μ-Peroxo-bis­[aceto­nitrile­bis­(ethyl­enedi­amine)­cobalt(III)] tetratriflate

The crystals of the title compound, {[Co(en)₂(MeCN)]₂(μ-O₂)}(CF₃SO₃)₄ or [Co₂(O₂)(C₂H₃N)₂(C₂H₈N₂)₄](CF₃O₃S)₄, are built of binuclear tetracations and tri­fluoro­methane­sulfonate anions. The cation occupies a special position on the inversion center; the separation between the Co atoms, which have a slightly distorted octahedral coordination, is 4.4966 (7) Å, with Co—N(MeCN), Co—O, and average Co—N(en) distances of 1.938 (2), 1.8736 (17), and 1.950 Å, respectively. Both aceto­nitriles are trans to the O—O bridge, the O—O distance being 1.496 (3) Å. The [Co(en)₂] moieties have δδ and the inversion-related λλ conformations.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.040
• wR factor = 0.100
• Data-to-parameter ratio = 13.3

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



FORMU_01  There is a discrepancy between the atom counts in the
          _chemical_formula_sum and _chemical_formula_moiety. This is
          usually due to the moiety formula being in the wrong format.
          Atom count from _chemical_formula_sum:   C16 H38 Co2 F12 N10 O14 S4
          Atom count from _chemical_formula_moiety:C13 H38 Co2 F3 N10 O5 S4

---

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART and SAINT; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

µ-Peroxo-bis[acetonitrilebis(ethylenediamine)cobalt(III)] tetratriflate

Crystal data

[Co2(O2)(C2H3N)2(C2H8N2)4](CF3O3S)4	F(000) = 1084
Mr = 1068.64	Dx = 1.809 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.164 (1) Å	Cell parameters from 6714 reflections
b = 8.3883 (7) Å	θ = 2.3–32.2°
c = 17.939 (2) Å	µ = 1.18 mm^−1
β = 97.869 (2)°	T = 100 K
V = 1962.2 (3) Å^3	Plate, brown
Z = 2	0.35 × 0.13 × 0.04 mm

Data collection

Bruker CCD area-detector diffractometer	4487 independent reflections
Radiation source: fine-focus sealed tube	3403 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.053
Detector resolution: 8.333 pixels mm^-1	θmax = 27.5°, θmin = 1.8°
ω scans	h = −17→17
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	k = −10→10
Tmin = 0.661, Tmax = 0.954	l = −23→23
17919 measured reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.100	All H-atom parameters refined
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0534P)^2] where P = (Fo^2 + 2Fc^2)/3
4487 reflections	(Δ/σ)max < 0.001
338 parameters	Δρmax = 1.49 e Å^−3
0 restraints	Δρmin = −0.46 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. There is a large peak (1.493) between O atoms of a trifluoromethanesulfonate anion. This was not modeled for disorder.

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

	x	y	z	Uiso*/Ueq
Co1	0.95240 (3)	0.47270 (4)	0.614997 (19)	0.01424 (11)
N1	0.87235 (17)	0.6585 (3)	0.57791 (14)	0.0188 (5)
H1C	0.8891 (19)	0.742 (3)	0.6075 (15)	0.011 (7)*
H1D	0.887 (2)	0.674 (4)	0.5330 (18)	0.030 (9)*
N2	0.82478 (17)	0.3506 (3)	0.59154 (13)	0.0184 (5)
H2C	0.829 (2)	0.252 (4)	0.5700 (16)	0.027 (8)*
H2D	0.797 (2)	0.324 (4)	0.6311 (18)	0.032 (9)*
N3	1.07747 (17)	0.5956 (3)	0.63948 (14)	0.0210 (5)
H3C	1.084 (2)	0.649 (4)	0.6009 (19)	0.033 (9)*
H3D	1.074 (2)	0.669 (4)	0.6781 (18)	0.028 (8)*
N4	1.03347 (19)	0.2871 (3)	0.65166 (14)	0.0203 (5)
H4C	1.004 (2)	0.226 (3)	0.6725 (16)	0.016 (8)*
H4D	1.057 (2)	0.245 (4)	0.6161 (18)	0.027 (9)*
N5	0.91739 (17)	0.5045 (2)	0.71539 (12)	0.0165 (5)
O1	0.98294 (14)	0.4264 (2)	0.51833 (10)	0.0179 (4)
C1	0.7616 (2)	0.6199 (3)	0.57373 (17)	0.0235 (6)
H1A	0.722 (2)	0.695 (3)	0.5432 (16)	0.023 (8)*
H1B	0.740 (2)	0.625 (3)	0.6209 (16)	0.015 (7)*
C1S	0.6427 (2)	0.0119 (3)	0.43952 (18)	0.0277 (7)
C2	0.7480 (2)	0.4502 (3)	0.54432 (16)	0.0227 (6)
H2A	0.678 (2)	0.412 (3)	0.5469 (15)	0.017 (7)*
H2B	0.764 (2)	0.441 (3)	0.4952 (16)	0.011 (7)*
C2S	1.0129 (2)	0.9958 (4)	0.84590 (19)	0.0323 (7)
C3	1.1653 (2)	0.4865 (4)	0.66262 (18)	0.0249 (6)
H3A	1.215 (2)	0.544 (3)	0.6899 (18)	0.026 (8)*
H3B	1.192 (2)	0.460 (3)	0.6205 (18)	0.019 (7)*
C4	1.1261 (2)	0.3428 (4)	0.70069 (16)	0.0248 (6)
H4A	1.177 (2)	0.263 (4)	0.7093 (16)	0.031 (8)*
H4B	1.107 (2)	0.369 (3)	0.7438 (16)	0.016 (7)*
C5	0.8905 (2)	0.5083 (3)	0.77336 (15)	0.0173 (5)
C6	0.8576 (2)	0.5081 (4)	0.84776 (16)	0.0243 (6)
H6A	0.880 (3)	0.403 (4)	0.8718 (19)	0.044 (10)*
H6B	0.784 (3)	0.528 (4)	0.839 (2)	0.047 (11)*
H6C	0.897 (3)	0.598 (4)	0.876 (2)	0.050 (11)*
S1	0.78269 (6)	0.00307 (8)	0.45621 (4)	0.02356 (17)
S2	0.91535 (5)	0.96188 (8)	0.76462 (4)	0.01970 (16)
O2	0.80552 (16)	0.0201 (2)	0.53733 (12)	0.0301 (5)
O3	0.81203 (17)	0.1364 (3)	0.41367 (14)	0.0426 (6)
O4	0.80549 (15)	−0.1526 (2)	0.42878 (11)	0.0271 (5)
O5	0.88520 (15)	1.1223 (2)	0.74171 (12)	0.0272 (5)
O6	0.83780 (15)	0.8702 (2)	0.79523 (11)	0.0261 (4)
O7	0.97052 (17)	0.8776 (2)	0.71217 (12)	0.0360 (5)
F1	0.60858 (14)	0.1520 (2)	0.46152 (13)	0.0497 (6)
F2	0.60654 (16)	−0.0094 (3)	0.36709 (11)	0.0493 (6)
F3	0.59947 (12)	−0.10182 (19)	0.47735 (9)	0.0277 (4)
F4	0.97413 (15)	1.0742 (3)	0.90026 (11)	0.0528 (6)
F5	1.09024 (13)	1.0846 (2)	0.82679 (11)	0.0409 (5)
F6	1.05254 (19)	0.8615 (3)	0.87451 (14)	0.0733 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01937 (19)	0.01210 (18)	0.01308 (18)	−0.00017 (13)	0.00877 (13)	0.00023 (13)
N1	0.0249 (12)	0.0147 (11)	0.0188 (12)	0.0002 (9)	0.0107 (10)	0.0005 (10)
N2	0.0238 (12)	0.0159 (11)	0.0175 (12)	−0.0028 (9)	0.0102 (10)	−0.0018 (9)
N3	0.0256 (13)	0.0207 (12)	0.0192 (12)	−0.0040 (9)	0.0123 (10)	−0.0024 (10)
N4	0.0263 (13)	0.0194 (12)	0.0183 (12)	0.0013 (10)	0.0141 (10)	0.0021 (10)
N5	0.0211 (11)	0.0125 (11)	0.0168 (11)	−0.0003 (8)	0.0053 (9)	−0.0002 (8)
O1	0.0280 (10)	0.0134 (9)	0.0149 (9)	−0.0018 (7)	0.0131 (8)	−0.0001 (7)
C1	0.0213 (14)	0.0228 (15)	0.0286 (16)	0.0057 (11)	0.0117 (12)	0.0052 (12)
C1S	0.0295 (16)	0.0245 (15)	0.0294 (16)	0.0028 (12)	0.0045 (13)	0.0060 (12)
C2	0.0205 (14)	0.0286 (16)	0.0203 (15)	−0.0009 (12)	0.0077 (11)	−0.0004 (12)
C2S	0.0267 (16)	0.0337 (18)	0.0358 (18)	−0.0033 (12)	0.0017 (14)	0.0077 (14)
C3	0.0205 (14)	0.0318 (16)	0.0235 (15)	−0.0014 (12)	0.0070 (12)	−0.0044 (13)
C4	0.0273 (15)	0.0342 (17)	0.0139 (14)	0.0063 (13)	0.0072 (12)	0.0006 (12)
C5	0.0198 (13)	0.0142 (13)	0.0184 (13)	0.0002 (10)	0.0045 (10)	0.0003 (10)
C6	0.0312 (16)	0.0266 (16)	0.0175 (14)	0.0005 (12)	0.0119 (12)	0.0011 (12)
S1	0.0255 (4)	0.0192 (4)	0.0277 (4)	−0.0005 (3)	0.0102 (3)	0.0002 (3)
S2	0.0223 (3)	0.0162 (3)	0.0227 (3)	−0.0011 (3)	0.0104 (3)	0.0000 (3)
O2	0.0316 (12)	0.0278 (11)	0.0314 (12)	−0.0005 (9)	0.0063 (9)	−0.0089 (9)
O3	0.0387 (13)	0.0385 (13)	0.0538 (16)	−0.0055 (10)	0.0176 (11)	0.0166 (11)
O4	0.0353 (12)	0.0247 (11)	0.0247 (11)	0.0028 (9)	0.0161 (9)	−0.0056 (8)
O5	0.0260 (11)	0.0200 (10)	0.0363 (12)	−0.0009 (8)	0.0067 (9)	0.0071 (9)
O6	0.0281 (11)	0.0215 (10)	0.0316 (11)	−0.0057 (8)	0.0145 (9)	0.0008 (9)
O7	0.0412 (13)	0.0302 (12)	0.0425 (13)	−0.0048 (10)	0.0264 (11)	−0.0099 (10)
F1	0.0362 (11)	0.0256 (10)	0.0891 (17)	0.0111 (8)	0.0146 (11)	0.0045 (10)
F2	0.0410 (12)	0.0779 (16)	0.0270 (10)	−0.0075 (10)	−0.0026 (9)	0.0205 (10)
F3	0.0255 (9)	0.0320 (9)	0.0269 (9)	−0.0012 (7)	0.0075 (7)	0.0050 (7)
F4	0.0451 (12)	0.0852 (16)	0.0304 (11)	−0.0267 (11)	0.0135 (9)	−0.0165 (11)
F5	0.0212 (9)	0.0542 (12)	0.0480 (12)	−0.0091 (8)	0.0071 (8)	0.0023 (10)
F6	0.0690 (16)	0.0571 (15)	0.0842 (18)	0.0029 (12)	−0.0241 (14)	0.0390 (13)

Geometric parameters (Å, º)

Co1—O1	1.8736 (17)	C1S—F1	1.336 (3)
Co1—N5	1.938 (2)	C1S—F3	1.342 (3)
Co1—N3	1.941 (2)	C1S—S1	1.827 (3)
Co1—N1	1.947 (2)	C2—H2A	0.98 (3)
Co1—N4	1.950 (2)	C2—H2B	0.94 (3)
Co1—N2	1.963 (2)	C2S—F6	1.316 (4)
N1—C1	1.485 (4)	C2S—F4	1.334 (4)
N1—H1C	0.89 (3)	C2S—F5	1.343 (3)
N1—H1D	0.87 (3)	C2S—S2	1.828 (3)
N2—C2	1.485 (4)	C3—C4	1.511 (4)
N2—H2C	0.92 (3)	C3—H3A	0.90 (3)
N2—H2D	0.87 (3)	C3—H3B	0.90 (3)
N3—C3	1.489 (4)	C4—H4A	0.95 (3)
N3—H3C	0.84 (3)	C4—H4B	0.87 (3)
N3—H3D	0.93 (3)	C5—C6	1.459 (4)
N4—C4	1.478 (4)	C6—H6A	1.01 (3)
N4—H4C	0.77 (3)	C6—H6B	0.97 (4)
N4—H4D	0.83 (3)	C6—H6C	1.01 (4)
N5—C5	1.144 (3)	S1—O3	1.436 (2)
O1—O1^i	1.496 (3)	S1—O4	1.4417 (19)
C1—C2	1.520 (4)	S1—O2	1.452 (2)
C1—H1A	0.95 (3)	S2—O6	1.4451 (19)
C1—H1B	0.93 (3)	S2—O5	1.446 (2)
C1S—F2	1.333 (4)	S2—O7	1.449 (2)
O1—Co1—N5	175.78 (8)	F2—C1S—F3	106.1 (2)
O1—Co1—N3	92.10 (9)	F1—C1S—F3	107.0 (2)
N5—Co1—N3	91.08 (10)	F2—C1S—S1	111.8 (2)
O1—Co1—N1	91.39 (9)	F1—C1S—S1	111.1 (2)
N5—Co1—N1	91.20 (9)	F3—C1S—S1	112.11 (19)
N3—Co1—N1	93.13 (10)	N2—C2—C1	106.8 (2)
O1—Co1—N4	88.27 (9)	N2—C2—H2A	111.1 (16)
N5—Co1—N4	89.16 (10)	C1—C2—H2A	110.8 (16)
N3—Co1—N4	86.55 (11)	N2—C2—H2B	105.7 (16)
N1—Co1—N4	179.52 (11)	C1—C2—H2B	111.8 (16)
O1—Co1—N2	88.82 (9)	H2A—C2—H2B	110 (2)
N5—Co1—N2	88.03 (9)	F6—C2S—F4	107.9 (3)
N3—Co1—N2	178.98 (10)	F6—C2S—F5	107.5 (3)
N1—Co1—N2	86.39 (10)	F4—C2S—F5	107.0 (3)
N4—Co1—N2	93.93 (10)	F6—C2S—S2	112.1 (2)
C1—N1—Co1	108.92 (17)	F4—C2S—S2	111.3 (2)
C1—N1—H1C	111.4 (17)	F5—C2S—S2	110.9 (2)
Co1—N1—H1C	110.2 (17)	N3—C3—C4	108.4 (2)
C1—N1—H1D	109 (2)	N3—C3—H3A	107.6 (19)
Co1—N1—H1D	105 (2)	C4—C3—H3A	116.6 (19)
H1C—N1—H1D	112 (3)	N3—C3—H3B	106.9 (18)
C2—N2—Co1	108.95 (17)	C4—C3—H3B	112.2 (18)
C2—N2—H2C	110.3 (18)	H3A—C3—H3B	105 (3)
Co1—N2—H2C	117.2 (18)	N4—C4—C3	106.8 (2)
C2—N2—H2D	106 (2)	N4—C4—H4A	112.6 (18)
Co1—N2—H2D	114 (2)	C3—C4—H4A	111.0 (19)
H2C—N2—H2D	100 (3)	N4—C4—H4B	107.4 (18)
C3—N3—Co1	109.79 (18)	C3—C4—H4B	110.6 (18)
C3—N3—H3C	113 (2)	H4A—C4—H4B	108 (2)
Co1—N3—H3C	106 (2)	N5—C5—C6	178.1 (3)
C3—N3—H3D	108.2 (19)	C5—C6—H6A	107 (2)
Co1—N3—H3D	113.1 (18)	C5—C6—H6B	106 (2)
H3C—N3—H3D	106 (3)	H6A—C6—H6B	116 (3)
C4—N4—Co1	108.48 (18)	C5—C6—H6C	105 (2)
C4—N4—H4C	110 (2)	H6A—C6—H6C	110 (3)
Co1—N4—H4C	114 (2)	H6B—C6—H6C	112 (3)
C4—N4—H4D	103 (2)	O3—S1—O4	116.12 (13)
Co1—N4—H4D	109 (2)	O3—S1—O2	114.97 (14)
H4C—N4—H4D	111 (3)	O4—S1—O2	114.02 (12)
C5—N5—Co1	172.5 (2)	O3—S1—C1S	102.69 (14)
O1^i—O1—Co1	110.57 (16)	O4—S1—C1S	103.50 (13)
N1—C1—C2	106.9 (2)	O2—S1—C1S	103.06 (14)
N1—C1—H1A	109.9 (17)	O6—S2—O5	114.98 (12)
C2—C1—H1A	113.4 (17)	O6—S2—O7	115.49 (12)
N1—C1—H1B	111.3 (17)	O5—S2—O7	114.31 (13)
C2—C1—H1B	108.6 (17)	O6—S2—C2S	103.61 (13)
H1A—C1—H1B	107 (2)	O5—S2—C2S	102.54 (13)
F2—C1S—F1	108.4 (2)	O7—S2—C2S	103.54 (15)
O1—Co1—N1—C1	104.30 (18)	N1—C1—C2—N2	50.9 (3)
N5—Co1—N1—C1	−72.37 (19)	Co1—N3—C3—C4	−31.6 (3)
N3—Co1—N1—C1	−163.52 (19)	Co1—N4—C4—C3	−42.0 (3)
N2—Co1—N1—C1	15.58 (18)	N3—C3—C4—N4	48.0 (3)
O1—Co1—N2—C2	−78.47 (17)	F2—C1S—S1—O3	63.2 (2)
N5—Co1—N2—C2	104.33 (18)	F1—C1S—S1—O3	−58.1 (2)
N1—Co1—N2—C2	13.00 (18)	F3—C1S—S1—O3	−177.8 (2)
N4—Co1—N2—C2	−166.65 (18)	F2—C1S—S1—O4	−58.0 (2)
O1—Co1—N3—C3	−81.52 (18)	F1—C1S—S1—O4	−179.3 (2)
N5—Co1—N3—C3	95.71 (19)	F3—C1S—S1—O4	61.0 (2)
N1—Co1—N3—C3	−173.03 (19)	F2—C1S—S1—O2	−177.06 (19)
N4—Co1—N3—C3	6.62 (19)	F1—C1S—S1—O2	61.6 (2)
O1—Co1—N4—C4	112.44 (18)	F3—C1S—S1—O2	−58.0 (2)
N5—Co1—N4—C4	−70.90 (18)	F6—C2S—S2—O6	61.6 (3)
N3—Co1—N4—C4	20.24 (19)	F4—C2S—S2—O6	−59.4 (2)
N2—Co1—N4—C4	−158.86 (18)	F5—C2S—S2—O6	−178.3 (2)
N3—Co1—O1—O1^i	−46.18 (19)	F6—C2S—S2—O5	−178.5 (2)
N1—Co1—O1—O1^i	47.01 (18)	F4—C2S—S2—O5	60.6 (2)
N4—Co1—O1—O1^i	−132.65 (19)	F5—C2S—S2—O5	−58.4 (2)
N2—Co1—O1—O1^i	133.38 (18)	F6—C2S—S2—O7	−59.3 (3)
Co1—N1—C1—C2	−40.1 (3)	F4—C2S—S2—O7	179.7 (2)
Co1—N2—C2—C1	−37.9 (2)	F5—C2S—S2—O7	60.7 (2)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O7	0.89 (3)	2.33 (3)	3.162 (3)	157 (2)
N1—H1D···O1^i	0.87 (3)	2.22 (3)	2.832 (3)	128 (3)
N1—H1D···O4^ii	0.87 (3)	2.49 (3)	3.130 (3)	131 (3)
N2—H2C···O2	0.92 (3)	2.04 (3)	2.937 (3)	164 (3)
N2—H2D···O6^iii	0.87 (3)	2.38 (3)	3.150 (3)	147 (3)
N3—H3C···O1^i	0.84 (3)	2.29 (3)	2.840 (3)	123 (3)
N3—H3C···O3^i	0.84 (3)	2.29 (3)	2.908 (3)	130 (3)
N3—H3D···O7	0.93 (3)	2.35 (3)	3.127 (3)	141 (2)
N4—H4C···O5^iv	0.77 (3)	2.30 (3)	3.032 (3)	160 (3)
N4—H4D···O4^v	0.83 (3)	2.22 (3)	2.947 (3)	147 (3)

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