radiation, λ = 1.54178 Å
Trigonal, P3	Cell parameters from 9548 reflections
a = 16.6906 (3) Å	θ = 3.1–68.1°
c = 9.1346 (2) Å	µ = 4.89 mm^−1
V = 2203.76 (9) Å^3	T = 180 K
Z = 2	Shard, dark green
F(000) = 936	0.12 × 0.11 × 0.04 mm

Data collection

Bruker X8 Proteum diffractometer	2682 independent reflections
Radiation source: fine-focus rotating anode	2571 reflections with I > 2σ(I)
Detector resolution: 5.6 pixels mm^-1	Rint = 0.038
φ and ω scans	θmax = 68.1°, θmin = 3.1°
Absorption correction: multi-scan [SADABS (Krause et al., 2015), XABS2 (Parkin et al., 1995)]	h = −20→14
Tmin = 0.580, Tmax = 0.753	k = −20→20
30546 measured reflections	l = −10→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.083	w = 1/[σ^2(Fo^2) + (0.0455P)^2 + 0.5678P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max = 0.001
2682 reflections	Δρmax = 0.20 e Å^−3
179 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL2019/3 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00080 (18)

Special details

Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998).

The crystals underwent a reversible phase transition to a triply twinned incommensurately modulated phase when cooled to 90K. Visual inspection of crystal integrity and diffraction quality vs temperature established a safe temperature for data collection of -93° C.

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 progress was checked using PLATO (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.333333	0.666667	0.48360 (4)	0.03514 (14)
S1	0.21178 (3)	0.58999 (3)	0.34007 (5)	0.04670 (15)
O1	0.30064 (7)	0.56544 (7)	0.61574 (12)	0.0381 (3)
N1	0.14855 (9)	0.45396 (10)	0.55380 (14)	0.0397 (3)
N2	0.06185 (9)	0.42651 (11)	0.35035 (14)	0.0446 (3)
N3	0.20338 (13)	0.32053 (16)	1.18453 (19)	0.0637 (5)
O2	0.16284 (15)	0.23576 (15)	1.18709 (19)	0.0855 (5)
O3	0.24204 (13)	0.36914 (15)	1.28994 (17)	0.0922 (6)
C1	0.13955 (11)	0.48454 (12)	0.42182 (16)	0.0385 (4)
C2	0.22264 (10)	0.49475 (11)	0.63716 (16)	0.0337 (3)
C3	0.21352 (11)	0.44836 (11)	0.78216 (16)	0.0355 (3)
C4	0.14649 (12)	0.35663 (13)	0.80514 (18)	0.0442 (4)
H4A	0.102965	0.323122	0.730224	0.053*
C5	0.14277 (13)	0.31379 (14)	0.9367 (2)	0.0506 (4)
H5A	0.098657	0.250373	0.951941	0.061*
C6	0.20480 (13)	0.36553 (15)	1.04516 (18)	0.0475 (4)
C7	0.26939 (13)	0.45713 (14)	1.02840 (19)	0.0501 (4)
H7A	0.309495	0.491487	1.106539	0.060*
C8	0.27465 (12)	0.49831 (13)	0.89451 (18)	0.0437 (4)
H8A	0.320351	0.561190	0.879134	0.052*
C9	−0.00988 (12)	0.34040 (15)	0.4202 (2)	0.0567 (5)
H9A	−0.071422	0.325873	0.383010	0.068*
H9B	−0.009034	0.350294	0.527181	0.068*
C10	0.00396 (16)	0.25957 (16)	0.3914 (3)	0.0696 (6)
H10A	−0.046291	0.203954	0.437066	0.104*
H10B	0.063308	0.272139	0.432840	0.104*
H10C	0.003909	0.249866	0.285617	0.104*
C11	0.03874 (12)	0.44629 (14)	0.20525 (18)	0.0477 (4)
H11A	0.002515	0.387563	0.150922	0.057*
H11B	0.096499	0.485334	0.150052	0.057*
C12	−0.01665 (15)	0.49554 (18)	0.2149 (2)	0.0637 (6)
H12A	−0.033471	0.504856	0.116135	0.096*
H12B	0.020665	0.555658	0.262676	0.096*
H12C	−0.072966	0.457932	0.272089	0.096*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.03772 (18)	0.03772 (18)	0.0300 (2)	0.01886 (9)	0.000	0.000
S1	0.0477 (2)	0.0531 (3)	0.0353 (2)	0.0221 (2)	−0.00973 (17)	0.00513 (17)
O1	0.0392 (6)	0.0374 (6)	0.0367 (6)	0.0184 (5)	−0.0083 (4)	−0.0005 (4)
N1	0.0343 (7)	0.0538 (8)	0.0258 (6)	0.0180 (6)	−0.0017 (5)	0.0002 (6)
N2	0.0341 (7)	0.0661 (9)	0.0272 (7)	0.0203 (7)	−0.0042 (5)	−0.0021 (6)
N3	0.0647 (11)	0.0996 (15)	0.0439 (10)	0.0539 (11)	0.0078 (8)	0.023 (1)
O2	0.1145 (15)	0.1025 (14)	0.0634 (10)	0.0722 (12)	0.018 (1)	0.0327 (10)
O3	0.0829 (12)	0.1351 (17)	0.0430 (9)	0.0427 (11)	−0.0153 (8)	0.0233 (10)
C1	0.0334 (8)	0.0541 (9)	0.0284 (8)	0.0220 (7)	−0.0003 (6)	−0.0029 (6)
C2	0.0372 (8)	0.0409 (8)	0.0282 (7)	0.0233 (7)	−0.0021 (6)	−0.0047 (6)
C3	0.0381 (8)	0.0475 (9)	0.0274 (7)	0.0262 (7)	−0.0014 (6)	−0.0024 (6)
C4	0.0418 (9)	0.0528 (10)	0.0331 (8)	0.0201 (8)	−0.0019 (7)	0.0004 (7)
C5	0.0493 (10)	0.0576 (11)	0.0435 (10)	0.0256 (9)	0.0060 (8)	0.0114 (8)
C6	0.0507 (10)	0.0752 (13)	0.0309 (8)	0.0421 (10)	0.0030 (7)	0.0095 (8)
C7	0.0539 (10)	0.0723 (13)	0.0316 (9)	0.0372 (10)	−0.0099 (7)	−0.0056 (8)
C8	0.0472 (9)	0.0519 (10)	0.0354 (9)	0.0273 (8)	−0.0082 (7)	−0.0050 (7)
C9	0.0336 (9)	0.0778 (14)	0.0365 (9)	0.0112 (9)	−0.0016 (7)	−0.0002 (8)
C10	0.0578 (12)	0.0661 (14)	0.0576 (13)	0.0105 (10)	0.0003 (10)	0.0028 (10)
C11	0.0418 (9)	0.0761 (12)	0.0287 (8)	0.0321 (9)	−0.0069 (7)	−0.0065 (8)
C12	0.0608 (12)	0.1016 (17)	0.0469 (11)	0.0541 (13)	−0.0111 (9)	−0.0114 (11)

Geometric parameters (Å, º)

Co1—O1^i	1.9202 (11)	C4—H4A	0.9500
Co1—O1^ii	1.9202 (11)	C5—C6	1.380 (3)
Co1—O1	1.9202 (11)	C5—H5A	0.9500
Co1—S1	2.2082 (5)	C6—C7	1.369 (3)
Co1—S1^i	2.2082 (5)	C7—C8	1.384 (2)
Co1—S1^ii	2.2082 (5)	C7—H7A	0.9500
S1—C1	1.7284 (17)	C8—H8A	0.9500
O1—C2	1.2606 (19)	C9—C10	1.501 (3)
N1—C2	1.316 (2)	C9—H9A	0.9900
N1—C1	1.347 (2)	C9—H9B	0.9900
N2—C1	1.338 (2)	C10—H10A	0.9800
N2—C11	1.464 (2)	C10—H10B	0.9800
N2—C9	1.478 (2)	C10—H10C	0.9800
N3—O3	1.216 (3)	C11—C12	1.516 (3)
N3—O2	1.226 (3)	C11—H11A	0.9900
N3—C6	1.472 (2)	C11—H11B	0.9900
C2—C3	1.503 (2)	C12—H12A	0.9800
C3—C4	1.388 (2)	C12—H12B	0.9800
C3—C8	1.392 (2)	C12—H12C	0.9800
C4—C5	1.384 (2)
O1^i—Co1—O1^ii	84.68 (5)	C5—C4—H4A	119.9
O1^i—Co1—O1	84.68 (5)	C3—C4—H4A	119.9
O1^ii—Co1—O1	84.68 (5)	C6—C5—C4	118.31 (18)
O1^i—Co1—S1	91.87 (4)	C6—C5—H5A	120.8
O1^ii—Co1—S1	176.56 (3)	C4—C5—H5A	120.8
O1—Co1—S1	95.09 (3)	C7—C6—C5	122.94 (16)
O1^i—Co1—S1^i	95.09 (3)	C7—C6—N3	117.99 (18)
O1^ii—Co1—S1^i	91.87 (4)	C5—C6—N3	119.06 (19)
O1—Co1—S1^i	176.56 (4)	C6—C7—C8	118.19 (17)
S1—Co1—S1^i	88.35 (2)	C6—C7—H7A	120.9
O1^i—Co1—S1^ii	176.56 (3)	C8—C7—H7A	120.9
O1^ii—Co1—S1^ii	95.09 (3)	C7—C8—C3	120.56 (17)
O1—Co1—S1^ii	91.87 (4)	C7—C8—H8A	119.7
S1—Co1—S1^ii	88.35 (2)	C3—C8—H8A	119.7
S1^i—Co1—S1^ii	88.35 (2)	N2—C9—C10	112.60 (16)
C1—S1—Co1^ii	107.73 (5)	N2—C9—H9A	109.1
C1—S1—Co1	107.73 (5)	C10—C9—H9A	109.1
C1—S1—Co1^i	107.73 (5)	N2—C9—H9B	109.1
C2—O1—Co1^ii	128.85 (10)	C10—C9—H9B	109.1
C2—O1—Co1^i	128.85 (10)	H9A—C9—H9B	107.8
C2—O1—Co1	128.85 (10)	C9—C10—H10A	109.5
C2—N1—C1	125.19 (14)	C9—C10—H10B	109.5
C1—N2—C11	123.23 (15)	H10A—C10—H10B	109.5
C1—N2—C9	120.92 (14)	C9—C10—H10C	109.5
C11—N2—C9	115.69 (14)	H10A—C10—H10C	109.5
O3—N3—O2	123.89 (19)	H10B—C10—H10C	109.5
O3—N3—C6	118.5 (2)	N2—C11—C12	111.76 (15)
O2—N3—C6	117.7 (2)	N2—C11—H11A	109.3
N2—C1—N1	114.46 (15)	C12—C11—H11A	109.3
N2—C1—S1	117.16 (12)	N2—C11—H11B	109.3
N1—C1—S1	128.28 (12)	C12—C11—H11B	109.3
O1—C2—N1	131.15 (14)	H11A—C11—H11B	107.9
O1—C2—C3	114.22 (13)	C11—C12—H12A	109.5
N1—C2—C3	114.62 (14)	C11—C12—H12B	109.5
C4—C3—C8	119.62 (15)	H12A—C12—H12B	109.5
C4—C3—C2	121.31 (14)	C11—C12—H12C	109.5
C8—C3—C2	119.07 (15)	H12A—C12—H12C	109.5
C5—C4—C3	120.29 (16)	H12B—C12—H12C	109.5
C11—N2—C1—N1	−179.82 (15)	N1—C2—C3—C4	19.9 (2)
C9—N2—C1—N1	4.9 (2)	O1—C2—C3—C8	19.8 (2)
C11—N2—C1—S1	3.5 (2)	N1—C2—C3—C8	−161.13 (15)
C9—N2—C1—S1	−171.79 (14)	C8—C3—C4—C5	−2.7 (3)
C2—N1—C1—N2	173.13 (15)	C2—C3—C4—C5	176.26 (15)
C2—N1—C1—S1	−10.6 (2)	C3—C4—C5—C6	2.5 (3)
Co1^ii—S1—C1—N2	−178.97 (11)	C4—C5—C6—C7	0.2 (3)
Co1—S1—C1—N2	−178.97 (11)	C4—C5—C6—N3	−178.52 (16)
Co1^i—S1—C1—N2	−178.97 (11)	O3—N3—C6—C7	17.8 (3)
Co1^ii—S1—C1—N1	4.85 (17)	O2—N3—C6—C7	−162.28 (18)
Co1—S1—C1—N1	4.85 (17)	O3—N3—C6—C5	−163.37 (19)
Co1^i—S1—C1—N1	4.85 (17)	O2—N3—C6—C5	16.5 (3)
Co1^ii—O1—C2—N1	22.6 (2)	C5—C6—C7—C8	−2.5 (3)
Co1^i—O1—C2—N1	22.6 (2)	N3—C6—C7—C8	176.20 (16)
Co1—O1—C2—N1	22.6 (2)	C6—C7—C8—C3	2.2 (3)
Co1^ii—O1—C2—C3	−158.52 (10)	C4—C3—C8—C7	0.3 (3)
Co1^i—O1—C2—C3	−158.52 (10)	C2—C3—C8—C7	−178.67 (15)
Co1—O1—C2—C3	−158.52 (10)	C1—N2—C9—C10	−90.7 (2)
C1—N1—C2—O1	−3.4 (3)	C11—N2—C9—C10	93.7 (2)
C1—N1—C2—C3	177.75 (14)	C1—N2—C11—C12	−90.7 (2)
O1—C2—C3—C4	−159.17 (15)	C9—N2—C11—C12	84.8 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···S1	0.98	3.03	3.510 (2)	112
C7—H7A···S1^iii	0.95	2.91	3.8362 (19)	166
C9—H9B···O3^iv	0.99	2.53	3.213 (2)	126

Symmetry codes: (iii) −y+1, x−y+1, z+1; (iv) x−y, x, −z+2.