Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015122/qa0452sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015122/qa0452Isup2.hkl |
CCDC reference: 156197
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.
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 Uiso(H) = 1.2Ueq(parent atom). The nitrate O atoms also show positional disorder, suggesting that there are two possible orientations of the ion with 50% probability each.
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.
[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) Å3 | 0.5 × 0.5 × 0.2 mm |
Z = 4 |
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 on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.032 | w = 1/[σ2(Fo2) + (0.0406P)2 + 1.0531P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 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 |
[CoCl(NO2)(C2H8N2)2](NO3) | V = 1172.7 (3) Å3 |
Mr = 322.59 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 6.601 (2) Å | µ = 1.71 mm−1 |
b = 12.721 (2) Å | T = 298 K |
c = 14.072 (1) Å | 0.5 × 0.5 × 0.2 mm |
β = 97.06 (1)° |
Rigaku AFC-7R diffractometer | 2494 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.006 |
Tmin = 0.605, Tmax = 0.710 | 3 standard reflections every 150 reflections |
2930 measured reflections | intensity decay: none |
2703 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 205 parameters |
wR(F2) = 0.082 | H-atom parameters not refined |
S = 1.10 | Δρmax = 0.75 e Å−3 |
2703 reflections | Δρmin = −0.67 e Å−3 |
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). |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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 |
Experimental details
Crystal data | |
Chemical formula | [CoCl(NO2)(C2H8N2)2](NO3) |
Mr | 322.59 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 6.601 (2), 12.721 (2), 14.072 (1) |
β (°) | 97.06 (1) |
V (Å3) | 1172.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.71 |
Crystal size (mm) | 0.5 × 0.5 × 0.2 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.605, 0.710 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2930, 2703, 2494 |
Rint | 0.006 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.082, 1.10 |
No. of reflections | 2703 |
No. of parameters | 205 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.75, −0.67 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), TEXSAN.
Co1—Cl2 | 2.2801 (8) | Co1—N20 | 1.961 (2) |
Co1—N17 | 1.888 (4) | Co1—N21 | 1.951 (2) |
Co1—N18 | 1.955 (2) | O8—N17 | 1.235 (5) |
Co1—N19 | 1.952 (2) | O9—N17 | 1.240 (4) |
Cl2—Co1—N17 | 179.3 (1) | O8—N17—O9 | 120.6 (4) |
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) Å3 and Z = 4 at 300 K.