Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808039846/hg2446sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536808039846/hg2446Isup2.hkl |
CCDC reference: 717154
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.078
- Data-to-parameter ratio = 11.0
checkCIF/PLATON results
No syntax errors found
Alert level C Value of measurement temperature given = 298.000 Value of melting point given = 0.000 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O2 PLAT432_ALERT_2_C Short Inter X...Y Contact O6 .. C7 .. 2.98 Ang. PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Copper(II) picrate tetrahydrate and 5,5'-dihydroxy-2,2'-[1,1'-(propane-1,3-diyldioxydinitrilo)diethlidyne]diphenol were synthesized by an analogous method (Dong et al., 2007a). A ethyl acetate-N,N-dimethylformamide mixed solution (2 ml) of 5,5'-dihydroxy-2,2'-[1,1'-(propane-1,3-diyldioxydinitrilo)diethlidyne]diphenol (4.1 mg, 0.01 mmol) was added dropwise to a acetone solution (2 ml) of copper(II) picrate tetrahydrate (6.1 mg, 0.01 mmol) at room temperature. The brilliant yellow solution obtained was placed in n-hexane sphere and allowed to stand at room temperature for about several weeks. Along with diffusion of n-hexane into the mixed solution of the complex, Green block-like single crystals of bis(N,N-dimethylformamide-κ O)bis(2,4,6-trinitrophenolato- κ2 O,O')copper(II) complex suitable for X-ray crystallographic analysis were obtained. Anal. Calc. for C18H18CuN8O16: C, 34,51; H, 3.48; N, 16.10; Cu, 9.13%. Found: C, 34,73; H, 3.51; N, 16.17; Cu, 9.01%.
Non-H atoms were refined anisotropically. H atoms were treated as riding atoms with distances C—H = 0.96 (CH3), 0.97 (CH2), 0.93 Å (CH), Uiso(H) = 1.2 Ueq(C) and 1.5 Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu(C6H2N3O7)2(C3H7NO)2] | Z = 1 |
Mr = 665.94 | F(000) = 339 |
Triclinic, P1 | Dx = 1.741 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.062 (1) Å | Cell parameters from 2174 reflections |
b = 8.3361 (11) Å | θ = 2.5–27.5° |
c = 9.8429 (14) Å | µ = 0.96 mm−1 |
α = 73.945 (1)° | T = 298 K |
β = 88.796 (2)° | Block-like, green |
γ = 87.968 (2)° | 0.45 × 0.42 × 0.30 mm |
V = 635.25 (15) Å3 |
Siemens SMART 1000 CCD area-detector diffractometer | 2198 independent reflections |
Radiation source: fine-focus sealed tube | 1973 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.673, Tmax = 0.762 | k = −9→6 |
3320 measured reflections | l = −11→11 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H-atom parameters constrained |
wR(F2) = 0.078 | w = 1/[σ2(Fo2) + (0.036P)2 + 0.273P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
2198 reflections | Δρmax = 0.22 e Å−3 |
199 parameters | Δρmin = −0.36 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.141 (6) |
[Cu(C6H2N3O7)2(C3H7NO)2] | γ = 87.968 (2)° |
Mr = 665.94 | V = 635.25 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.062 (1) Å | Mo Kα radiation |
b = 8.3361 (11) Å | µ = 0.96 mm−1 |
c = 9.8429 (14) Å | T = 298 K |
α = 73.945 (1)° | 0.45 × 0.42 × 0.30 mm |
β = 88.796 (2)° |
Siemens SMART 1000 CCD area-detector diffractometer | 2198 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1973 reflections with I > 2σ(I) |
Tmin = 0.673, Tmax = 0.762 | Rint = 0.020 |
3320 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.078 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.22 e Å−3 |
2198 reflections | Δρmin = −0.36 e Å−3 |
199 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.02554 (17) | |
N1 | 0.5597 (3) | 0.5206 (2) | 0.1667 (2) | 0.0339 (5) | |
N2 | 0.8515 (3) | 1.0013 (3) | −0.1186 (2) | 0.0407 (5) | |
N3 | 0.5610 (3) | 1.0497 (2) | 0.3079 (2) | 0.0341 (5) | |
N4 | 0.9697 (2) | 0.3374 (2) | 0.4240 (2) | 0.0289 (4) | |
O1 | 0.4863 (2) | 0.71913 (19) | 0.36927 (16) | 0.0332 (4) | |
O2 | 0.4407 (2) | 0.4683 (2) | 0.2441 (2) | 0.0497 (5) | |
O3 | 0.6381 (3) | 0.4363 (2) | 0.1017 (2) | 0.0496 (5) | |
O4 | 0.9214 (3) | 0.9088 (3) | −0.1814 (2) | 0.0587 (6) | |
O5 | 0.8672 (3) | 1.1525 (3) | −0.1527 (2) | 0.0639 (6) | |
O6 | 0.6713 (3) | 1.1133 (3) | 0.3553 (2) | 0.0552 (5) | |
O7 | 0.4137 (3) | 1.0653 (2) | 0.3315 (2) | 0.0556 (5) | |
O8 | 0.72371 (18) | 0.47226 (19) | 0.43167 (16) | 0.0306 (4) | |
C1 | 0.5606 (3) | 0.7778 (3) | 0.2512 (2) | 0.0255 (5) | |
C2 | 0.6088 (3) | 0.6916 (3) | 0.1486 (2) | 0.0265 (5) | |
C3 | 0.7030 (3) | 0.7633 (3) | 0.0293 (2) | 0.0301 (5) | |
H3 | 0.7350 | 0.7018 | −0.0331 | 0.036* | |
C4 | 0.7490 (3) | 0.9268 (3) | 0.0041 (2) | 0.0298 (5) | |
C5 | 0.7014 (3) | 1.0223 (3) | 0.0951 (2) | 0.0287 (5) | |
H5 | 0.7312 | 1.1331 | 0.0767 | 0.034* | |
C6 | 0.6098 (3) | 0.9480 (3) | 0.2118 (2) | 0.0259 (5) | |
C7 | 0.8263 (3) | 0.3548 (3) | 0.4840 (2) | 0.0278 (5) | |
H7 | 0.7989 | 0.2774 | 0.5687 | 0.033* | |
C8 | 1.0134 (3) | 0.4484 (4) | 0.2868 (3) | 0.0434 (6) | |
H8A | 0.9757 | 0.4034 | 0.2134 | 0.065* | |
H8B | 1.1317 | 0.4587 | 0.2795 | 0.065* | |
H8C | 0.9615 | 0.5564 | 0.2768 | 0.065* | |
C9 | 1.0878 (3) | 0.2028 (3) | 0.4895 (3) | 0.0402 (6) | |
H9A | 1.0476 | 0.1441 | 0.5817 | 0.060* | |
H9B | 1.1933 | 0.2489 | 0.4979 | 0.060* | |
H9C | 1.1001 | 0.1270 | 0.4320 | 0.060* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0244 (2) | 0.0238 (2) | 0.0255 (2) | −0.00033 (15) | 0.00563 (15) | −0.00252 (15) |
N1 | 0.0396 (12) | 0.0273 (11) | 0.0347 (11) | −0.0003 (9) | −0.0077 (9) | −0.0081 (9) |
N2 | 0.0390 (12) | 0.0539 (15) | 0.0278 (11) | −0.0100 (11) | 0.0067 (9) | −0.0084 (10) |
N3 | 0.0480 (13) | 0.0224 (10) | 0.0299 (10) | 0.0035 (9) | 0.0070 (9) | −0.0051 (8) |
N4 | 0.0255 (10) | 0.0290 (10) | 0.0325 (10) | 0.0012 (8) | 0.0019 (8) | −0.0097 (8) |
O1 | 0.0358 (9) | 0.0260 (8) | 0.0316 (9) | 0.0026 (7) | 0.0142 (7) | 0.0011 (7) |
O2 | 0.0463 (11) | 0.0393 (10) | 0.0610 (12) | −0.0169 (9) | 0.0065 (9) | −0.0085 (9) |
O3 | 0.0708 (14) | 0.0310 (10) | 0.0510 (12) | 0.0033 (9) | −0.0010 (10) | −0.0187 (9) |
O4 | 0.0601 (13) | 0.0758 (15) | 0.0440 (12) | −0.0094 (11) | 0.0237 (10) | −0.0236 (11) |
O5 | 0.0878 (17) | 0.0495 (13) | 0.0479 (12) | −0.0253 (12) | 0.0274 (11) | −0.0019 (10) |
O6 | 0.0705 (14) | 0.0512 (12) | 0.0538 (12) | −0.0025 (11) | −0.0067 (10) | −0.0306 (10) |
O7 | 0.0498 (13) | 0.0475 (12) | 0.0714 (14) | 0.0092 (9) | 0.0224 (10) | −0.0225 (10) |
O8 | 0.0249 (8) | 0.0303 (9) | 0.0318 (9) | 0.0019 (7) | 0.0065 (6) | −0.0015 (7) |
C1 | 0.0218 (11) | 0.0253 (11) | 0.0256 (11) | 0.0035 (9) | −0.0002 (9) | −0.0013 (9) |
C2 | 0.0273 (12) | 0.0235 (11) | 0.0274 (11) | 0.0003 (9) | −0.0013 (9) | −0.0047 (9) |
C3 | 0.0316 (12) | 0.0328 (13) | 0.0262 (12) | 0.0031 (10) | 0.0000 (9) | −0.0088 (9) |
C4 | 0.0286 (12) | 0.0348 (13) | 0.0226 (11) | −0.0015 (10) | 0.0024 (9) | −0.0026 (9) |
C5 | 0.0300 (12) | 0.0239 (11) | 0.0292 (12) | −0.0041 (9) | 0.0008 (9) | −0.0020 (9) |
C6 | 0.0268 (11) | 0.0247 (11) | 0.0259 (11) | 0.0031 (9) | 0.0010 (9) | −0.0069 (9) |
C7 | 0.0284 (12) | 0.0273 (12) | 0.0267 (11) | −0.0027 (9) | 0.0025 (9) | −0.0060 (9) |
C8 | 0.0360 (14) | 0.0516 (16) | 0.0381 (14) | −0.0010 (12) | 0.0132 (11) | −0.0059 (12) |
C9 | 0.0323 (13) | 0.0369 (14) | 0.0517 (16) | 0.0065 (11) | −0.0001 (11) | −0.0135 (12) |
Cu1—O1i | 1.9226 (15) | O1—C1 | 1.275 (3) |
Cu1—O1 | 1.9226 (15) | O8—C7 | 1.261 (3) |
Cu1—O8 | 1.9401 (15) | C1—C6 | 1.431 (3) |
Cu1—O8i | 1.9401 (15) | C1—C2 | 1.432 (3) |
Cu1—O2 | 2.659 (2) | C2—C3 | 1.385 (3) |
N1—O3 | 1.226 (3) | C3—C4 | 1.379 (3) |
N1—O2 | 1.228 (3) | C3—H3 | 0.9300 |
N1—C2 | 1.455 (3) | C4—C5 | 1.393 (3) |
N2—O5 | 1.222 (3) | C5—C6 | 1.361 (3) |
N2—O4 | 1.230 (3) | C5—H5 | 0.9300 |
N2—C4 | 1.452 (3) | C7—H7 | 0.9300 |
N3—O6 | 1.215 (3) | C8—H8A | 0.9600 |
N3—O7 | 1.215 (3) | C8—H8B | 0.9600 |
N3—C6 | 1.474 (3) | C8—H8C | 0.9600 |
N4—C7 | 1.310 (3) | C9—H9A | 0.9600 |
N4—C8 | 1.455 (3) | C9—H9B | 0.9600 |
N4—C9 | 1.459 (3) | C9—H9C | 0.9600 |
O1i—Cu1—O1 | 180.0 | C3—C2—N1 | 116.6 (2) |
O1i—Cu1—O8 | 90.87 (6) | C1—C2—N1 | 120.38 (19) |
O1—Cu1—O8 | 89.13 (6) | C4—C3—C2 | 119.3 (2) |
O1i—Cu1—O8i | 89.13 (6) | C4—C3—H3 | 120.4 |
O1—Cu1—O8i | 90.87 (6) | C2—C3—H3 | 120.4 |
O8—Cu1—O8i | 180.000 (1) | C3—C4—C5 | 121.5 (2) |
O1i—Cu1—O2 | 108.49 (7) | C3—C4—N2 | 119.6 (2) |
O1—Cu1—O2 | 71.51 (7) | C5—C4—N2 | 118.9 (2) |
O8—Cu1—O2 | 78.81 (6) | C6—C5—C4 | 117.8 (2) |
O8i—Cu1—O2 | 101.19 (6) | C6—C5—H5 | 121.1 |
O3—N1—O2 | 123.1 (2) | C4—C5—H5 | 121.1 |
O3—N1—C2 | 118.1 (2) | C5—C6—C1 | 125.5 (2) |
O2—N1—C2 | 118.8 (2) | C5—C6—N3 | 117.3 (2) |
O5—N2—O4 | 123.1 (2) | C1—C6—N3 | 117.15 (18) |
O5—N2—C4 | 118.4 (2) | O8—C7—N4 | 122.7 (2) |
O4—N2—C4 | 118.5 (2) | O8—C7—H7 | 118.7 |
O6—N3—O7 | 125.3 (2) | N4—C7—H7 | 118.7 |
O6—N3—C6 | 117.4 (2) | N4—C8—H8A | 109.5 |
O7—N3—C6 | 117.3 (2) | N4—C8—H8B | 109.5 |
C7—N4—C8 | 120.7 (2) | H8A—C8—H8B | 109.5 |
C7—N4—C9 | 121.3 (2) | N4—C8—H8C | 109.5 |
C8—N4—C9 | 117.95 (19) | H8A—C8—H8C | 109.5 |
C1—O1—Cu1 | 130.29 (14) | H8B—C8—H8C | 109.5 |
N1—O2—Cu1 | 108.53 (14) | N4—C9—H9A | 109.5 |
C7—O8—Cu1 | 126.60 (14) | N4—C9—H9B | 109.5 |
O1—C1—C6 | 119.4 (2) | H9A—C9—H9B | 109.5 |
O1—C1—C2 | 127.7 (2) | N4—C9—H9C | 109.5 |
C6—C1—C2 | 112.79 (19) | H9A—C9—H9C | 109.5 |
C3—C2—C1 | 123.0 (2) | H9B—C9—H9C | 109.5 |
O8—Cu1—O1—C1 | 27.0 (2) | N1—C2—C3—C4 | 178.0 (2) |
O8i—Cu1—O1—C1 | −153.0 (2) | C2—C3—C4—C5 | −0.7 (3) |
O2—Cu1—O1—C1 | −51.52 (19) | C2—C3—C4—N2 | 178.4 (2) |
O3—N1—O2—Cu1 | 123.9 (2) | O5—N2—C4—C3 | 167.6 (2) |
C2—N1—O2—Cu1 | −57.3 (2) | O4—N2—C4—C3 | −14.0 (3) |
O1i—Cu1—O2—N1 | −115.98 (15) | O5—N2—C4—C5 | −13.3 (3) |
O1—Cu1—O2—N1 | 64.02 (15) | O4—N2—C4—C5 | 165.1 (2) |
O8—Cu1—O2—N1 | −28.83 (15) | C3—C4—C5—C6 | 1.1 (3) |
O8i—Cu1—O2—N1 | 151.17 (15) | N2—C4—C5—C6 | −177.9 (2) |
O1i—Cu1—O8—C7 | −8.81 (18) | C4—C5—C6—C1 | 1.4 (3) |
O1—Cu1—O8—C7 | 171.19 (18) | C4—C5—C6—N3 | 179.6 (2) |
O2—Cu1—O8—C7 | −117.49 (19) | O1—C1—C6—C5 | 174.3 (2) |
Cu1—O1—C1—C6 | −144.15 (17) | C2—C1—C6—C5 | −3.9 (3) |
Cu1—O1—C1—C2 | 33.8 (3) | O1—C1—C6—N3 | −3.9 (3) |
O1—C1—C2—C3 | −173.8 (2) | C2—C1—C6—N3 | 177.93 (19) |
C6—C1—C2—C3 | 4.3 (3) | O6—N3—C6—C5 | −56.1 (3) |
O1—C1—C2—N1 | 5.9 (3) | O7—N3—C6—C5 | 122.8 (2) |
C6—C1—C2—N1 | −176.03 (19) | O6—N3—C6—C1 | 122.2 (2) |
O3—N1—C2—C3 | 19.5 (3) | O7—N3—C6—C1 | −58.9 (3) |
O2—N1—C2—C3 | −159.3 (2) | Cu1—O8—C7—N4 | 173.74 (16) |
O3—N1—C2—C1 | −160.2 (2) | C8—N4—C7—O8 | −4.3 (3) |
O2—N1—C2—C1 | 21.0 (3) | C9—N4—C7—O8 | 178.2 (2) |
C1—C2—C3—C4 | −2.2 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C6H2N3O7)2(C3H7NO)2] |
Mr | 665.94 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.062 (1), 8.3361 (11), 9.8429 (14) |
α, β, γ (°) | 73.945 (1), 88.796 (2), 87.968 (2) |
V (Å3) | 635.25 (15) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.45 × 0.42 × 0.30 |
Data collection | |
Diffractometer | Siemens SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.673, 0.762 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3320, 2198, 1973 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.078, 1.08 |
No. of reflections | 2198 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.36 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
2,4,6-Trinitrophenoxides, 'picrates', play an important role in the modern coordination chemistry (Dong et al., 1998; Dong et al., 2007a). Picrate anion with extraordinary varieties in the binding of complexes, has great potential in building coordination networks (Liu et al., 2008). They can act as the bridging mono- (Arnaud-Neu et al., 2005; Wang et al., 2003), di- (Marchand et al., 2003; Song et al., 2007), tri- (Harrowfield et al., 1995; Dong et al., 1998; Dong et al., 2007a), tetra- (Venkatasubramanian et al., 1985) or penta- (Dong et al., 2007b; Harrowfield et al., 1998) dentate ligands via the phenolic oxygen, ortho-nitro oxygen and para-nitro oxygen atoms to build coordination networks as well as interlink the one-dimensional or two-dimensional molecules into frameworks via the hydrogen bonds (Muthamizhchelvan et al., 2005) or π-π stacking interactions (Talanova et al., 1999). Here, in continuation of our previous studies on synthesis and structural characterization of transition metal complexes with salen-type bisoxime chelating ligands, a single-crystal of unexpected complex, bis(N,N-dimethylformamide-κ O)bis(2,4,6-trinitrophenolato- κ2 O,O')copper(II), was obtained and structurally characterized by X-ray crystallography.
The crystal structure of the title complex consists of discrete C18H18CuN8O16 molecules (Fig. 1), in which all bond lengths are in normal ranges. The two benzene rings in each molecule of the title complex are parallel and the distance between them is 2.115 (2)Å. The central CuII atom is located on a crystallographic inversion center. The carbonyl oxygens O8, O8i and the phenoxy oxygens O1, O1i(symmetry code (i) -x=1, -y+1, -z+1) coordinate to the copper atom to form a distorted square planar structure with Cu1-O2 and Cu1-O8 bond lengths of 1.9226 (15) and 1.9401 (15)Å respectively. The two ortho-nitro oxygen atoms (O2 and O2i) occupy axial positions with Cu1-O2 = 2.659 (2)Å to give a distorted octahedral coordination geometry around the copper atom.