trans-Chloro­bis­(ethyl­enedi­amine-N,N')­nitro­cobalt(III) nitrate

In the title compound, trans-[CoCl(NO₂)(C₂H₈N₂)₂]NO₃, a distorted octahedral Co^III complex shows an orientational disorder such that the positions of the nitro and chloro ligands are exchanged. The occupation factors of the major and minor orientations are 84 and 16%, respectively. The O atoms of the nitrate ion are disordered over two sites.

S1. Comment

Certain nitrocobalt(III) complexes show nitro-to-nitrito linkage isomerization in the solid state by irradiation of visible light (Adell, 1971; Grenthe & Nordin, 1979; Masciocchi et al., 1994). Although the title crystal, (I), is photostable, the structure was determined as part of a study on photoisomerization. \scheme

In (I), the complex cation has two possible orientations. Furthermore, the O atoms of nitrate ion are disordered over two sites. A similar disorder of NO₃⁻ was observed in crystals of trans-[Co(en)₂Cl₂]NO₃ (en is ethylenediamine; Kita et al., 1994), but not in trans-[Co(en)₂(NO₂)₂]NO₃ (Bortin, 1976).

The crystals of trans-[Co(en)₂Cl(NO₂)]CF₃SO₃ were also prepared in the present study to indicate that there is an orientational disorder of the complex cation: monoclinic, space group P2₁/c, a = 6.638 (4), b = 17.222 (4), c = 12.725 (3) Å, β = 101.64 (3)°, V = 1424.8 (8) ų and Z = 4 at 300 K.

S2. Experimental

The title compound was prepared by a literature method (Adell, 1971). The crystals of (I) were grown from a hot aqueous solution by slow cooling.

S3. Refinement

A split-site model was applicable for the positional disorder of the nitro and chloro ligands. The site-occupation factor of the major orientation (atoms N17, O8, O9, and Cl2) was fixed to 84% after some refinements. In the minor orientation, nitro-O atoms are further disordered over two sites with 8% probability each (atoms O4—O7). The Co1—N16 bond distance was restrained to be 1.90 Å (s.u. 0.01 Å) and the nitro N16—O distances to be 1.24 Å (s.u. 0.01 Å). The minor Cl3, O4–O7 and N16 atoms were refined isotropically. All H-atom positional parameters were calculated geometrically and fixed with U_iso(H) = 1.2U_eq(parent atom). The nitrate O atoms also show positional disorder, suggesting that there are two possible orientations of the ion with 50% probability each.

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

[CoCl(NO2)(C2H8N2)2](NO3)	Dx = 1.827 Mg m^−3
Mr = 322.59	Mo Kα radiation, λ = 0.71073 Å
Monoclinic, P21/c	Cell parameters from 25 reflections
a = 6.601 (2) Å	θ = 13.9–14.9°
b = 12.721 (2) Å	µ = 1.71 mm^−1
c = 14.072 (1) Å	T = 298 K
β = 97.06 (1)°	Prismatic, orange–red
V = 1172.7 (3) Å^3	0.5 × 0.5 × 0.2 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.006
θ–2θ scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: ψ scan (North et al., 1968)	h = 0→9
Tmin = 0.605, Tmax = 0.710	k = 0→17
2930 measured reflections	l = −18→18
2703 independent reflections	3 standard reflections every 150 reflections
2494 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.032	w = 1/[σ^2(Fo^2) + (0.0406P)^2 + 1.0531P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.082	(Δ/σ)max = 0.001
S = 1.10	Δρmax = 0.75 e Å^−3
2703 reflections	Δρmin = −0.67 e Å^−3
205 parameters

Special details

Refinement. Refinement was based on F² against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F², and conventional R-factor (R) was calculated on F, with F set to zero for negative F². The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Co1	0.20504 (4)	0.09122 (2)	0.26611 (2)	0.0217 (1)
Cl2	−0.0650 (1)	−0.02185 (6)	0.24844 (6)	0.0405 (2)	0.84
Cl3	0.483 (2)	0.2025 (9)	0.2854 (9)	0.07987 (4)*	0.16
O4	−0.162 (3)	0.014 (2)	0.192 (2)	0.05302 (7)*	0.08
O5	−0.017 (3)	−0.080 (2)	0.310 (1)	0.03871 (6)*	0.08
O6	−0.058 (3)	−0.063 (2)	0.183 (1)	0.04049 (6)*	0.08
O7	−0.145 (4)	−0.008 (2)	0.313 (2)	0.05620 (8)*	0.08
O8	0.4166 (4)	0.2698 (2)	0.2378 (2)	0.0572 (7)	0.84
O9	0.5902 (3)	0.1581 (2)	0.3292 (2)	0.0594 (7)	0.84
O10	0.7948 (8)	0.2587 (6)	0.5971 (4)	0.088 (2)	0.55
O11	0.5011 (9)	0.2926 (4)	0.5229 (3)	0.070 (1)	0.55
O12	0.5938 (8)	0.1350 (3)	0.5507 (3)	0.058 (1)	0.55
O13	0.707 (1)	0.3287 (4)	0.5609 (5)	0.079 (2)	0.45
O14	0.7962 (9)	0.1782 (4)	0.6064 (4)	0.063 (1)	0.45
O15	0.486 (1)	0.203 (1)	0.5463 (6)	0.140 (5)	0.45
N16	−0.017 (3)	−0.005 (2)	0.254 (1)	0.2271 (3)*	0.16
N17	0.4299 (6)	0.1841 (3)	0.2794 (3)	0.0401 (8)	0.84
N18	0.0249 (3)	0.2067 (1)	0.2927 (1)	0.0290 (4)
N19	0.2387 (3)	0.0660 (2)	0.4040 (1)	0.0338 (4)
N20	0.1680 (3)	0.1158 (2)	0.1275 (1)	0.0330 (4)
N21	0.3870 (3)	−0.0231 (2)	0.2397 (1)	0.0315 (4)
N22	0.6410 (4)	0.2319 (2)	0.5622 (2)	0.0445 (5)
C23	0.0504 (4)	0.2282 (2)	0.3971 (2)	0.0373 (5)
C24	0.0768 (4)	0.1237 (2)	0.4472 (2)	0.0384 (5)
C25	0.2357 (4)	0.0205 (2)	0.0790 (2)	0.0430 (6)
C26	0.4247 (4)	−0.0193 (2)	0.1374 (2)	0.0426 (6)
H18A	0.0595	0.2678	0.2594	0.0347*
H18B	−0.1124	0.1878	0.2723	0.0347*
H19A	0.3690	0.0906	0.4312	0.0405*
H19B	0.2275	−0.0069	0.4160	0.0405*
H20A	0.2473	0.1744	0.1129	0.0395*
H20B	0.0281	0.1288	0.1065	0.0395*
H21A	0.5130	−0.0158	0.2797	0.0381*
H21B	0.3260	−0.0883	0.2523	0.0381*
H23A	0.1670	0.2712	0.4141	0.0446*
H23B	−0.0674	0.2631	0.4143	0.0446*
H24A	0.1170	0.1339	0.5137	0.0458*
H24B	−0.0473	0.0853	0.4381	0.0458*
H25A	0.2644	0.0381	0.0164	0.0513*
H25B	0.1322	−0.0317	0.0750	0.0513*
H26A	0.5358	0.0264	0.1305	0.0511*
H26B	0.4558	−0.0879	0.1165	0.0511*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0202 (1)	0.0202 (2)	0.0246 (2)	0.00020 (9)	0.0021 (1)	−0.00016 (9)
Cl2	0.0338 (3)	0.0332 (3)	0.0543 (4)	−0.0036 (3)	0.0051 (3)	−0.0042 (3)
O8	0.067 (2)	0.031 (1)	0.078 (2)	−0.024 (1)	0.030 (1)	−0.006 (1)
O9	0.0211 (10)	0.087 (2)	0.069 (2)	−0.013 (1)	−0.001 (1)	−0.021 (1)
O10	0.052 (3)	0.137 (6)	0.073 (3)	−0.042 (4)	0.001 (2)	−0.029 (4)
O11	0.098 (4)	0.054 (3)	0.059 (3)	0.033 (3)	0.020 (2)	0.023 (2)
O12	0.079 (3)	0.037 (2)	0.055 (2)	0.005 (2)	−0.005 (2)	−0.001 (2)
O13	0.094 (5)	0.043 (3)	0.100 (5)	0.008 (3)	0.016 (4)	0.016 (3)
O14	0.072 (3)	0.047 (3)	0.074 (3)	0.017 (3)	0.024 (3)	0.011 (3)
O15	0.048 (4)	0.29 (2)	0.081 (5)	−0.067 (7)	0.017 (3)	−0.100 (8)
N17	0.035 (2)	0.046 (2)	0.043 (2)	−0.008 (1)	0.020 (1)	−0.021 (1)
N18	0.0301 (9)	0.0230 (8)	0.0348 (9)	0.0031 (7)	0.0077 (7)	0.0014 (7)
N19	0.0331 (9)	0.0384 (10)	0.0290 (9)	0.0045 (8)	0.0010 (7)	0.0026 (8)
N20	0.0374 (10)	0.0331 (9)	0.0287 (9)	0.0039 (8)	0.0041 (8)	0.0037 (7)
N21	0.0302 (9)	0.0300 (9)	0.0343 (9)	0.0075 (7)	0.0033 (7)	−0.0021 (7)
N22	0.054 (1)	0.044 (1)	0.039 (1)	0.004 (1)	0.017 (1)	−0.0012 (9)
C23	0.041 (1)	0.034 (1)	0.039 (1)	0.0010 (10)	0.0121 (10)	−0.0091 (10)
C24	0.042 (1)	0.044 (1)	0.031 (1)	0.003 (1)	0.0109 (10)	−0.0008 (10)
C25	0.052 (1)	0.047 (1)	0.030 (1)	0.006 (1)	0.005 (1)	−0.007 (1)
C26	0.045 (1)	0.047 (1)	0.038 (1)	0.011 (1)	0.010 (1)	−0.008 (1)

Geometric parameters (Å, º)

Co1—Cl2	2.2801 (8)	N18—H18A	0.949
Co1—Cl3	2.31 (1)	N18—H18B	0.948
Co1—N16	1.90 (2)	N19—C24	1.487 (3)
Co1—N17	1.888 (4)	N19—H19A	0.950
Co1—N18	1.955 (2)	N19—H19B	0.947
Co1—N19	1.952 (2)	N20—C25	1.486 (3)
Co1—N20	1.961 (2)	N20—H20A	0.948
Co1—N21	1.951 (2)	N20—H20B	0.948
O4—N16	1.24 (3)	N21—C26	1.491 (3)
O5—N16	1.24 (3)	N21—H21A	0.950
O6—N16	1.25 (3)	N21—H21B	0.948
O7—N16	1.25 (3)	C23—C24	1.504 (4)
O8—N17	1.235 (5)	C23—H23A	0.951
O9—N17	1.240 (4)	C23—H23B	0.952
O10—N22	1.125 (6)	C24—H24A	0.950
O11—N22	1.276 (6)	C24—H24B	0.949
O12—N22	1.276 (5)	C25—C26	1.496 (4)
O13—N22	1.306 (6)	C25—H25A	0.951
O14—N22	1.321 (6)	C25—H25B	0.949
O15—N22	1.085 (8)	C26—H26A	0.951
N18—C23	1.484 (3)	C26—H26B	0.951
Cl2—Co1—N17	179.3 (1)	H19A—N19—H19B	109.7
Cl2—Co1—N18	90.53 (6)	Co1—N20—C25	108.6 (1)
Cl2—Co1—N19	89.82 (6)	Co1—N20—H20A	109.6
Cl2—Co1—N20	89.53 (6)	Co1—N20—H20B	109.6
Cl2—Co1—N21	90.03 (6)	C25—N20—H20A	109.7
Cl3—Co1—N16	177.3 (7)	C25—N20—H20B	109.6
Cl3—Co1—N18	90.6 (3)	H20A—N20—H20B	109.8
Cl3—Co1—N19	89.5 (3)	Co1—N21—C26	109.8 (1)
Cl3—Co1—N20	91.1 (3)	Co1—N21—H21A	109.2
Cl3—Co1—N21	88.8 (3)	Co1—N21—H21B	109.3
N16—Co1—N18	91.1 (6)	C26—N21—H21A	109.3
N16—Co1—N19	88.5 (6)	C26—N21—H21B	109.4
N16—Co1—N20	90.8 (6)	H21A—N21—H21B	109.7
N16—Co1—N21	89.5 (6)	O10—N22—O11	124.9 (5)
N17—Co1—N18	90.0 (1)	O10—N22—O12	122.8 (5)
N17—Co1—N19	90.7 (1)	O11—N22—O12	112.1 (4)
N17—Co1—N20	90.0 (1)	O13—N22—O14	104.8 (4)
N17—Co1—N21	89.5 (1)	O13—N22—O15	128.8 (8)
N18—Co1—N19	86.04 (8)	O14—N22—O15	125.1 (8)
N18—Co1—N20	93.79 (8)	N18—C23—C24	107.1 (2)
N18—Co1—N21	179.44 (8)	N18—C23—H23A	110.2
N19—Co1—N20	179.32 (8)	N18—C23—H23B	109.9
N19—Co1—N21	93.95 (8)	C24—C23—H23A	110.3
N20—Co1—N21	86.23 (8)	C24—C23—H23B	110.1
Co1—N16—O4	117 (1)	H23A—C23—H23B	109.2
Co1—N16—O5	120 (1)	N19—C24—C23	107.0 (2)
Co1—N16—O6	122 (1)	N19—C24—H24A	110.0
Co1—N16—O7	122 (1)	N19—C24—H24B	110.0
O4—N16—O5	122 (2)	C23—C24—H24A	110.1
O6—N16—O7	114 (2)	C23—C24—H24B	110.1
Co1—N17—O8	119.7 (3)	H24A—C24—H24B	109.5
Co1—N17—O9	119.7 (3)	N20—C25—C26	107.5 (2)
O8—N17—O9	120.6 (4)	N20—C25—H25A	109.8
Co1—N18—C23	109.3 (1)	N20—C25—H25B	110.1
Co1—N18—H18A	109.4	C26—C25—H25A	110.0
Co1—N18—H18B	109.4	C26—C25—H25B	110.0
C23—N18—H18A	109.5	H25A—C25—H25B	109.5
C23—N18—H18B	109.5	N21—C26—C25	108.4 (2)
H18A—N18—H18B	109.7	N21—C26—H26A	109.9
Co1—N19—C24	109.0 (1)	N21—C26—H26B	109.8
Co1—N19—H19A	109.5	C25—C26—H26A	109.8
Co1—N19—H19B	109.6	C25—C26—H26B	109.7
C24—N19—H19A	109.5	H26A—C26—H26B	109.3
C24—N19—H19B	109.6