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

In the title compound, trans-[CoCl(NO₂)(C₂H₈N₂)₂]ClO₄, there are two independent Co^III complexes with a distorted octahedral coordination, and they show an orientational disorder such that the positions of the nitro and chloro ligands are exchanged. As a result, the averaged structure has inversion centres at the Co atoms. The perchlorate-O atoms 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). Although the title crystal, (I), is photostable, the structure was determined as part of a study on photoisomerization. \scheme

The crystals of trans-[Co(en)₂Cl(NO₂)]PF₆ (en is ethylenediamine) were also prepared in the present study to indicate that the structure is isomorphous with (I); triclinic, space group P1, with a = 8.745 (1), b = 12.791 (1), c = 6.489 (1) Å, α = 101.18 (1), β = 103.36 (1), γ = 79.44 (1)°, V = 685.4 (1) ų and Z = 2 at 297 K.

S2. Experimental

The title compound was prepared from the nitrate salt (Adell, 1971) by anion exchange. Crystals of (I) were grown from an aqueous solution.

S3. Refinement

The Co1 and Co2 atoms lie on centres of symmetry. A split-site model was applicable for the positional disorder of the nitro and chloro ligands. In the complex involving the Co1 atom, the nitro-O atoms are further disordered over two sites, the O6/O7 and O8/O9 atoms, with 35 and 15% probabilities, respectively. The minor O8 and O9 atoms were refined isotropically. The Co1—N20 bond distance was restrained to be 1.95 Å (s.u. = 0.001 Å) and the nitro N20—O distances to be 1.24 Å (s.u. = 0.001 Å). There is a positional disorder of the ethylenediamine C atoms, which were split into two sites with 50% probability each (atoms C26–C29). In the complex involving the Co2 atom, a large anisotropic displacement parameter of Cl4 suggested positional disorder. However, the split-site model of the Cl position was not applicable. All H-atom positional parameters were calculated geometrically and fixed with U_iso(H) = 1.2U_eq(parent atom). The perchlorate O atoms have positional disorder (atoms O12–O19), suggesting that the perchlorate ion has two possible orientations 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](ClO4)	Z = 2
Mr = 360.04	Dx = 1.865 Mg m^−3
Triclinic, P1	Mo Kα radiation, λ = 0.71073 Å
a = 8.349 (2) Å	Cell parameters from 25 reflections
b = 12.644 (3) Å	θ = 14.6–15.0°
c = 6.556 (3) Å	µ = 1.78 mm^−1
α = 103.19 (3)°	T = 298 K
β = 105.11 (3)°	Prismatic, orange–red
γ = 77.30 (2)°	0.5 × 0.4 × 0.3 mm
V = 641.0 (4) Å^3

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.015
θ–2θ scans	θmax = 30.0°, θmin = 2.5°
Absorption correction: ψ scan (North et al., 1968)	h = −11→11
Tmin = 0.517, Tmax = 0.586	k = −17→17
4041 measured reflections	l = 0→9
3734 independent reflections	3 standard reflections every 150 reflections
3409 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.042	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 0.697P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.112	(Δ/σ)max = 0.001
S = 1.18	Δρmax = 0.58 e Å^−3
3734 reflections	Δρmin = −0.47 e Å^−3
264 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	0.0000	0.0000	0.0000	0.0317 (1)
Co2	0.0000	0.5000	0.0000	0.0286 (1)
Cl3	0.0774 (4)	0.0893 (3)	−0.2143 (6)	0.0496 (6)	0.50
Cl4	−0.0221 (8)	0.6231 (4)	−0.219 (1)	0.117 (2)	0.50
Cl5	−0.3908 (1)	0.28553 (7)	−0.5555 (1)	0.0586 (2)
O6	0.018 (1)	−0.1216 (8)	0.308 (1)	0.064 (2)	0.35
O7	−0.2319 (9)	−0.0622 (10)	0.168 (2)	0.093 (3)	0.35
O8	0.005 (3)	−0.164 (1)	0.192 (6)	0.1079 (1)*	0.15
O9	−0.153 (3)	−0.017 (2)	0.312 (3)	0.10181 (10)*	0.15
O10	0.0971 (7)	0.4092 (5)	0.3659 (7)	0.056 (1)	0.50
O11	−0.0642 (6)	0.3144 (3)	0.0930 (7)	0.050 (1)	0.50
O12	−0.408 (2)	0.282 (1)	−0.355 (2)	0.121 (6)	0.50
O13	−0.491 (2)	0.226 (1)	−0.723 (2)	0.155 (4)	0.50
O14	−0.227 (1)	0.241 (1)	−0.589 (2)	0.123 (3)	0.50
O15	−0.429 (2)	0.3990 (8)	−0.585 (2)	0.174 (7)	0.50
O16	−0.355 (2)	0.2876 (6)	−0.322 (2)	0.069 (3)	0.50
O17	−0.351 (2)	0.1690 (7)	−0.646 (1)	0.125 (4)	0.50
O18	−0.296 (2)	0.351 (1)	−0.576 (2)	0.140 (5)	0.50
O19	−0.5645 (9)	0.3134 (9)	−0.638 (2)	0.110 (3)	0.50
N20	−0.0805 (9)	−0.072 (1)	0.170 (2)	0.062 (4)	0.50
N21	−0.0910 (3)	−0.1019 (2)	−0.2555 (4)	0.0453 (5)
N22	−0.2216 (3)	0.0929 (2)	−0.0490 (4)	0.0491 (6)
N23	0.0093 (7)	0.3948 (6)	0.180 (1)	0.034 (1)	0.50
N24	0.2438 (3)	0.4939 (2)	0.0913 (4)	0.0414 (5)
N25	0.0489 (3)	0.3775 (2)	−0.2305 (3)	0.0381 (4)
C26	−0.2778 (4)	−0.0772 (6)	−0.325 (2)	0.085 (4)	0.50
C27	−0.329 (1)	0.0442 (6)	−0.253 (1)	0.086 (4)	0.50
C28	−0.2626 (6)	−0.0452 (7)	−0.346 (1)	0.060 (2)	0.50
C29	−0.3479 (9)	0.0215 (7)	−0.172 (1)	0.065 (2)	0.50
C30	0.3232 (4)	0.4293 (3)	−0.0870 (5)	0.0505 (7)
C31	0.2324 (4)	0.3341 (2)	−0.1871 (5)	0.0491 (6)
H21A	−0.0597	−0.1745	−0.2250	0.0544*	0.50
H21B	−0.0435	−0.0977	−0.3697	0.0544*	0.50
H21C	−0.0970	−0.1689	−0.2177	0.0544*	0.50
H21D	−0.0222	−0.1170	−0.3571	0.0544*	0.50
H22A	−0.2731	0.0976	0.0667	0.0590*	0.50
H22B	−0.2096	0.1646	−0.0580	0.0590*	0.50
H22C	−0.2486	0.1286	0.0849	0.0590*	0.50
H22D	−0.2214	0.1467	−0.1291	0.0590*	0.50
H24A	0.2860	0.4595	0.2137	0.0497*
H24B	0.2688	0.5665	0.1264	0.0497*
H25A	−0.0111	0.3207	−0.2367	0.0458*
H25B	0.0154	0.4026	−0.3637	0.0458*
H26A	−0.3282	−0.1176	−0.2606	0.1046*	0.50
H26B	−0.3113	−0.0964	−0.4773	0.1046*	0.50
H27A	−0.4410	0.0569	−0.2351	0.1031*	0.50
H27B	−0.3248	0.0806	−0.3633	0.1031*	0.50
H28A	−0.3284	−0.0993	−0.4298	0.0722*	0.50
H28B	−0.2540	0.0020	−0.4348	0.0722*	0.50
H29A	−0.3661	−0.0237	−0.0852	0.0781*	0.50
H29B	−0.4523	0.0641	−0.2286	0.0781*	0.50
H30A	0.4390	0.4033	−0.0329	0.0606*
H30B	0.3128	0.4738	−0.1901	0.0606*
H31A	0.2588	0.2832	−0.0917	0.0588*
H31B	0.2648	0.2982	−0.3178	0.0588*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0441 (3)	0.0231 (2)	0.0282 (2)	−0.0047 (2)	0.0081 (2)	0.0060 (2)
Co2	0.0367 (2)	0.0245 (2)	0.0281 (2)	−0.0059 (2)	0.0118 (2)	0.0055 (2)
Cl3	0.070 (1)	0.046 (1)	0.037 (1)	−0.0166 (10)	0.0159 (9)	0.0065 (8)
Cl4	0.156 (4)	0.069 (2)	0.156 (4)	0.022 (2)	0.106 (3)	0.040 (2)
Cl5	0.0490 (4)	0.0649 (5)	0.0501 (4)	0.0043 (3)	0.0089 (3)	0.0028 (3)
O6	0.060 (4)	0.087 (5)	0.058 (4)	−0.008 (4)	0.012 (4)	0.045 (5)
O7	0.050 (4)	0.135 (8)	0.131 (8)	−0.011 (5)	0.027 (5)	0.092 (7)
O10	0.077 (3)	0.076 (3)	0.017 (2)	−0.021 (3)	−0.005 (2)	0.021 (2)
O11	0.089 (3)	0.021 (2)	0.053 (2)	−0.030 (2)	0.020 (2)	0.007 (2)
O12	0.088 (8)	0.20 (1)	0.075 (8)	−0.010 (6)	0.049 (7)	0.003 (7)
O13	0.115 (8)	0.16 (1)	0.147 (9)	−0.064 (8)	−0.021 (7)	−0.029 (8)
O14	0.084 (5)	0.171 (10)	0.113 (7)	0.019 (6)	0.056 (5)	0.023 (7)
O15	0.28 (2)	0.064 (5)	0.119 (8)	0.015 (8)	−0.02 (1)	0.026 (5)
O16	0.099 (7)	0.046 (3)	0.050 (3)	−0.005 (3)	0.009 (4)	0.004 (2)
O17	0.181 (10)	0.082 (5)	0.072 (5)	0.034 (6)	0.034 (6)	−0.019 (4)
O18	0.126 (8)	0.23 (2)	0.115 (7)	−0.102 (9)	0.028 (7)	0.053 (9)
O19	0.060 (4)	0.126 (7)	0.136 (7)	0.008 (4)	−0.010 (4)	0.067 (6)
N20	0.073 (6)	0.062 (7)	0.041 (6)	0.009 (4)	0.010 (3)	0.011 (3)
N21	0.067 (2)	0.037 (1)	0.034 (1)	−0.016 (1)	0.009 (1)	0.0032 (8)
N22	0.050 (1)	0.043 (1)	0.052 (1)	0.002 (1)	0.012 (1)	0.012 (1)
N23	0.024 (2)	0.025 (3)	0.041 (3)	−0.006 (2)	0.004 (2)	−0.018 (2)
N24	0.039 (1)	0.040 (1)	0.044 (1)	−0.0077 (9)	0.0099 (9)	0.0022 (9)
N25	0.049 (1)	0.0321 (9)	0.036 (1)	−0.0089 (8)	0.0170 (9)	0.0011 (8)
C26	0.064 (6)	0.085 (7)	0.102 (9)	−0.052 (5)	0.012 (5)	−0.023 (6)
C27	0.063 (5)	0.063 (5)	0.105 (8)	−0.006 (4)	−0.033 (6)	0.025 (6)
C28	0.049 (4)	0.083 (6)	0.048 (4)	−0.042 (4)	0.000 (3)	−0.009 (4)
C29	0.048 (4)	0.083 (6)	0.066 (5)	−0.006 (4)	0.011 (3)	0.027 (4)
C30	0.044 (1)	0.052 (2)	0.060 (2)	−0.008 (1)	0.024 (1)	0.004 (1)
C31	0.052 (2)	0.039 (1)	0.057 (2)	−0.002 (1)	0.024 (1)	0.000 (1)

Geometric parameters (Å, º)

Co1—Cl3	2.277 (4)	N22—C27	1.490 (8)
Co1—N20	1.91 (2)	N22—C29	1.490 (8)
Co1—N21	1.956 (2)	N22—H22A	0.950
Co1—N22	1.952 (2)	N22—H22B	0.950
Co2—Cl4	2.297 (7)	N22—H22C	0.950
Co2—N23	1.947 (8)	N22—H22D	0.950
Co2—N24	1.956 (2)	N24—C30	1.484 (4)
Co2—N25	1.956 (2)	N24—H24A	0.950
Cl5—O12	1.37 (2)	N24—H24B	0.950
Cl5—O13	1.38 (1)	N25—C31	1.484 (4)
Cl5—O14	1.41 (1)	N25—H25A	0.950
Cl5—O15	1.45 (1)	N25—H25B	0.950
Cl5—O16	1.48 (1)	C26—C27	1.50 (1)
Cl5—O17	1.458 (8)	C26—H26A	0.951
Cl5—O18	1.32 (2)	C26—H26B	0.951
Cl5—O19	1.405 (7)	C27—H27A	0.947
O6—N20	1.24 (1)	C27—H27B	0.951
O7—N20	1.24 (1)	C28—C29	1.50 (1)
O8—N20	1.24 (2)	C28—H28A	0.952
O9—N20	1.24 (3)	C28—H28B	0.947
O10—N23	1.244 (7)	C29—H29A	0.950
O11—N23	1.250 (8)	C29—H29B	0.951
N21—C26	1.490 (4)	C30—C31	1.495 (5)
N21—C28	1.490 (6)	C30—H30A	0.950
N21—H21A	0.950	C30—H30B	0.950
N21—H21B	0.950	C31—H31A	0.950
N21—H21C	0.950	C31—H31B	0.950
N21—H21D	0.950
Cl3—Co1—N20	176.1 (2)	Co1—N22—H22B	109.4
Cl3—Co1—N21	89.2 (1)	Co1—N22—H22C	109.7
Cl3—Co1—N21^i	90.8 (1)	Co1—N22—H22D	109.7
Cl3—Co1—N22	88.4 (1)	C27—N22—H22A	109.4
Cl3—Co1—N22^i	91.6 (1)	C27—N22—H22B	109.4
N20—Co1—N21	89.1 (4)	C29—N22—H22C	109.8
N20—Co1—N21^i	90.9 (4)	C29—N22—H22D	109.7
N20—Co1—N22	88.0 (3)	H22A—N22—H22B	109.4
N20—Co1—N22^i	92.0 (3)	H22C—N22—H22D	109.5
N21—Co1—N21^i	180.0	Co2—N23—O10	117.4 (6)
N21—Co1—N22	86.37 (9)	Co2—N23—O11	116.7 (5)
N21—Co1—N22^i	93.63 (9)	O10—N23—O11	125.7 (7)
N21^i—Co1—N22	93.63 (9)	Co2—N24—C30	108.9 (2)
N22—Co1—N22^i	180.0	Co2—N24—H24A	109.6
Cl4—Co2—N23	177.7 (2)	Co2—N24—H24B	109.6
Cl4—Co2—N24	91.3 (2)	C30—N24—H24A	109.6
Cl4—Co2—N24^ii	88.7 (2)	C30—N24—H24B	109.6
Cl4—Co2—N25	90.1 (2)	H24A—N24—H24B	109.5
Cl4—Co2—N25^ii	89.9 (2)	Co2—N25—C31	109.3 (2)
N23—Co2—N24	91.0 (2)	Co2—N25—H25A	109.5
N23—Co2—N24^ii	89.0 (2)	Co2—N25—H25B	109.5
N23—Co2—N25	89.6 (2)	C31—N25—H25A	109.5
N23—Co2—N25^ii	90.4 (2)	C31—N25—H25B	109.5
N24—Co2—N24^ii	180.0	H25A—N25—H25B	109.4
N24—Co2—N25	85.97 (9)	N21—C26—C27	106.7 (6)
N24—Co2—N25^ii	94.03 (9)	N21—C26—H26A	110.2
N24^ii—Co2—N25	94.03 (9)	N21—C26—H26B	110.1
N25—Co2—N25^ii	180.0	C27—C26—H26A	110.2
O12—Cl5—O13	115.0 (9)	C27—C26—H26B	110.3
O12—Cl5—O14	113.1 (7)	H26A—C26—H26B	109.3
O12—Cl5—O15	109.3 (9)	N22—C27—C26	114.9 (7)
O13—Cl5—O14	102.8 (7)	N22—C27—H27A	108.3
O13—Cl5—O15	108.1 (8)	N22—C27—H27B	108.0
O14—Cl5—O15	108 (1)	C26—C27—H27A	108.1
O16—Cl5—O17	103.9 (4)	C26—C27—H27B	107.9
O16—Cl5—O18	104.5 (6)	H27A—C27—H27B	109.7
O16—Cl5—O19	110.7 (7)	N21—C28—C29	111.2 (5)
O17—Cl5—O18	117.2 (8)	N21—C28—H28A	108.9
O17—Cl5—O19	104.0 (7)	N21—C28—H28B	109.2
O18—Cl5—O19	116.0 (8)	C29—C28—H28A	108.8
Co1—N20—O6	121.1 (7)	C29—C28—H28B	109.1
Co1—N20—O7	122 (1)	H28A—C28—H28B	109.6
Co1—N20—O8	112 (1)	N22—C29—C28	101.1 (5)
Co1—N20—O9	120 (1)	N22—C29—H29A	111.5
O6—N20—O7	115 (1)	N22—C29—H29B	111.4
O8—N20—O9	120 (2)	C28—C29—H29A	111.8
Co1—N21—C26	113.3 (4)	C28—C29—H29B	111.5
Co1—N21—C28	106.0 (3)	H29A—C29—H29B	109.3
Co1—N21—H21A	108.5	N24—C30—C31	107.0 (3)
Co1—N21—H21B	108.5	N24—C30—H30A	110.1
Co1—N21—H21C	110.3	N24—C30—H30B	110.1
Co1—N21—H21D	110.3	C31—C30—H30A	110.1
C26—N21—H21A	108.6	C31—C30—H30B	110.1
C26—N21—H21B	108.5	H30A—C30—H30B	109.4
C28—N21—H21C	110.5	N25—C31—C30	108.0 (2)
C28—N21—H21D	110.2	N25—C31—H31A	109.9
H21A—N21—H21B	109.5	N25—C31—H31B	109.8
H21C—N21—H21D	109.5	C30—C31—H31A	109.8
Co1—N22—C27	109.7 (4)	C30—C31—H31B	109.8
Co1—N22—C29	108.4 (3)	H31A—C31—H31B	109.5
Co1—N22—H22A	109.4

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