Inverse bilayer structure of mononuclear Co^II and Ni^II complexes of the type M(H₂O)₃(SO₄)(4-CNpy)₂

Two new metal compounds of the formula [M(H₂O)₃(SO₄)(4-CNpy)₂]·H₂O [M = Ni (1) and Co (2), 4-CNpy = 4-cyanopyridine] have been prepared and studied by X-ray diffraction. In both of these compounds the 4-CNpy ligands are coordinated via pyridyl-N atoms to the metal ions in a cis fashion. The neutral complexes along with the uncoordinated H₂O molecules are glued together preferentially into inverse bilayers by non-covalent interactions, including unique interlayer π–π interactions between antiparallel nitrile groups. Hartree–Fock and density-functional theory (DFT) calculations indicate that the π–π interactions are energetically significant. The unit-cell similarity index (Π) of 0.0046 for the compounds suggests their isostructurality, which is also supported by their X-ray powder diffraction patterns that can be almost superimposed.

Computing details

Program(s) used to solve structure: SHELHS-97 (Sheldrick, 1997) for niso4. For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

(niso4) Tris(aqua)bis(4-cyanopyridine)nickel(II) sulfate·H₂O

Crystal data

C12H16N4NiO8S	Z = 4
Mr = 435.06	F(000) = 896
Monoclinic, P21/c	Dx = 1.587 Mg m^−3
a = 17.2117 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.4275 (4) Å	µ = 1.23 mm^−1
c = 12.5984 (6) Å	T = 293 K
β = 94.644 (1)°	Rectangular block, blue
V = 1821.42 (15) Å^3	0.40 × 0.35 × 0.20 mm

Data collection

Bruker AXS CCD diffractometer	4058 independent reflections
Radiation source: fine-focus sealed tube	3447 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 28.0°, θmin = 2.4°
Absorption correction: multi-scan SADABS	h = −21→20
Tmin = 0.757, Tmax = 1.000	k = −9→10
10611 measured reflections	l = −7→16

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)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.064	w = 1/[σ^2(Fo^2) + (0.0315P)^2 + 0.4846P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
4058 reflections	Δρmax = 0.30 e Å^−3
268 parameters	Δρmin = −0.33 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0026 (4)

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
Ni1	0.152558 (11)	0.54351 (2)	0.797708 (15)	0.02633 (7)
S1	0.11529 (2)	0.92192 (4)	0.83390 (3)	0.02831 (10)
O1	0.08019 (7)	0.61324 (16)	0.66800 (10)	0.0349 (3)
H1A	0.0404 (16)	0.565 (3)	0.646 (2)	0.074 (8)*
H1B	0.0712 (14)	0.712 (3)	0.6740 (19)	0.063 (7)*
O2	0.15262 (9)	0.31550 (15)	0.73347 (12)	0.0438 (3)
H2A	0.1552 (14)	0.240 (3)	0.769 (2)	0.066 (8)*
H2B	0.1285 (14)	0.297 (3)	0.675 (2)	0.067 (8)*
O3	0.05605 (8)	0.50030 (17)	0.88414 (11)	0.0390 (3)
H3A	0.0168 (15)	0.490 (3)	0.849 (2)	0.060 (7)*
H3B	0.0622 (14)	0.425 (3)	0.927 (2)	0.069 (8)*
N1	0.22368 (8)	0.47184 (16)	0.93203 (10)	0.0303 (3)
N2	0.25035 (8)	0.59205 (16)	0.70649 (11)	0.0323 (3)
O4	0.16119 (7)	0.77496 (13)	0.85706 (9)	0.0336 (3)
O5	0.08827 (7)	0.92793 (14)	0.71873 (9)	0.0372 (3)
O6	0.04725 (9)	0.92801 (18)	0.89786 (12)	0.0555 (4)
O7	0.16605 (9)	1.05980 (14)	0.86198 (11)	0.0496 (4)
C1	0.20928 (10)	0.5259 (2)	1.02928 (13)	0.0348 (4)
H1	0.1663	0.5911	1.0355	0.042*
C2	0.25616 (11)	0.4878 (3)	1.12034 (14)	0.0424 (4)
H2	0.2444	0.5251	1.1867	0.051*
C3	0.32129 (10)	0.3923 (3)	1.11026 (14)	0.0446 (4)
C4	0.33618 (11)	0.3333 (2)	1.01051 (16)	0.0475 (5)
H4	0.3788	0.2681	1.0022	0.057*
C5	0.28524 (10)	0.3752 (2)	0.92417 (14)	0.0406 (4)
H5	0.2940	0.3345	0.8576	0.049*
C6	0.37291 (12)	0.3554 (4)	1.20477 (17)	0.0652 (7)
N3	0.41228 (12)	0.3274 (4)	1.27990 (17)	0.1003 (10)
C7	0.24366 (10)	0.5589 (2)	0.60130 (14)	0.0384 (4)
H7	0.1971	0.5154	0.5719	0.046*
C8	0.30273 (11)	0.5864 (2)	0.53484 (14)	0.0433 (4)
H8	0.2958	0.5623	0.4627	0.052*
C9	0.37262 (10)	0.6511 (3)	0.57867 (15)	0.0462 (4)
C10	0.38117 (11)	0.6853 (3)	0.68756 (16)	0.0496 (5)
H10	0.4275	0.7269	0.7190	0.059*
C11	0.31841 (10)	0.6554 (2)	0.74763 (14)	0.0404 (4)
H11	0.3235	0.6802	0.8198	0.049*
C12	0.43379 (12)	0.6858 (4)	0.50822 (18)	0.0698 (7)
N4	0.47817 (13)	0.7166 (4)	0.44924 (18)	0.1124 (12)
O8	0.07449 (10)	0.25838 (17)	0.52504 (11)	0.0448 (3)
H8A	0.0314 (15)	0.286 (3)	0.5423 (18)	0.058 (7)*
H8B	0.0910 (16)	0.326 (3)	0.492 (2)	0.075 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02690 (11)	0.02506 (11)	0.02639 (11)	−0.00021 (7)	−0.00190 (7)	0.00150 (7)
S1	0.0318 (2)	0.02456 (19)	0.0282 (2)	0.00245 (14)	−0.00001 (15)	0.00102 (14)
O1	0.0351 (7)	0.0325 (7)	0.0352 (6)	−0.0010 (5)	−0.0088 (5)	−0.0008 (5)
O2	0.0686 (9)	0.0263 (6)	0.0347 (7)	−0.0026 (6)	−0.0075 (6)	0.0006 (6)
O3	0.0299 (7)	0.0478 (7)	0.0384 (7)	−0.0058 (5)	−0.0020 (5)	0.0084 (6)
N1	0.0308 (7)	0.0307 (7)	0.0290 (7)	0.0020 (5)	−0.0007 (5)	0.0026 (5)
N2	0.0320 (7)	0.0346 (7)	0.0300 (7)	−0.0020 (5)	0.0009 (5)	0.0003 (6)
O4	0.0367 (6)	0.0259 (5)	0.0363 (6)	0.0048 (4)	−0.0082 (5)	−0.0015 (5)
O5	0.0384 (7)	0.0386 (6)	0.0328 (6)	0.0033 (5)	−0.0072 (5)	0.0010 (5)
O6	0.0524 (9)	0.0654 (9)	0.0513 (8)	0.0215 (7)	0.0203 (7)	0.0106 (7)
O7	0.0683 (9)	0.0274 (6)	0.0488 (8)	−0.0101 (6)	−0.0220 (7)	0.0050 (5)
C1	0.0320 (8)	0.0390 (9)	0.0333 (8)	−0.0002 (7)	0.0023 (7)	0.0009 (7)
C2	0.0374 (9)	0.0606 (12)	0.0290 (8)	−0.0081 (8)	0.0016 (7)	0.0028 (8)
C3	0.0341 (9)	0.0610 (12)	0.0376 (10)	−0.0073 (8)	−0.0045 (7)	0.0166 (9)
C4	0.0352 (10)	0.0546 (12)	0.0517 (11)	0.0119 (8)	−0.0018 (8)	0.0116 (9)
C5	0.0414 (10)	0.0427 (10)	0.0374 (9)	0.0110 (8)	0.0010 (7)	0.0018 (8)
C6	0.0401 (11)	0.108 (2)	0.0462 (12)	−0.0063 (12)	−0.0050 (9)	0.0269 (13)
N3	0.0536 (12)	0.183 (3)	0.0608 (13)	−0.0039 (15)	−0.0151 (10)	0.0500 (16)
C7	0.0351 (9)	0.0450 (10)	0.0345 (9)	−0.0061 (7)	−0.0002 (7)	−0.0004 (7)
C8	0.0403 (10)	0.0571 (11)	0.0326 (9)	−0.0005 (8)	0.0031 (7)	0.0012 (8)
C9	0.0338 (9)	0.0633 (12)	0.0418 (10)	−0.0017 (9)	0.0041 (8)	0.0105 (9)
C10	0.0324 (9)	0.0680 (13)	0.0472 (11)	−0.0097 (9)	−0.0036 (8)	0.0067 (10)
C11	0.0372 (9)	0.0518 (11)	0.0314 (8)	−0.0054 (8)	−0.0031 (7)	−0.0001 (8)
C12	0.0375 (11)	0.123 (2)	0.0484 (12)	−0.0137 (13)	0.0015 (9)	0.0104 (13)
N4	0.0528 (13)	0.226 (4)	0.0598 (14)	−0.0377 (17)	0.0106 (11)	0.0197 (17)
O8	0.0554 (9)	0.0402 (7)	0.0394 (7)	0.0008 (7)	0.0069 (6)	0.0016 (6)

Geometric parameters (Å, º)

Ni1—O1	2.0585 (12)	C1—H1	0.9300
Ni1—O2	2.0851 (13)	C2—C3	1.394 (3)
Ni1—O4	2.0899 (11)	C2—H2	0.9300
Ni1—O3	2.0906 (13)	C3—C4	1.394 (3)
Ni1—N1	2.0956 (13)	C3—C6	1.460 (3)
Ni1—N2	2.1527 (14)	C4—C5	1.386 (2)
S1—O6	1.4751 (14)	C4—H4	0.9300
S1—O7	1.4794 (12)	C5—H5	0.9300
S1—O4	1.4852 (11)	C6—N3	1.143 (3)
S1—O5	1.4883 (12)	C7—C8	1.388 (3)
O1—H1A	0.82 (3)	C7—H7	0.9300
O1—H1B	0.85 (3)	C8—C9	1.394 (3)
O2—H2A	0.78 (3)	C8—H8	0.9300
O2—H2B	0.83 (3)	C9—C10	1.398 (3)
O3—H3A	0.78 (3)	C9—C12	1.460 (3)
O3—H3B	0.84 (3)	C10—C11	1.391 (3)
N1—C5	1.347 (2)	C10—H10	0.9300
N1—C1	1.349 (2)	C11—H11	0.9300
N2—C7	1.350 (2)	C12—N4	1.138 (3)
N2—C11	1.352 (2)	O8—H8A	0.82 (2)
C1—C2	1.386 (2)	O8—H8B	0.77 (3)
O1—Ni1—O2	88.52 (6)	C11—N2—Ni1	124.13 (11)
O1—Ni1—O4	92.21 (5)	S1—O4—Ni1	133.37 (7)
O2—Ni1—O4	175.37 (5)	N1—C1—C2	122.45 (17)
O1—Ni1—O3	90.46 (6)	N1—C1—H1	118.8
O2—Ni1—O3	93.84 (6)	C2—C1—H1	118.8
O4—Ni1—O3	90.72 (5)	C1—C2—C3	118.48 (17)
O1—Ni1—N1	178.50 (5)	C1—C2—H2	120.8
O2—Ni1—N1	91.67 (6)	C3—C2—H2	120.8
O4—Ni1—N1	87.72 (5)	C2—C3—C4	119.71 (16)
O3—Ni1—N1	88.05 (6)	C2—C3—C6	119.29 (19)
O1—Ni1—N2	88.34 (5)	C4—C3—C6	121.0 (2)
O2—Ni1—N2	86.73 (6)	C5—C4—C3	117.76 (18)
O4—Ni1—N2	88.72 (5)	C5—C4—H4	121.1
O3—Ni1—N2	178.65 (5)	C3—C4—H4	121.1
N1—Ni1—N2	93.15 (5)	N1—C5—C4	123.21 (17)
O6—S1—O7	108.76 (9)	N1—C5—H5	118.4
O6—S1—O4	110.79 (8)	C4—C5—H5	118.4
O7—S1—O4	108.27 (7)	N3—C6—C3	178.8 (3)
O6—S1—O5	109.40 (8)	N2—C7—C8	123.31 (16)
O7—S1—O5	109.77 (7)	N2—C7—H7	118.3
O4—S1—O5	109.82 (7)	C8—C7—H7	118.3
Ni1—O1—H1A	124.1 (18)	C7—C8—C9	118.51 (17)
Ni1—O1—H1B	108.2 (16)	C7—C8—H8	120.7
H1A—O1—H1B	111 (2)	C9—C8—H8	120.7
Ni1—O2—H2A	122.2 (19)	C8—C9—C10	119.24 (17)
Ni1—O2—H2B	120.0 (17)	C8—C9—C12	118.63 (18)
H2A—O2—H2B	111 (2)	C10—C9—C12	122.10 (18)
Ni1—O3—H3A	114.4 (18)	C11—C10—C9	118.15 (16)
Ni1—O3—H3B	114.0 (17)	C11—C10—H10	120.9
H3A—O3—H3B	110 (2)	C9—C10—H10	120.9
C5—N1—C1	118.33 (14)	N2—C11—C10	123.36 (16)
C5—N1—Ni1	121.78 (11)	N2—C11—H11	118.3
C1—N1—Ni1	119.87 (11)	C10—C11—H11	118.3
C7—N2—C11	117.41 (15)	N4—C12—C9	176.0 (3)
C7—N2—Ni1	118.46 (11)	H8A—O8—H8B	108 (3)
O1—Ni1—N1—C5	140 (2)	N1—Ni1—O4—S1	−162.57 (11)
O2—Ni1—N1—C5	42.49 (14)	N2—Ni1—O4—S1	104.22 (10)
O4—Ni1—N1—C5	−132.92 (14)	C5—N1—C1—C2	1.2 (3)
O3—Ni1—N1—C5	136.28 (14)	Ni1—N1—C1—C2	−177.31 (14)
N2—Ni1—N1—C5	−44.32 (14)	N1—C1—C2—C3	1.1 (3)
O1—Ni1—N1—C1	−42 (2)	C1—C2—C3—C4	−2.2 (3)
O2—Ni1—N1—C1	−139.08 (13)	C1—C2—C3—C6	177.88 (19)
O4—Ni1—N1—C1	45.51 (12)	C2—C3—C4—C5	1.0 (3)
O3—Ni1—N1—C1	−45.29 (13)	C6—C3—C4—C5	−179.1 (2)
N2—Ni1—N1—C1	134.10 (12)	C1—N1—C5—C4	−2.5 (3)
O1—Ni1—N2—C7	−36.74 (13)	Ni1—N1—C5—C4	175.95 (15)
O2—Ni1—N2—C7	51.87 (13)	C3—C4—C5—N1	1.4 (3)
O4—Ni1—N2—C7	−128.99 (13)	C2—C3—C6—N3	17 (15)
O3—Ni1—N2—C7	−63 (2)	C4—C3—C6—N3	−163 (15)
N1—Ni1—N2—C7	143.37 (13)	C11—N2—C7—C8	0.1 (3)
O1—Ni1—N2—C11	142.65 (14)	Ni1—N2—C7—C8	179.50 (14)
O2—Ni1—N2—C11	−128.73 (15)	N2—C7—C8—C9	0.2 (3)
O4—Ni1—N2—C11	50.41 (14)	C7—C8—C9—C10	0.3 (3)
O3—Ni1—N2—C11	116 (2)	C7—C8—C9—C12	−177.7 (2)
N1—Ni1—N2—C11	−37.23 (14)	C8—C9—C10—C11	−1.1 (3)
O6—S1—O4—Ni1	85.58 (12)	C12—C9—C10—C11	176.9 (2)
O7—S1—O4—Ni1	−155.24 (10)	C7—N2—C11—C10	−0.9 (3)
O5—S1—O4—Ni1	−35.39 (12)	Ni1—N2—C11—C10	179.70 (15)
O1—Ni1—O4—S1	15.93 (11)	C9—C10—C11—N2	1.4 (3)
O2—Ni1—O4—S1	114.9 (6)	C8—C9—C12—N4	44 (5)
O3—Ni1—O4—S1	−74.55 (11)	C10—C9—C12—N4	−133 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O6^i	0.82 (3)	1.95 (3)	2.7644 (19)	173 (3)
O1—H1B···O5	0.85 (3)	1.92 (3)	2.7289 (18)	158 (2)
O2—H2A···O7^ii	0.78 (3)	1.92 (3)	2.6940 (19)	177 (3)
O2—H2B···O8	0.83 (3)	2.07 (3)	2.892 (2)	176 (2)
O3—H3A···O5^i	0.78 (3)	2.00 (3)	2.7750 (18)	168 (3)
O3—H3B···O8^iii	0.84 (3)	1.98 (3)	2.813 (2)	178 (2)
O8—H8A···O6^i	0.82 (2)	2.00 (3)	2.776 (2)	157 (2)

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

(coso4) Tris(aqua)bis(4-cyanopyridine)cobalt(II) sulfate·H₂O

Crystal data

C12H16CoN4O8S	Z = 4
Mr = 435.28	F(000) = 892
Monoclinic, P21/c	Dx = 1.612 Mg m^−3
a = 17.1467 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.3504 (1) Å	µ = 1.12 mm^−1
c = 12.5644 (2) Å	T = 293 K
β = 94.509 (1)°	Rectangular block, pink
V = 1793.43 (5) Å^3	0.42 × 0.37 × 0.11 mm

Data collection

Bruker AXS CCD diffractometer	4431 independent reflections
Radiation source: fine-focus sealed tube	3899 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
φ and ω scans	θmax = 28.3°, θmin = 2.7°
Absorption correction: multi-scan SADABS	h = −22→22
Tmin = 0.854, Tmax = 1.000	k = −11→11
19138 measured reflections	l = −15→16

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0404P)^2 + 0.4131P] where P = (Fo^2 + 2Fc^2)/3
4431 reflections	(Δ/σ)max = 0.001
267 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.30 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
Co1	0.347911 (11)	0.54268 (2)	0.701274 (15)	0.02546 (7)
C1	0.28962 (9)	0.5240 (2)	0.46737 (12)	0.0349 (3)
H1	0.3331	0.5889	0.4612	0.042*
C2	0.24277 (10)	0.4879 (2)	0.37681 (13)	0.0422 (4)
H2	0.2544	0.5268	0.3105	0.051*
C3	0.17793 (10)	0.3925 (2)	0.38658 (14)	0.0449 (4)
C4	0.16295 (10)	0.3330 (2)	0.48571 (15)	0.0478 (4)
H4	0.1200	0.2676	0.4940	0.057*
C5	0.21364 (10)	0.3737 (2)	0.57149 (13)	0.0403 (4)
H5	0.2046	0.3324	0.6381	0.048*
C6	0.12672 (12)	0.3561 (4)	0.29256 (16)	0.0657 (7)
C11	0.17908 (10)	0.6516 (2)	0.75512 (13)	0.0417 (4)
H11	0.1730	0.6736	0.6824	0.050*
C10	0.11721 (10)	0.6822 (3)	0.81543 (15)	0.0503 (5)
H10	0.0703	0.7227	0.7843	0.060*
C9	0.12690 (10)	0.6507 (3)	0.92423 (14)	0.0462 (4)
C8	0.19719 (10)	0.5895 (2)	0.96756 (14)	0.0433 (4)
H8	0.2050	0.5673	1.0402	0.052*
C7	0.25545 (10)	0.5622 (2)	0.90028 (13)	0.0379 (4)
H7	0.3028	0.5209	0.9294	0.045*
C12	0.06661 (12)	0.6858 (4)	0.99473 (17)	0.0697 (7)
N1	0.27524 (7)	0.46961 (15)	0.56414 (10)	0.0301 (3)
N3	0.08772 (12)	0.3279 (4)	0.21778 (17)	0.1016 (10)
N2	0.24777 (8)	0.59170 (16)	0.79554 (10)	0.0329 (3)
N4	0.02224 (13)	0.7155 (5)	1.05338 (18)	0.1116 (12)
O3	0.44483 (8)	0.49496 (17)	0.61595 (11)	0.0388 (3)
O1	0.42110 (7)	0.61450 (15)	0.83403 (9)	0.0346 (2)
O2	0.34658 (9)	0.31413 (14)	0.76697 (11)	0.0425 (3)
O4	0.33940 (6)	0.77503 (12)	0.64328 (8)	0.0324 (2)
O7	0.33332 (9)	1.05982 (14)	0.63862 (11)	0.0495 (3)
O6	0.45155 (8)	0.92939 (18)	0.60150 (11)	0.0544 (4)
O5	0.41150 (7)	0.92986 (13)	0.78030 (9)	0.0355 (2)
O8	0.42600 (10)	0.25981 (17)	0.97318 (11)	0.0434 (3)
S1	0.38443 (2)	0.92315 (4)	0.66620 (3)	0.02701 (9)
H2A	0.3427 (14)	0.238 (3)	0.732 (2)	0.067 (8)*
H1A	0.4624 (15)	0.574 (3)	0.8556 (19)	0.064 (7)*
H1B	0.4282 (13)	0.715 (3)	0.8261 (18)	0.058 (6)*
H3B	0.4378 (13)	0.424 (3)	0.5727 (19)	0.056 (7)*
H3A	0.4849 (15)	0.489 (3)	0.6467 (19)	0.056 (7)*
H8A	0.4679 (15)	0.286 (3)	0.9585 (19)	0.063 (8)*
H8B	0.4116 (15)	0.326 (3)	1.0055 (19)	0.064 (8)*
H2B	0.3675 (14)	0.296 (3)	0.823 (2)	0.061 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.02677 (11)	0.02351 (11)	0.02545 (11)	0.00010 (7)	−0.00204 (7)	−0.00148 (7)
C1	0.0316 (8)	0.0405 (9)	0.0327 (8)	−0.0012 (6)	0.0023 (6)	−0.0012 (6)
C2	0.0370 (9)	0.0605 (11)	0.0289 (8)	0.0078 (8)	0.0010 (6)	−0.0021 (7)
C3	0.0341 (9)	0.0614 (11)	0.0378 (9)	0.0062 (8)	−0.0059 (7)	−0.0182 (8)
C4	0.0348 (9)	0.0563 (11)	0.0511 (10)	−0.0131 (8)	−0.0028 (8)	−0.0128 (9)
C5	0.0394 (9)	0.0447 (9)	0.0363 (8)	−0.0119 (7)	0.0000 (7)	−0.0007 (7)
C6	0.0388 (10)	0.110 (2)	0.0464 (11)	0.0076 (11)	−0.0074 (8)	−0.0311 (12)
C11	0.0381 (9)	0.0525 (10)	0.0334 (8)	0.0079 (7)	−0.0038 (7)	−0.0001 (7)
C10	0.0315 (9)	0.0727 (13)	0.0451 (10)	0.0113 (8)	−0.0066 (7)	−0.0069 (9)
C9	0.0324 (9)	0.0639 (12)	0.0426 (9)	0.0018 (8)	0.0046 (7)	−0.0099 (9)
C8	0.0389 (9)	0.0588 (11)	0.0322 (8)	0.0018 (8)	0.0034 (7)	−0.0013 (8)
C7	0.0337 (8)	0.0475 (10)	0.0322 (8)	0.0072 (7)	0.0006 (6)	0.0016 (7)
C12	0.0354 (10)	0.124 (2)	0.0489 (11)	0.0140 (12)	0.0011 (9)	−0.0121 (13)
N1	0.0305 (6)	0.0305 (6)	0.0288 (6)	−0.0035 (5)	−0.0010 (5)	−0.0032 (5)
N3	0.0550 (12)	0.186 (3)	0.0607 (12)	0.0060 (15)	−0.0150 (10)	−0.0505 (16)
N2	0.0325 (7)	0.0356 (7)	0.0304 (6)	0.0035 (5)	0.0006 (5)	−0.0003 (5)
N4	0.0516 (12)	0.221 (4)	0.0632 (13)	0.0348 (16)	0.0122 (10)	−0.0199 (17)
O3	0.0294 (6)	0.0468 (7)	0.0395 (6)	0.0064 (5)	−0.0026 (5)	−0.0104 (6)
O1	0.0353 (6)	0.0319 (6)	0.0347 (6)	0.0007 (5)	−0.0092 (5)	0.0009 (5)
O2	0.0674 (9)	0.0247 (6)	0.0336 (6)	0.0018 (5)	−0.0074 (6)	−0.0007 (5)
O4	0.0357 (5)	0.0252 (5)	0.0345 (5)	−0.0051 (4)	−0.0090 (4)	0.0020 (4)
O7	0.0693 (9)	0.0260 (6)	0.0486 (7)	0.0118 (5)	−0.0237 (6)	−0.0061 (5)
O6	0.0519 (8)	0.0647 (9)	0.0490 (8)	−0.0221 (7)	0.0196 (6)	−0.0117 (6)
O5	0.0377 (6)	0.0371 (6)	0.0299 (5)	−0.0027 (4)	−0.0080 (4)	−0.0012 (4)
O8	0.0548 (9)	0.0387 (7)	0.0370 (7)	0.0002 (6)	0.0053 (6)	−0.0015 (5)
S1	0.03156 (19)	0.02268 (17)	0.02625 (17)	−0.00238 (12)	−0.00122 (13)	−0.00079 (12)

Geometric parameters (Å, º)

Co1—O4	2.0736 (10)	C10—C9	1.389 (3)
Co1—O2	2.0802 (12)	C10—H10	0.9300
Co1—O3	2.0857 (12)	C9—C8	1.381 (2)
Co1—O1	2.0947 (11)	C9—C12	1.443 (3)
Co1—N1	2.1346 (12)	C8—C7	1.377 (2)
Co1—N2	2.1997 (13)	C8—H8	0.9300
C1—N1	1.339 (2)	C7—N2	1.335 (2)
C1—C2	1.374 (2)	C7—H7	0.9300
C1—H1	0.9300	C12—N4	1.128 (3)
C2—C3	1.381 (3)	O3—H3B	0.81 (2)
C2—H2	0.9300	O3—H3A	0.76 (3)
C3—C4	1.384 (3)	O1—H1A	0.81 (3)
C3—C6	1.448 (2)	O1—H1B	0.86 (3)
C4—C5	1.373 (2)	O2—H2A	0.77 (3)
C4—H4	0.9300	O2—H2B	0.77 (3)
C5—N1	1.334 (2)	O4—S1	1.4745 (10)
C5—H5	0.9300	O7—S1	1.4639 (12)
C6—N3	1.134 (3)	O6—S1	1.4612 (13)
C11—N2	1.342 (2)	O5—S1	1.4728 (11)
C11—C10	1.375 (2)	O8—H8A	0.79 (3)
C11—H11	0.9300	O8—H8B	0.74 (3)
O4—Co1—O2	174.38 (5)	C11—C10—H10	121.0
O4—Co1—O3	92.01 (5)	C9—C10—H10	121.0
O2—Co1—O3	93.60 (6)	C8—C9—C10	119.42 (16)
O4—Co1—O1	91.90 (5)	C8—C9—C12	118.57 (17)
O2—Co1—O1	88.35 (5)	C10—C9—C12	121.97 (17)
O3—Co1—O1	90.71 (5)	C7—C8—C9	118.15 (16)
O4—Co1—N1	87.90 (4)	C7—C8—H8	120.9
O2—Co1—N1	91.96 (5)	C9—C8—H8	120.9
O3—Co1—N1	88.20 (5)	N2—C7—C8	123.66 (16)
O1—Co1—N1	178.88 (5)	N2—C7—H7	118.2
O4—Co1—N2	88.78 (5)	C8—C7—H7	118.2
O2—Co1—N2	85.62 (5)	N4—C12—C9	176.7 (3)
O3—Co1—N2	178.36 (5)	C5—N1—C1	118.01 (13)
O1—Co1—N2	87.83 (5)	C5—N1—Co1	122.05 (11)
N1—Co1—N2	93.26 (5)	C1—N1—Co1	119.91 (10)
N1—C1—C2	122.71 (16)	C7—N2—C11	117.22 (14)
N1—C1—H1	118.6	C7—N2—Co1	118.40 (11)
C2—C1—H1	118.6	C11—N2—Co1	124.38 (11)
C1—C2—C3	118.38 (16)	Co1—O3—H3B	113.8 (16)
C1—C2—H2	120.8	Co1—O3—H3A	118.3 (18)
C3—C2—H2	120.8	H3B—O3—H3A	112 (2)
C2—C3—C4	119.65 (15)	Co1—O1—H1A	126.8 (17)
C2—C3—C6	119.30 (18)	Co1—O1—H1B	105.6 (15)
C4—C3—C6	121.05 (19)	H1A—O1—H1B	109 (2)
C5—C4—C3	117.84 (16)	Co1—O2—H2A	122.6 (19)
C5—C4—H4	121.1	Co1—O2—H2B	121.2 (18)
C3—C4—H4	121.1	H2A—O2—H2B	111 (3)
N1—C5—C4	123.36 (16)	S1—O4—Co1	134.02 (6)
N1—C5—H5	118.3	H8A—O8—H8B	106 (3)
C4—C5—H5	118.3	O6—S1—O7	108.88 (9)
N3—C6—C3	178.7 (3)	O6—S1—O5	109.78 (8)
N2—C11—C10	123.56 (15)	O7—S1—O5	109.74 (7)
N2—C11—H11	118.2	O6—S1—O4	110.16 (7)
C10—C11—H11	118.2	O7—S1—O4	108.25 (7)
C11—C10—C9	117.99 (16)	O5—S1—O4	110.01 (6)
N1—C1—C2—C3	0.5 (3)	O2—Co1—N1—C1	−139.94 (12)
C1—C2—C3—C4	−1.5 (3)	O3—Co1—N1—C1	−46.40 (12)
C1—C2—C3—C6	178.54 (18)	O1—Co1—N1—C1	−34 (3)
C2—C3—C4—C5	0.7 (3)	N2—Co1—N1—C1	134.33 (12)
C6—C3—C4—C5	−179.39 (19)	C8—C7—N2—C11	0.1 (3)
C3—C4—C5—N1	1.3 (3)	C8—C7—N2—Co1	179.36 (14)
C2—C3—C6—N3	28 (15)	C10—C11—N2—C7	−0.5 (3)
C4—C3—C6—N3	−152 (15)	C10—C11—N2—Co1	−179.68 (15)
N2—C11—C10—C9	0.7 (3)	O4—Co1—N2—C7	−126.89 (12)
C11—C10—C9—C8	−0.5 (3)	O2—Co1—N2—C7	53.57 (13)
C11—C10—C9—C12	177.1 (2)	O3—Co1—N2—C7	−8.1 (19)
C10—C9—C8—C7	0.1 (3)	O1—Co1—N2—C7	−34.94 (13)
C12—C9—C8—C7	−177.5 (2)	N1—Co1—N2—C7	145.29 (13)
C9—C8—C7—N2	0.0 (3)	O4—Co1—N2—C11	52.27 (14)
C8—C9—C12—N4	36 (6)	O2—Co1—N2—C11	−127.27 (14)
C10—C9—C12—N4	−141 (6)	O3—Co1—N2—C11	171.1 (18)
C4—C5—N1—C1	−2.4 (3)	O1—Co1—N2—C11	144.21 (14)
C4—C5—N1—Co1	175.68 (14)	N1—Co1—N2—C11	−35.56 (14)
C2—C1—N1—C5	1.5 (2)	O2—Co1—O4—S1	108.6 (5)
C2—C1—N1—Co1	−176.65 (13)	O3—Co1—O4—S1	−74.67 (10)
O4—Co1—N1—C5	−132.38 (13)	O1—Co1—O4—S1	16.10 (10)
O2—Co1—N1—C5	42.01 (13)	N1—Co1—O4—S1	−162.80 (10)
O3—Co1—N1—C5	135.54 (13)	N2—Co1—O4—S1	103.89 (10)
O1—Co1—N1—C5	148 (2)	Co1—O4—S1—O6	85.97 (11)
N2—Co1—N1—C5	−43.72 (13)	Co1—O4—S1—O7	−155.08 (10)
O4—Co1—N1—C1	45.68 (12)	Co1—O4—S1—O5	−35.18 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O6^i	0.81 (3)	1.95 (3)	2.7451 (18)	166 (2)
O1—H1B···O5	0.86 (3)	1.90 (3)	2.7203 (17)	161 (2)
O2—H2A···O7^ii	0.77 (3)	1.89 (3)	2.6654 (18)	176 (3)
O2—H2B···O8	0.77 (3)	2.09 (3)	2.8667 (19)	177 (2)
O3—H3A···O5^i	0.76 (3)	2.00 (3)	2.7493 (17)	169 (3)
O3—H3B···O8^iii	0.81 (2)	1.98 (2)	2.7850 (19)	176 (2)
O8—H8A···O6^i	0.79 (3)	2.02 (3)	2.758 (2)	156 (3)

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