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In the title compound, [Co(tpp)(NO2)(H2O)]·2dmf or [Co(C44H28N4)(NO2)(H2O)]·2C3H7NO, a distorted octahedral CoIII complex shows an orientational disorder such that the positions of the nitro and aqua ligands are exchanged. As a result, the averaged structure has an inversion centre at the Co atom. The di­methyl­form­amide mol­ecule also has a positional disorder.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015109/qa0451sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015109/qa0451Isup2.hkl
Contains datablock I

CCDC reference: 156196

Comment top

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.

Experimental top

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.

Refinement top

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).

Computing details top

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.

(I) top
Crystal data top
[Co(C44H28N4)(H2O)(NO2)]·2C3H7NOZ = 1
Mr = 881.87Dx = 1.348 Mg m3
Triclinic, P1Mo Kα radiation, λ = 0.71073 Å
a = 10.355 (1) ÅCell parameters from 24 reflections
b = 11.815 (2) Åθ = 13.7–15.0°
c = 9.900 (1) ŵ = 0.45 mm1
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
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.016
θ–2θ scansθmax = 27.5°, θmin = 2.5°
Absorption correction: integration
(Coppens et al., 1965)
h = 013
Tmin = 0.900, Tmax = 0.928k = 1515
5271 measured reflectionsl = 1313
4996 independent reflections3 standard reflections every 150 reflections
3676 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2H-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 = 1.01Δρmax = 0.33 e Å3
4996 reflectionsΔρmin = 0.21 e Å3
340 parameters
Crystal data top
[Co(C44H28N4)(H2O)(NO2)]·2C3H7NOγ = 107.58 (1)°
Mr = 881.87V = 1086.0 (3) Å3
Triclinic, P1Z = 1
a = 10.355 (1) ÅMo Kα radiation
b = 11.815 (2) ŵ = 0.45 mm1
c = 9.900 (1) ÅT = 298 K
α = 105.06 (1)°0.6 × 0.2 × 0.15 mm
β = 97.47 (1)°
Data collection top
Rigaku AFC-7R
diffractometer
3676 reflections with I > 2σ(I)
Absorption correction: integration
(Coppens et al., 1965)
Rint = 0.016
Tmin = 0.900, Tmax = 0.9283 standard reflections every 150 reflections
5271 measured reflections intensity decay: none
4996 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043340 parameters
wR(F2) = 0.123H-atom parameters not refined
S = 1.01Δρmax = 0.33 e Å3
4996 reflectionsΔρmin = 0.21 e Å3
Special details top

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).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.00000.00000.00000.0430 (1)
O20.2505 (4)0.2009 (4)0.0530 (5)0.079 (1)0.50
O30.2073 (5)0.0713 (4)0.1512 (6)0.090 (1)0.50
O40.1700 (2)0.1054 (2)0.0363 (2)0.0493 (4)0.50
O50.3833 (5)0.2416 (5)0.2027 (5)0.088 (1)0.50
O60.6745 (5)0.0083 (5)0.1683 (6)0.104 (2)0.50
N70.1700 (2)0.1054 (2)0.0363 (2)0.0493 (4)0.50
N80.1103 (2)0.0033 (2)0.1775 (2)0.0445 (4)
N90.0276 (2)0.1532 (2)0.1108 (2)0.0421 (4)
N100.5472 (9)0.1796 (7)0.3089 (7)0.073 (2)0.50
N110.633 (1)0.1629 (7)0.3225 (8)0.078 (2)0.50
C120.1431 (3)0.0808 (2)0.3131 (2)0.0466 (5)
C130.1032 (2)0.1845 (2)0.3525 (2)0.0452 (5)
C140.0222 (2)0.2163 (2)0.2555 (2)0.0447 (5)
C150.0241 (3)0.3209 (2)0.2952 (3)0.0524 (6)
C160.0998 (3)0.3225 (2)0.1758 (3)0.0521 (6)
C170.1021 (2)0.2187 (2)0.0598 (2)0.0440 (5)
C180.1710 (2)0.1901 (2)0.0804 (2)0.0448 (5)
C190.1749 (2)0.0876 (2)0.1904 (2)0.0468 (5)
C200.2491 (3)0.0543 (2)0.3359 (3)0.0561 (6)
C210.2300 (3)0.0490 (2)0.4115 (3)0.0556 (6)
C220.1527 (3)0.2682 (2)0.5041 (2)0.0463 (5)
C230.1035 (3)0.2310 (3)0.6150 (3)0.0632 (7)
C240.1517 (4)0.3094 (4)0.7554 (3)0.0797 (10)
C250.2492 (4)0.4250 (3)0.7850 (3)0.084 (1)
C260.3000 (4)0.4639 (3)0.6791 (4)0.0793 (9)
C270.2524 (3)0.3860 (2)0.5377 (3)0.0597 (6)
C280.2446 (2)0.2744 (2)0.1158 (2)0.0447 (5)
C290.3858 (3)0.2438 (2)0.1246 (3)0.0610 (6)
C300.4530 (3)0.3222 (3)0.1569 (4)0.0711 (8)
C310.3804 (3)0.4307 (3)0.1784 (3)0.0670 (7)
C320.2425 (3)0.4611 (2)0.1707 (3)0.0659 (7)
C330.1734 (3)0.3836 (2)0.1393 (3)0.0558 (6)
C340.4589 (9)0.1745 (7)0.1993 (8)0.068 (2)0.50
C350.622 (1)0.096 (1)0.292 (1)0.104 (4)0.50
C360.5648 (10)0.2575 (8)0.4534 (8)0.099 (2)0.50
C370.7022 (10)0.0881 (7)0.2885 (8)0.078 (2)0.50
C380.680 (1)0.2609 (8)0.4602 (9)0.109 (3)0.50
C390.524 (1)0.161 (1)0.217 (2)0.110 (4)0.50
H150.00450.37840.38890.0628*
H160.14390.38130.16910.0623*
H200.30230.09740.37210.0670*
H210.27160.08570.51120.0666*
H230.03540.15030.59430.0756*
H240.11700.28270.83040.0956*
H250.28210.47910.88150.1006*
H260.36840.54470.70160.0953*
H270.28830.41370.46380.0714*
H290.43710.16890.10840.0730*
H300.55040.29990.16410.0851*
H310.42660.48470.19860.0803*
H320.19220.53620.18700.0789*
H330.07630.40640.13390.0669*
H340.44920.11640.10900.0818*0.50
H35A0.55840.01240.26100.1241*0.50
H35B0.67630.10820.22370.1241*0.50
H35C0.68150.11170.38210.1241*0.50
H36A0.63400.24690.51640.1191*0.50
H36B0.59270.34310.45630.1191*0.50
H36C0.47920.23550.48220.1191*0.50
H370.77740.09470.35930.0932*0.50
H38A0.77070.31550.46740.1310*0.50
H38B0.68060.22450.53510.1310*0.50
H38C0.61810.30640.46750.1310*0.50
H39A0.55920.18190.13910.1280*0.50
H39B0.48320.22080.25860.1280*0.50
H39C0.45320.08020.18130.1280*0.50
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0549 (3)0.0329 (2)0.0434 (2)0.0247 (2)0.0015 (2)0.0092 (2)
O20.065 (2)0.067 (2)0.081 (3)0.001 (2)0.010 (2)0.014 (2)
O30.084 (3)0.065 (2)0.115 (4)0.020 (2)0.055 (3)0.014 (2)
O40.052 (1)0.0420 (9)0.056 (1)0.0185 (8)0.0082 (8)0.0174 (8)
O50.079 (3)0.089 (3)0.080 (3)0.021 (3)0.002 (2)0.022 (2)
O60.084 (3)0.077 (3)0.122 (4)0.013 (2)0.048 (3)0.009 (3)
N70.052 (1)0.0420 (9)0.056 (1)0.0185 (8)0.0082 (8)0.0174 (8)
N80.056 (1)0.0341 (8)0.0459 (10)0.0249 (8)0.0023 (8)0.0102 (7)
N90.049 (1)0.0328 (8)0.0459 (10)0.0216 (8)0.0031 (8)0.0105 (7)
N100.073 (4)0.074 (4)0.067 (4)0.021 (3)0.013 (4)0.024 (3)
N110.111 (6)0.057 (4)0.068 (4)0.026 (5)0.036 (4)0.021 (3)
C120.058 (1)0.039 (1)0.043 (1)0.0228 (10)0.0025 (10)0.0099 (9)
C130.057 (1)0.037 (1)0.043 (1)0.0220 (10)0.0057 (10)0.0105 (9)
C140.055 (1)0.0341 (10)0.045 (1)0.0226 (9)0.0058 (10)0.0081 (9)
C150.068 (2)0.040 (1)0.051 (1)0.030 (1)0.008 (1)0.0061 (10)
C160.064 (1)0.041 (1)0.056 (1)0.033 (1)0.007 (1)0.0090 (10)
C170.049 (1)0.0352 (10)0.052 (1)0.0241 (9)0.0057 (10)0.0113 (9)
C180.049 (1)0.037 (1)0.053 (1)0.0239 (9)0.0060 (10)0.0146 (9)
C190.056 (1)0.039 (1)0.051 (1)0.027 (1)0.004 (1)0.0147 (9)
C200.071 (2)0.052 (1)0.051 (1)0.037 (1)0.001 (1)0.014 (1)
C210.072 (2)0.052 (1)0.044 (1)0.034 (1)0.003 (1)0.011 (1)
C220.059 (1)0.042 (1)0.042 (1)0.030 (1)0.0058 (10)0.0093 (9)
C230.072 (2)0.069 (2)0.058 (2)0.033 (1)0.018 (1)0.023 (1)
C240.107 (2)0.116 (3)0.050 (2)0.080 (2)0.028 (2)0.030 (2)
C250.121 (3)0.091 (2)0.050 (2)0.080 (2)0.007 (2)0.000 (2)
C260.093 (2)0.049 (1)0.079 (2)0.034 (2)0.021 (2)0.000 (1)
C270.073 (2)0.046 (1)0.058 (1)0.025 (1)0.002 (1)0.015 (1)
C280.051 (1)0.041 (1)0.045 (1)0.0270 (10)0.0022 (9)0.0099 (9)
C290.054 (1)0.051 (1)0.084 (2)0.026 (1)0.013 (1)0.024 (1)
C300.053 (1)0.077 (2)0.092 (2)0.041 (1)0.009 (1)0.023 (2)
C310.079 (2)0.066 (2)0.069 (2)0.051 (2)0.002 (1)0.020 (1)
C320.081 (2)0.053 (1)0.079 (2)0.037 (1)0.015 (1)0.033 (1)
C330.053 (1)0.049 (1)0.073 (2)0.027 (1)0.010 (1)0.023 (1)
C340.070 (5)0.061 (4)0.056 (3)0.008 (3)0.010 (4)0.010 (3)
C350.066 (6)0.097 (8)0.128 (9)0.019 (7)0.001 (6)0.028 (7)
C360.096 (5)0.107 (6)0.062 (4)0.014 (5)0.004 (4)0.005 (4)
C370.083 (5)0.066 (4)0.081 (5)0.016 (4)0.027 (4)0.026 (4)
C380.180 (9)0.085 (5)0.076 (5)0.046 (6)0.053 (6)0.036 (4)
C390.095 (8)0.127 (9)0.16 (1)0.062 (7)0.053 (10)0.084 (9)
Geometric parameters (Å, º) top
Co1—O41.962 (2)C21—H210.950
Co1—O4i1.962 (2)C22—C231.385 (4)
Co1—N71.962 (2)C22—C271.385 (3)
Co1—N7i1.962 (2)C23—C241.381 (4)
Co1—N81.983 (2)C23—H230.950
Co1—N8i1.983 (2)C24—C251.361 (5)
Co1—N91.981 (2)C24—H240.951
Co1—N9i1.981 (2)C25—C261.355 (5)
O5—C341.27 (1)C25—H250.950
O6—C371.247 (9)C26—C271.388 (4)
N7—O21.214 (4)C26—H260.950
N7—O31.255 (6)C27—H270.950
N8—C121.375 (3)C28—C291.381 (4)
N8—C19i1.380 (4)C28—C331.374 (4)
N9—C141.377 (3)C29—C301.390 (5)
N9—C171.382 (3)C29—H290.950
N10—C341.30 (1)C30—C311.362 (5)
N10—C351.42 (2)C30—H300.950
N10—C361.44 (1)C31—C321.349 (5)
N11—C371.30 (1)C31—H310.950
N11—C381.451 (10)C32—C331.390 (5)
N11—C391.43 (2)C32—H320.950
C12—C131.387 (4)C33—H330.950
C12—C21i1.438 (4)C34—H340.947
C13—C141.390 (4)C35—H35A0.950
C13—C221.489 (3)C35—H35B0.946
C14—C151.437 (4)C35—H35C0.952
C15—C161.339 (4)C36—H36A0.947
C15—H150.950C36—H36B0.955
C16—C171.438 (3)C36—H36C0.949
C16—H160.950C37—H370.947
C17—C181.380 (3)C38—H38A0.948
C18—C191.389 (3)C38—H38B0.950
C18—C281.506 (4)C38—H38C0.949
C19—C201.434 (3)C39—H39A0.948
C20—C211.341 (4)C39—H39B0.956
C20—H200.950C39—H39C0.956
O4—Co1—O4i180.0C23—C24—C25119.4 (3)
O4—Co1—N890.00 (8)C23—C24—H24120.2
O4—Co1—N8i90.00 (8)C25—C24—H24120.4
O4—Co1—N989.25 (7)C24—C25—C26120.9 (3)
O4—Co1—N9i90.75 (7)C24—C25—H25119.5
N7—Co1—N7i180.0C26—C25—H25119.6
N8—Co1—N8i180.0C25—C26—C27120.2 (3)
N8—Co1—N990.14 (8)C25—C26—H26120.0
N8—Co1—N9i89.86 (8)C27—C26—H26119.9
N9—Co1—N9i180.0C22—C27—C26120.2 (3)
Co1—N7—O2123.0 (3)C22—C27—H27119.9
Co1—N7—O3120.9 (2)C26—C27—H27119.9
O2—N7—O3115.8 (3)C18—C28—C29120.5 (2)
Co1—N8—C12127.3 (2)C18—C28—C33121.1 (2)
Co1—N8—C19i127.4 (1)C29—C28—C33118.4 (3)
C12—N8—C19i105.2 (2)C28—C29—C30120.2 (3)
Co1—N9—C14127.2 (2)C28—C29—H29119.9
Co1—N9—C17127.4 (1)C30—C29—H29119.9
C14—N9—C17105.4 (2)C29—C30—C31120.5 (3)
C34—N10—C35119.9 (8)C29—C30—H30119.8
C34—N10—C36123.6 (9)C31—C30—H30119.7
C35—N10—C36116.1 (9)C30—C31—C32119.7 (3)
C37—N11—C38120.0 (9)C30—C31—H31120.2
C37—N11—C39120.1 (9)C32—C31—H31120.1
C38—N11—C39119 (1)C31—C32—C33120.7 (3)
N8—C12—C13126.2 (2)C31—C32—H32119.6
N8—C12—C21i110.3 (2)C33—C32—H32119.7
C13—C12—C21i123.5 (2)C28—C33—C32120.5 (2)
C12—C13—C14122.9 (2)C28—C33—H33119.8
C12—C13—C22118.8 (2)C32—C33—H33119.7
C14—C13—C22118.3 (2)O5—C34—N10125.3 (7)
N9—C14—C13126.2 (2)O5—C34—H34116.4
N9—C14—C15110.1 (2)N10—C34—H34118.3
C13—C14—C15123.7 (2)N10—C35—H35A109.1
C14—C15—C16107.4 (2)N10—C35—H35B109.6
C14—C15—H15126.3N10—C35—H35C109.2
C16—C15—H15126.3H35A—C35—H35B109.9
C15—C16—C17107.2 (2)H35A—C35—H35C109.3
C15—C16—H16126.4H35B—C35—H35C109.7
C17—C16—H16126.4N10—C36—H36A109.9
N9—C17—C16109.9 (2)N10—C36—H36B109.2
N9—C17—C18126.2 (2)N10—C36—H36C109.4
C16—C17—C18123.8 (2)H36A—C36—H36B109.3
C17—C18—C19123.0 (2)H36A—C36—H36C109.8
C17—C18—C28118.4 (2)H36B—C36—H36C109.2
C19—C18—C28118.5 (2)O6—C37—N11123.5 (8)
N8i—C19—C18126.0 (2)O6—C37—H37118.3
N8i—C19—C20110.1 (2)N11—C37—H37118.2
C18—C19—C20123.9 (3)N11—C38—H38A109.4
C19—C20—C21107.4 (3)N11—C38—H38B109.4
C19—C20—H20126.3N11—C38—H38C109.2
C21—C20—H20126.3H38A—C38—H38B109.6
C12i—C21—C20106.9 (2)H38A—C38—H38C109.7
C12i—C21—H21133.1H38B—C38—H38C109.6
C20—C21—H21120.0N11—C39—H39A110.4
C13—C22—C23121.9 (2)N11—C39—H39B109.8
C13—C22—C27119.9 (2)N11—C39—H39C109.9
C23—C22—C27118.2 (2)H39A—C39—H39B109.1
C22—C23—C24121.1 (3)H39A—C39—H39C109.1
C22—C23—H23119.5H39B—C39—H39C108.5
C24—C23—H23119.4
Symmetry code: (i) x, y, z.

Experimental details

Crystal data
Chemical formula[Co(C44H28N4)(H2O)(NO2)]·2C3H7NO
Mr881.87
Crystal system, space groupTriclinic, 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)
V3)1086.0 (3)
Z1
Radiation typeMo Kα
µ (mm1)0.45
Crystal size (mm)0.6 × 0.2 × 0.15
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correctionIntegration
(Coppens et al., 1965)
Tmin, Tmax0.900, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
5271, 4996, 3676
Rint0.016
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.123, 1.01
No. of reflections4996
No. of parameters340
No. of restraints?
H-atom treatmentH-atom parameters not refined
Δρmax, Δρmin (e Å3)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.

Selected geometric parameters (Å, º) top
Co1—O41.962 (2)Co1—N91.981 (2)
Co1—N71.962 (2)N7—O21.214 (4)
Co1—N81.983 (2)N7—O31.255 (6)
O2—N7—O3115.8 (3)
 

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