Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015109/qa0451sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015109/qa0451Isup2.hkl |
CCDC reference: 156196
The preparation of the title complex has been described previously (Seki et al., 1997). Crystals of (I) were grown from a dmf solution. The crystal specimen was sealed in a capillary with the mother liquor to avoid efflorescence.
The CoIII—OH2 bond distances in other Co(tpp) complexes are in the range 1.932 (8)–1.979 (3) Å (Masuda et al., 1982; Iimura et al., 1988), and CoIII—NO2 distances are in the range 1.897 (11)–1.948 (4) Å (Kaduk & Scheidt, 1974; Yamamoto & Iitaka, 1989). Therefore, a split-site model was not applicable for positional disorder of the nitro N7 and aqua O4 atoms. It was assumed that the N7 and O4 atoms share the same positional and atomic displacement parameters. The dmf molecule exists near the axial ligands, showing positional disorder. Two possible positions having different orientations were assumed with 50% probability each. The H atoms of the aqua ligand were not introduced because they were not located from difference syntheses. The other H-atom positional parameters were calculated geometrically and fixed (C—H = 0.95 Å) with Uiso(H) = 1.2Ueq(parent atom).
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); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: TEXSAN.
[Co(C44H28N4)(H2O)(NO2)]·2C3H7NO | Z = 1 |
Mr = 881.87 | Dx = 1.348 Mg m−3 |
Triclinic, P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.355 (1) Å | Cell parameters from 24 reflections |
b = 11.815 (2) Å | θ = 13.7–15.0° |
c = 9.900 (1) Å | µ = 0.45 mm−1 |
α = 105.06 (1)° | T = 298 K |
β = 97.47 (1)° | Prismatic, violet |
γ = 107.58 (1)° | 0.6 × 0.2 × 0.15 mm |
V = 1086.0 (3) Å3 |
Rigaku AFC-7R diffractometer | Rint = 0.016 |
θ–2θ scans | θmax = 27.5°, θmin = 2.5° |
Absorption correction: integration (Coppens et al., 1965) | h = 0→13 |
Tmin = 0.900, Tmax = 0.928 | k = −15→15 |
5271 measured reflections | l = −13→13 |
4996 independent reflections | 3 standard reflections every 150 reflections |
3676 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | H-atom parameters not refined |
R[F2 > 2σ(F2)] = 0.043 | w = 1/[σ2(Fo2) + (0.0567P)2 + 0.3931P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.123 | (Δ/σ)max = 0.001 |
S = 1.01 | Δρmax = 0.33 e Å−3 |
4996 reflections | Δρmin = −0.21 e Å−3 |
340 parameters |
[Co(C44H28N4)(H2O)(NO2)]·2C3H7NO | γ = 107.58 (1)° |
Mr = 881.87 | V = 1086.0 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 10.355 (1) Å | Mo Kα radiation |
b = 11.815 (2) Å | µ = 0.45 mm−1 |
c = 9.900 (1) Å | T = 298 K |
α = 105.06 (1)° | 0.6 × 0.2 × 0.15 mm |
β = 97.47 (1)° |
Rigaku AFC-7R diffractometer | 3676 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.016 |
Tmin = 0.900, Tmax = 0.928 | 3 standard reflections every 150 reflections |
5271 measured reflections | intensity decay: none |
4996 independent reflections |
R[F2 > 2σ(F2)] = 0.043 | 340 parameters |
wR(F2) = 0.123 | H-atom parameters not refined |
S = 1.01 | Δρmax = 0.33 e Å−3 |
4996 reflections | Δρmin = −0.21 e Å−3 |
Refinement. Refinement using reflections with F2 > 0.0 σ(F2). The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Co1 | 0.0000 | 0.0000 | 0.0000 | 0.0430 (1) | |
O2 | −0.2505 (4) | −0.2009 (4) | −0.0530 (5) | 0.079 (1) | 0.50 |
O3 | −0.2073 (5) | −0.0713 (4) | 0.1512 (6) | 0.090 (1) | 0.50 |
O4 | −0.1700 (2) | −0.1054 (2) | 0.0363 (2) | 0.0493 (4) | 0.50 |
O5 | 0.3833 (5) | 0.2416 (5) | 0.2027 (5) | 0.088 (1) | 0.50 |
O6 | −0.6745 (5) | −0.0083 (5) | −0.1683 (6) | 0.104 (2) | 0.50 |
N7 | −0.1700 (2) | −0.1054 (2) | 0.0363 (2) | 0.0493 (4) | 0.50 |
N8 | −0.1103 (2) | 0.0033 (2) | −0.1775 (2) | 0.0445 (4) | |
N9 | 0.0276 (2) | −0.1532 (2) | −0.1108 (2) | 0.0421 (4) | |
N10 | 0.5472 (9) | 0.1796 (7) | 0.3089 (7) | 0.073 (2) | 0.50 |
N11 | −0.633 (1) | −0.1629 (7) | −0.3225 (8) | 0.078 (2) | 0.50 |
C12 | −0.1431 (3) | −0.0808 (2) | −0.3131 (2) | 0.0466 (5) | |
C13 | −0.1032 (2) | −0.1845 (2) | −0.3525 (2) | 0.0452 (5) | |
C14 | −0.0222 (2) | −0.2163 (2) | −0.2555 (2) | 0.0447 (5) | |
C15 | 0.0241 (3) | −0.3209 (2) | −0.2952 (3) | 0.0524 (6) | |
C16 | 0.0998 (3) | −0.3225 (2) | −0.1758 (3) | 0.0521 (6) | |
C17 | 0.1021 (2) | −0.2187 (2) | −0.0598 (2) | 0.0440 (5) | |
C18 | 0.1710 (2) | −0.1901 (2) | 0.0804 (2) | 0.0448 (5) | |
C19 | 0.1749 (2) | −0.0876 (2) | 0.1904 (2) | 0.0468 (5) | |
C20 | 0.2491 (3) | −0.0543 (2) | 0.3359 (3) | 0.0561 (6) | |
C21 | 0.2300 (3) | 0.0490 (2) | 0.4115 (3) | 0.0556 (6) | |
C22 | −0.1527 (3) | −0.2682 (2) | −0.5041 (2) | 0.0463 (5) | |
C23 | −0.1035 (3) | −0.2310 (3) | −0.6150 (3) | 0.0632 (7) | |
C24 | −0.1517 (4) | −0.3094 (4) | −0.7554 (3) | 0.0797 (10) | |
C25 | −0.2492 (4) | −0.4250 (3) | −0.7850 (3) | 0.084 (1) | |
C26 | −0.3000 (4) | −0.4639 (3) | −0.6791 (4) | 0.0793 (9) | |
C27 | −0.2524 (3) | −0.3860 (2) | −0.5377 (3) | 0.0597 (6) | |
C28 | 0.2446 (2) | −0.2744 (2) | 0.1158 (2) | 0.0447 (5) | |
C29 | 0.3858 (3) | −0.2438 (2) | 0.1246 (3) | 0.0610 (6) | |
C30 | 0.4530 (3) | −0.3222 (3) | 0.1569 (4) | 0.0711 (8) | |
C31 | 0.3804 (3) | −0.4307 (3) | 0.1784 (3) | 0.0670 (7) | |
C32 | 0.2425 (3) | −0.4611 (2) | 0.1707 (3) | 0.0659 (7) | |
C33 | 0.1734 (3) | −0.3836 (2) | 0.1393 (3) | 0.0558 (6) | |
C34 | 0.4589 (9) | 0.1745 (7) | 0.1993 (8) | 0.068 (2) | 0.50 |
C35 | 0.622 (1) | 0.096 (1) | 0.292 (1) | 0.104 (4) | 0.50 |
C36 | 0.5648 (10) | 0.2575 (8) | 0.4534 (8) | 0.099 (2) | 0.50 |
C37 | −0.7022 (10) | −0.0881 (7) | −0.2885 (8) | 0.078 (2) | 0.50 |
C38 | −0.680 (1) | −0.2609 (8) | −0.4602 (9) | 0.109 (3) | 0.50 |
C39 | −0.524 (1) | −0.161 (1) | −0.217 (2) | 0.110 (4) | 0.50 |
H15 | 0.0045 | −0.3784 | −0.3889 | 0.0628* | |
H16 | 0.1439 | −0.3813 | −0.1691 | 0.0623* | |
H20 | 0.3023 | −0.0974 | 0.3721 | 0.0670* | |
H21 | 0.2716 | 0.0857 | 0.5112 | 0.0666* | |
H23 | −0.0354 | −0.1503 | −0.5943 | 0.0756* | |
H24 | −0.1170 | −0.2827 | −0.8304 | 0.0956* | |
H25 | −0.2821 | −0.4791 | −0.8815 | 0.1006* | |
H26 | −0.3684 | −0.5447 | −0.7016 | 0.0953* | |
H27 | −0.2883 | −0.4137 | −0.4638 | 0.0714* | |
H29 | 0.4371 | −0.1689 | 0.1084 | 0.0730* | |
H30 | 0.5504 | −0.2999 | 0.1641 | 0.0851* | |
H31 | 0.4266 | −0.4847 | 0.1986 | 0.0803* | |
H32 | 0.1922 | −0.5362 | 0.1870 | 0.0789* | |
H33 | 0.0763 | −0.4064 | 0.1339 | 0.0669* | |
H34 | 0.4492 | 0.1164 | 0.1090 | 0.0818* | 0.50 |
H35A | 0.5584 | 0.0124 | 0.2610 | 0.1241* | 0.50 |
H35B | 0.6763 | 0.1082 | 0.2237 | 0.1241* | 0.50 |
H35C | 0.6815 | 0.1117 | 0.3821 | 0.1241* | 0.50 |
H36A | 0.6340 | 0.2469 | 0.5164 | 0.1191* | 0.50 |
H36B | 0.5927 | 0.3431 | 0.4563 | 0.1191* | 0.50 |
H36C | 0.4792 | 0.2355 | 0.4822 | 0.1191* | 0.50 |
H37 | −0.7774 | −0.0947 | −0.3593 | 0.0932* | 0.50 |
H38A | −0.7707 | −0.3155 | −0.4674 | 0.1310* | 0.50 |
H38B | −0.6806 | −0.2245 | −0.5351 | 0.1310* | 0.50 |
H38C | −0.6181 | −0.3064 | −0.4675 | 0.1310* | 0.50 |
H39A | −0.5592 | −0.1819 | −0.1391 | 0.1280* | 0.50 |
H39B | −0.4832 | −0.2208 | −0.2586 | 0.1280* | 0.50 |
H39C | −0.4532 | −0.0802 | −0.1813 | 0.1280* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0549 (3) | 0.0329 (2) | 0.0434 (2) | 0.0247 (2) | 0.0015 (2) | 0.0092 (2) |
O2 | 0.065 (2) | 0.067 (2) | 0.081 (3) | −0.001 (2) | 0.010 (2) | 0.014 (2) |
O3 | 0.084 (3) | 0.065 (2) | 0.115 (4) | 0.020 (2) | 0.055 (3) | 0.014 (2) |
O4 | 0.052 (1) | 0.0420 (9) | 0.056 (1) | 0.0185 (8) | 0.0082 (8) | 0.0174 (8) |
O5 | 0.079 (3) | 0.089 (3) | 0.080 (3) | 0.021 (3) | −0.002 (2) | 0.022 (2) |
O6 | 0.084 (3) | 0.077 (3) | 0.122 (4) | 0.013 (2) | 0.048 (3) | −0.009 (3) |
N7 | 0.052 (1) | 0.0420 (9) | 0.056 (1) | 0.0185 (8) | 0.0082 (8) | 0.0174 (8) |
N8 | 0.056 (1) | 0.0341 (8) | 0.0459 (10) | 0.0249 (8) | 0.0023 (8) | 0.0102 (7) |
N9 | 0.049 (1) | 0.0328 (8) | 0.0459 (10) | 0.0216 (8) | 0.0031 (8) | 0.0105 (7) |
N10 | 0.073 (4) | 0.074 (4) | 0.067 (4) | 0.021 (3) | 0.013 (4) | 0.024 (3) |
N11 | 0.111 (6) | 0.057 (4) | 0.068 (4) | 0.026 (5) | 0.036 (4) | 0.021 (3) |
C12 | 0.058 (1) | 0.039 (1) | 0.043 (1) | 0.0228 (10) | 0.0025 (10) | 0.0099 (9) |
C13 | 0.057 (1) | 0.037 (1) | 0.043 (1) | 0.0220 (10) | 0.0057 (10) | 0.0105 (9) |
C14 | 0.055 (1) | 0.0341 (10) | 0.045 (1) | 0.0226 (9) | 0.0058 (10) | 0.0081 (9) |
C15 | 0.068 (2) | 0.040 (1) | 0.051 (1) | 0.030 (1) | 0.008 (1) | 0.0061 (10) |
C16 | 0.064 (1) | 0.041 (1) | 0.056 (1) | 0.033 (1) | 0.007 (1) | 0.0090 (10) |
C17 | 0.049 (1) | 0.0352 (10) | 0.052 (1) | 0.0241 (9) | 0.0057 (10) | 0.0113 (9) |
C18 | 0.049 (1) | 0.037 (1) | 0.053 (1) | 0.0239 (9) | 0.0060 (10) | 0.0146 (9) |
C19 | 0.056 (1) | 0.039 (1) | 0.051 (1) | 0.027 (1) | 0.004 (1) | 0.0147 (9) |
C20 | 0.071 (2) | 0.052 (1) | 0.051 (1) | 0.037 (1) | −0.001 (1) | 0.014 (1) |
C21 | 0.072 (2) | 0.052 (1) | 0.044 (1) | 0.034 (1) | −0.003 (1) | 0.011 (1) |
C22 | 0.059 (1) | 0.042 (1) | 0.042 (1) | 0.030 (1) | 0.0058 (10) | 0.0093 (9) |
C23 | 0.072 (2) | 0.069 (2) | 0.058 (2) | 0.033 (1) | 0.018 (1) | 0.023 (1) |
C24 | 0.107 (2) | 0.116 (3) | 0.050 (2) | 0.080 (2) | 0.028 (2) | 0.030 (2) |
C25 | 0.121 (3) | 0.091 (2) | 0.050 (2) | 0.080 (2) | −0.007 (2) | 0.000 (2) |
C26 | 0.093 (2) | 0.049 (1) | 0.079 (2) | 0.034 (2) | −0.021 (2) | 0.000 (1) |
C27 | 0.073 (2) | 0.046 (1) | 0.058 (1) | 0.025 (1) | 0.002 (1) | 0.015 (1) |
C28 | 0.051 (1) | 0.041 (1) | 0.045 (1) | 0.0270 (10) | 0.0022 (9) | 0.0099 (9) |
C29 | 0.054 (1) | 0.051 (1) | 0.084 (2) | 0.026 (1) | 0.013 (1) | 0.024 (1) |
C30 | 0.053 (1) | 0.077 (2) | 0.092 (2) | 0.041 (1) | 0.009 (1) | 0.023 (2) |
C31 | 0.079 (2) | 0.066 (2) | 0.069 (2) | 0.051 (2) | 0.002 (1) | 0.020 (1) |
C32 | 0.081 (2) | 0.053 (1) | 0.079 (2) | 0.037 (1) | 0.015 (1) | 0.033 (1) |
C33 | 0.053 (1) | 0.049 (1) | 0.073 (2) | 0.027 (1) | 0.010 (1) | 0.023 (1) |
C34 | 0.070 (5) | 0.061 (4) | 0.056 (3) | 0.008 (3) | 0.010 (4) | 0.010 (3) |
C35 | 0.066 (6) | 0.097 (8) | 0.128 (9) | 0.019 (7) | −0.001 (6) | 0.028 (7) |
C36 | 0.096 (5) | 0.107 (6) | 0.062 (4) | 0.014 (5) | 0.004 (4) | 0.005 (4) |
C37 | 0.083 (5) | 0.066 (4) | 0.081 (5) | 0.016 (4) | 0.027 (4) | 0.026 (4) |
C38 | 0.180 (9) | 0.085 (5) | 0.076 (5) | 0.046 (6) | 0.053 (6) | 0.036 (4) |
C39 | 0.095 (8) | 0.127 (9) | 0.16 (1) | 0.062 (7) | 0.053 (10) | 0.084 (9) |
Co1—O4 | 1.962 (2) | C21—H21 | 0.950 |
Co1—O4i | 1.962 (2) | C22—C23 | 1.385 (4) |
Co1—N7 | 1.962 (2) | C22—C27 | 1.385 (3) |
Co1—N7i | 1.962 (2) | C23—C24 | 1.381 (4) |
Co1—N8 | 1.983 (2) | C23—H23 | 0.950 |
Co1—N8i | 1.983 (2) | C24—C25 | 1.361 (5) |
Co1—N9 | 1.981 (2) | C24—H24 | 0.951 |
Co1—N9i | 1.981 (2) | C25—C26 | 1.355 (5) |
O5—C34 | 1.27 (1) | C25—H25 | 0.950 |
O6—C37 | 1.247 (9) | C26—C27 | 1.388 (4) |
N7—O2 | 1.214 (4) | C26—H26 | 0.950 |
N7—O3 | 1.255 (6) | C27—H27 | 0.950 |
N8—C12 | 1.375 (3) | C28—C29 | 1.381 (4) |
N8—C19i | 1.380 (4) | C28—C33 | 1.374 (4) |
N9—C14 | 1.377 (3) | C29—C30 | 1.390 (5) |
N9—C17 | 1.382 (3) | C29—H29 | 0.950 |
N10—C34 | 1.30 (1) | C30—C31 | 1.362 (5) |
N10—C35 | 1.42 (2) | C30—H30 | 0.950 |
N10—C36 | 1.44 (1) | C31—C32 | 1.349 (5) |
N11—C37 | 1.30 (1) | C31—H31 | 0.950 |
N11—C38 | 1.451 (10) | C32—C33 | 1.390 (5) |
N11—C39 | 1.43 (2) | C32—H32 | 0.950 |
C12—C13 | 1.387 (4) | C33—H33 | 0.950 |
C12—C21i | 1.438 (4) | C34—H34 | 0.947 |
C13—C14 | 1.390 (4) | C35—H35A | 0.950 |
C13—C22 | 1.489 (3) | C35—H35B | 0.946 |
C14—C15 | 1.437 (4) | C35—H35C | 0.952 |
C15—C16 | 1.339 (4) | C36—H36A | 0.947 |
C15—H15 | 0.950 | C36—H36B | 0.955 |
C16—C17 | 1.438 (3) | C36—H36C | 0.949 |
C16—H16 | 0.950 | C37—H37 | 0.947 |
C17—C18 | 1.380 (3) | C38—H38A | 0.948 |
C18—C19 | 1.389 (3) | C38—H38B | 0.950 |
C18—C28 | 1.506 (4) | C38—H38C | 0.949 |
C19—C20 | 1.434 (3) | C39—H39A | 0.948 |
C20—C21 | 1.341 (4) | C39—H39B | 0.956 |
C20—H20 | 0.950 | C39—H39C | 0.956 |
O4—Co1—O4i | 180.0 | C23—C24—C25 | 119.4 (3) |
O4—Co1—N8 | 90.00 (8) | C23—C24—H24 | 120.2 |
O4—Co1—N8i | 90.00 (8) | C25—C24—H24 | 120.4 |
O4—Co1—N9 | 89.25 (7) | C24—C25—C26 | 120.9 (3) |
O4—Co1—N9i | 90.75 (7) | C24—C25—H25 | 119.5 |
N7—Co1—N7i | 180.0 | C26—C25—H25 | 119.6 |
N8—Co1—N8i | 180.0 | C25—C26—C27 | 120.2 (3) |
N8—Co1—N9 | 90.14 (8) | C25—C26—H26 | 120.0 |
N8—Co1—N9i | 89.86 (8) | C27—C26—H26 | 119.9 |
N9—Co1—N9i | 180.0 | C22—C27—C26 | 120.2 (3) |
Co1—N7—O2 | 123.0 (3) | C22—C27—H27 | 119.9 |
Co1—N7—O3 | 120.9 (2) | C26—C27—H27 | 119.9 |
O2—N7—O3 | 115.8 (3) | C18—C28—C29 | 120.5 (2) |
Co1—N8—C12 | 127.3 (2) | C18—C28—C33 | 121.1 (2) |
Co1—N8—C19i | 127.4 (1) | C29—C28—C33 | 118.4 (3) |
C12—N8—C19i | 105.2 (2) | C28—C29—C30 | 120.2 (3) |
Co1—N9—C14 | 127.2 (2) | C28—C29—H29 | 119.9 |
Co1—N9—C17 | 127.4 (1) | C30—C29—H29 | 119.9 |
C14—N9—C17 | 105.4 (2) | C29—C30—C31 | 120.5 (3) |
C34—N10—C35 | 119.9 (8) | C29—C30—H30 | 119.8 |
C34—N10—C36 | 123.6 (9) | C31—C30—H30 | 119.7 |
C35—N10—C36 | 116.1 (9) | C30—C31—C32 | 119.7 (3) |
C37—N11—C38 | 120.0 (9) | C30—C31—H31 | 120.2 |
C37—N11—C39 | 120.1 (9) | C32—C31—H31 | 120.1 |
C38—N11—C39 | 119 (1) | C31—C32—C33 | 120.7 (3) |
N8—C12—C13 | 126.2 (2) | C31—C32—H32 | 119.6 |
N8—C12—C21i | 110.3 (2) | C33—C32—H32 | 119.7 |
C13—C12—C21i | 123.5 (2) | C28—C33—C32 | 120.5 (2) |
C12—C13—C14 | 122.9 (2) | C28—C33—H33 | 119.8 |
C12—C13—C22 | 118.8 (2) | C32—C33—H33 | 119.7 |
C14—C13—C22 | 118.3 (2) | O5—C34—N10 | 125.3 (7) |
N9—C14—C13 | 126.2 (2) | O5—C34—H34 | 116.4 |
N9—C14—C15 | 110.1 (2) | N10—C34—H34 | 118.3 |
C13—C14—C15 | 123.7 (2) | N10—C35—H35A | 109.1 |
C14—C15—C16 | 107.4 (2) | N10—C35—H35B | 109.6 |
C14—C15—H15 | 126.3 | N10—C35—H35C | 109.2 |
C16—C15—H15 | 126.3 | H35A—C35—H35B | 109.9 |
C15—C16—C17 | 107.2 (2) | H35A—C35—H35C | 109.3 |
C15—C16—H16 | 126.4 | H35B—C35—H35C | 109.7 |
C17—C16—H16 | 126.4 | N10—C36—H36A | 109.9 |
N9—C17—C16 | 109.9 (2) | N10—C36—H36B | 109.2 |
N9—C17—C18 | 126.2 (2) | N10—C36—H36C | 109.4 |
C16—C17—C18 | 123.8 (2) | H36A—C36—H36B | 109.3 |
C17—C18—C19 | 123.0 (2) | H36A—C36—H36C | 109.8 |
C17—C18—C28 | 118.4 (2) | H36B—C36—H36C | 109.2 |
C19—C18—C28 | 118.5 (2) | O6—C37—N11 | 123.5 (8) |
N8i—C19—C18 | 126.0 (2) | O6—C37—H37 | 118.3 |
N8i—C19—C20 | 110.1 (2) | N11—C37—H37 | 118.2 |
C18—C19—C20 | 123.9 (3) | N11—C38—H38A | 109.4 |
C19—C20—C21 | 107.4 (3) | N11—C38—H38B | 109.4 |
C19—C20—H20 | 126.3 | N11—C38—H38C | 109.2 |
C21—C20—H20 | 126.3 | H38A—C38—H38B | 109.6 |
C12i—C21—C20 | 106.9 (2) | H38A—C38—H38C | 109.7 |
C12i—C21—H21 | 133.1 | H38B—C38—H38C | 109.6 |
C20—C21—H21 | 120.0 | N11—C39—H39A | 110.4 |
C13—C22—C23 | 121.9 (2) | N11—C39—H39B | 109.8 |
C13—C22—C27 | 119.9 (2) | N11—C39—H39C | 109.9 |
C23—C22—C27 | 118.2 (2) | H39A—C39—H39B | 109.1 |
C22—C23—C24 | 121.1 (3) | H39A—C39—H39C | 109.1 |
C22—C23—H23 | 119.5 | H39B—C39—H39C | 108.5 |
C24—C23—H23 | 119.4 |
Symmetry code: (i) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C44H28N4)(H2O)(NO2)]·2C3H7NO |
Mr | 881.87 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 10.355 (1), 11.815 (2), 9.900 (1) |
α, β, γ (°) | 105.06 (1), 97.47 (1), 107.58 (1) |
V (Å3) | 1086.0 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.45 |
Crystal size (mm) | 0.6 × 0.2 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.900, 0.928 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5271, 4996, 3676 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.123, 1.01 |
No. of reflections | 4996 |
No. of parameters | 340 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.33, −0.21 |
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), ORTEP-II (Johnson, 1976), TEXSAN.
Co1—O4 | 1.962 (2) | Co1—N9 | 1.981 (2) |
Co1—N7 | 1.962 (2) | N7—O2 | 1.214 (4) |
Co1—N8 | 1.983 (2) | N7—O3 | 1.255 (6) |
O2—N7—O3 | 115.8 (3) |
The nitro-to-nitrito photoisomerization of the title complex, [Co(tpp)(NO2)(H2O)], (I), where tpp is α,β,γ,δ-tetraphenylporphyrinate, was investigated in benzene solution using a laser flash technique. The thermodynamically less stable nitrito form was detected and the nitrito-to-nitro back reaction obeyed first-order kinetics with a rate constant k1 = 3.0 × 10 2 s−1 (Seki et al., 1997). The half-life (t1/2) was calculated to be 2.3 ms, which is much shorter than that of [Co(NH3)5(ONO)]2+ in an aqueous solution (k1 = 0.76×10−4 s−1, t1/2 = 2.5 h; Miyoshi et al., 1983). \scheme
The dimethylformamide (dmf) molecule exists near the axial ligands, and has two possible orientations with 50% probability each. In one of them (atoms O5, N10 and C34–C36), dmf seems to form a hydrogen bond with the aqua O4 atom, with an O5···O4i distance of 2.754 (4) Å [symmetry code: (i) −x, −y, −z]. In the other orientation, dmf (atoms O6, N11 and C37—C39) is close to the nitro ligand, with an O2···C39 distance of 3.30 (2) Å.