Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800018778/cf6015sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800018778/cf6015Isup2.hkl |
CCDC reference: 155835
The title compound, (I), was obtained as a by-product in the synthesis of trans-[Co(cyclam)(NCS)(NO2)]ClO4 from the reaction of trans-[Co(cyclam)(NCS)Cl]ClO4 (0.5 mmol) with NaNO2 (1.5 mmol) in 30 ml 0.03 M HNO3. Crystals of (I) were grown from a dimethyl sulfoxide solution by a diffusion of diethyl ether vapour.
X-ray intensities were measured for ±h,+k,±l (θ< 15°) and -h,+k,+l (15 <θ < 27.5°). The O atoms of the nitro ligands show positional disorder (atoms O3–O10), suggesting that there are two possible orientations with 65:35% occupancy for each NO2 group. All H-atom positional parameters were calculated geometrically and fixed with Uiso(H) = 1.2Ueq(parent atom).
Data collection: WinAFC (Rigaku Corporation, 1999); cell refinement: WinAFC; 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); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN.
Fig. 1. The structure of the complex cation in (I). Displacement ellipsoids are plotted at the 50% probability level. The disordered nitro O atoms with 35% occupancy have been omitted for clarity. |
[Co(NO2)2(C10H24N4)]ClO4 | Dx = 1.707 Mg m−3 |
Mr = 450.72 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 13.299 (3) Å | θ = 10.3–13.9° |
b = 19.820 (1) Å | µ = 1.19 mm−1 |
c = 6.6531 (7) Å | T = 297 K |
V = 1753.7 (5) Å3 | Plate, orange |
Z = 4 | 0.40 × 0.25 × 0.05 mm |
Rigaku AFC-7R diffractometer | Rint = 0.024 |
θ–2θ scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: integration (Coppens et al., 1965) | h = −17→8 |
Tmin = 0.752, Tmax = 0.942 | k = 0→25 |
3312 measured reflections | l = −4→8 |
2554 independent reflections | 3 standard reflections every 150 reflections |
2245 reflections with I > 2σ(I)' | intensity decay: none |
Refinement on F2 | w = 1/[σ2(Fo2) + (0.041P)2 + 3.4475P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.035 | (Δ/σ)max = 0.001 |
wR(F2) = 0.108 | Δρmax = 0.41 e Å−3 |
S = 1.08 | Δρmin = −0.55 e Å−3 |
2554 reflections | Absolute structure: (Flack, 1983), 225 Friedel pairs |
271 parameters | Absolute structure parameter: −0.05 (4) |
H-atom parameters constrained |
[Co(NO2)2(C10H24N4)]ClO4 | V = 1753.7 (5) Å3 |
Mr = 450.72 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 13.299 (3) Å | µ = 1.19 mm−1 |
b = 19.820 (1) Å | T = 297 K |
c = 6.6531 (7) Å | 0.40 × 0.25 × 0.05 mm |
Rigaku AFC-7R diffractometer | 2245 reflections with I > 2σ(I)' |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.024 |
Tmin = 0.752, Tmax = 0.942 | 3 standard reflections every 150 reflections |
3312 measured reflections | intensity decay: none |
2554 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.108 | Δρmax = 0.41 e Å−3 |
S = 1.08 | Δρmin = −0.55 e Å−3 |
2554 reflections | Absolute structure: (Flack, 1983), 225 Friedel pairs |
271 parameters | Absolute structure parameter: −0.05 (4) |
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 | −0.02236 (4) | −0.12630 (3) | 0.22719 (9) | 0.0289 (2) | |
Cl2 | 0.0420 (1) | 0.11990 (8) | 0.5995 (2) | 0.0561 (4) | |
O3 | −0.0563 (7) | −0.0715 (6) | 0.601 (1) | 0.091 (3) | 0.65 |
O4 | −0.1886 (7) | −0.1029 (7) | 0.484 (2) | 0.111 (4) | 0.65 |
O5 | −0.115 (2) | −0.1351 (10) | 0.602 (2) | 0.094 (6) | 0.35 |
O6 | −0.122 (2) | −0.0389 (7) | 0.490 (3) | 0.083 (5) | 0.35 |
O7 | 0.0728 (8) | −0.2147 (4) | −0.035 (2) | 0.082 (3) | 0.65 |
O8 | 0.0746 (9) | −0.1180 (5) | −0.141 (1) | 0.086 (3) | 0.65 |
O9 | 0.136 (1) | −0.139 (1) | −0.063 (3) | 0.097 (8) | 0.35 |
O10 | 0.012 (2) | −0.1886 (10) | −0.141 (2) | 0.094 (6) | 0.35 |
O11 | −0.0280 (6) | 0.1258 (3) | 0.7629 (9) | 0.121 (2) | |
O12 | 0.1098 (5) | 0.1723 (4) | 0.613 (1) | 0.147 (3) | |
O13 | −0.0134 (4) | 0.1254 (3) | 0.4198 (8) | 0.098 (2) | |
O14 | 0.0907 (5) | 0.0566 (3) | 0.6113 (9) | 0.091 (2) | |
N15 | −0.0993 (4) | −0.0967 (3) | 0.4640 (7) | 0.040 (1) | |
N16 | 0.0528 (4) | −0.1568 (2) | −0.0097 (7) | 0.038 (1) | |
N17 | 0.0690 (3) | −0.1740 (2) | 0.4135 (7) | 0.036 (1) | |
N18 | 0.0546 (3) | −0.0406 (2) | 0.2455 (7) | 0.0389 (9) | |
N19 | −0.1121 (4) | −0.0776 (3) | 0.0406 (7) | 0.042 (1) | |
N20 | −0.0977 (3) | −0.2124 (2) | 0.2146 (7) | 0.0389 (10) | |
C21 | 0.1780 (5) | −0.1618 (4) | 0.398 (1) | 0.055 (2) | |
C22 | 0.2027 (5) | −0.0879 (4) | 0.423 (1) | 0.055 (2) | |
C23 | 0.1662 (4) | −0.0437 (3) | 0.257 (1) | 0.056 (2) | |
C24 | 0.0189 (6) | 0.0057 (3) | 0.085 (1) | 0.057 (2) | |
C25 | −0.0924 (6) | −0.0033 (3) | 0.064 (1) | 0.061 (2) | |
C26 | −0.2200 (6) | −0.0942 (4) | 0.031 (1) | 0.064 (2) | |
C27 | −0.2376 (5) | −0.1691 (4) | 0.008 (1) | 0.068 (2) | |
C28 | −0.2083 (4) | −0.2118 (4) | 0.184 (1) | 0.058 (2) | |
C29 | −0.0667 (5) | −0.2544 (3) | 0.389 (1) | 0.050 (2) | |
C30 | 0.0446 (5) | −0.2484 (3) | 0.409 (1) | 0.053 (2) | |
H17 | 0.0505 | −0.1590 | 0.5441 | 0.0438* | |
H18 | 0.0338 | −0.0204 | 0.3682 | 0.0467* | |
H19 | −0.0872 | −0.0884 | −0.0894 | 0.0508* | |
H20 | −0.0716 | −0.2351 | 0.1003 | 0.0466* | |
H21A | 0.2008 | −0.1765 | 0.2704 | 0.0661* | |
H21B | 0.2113 | −0.1867 | 0.5006 | 0.0661* | |
H22A | 0.2738 | −0.0835 | 0.4311 | 0.0659* | |
H22B | 0.1733 | −0.0726 | 0.5450 | 0.0659* | |
H23A | 0.1913 | −0.0606 | 0.1332 | 0.0670* | |
H23B | 0.1912 | 0.0007 | 0.2781 | 0.0670* | |
H24A | 0.0513 | −0.0049 | −0.0380 | 0.0683* | |
H24B | 0.0335 | 0.0510 | 0.1213 | 0.0683* | |
H25A | −0.1158 | 0.0202 | −0.0516 | 0.0736* | |
H25B | −0.1258 | 0.0133 | 0.1797 | 0.0736* | |
H26A | −0.2491 | −0.0715 | −0.0801 | 0.0773* | |
H26B | −0.2514 | −0.0794 | 0.1518 | 0.0773* | |
H27A | −0.2002 | −0.1841 | −0.1048 | 0.0813* | |
H27B | −0.3073 | −0.1759 | −0.0158 | 0.0813* | |
H28A | −0.2307 | −0.2567 | 0.1616 | 0.0698* | |
H28B | −0.2396 | −0.1945 | 0.3017 | 0.0698* | |
H29A | −0.0848 | −0.3002 | 0.3665 | 0.0599* | |
H29B | −0.0987 | −0.2387 | 0.5079 | 0.0599* | |
H30A | 0.0770 | −0.2693 | 0.2985 | 0.0632* | |
H30B | 0.0663 | −0.2692 | 0.5307 | 0.0632* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0312 (3) | 0.0309 (3) | 0.0246 (3) | 0.0012 (3) | 0.0035 (3) | 0.0001 (3) |
Cl2 | 0.0669 (10) | 0.0504 (8) | 0.0509 (8) | 0.0029 (8) | −0.0089 (7) | 0.0043 (8) |
O3 | 0.090 (7) | 0.141 (9) | 0.042 (4) | −0.036 (7) | 0.019 (5) | −0.037 (5) |
O4 | 0.060 (6) | 0.19 (1) | 0.085 (7) | 0.000 (7) | 0.027 (5) | −0.063 (8) |
O5 | 0.12 (1) | 0.11 (1) | 0.049 (8) | 0.01 (1) | 0.049 (10) | 0.026 (10) |
O6 | 0.12 (2) | 0.046 (8) | 0.08 (1) | 0.029 (10) | 0.05 (1) | −0.001 (8) |
O7 | 0.110 (8) | 0.053 (5) | 0.084 (7) | 0.031 (5) | 0.051 (6) | −0.003 (5) |
O8 | 0.147 (10) | 0.064 (5) | 0.048 (5) | −0.003 (7) | 0.045 (6) | 0.003 (4) |
O9 | 0.07 (1) | 0.16 (2) | 0.06 (1) | −0.03 (1) | 0.019 (9) | −0.05 (1) |
O10 | 0.12 (2) | 0.11 (1) | 0.052 (8) | −0.05 (1) | 0.03 (1) | −0.040 (9) |
O11 | 0.206 (7) | 0.075 (3) | 0.082 (4) | 0.036 (5) | 0.052 (5) | −0.001 (4) |
O12 | 0.107 (5) | 0.114 (5) | 0.222 (9) | −0.049 (4) | −0.058 (6) | 0.062 (6) |
O13 | 0.106 (4) | 0.120 (5) | 0.069 (3) | 0.027 (5) | −0.028 (3) | 0.000 (3) |
O14 | 0.109 (4) | 0.074 (3) | 0.091 (4) | 0.037 (3) | −0.009 (4) | −0.005 (3) |
N15 | 0.044 (3) | 0.042 (3) | 0.034 (2) | −0.001 (2) | 0.010 (2) | 0.001 (2) |
N16 | 0.039 (2) | 0.044 (3) | 0.030 (2) | 0.000 (2) | 0.005 (2) | −0.003 (2) |
N17 | 0.037 (2) | 0.039 (2) | 0.033 (2) | −0.003 (2) | 0.002 (2) | 0.002 (2) |
N18 | 0.047 (2) | 0.040 (2) | 0.030 (2) | −0.005 (2) | 0.009 (2) | 0.000 (2) |
N19 | 0.042 (3) | 0.052 (3) | 0.033 (2) | 0.013 (2) | 0.002 (2) | 0.001 (2) |
N20 | 0.034 (2) | 0.048 (2) | 0.034 (2) | −0.005 (2) | 0.005 (2) | −0.007 (2) |
C21 | 0.034 (3) | 0.078 (4) | 0.053 (4) | 0.006 (3) | −0.008 (3) | 0.005 (4) |
C22 | 0.036 (3) | 0.076 (4) | 0.053 (4) | −0.012 (3) | −0.002 (3) | 0.000 (4) |
C23 | 0.050 (3) | 0.069 (4) | 0.048 (4) | −0.023 (3) | 0.010 (4) | −0.004 (4) |
C24 | 0.084 (4) | 0.036 (3) | 0.051 (3) | −0.004 (3) | 0.010 (4) | 0.009 (3) |
C25 | 0.085 (5) | 0.042 (3) | 0.056 (4) | 0.022 (3) | 0.003 (4) | 0.011 (3) |
C26 | 0.043 (4) | 0.084 (5) | 0.067 (5) | 0.021 (4) | −0.009 (3) | −0.003 (4) |
C27 | 0.039 (3) | 0.087 (5) | 0.077 (5) | −0.001 (4) | −0.016 (4) | −0.007 (5) |
C28 | 0.038 (3) | 0.075 (4) | 0.061 (4) | −0.017 (3) | 0.005 (3) | −0.009 (4) |
C29 | 0.061 (4) | 0.035 (3) | 0.054 (4) | −0.012 (3) | −0.002 (3) | 0.009 (3) |
C30 | 0.060 (4) | 0.043 (3) | 0.055 (4) | 0.006 (3) | −0.005 (3) | 0.013 (3) |
Co1—N15 | 1.968 (5) | N20—C29 | 1.487 (8) |
Co1—N16 | 1.962 (5) | N20—H20 | 0.950 |
Co1—N17 | 1.976 (4) | C21—C22 | 1.51 (1) |
Co1—N18 | 1.986 (4) | C21—H21A | 0.950 |
Co1—N19 | 1.974 (5) | C21—H21B | 0.950 |
Co1—N20 | 1.981 (4) | C22—C23 | 1.492 (10) |
Cl2—O11 | 1.436 (7) | C22—H22A | 0.950 |
Cl2—O12 | 1.379 (7) | C22—H22B | 0.950 |
Cl2—O13 | 1.409 (6) | C23—H23A | 0.950 |
Cl2—O14 | 1.414 (6) | C23—H23B | 0.950 |
O3—N15 | 1.18 (1) | C24—C25 | 1.50 (1) |
O4—N15 | 1.20 (1) | C24—H24A | 0.950 |
O5—N15 | 1.21 (2) | C24—H24B | 0.950 |
O6—N15 | 1.20 (2) | C25—H25A | 0.950 |
O7—N16 | 1.189 (10) | C25—H25B | 0.950 |
O8—N16 | 1.20 (1) | C26—C27 | 1.51 (1) |
O9—N16 | 1.21 (2) | C26—H26A | 0.950 |
O10—N16 | 1.21 (2) | C26—H26B | 0.950 |
N17—C21 | 1.473 (8) | C27—C28 | 1.50 (1) |
N17—C30 | 1.511 (8) | C27—H27A | 0.950 |
N17—H17 | 0.950 | C27—H27B | 0.950 |
N18—C23 | 1.487 (7) | C28—H28A | 0.951 |
N18—C24 | 1.484 (8) | C28—H28B | 0.950 |
N18—H18 | 0.950 | C29—C30 | 1.492 (10) |
N19—C25 | 1.504 (9) | C29—H29A | 0.950 |
N19—C26 | 1.474 (9) | C29—H29B | 0.950 |
N19—H19 | 0.950 | C30—H30A | 0.950 |
N20—C28 | 1.485 (7) | C30—H30B | 0.951 |
N15—Co1—N16 | 179.1 (2) | N17—C21—H21B | 108.9 |
N15—Co1—N17 | 87.7 (2) | C22—C21—H21A | 109.0 |
N15—Co1—N18 | 87.9 (2) | C22—C21—H21B | 109.0 |
N15—Co1—N19 | 92.5 (2) | H21A—C21—H21B | 109.5 |
N15—Co1—N20 | 91.6 (2) | C21—C22—C23 | 114.7 (6) |
N16—Co1—N17 | 92.5 (2) | C21—C22—H22A | 108.1 |
N16—Co1—N18 | 92.9 (2) | C21—C22—H22B | 108.2 |
N16—Co1—N19 | 87.3 (2) | C23—C22—H22A | 108.1 |
N16—Co1—N20 | 87.6 (2) | C23—C22—H22B | 108.2 |
N17—Co1—N18 | 93.1 (2) | H22A—C22—H22B | 109.4 |
N17—Co1—N19 | 179.1 (2) | N18—C23—C22 | 112.7 (5) |
N17—Co1—N20 | 85.7 (2) | N18—C23—H23A | 108.7 |
N18—Co1—N19 | 86.1 (2) | N18—C23—H23B | 108.7 |
N18—Co1—N20 | 178.7 (2) | C22—C23—H23A | 108.6 |
N19—Co1—N20 | 95.1 (2) | C22—C23—H23B | 108.6 |
O11—Cl2—O12 | 108.3 (5) | H23A—C23—H23B | 109.5 |
O11—Cl2—O13 | 107.3 (4) | N18—C24—C25 | 108.2 (5) |
O11—Cl2—O14 | 109.1 (4) | N18—C24—H24A | 109.8 |
O12—Cl2—O13 | 109.8 (5) | N18—C24—H24B | 109.8 |
O12—Cl2—O14 | 111.4 (4) | C25—C24—H24A | 109.8 |
O13—Cl2—O14 | 110.8 (4) | C25—C24—H24B | 109.8 |
Co1—N15—O3 | 119.3 (6) | H24A—C24—H24B | 109.4 |
Co1—N15—O4 | 124.8 (7) | N19—C25—C24 | 107.3 (5) |
Co1—N15—O5 | 120.7 (10) | N19—C25—H25A | 110.0 |
Co1—N15—O6 | 122.3 (10) | N19—C25—H25B | 110.0 |
O3—N15—O4 | 115.9 (8) | C24—C25—H25A | 110.0 |
O5—N15—O6 | 116 (1) | C24—C25—H25B | 110.0 |
Co1—N16—O7 | 121.7 (6) | H25A—C25—H25B | 109.4 |
Co1—N16—O8 | 120.6 (6) | N19—C26—C27 | 112.0 (6) |
Co1—N16—O9 | 127 (1) | N19—C26—H26A | 108.9 |
Co1—N16—O10 | 120.8 (10) | N19—C26—H26B | 108.9 |
O7—N16—O8 | 117.5 (8) | C27—C26—H26A | 108.8 |
O9—N16—O10 | 110 (1) | C27—C26—H26B | 108.8 |
Co1—N17—C21 | 118.9 (4) | H26A—C26—H26B | 109.5 |
Co1—N17—C30 | 108.9 (4) | C26—C27—C28 | 115.8 (7) |
Co1—N17—H17 | 105.4 | C26—C27—H27A | 107.9 |
C21—N17—C30 | 111.7 (5) | C26—C27—H27B | 107.9 |
C21—N17—H17 | 105.4 | C28—C27—H27A | 107.8 |
C30—N17—H17 | 105.4 | C28—C27—H27B | 107.8 |
Co1—N18—C23 | 118.9 (3) | H27A—C27—H27B | 109.5 |
Co1—N18—C24 | 108.6 (4) | N20—C28—C27 | 111.6 (5) |
Co1—N18—H18 | 105.2 | N20—C28—H28A | 108.9 |
C23—N18—C24 | 112.4 (5) | N20—C28—H28B | 108.9 |
C23—N18—H18 | 105.3 | C27—C28—H28A | 109.0 |
C24—N18—H18 | 105.2 | C27—C28—H28B | 109.0 |
Co1—N19—C25 | 108.0 (4) | H28A—C28—H28B | 109.4 |
Co1—N19—C26 | 120.4 (4) | N20—C29—C30 | 107.6 (5) |
Co1—N19—H19 | 104.6 | N20—C29—H29A | 109.9 |
C25—N19—C26 | 113.1 (5) | N20—C29—H29B | 110.0 |
C25—N19—H19 | 104.6 | C30—C29—H29A | 110.0 |
C26—N19—H19 | 104.6 | C30—C29—H29B | 110.0 |
Co1—N20—C28 | 120.0 (4) | H29A—C29—H29B | 109.4 |
Co1—N20—C29 | 108.0 (3) | N17—C30—C29 | 107.0 (5) |
Co1—N20—H20 | 104.9 | N17—C30—H30A | 110.1 |
C28—N20—C29 | 112.7 (5) | N17—C30—H30B | 110.1 |
C28—N20—H20 | 104.9 | C29—C30—H30A | 110.2 |
C29—N20—H20 | 104.9 | C29—C30—H30B | 110.1 |
N17—C21—C22 | 111.4 (5) | H30A—C30—H30B | 109.4 |
N17—C21—H21A | 109.0 |
Experimental details
Crystal data | |
Chemical formula | [Co(NO2)2(C10H24N4)]ClO4 |
Mr | 450.72 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 297 |
a, b, c (Å) | 13.299 (3), 19.820 (1), 6.6531 (7) |
V (Å3) | 1753.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.19 |
Crystal size (mm) | 0.40 × 0.25 × 0.05 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.752, 0.942 |
No. of measured, independent and observed [I > 2σ(I)'] reflections | 3312, 2554, 2245 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.108, 1.08 |
No. of reflections | 2554 |
No. of parameters | 271 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.55 |
Absolute structure | (Flack, 1983), 225 Friedel pairs |
Absolute structure parameter | −0.05 (4) |
Computer programs: WinAFC (Rigaku Corporation, 1999), WinAFC, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), TEXSAN.
The Co—NO2 bond distances are 1.962 (5) and 1.968 (5) Å. The Co—N bond distances of the cyclam are 1.974 (5)–1.986 (4) Å.