Download citation
Download citation
link to html
The mol­ecule of the title complex, [Cu(C6H2N3O7)2(C3H7NO)2], is disposed about a crystallographic centre of symmetry. The CuII cation is six-coordinated by two phenolate O atoms and two ortho-nitro O atoms of two picrate units and by two carbonyl O atoms from two coordinated dimethyl­formamide mol­ecules, forming a distorted octa­hedral geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808039846/hg2446sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536808039846/hg2446Isup2.hkl
Contains datablock I

CCDC reference: 717154

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](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

Comment top

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.

Related literature top

For background to 2,4,6-trinitrophenoxides, see: Arnaud-Neu, Harrowfield, Michel, Skelton & White (2005); Dong et al. (1998, 2007a,b); Harrowfield et al. (1995, 1998); Liu et al. (2008); Marchand et al. (2003); Muthamizhchelvan et al. (2005); Song et al. (2007); Talanova et al. (1999); Venkatasubramanian et al. (1985); Wang et al. (2003).

Experimental top

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%.

Refinement top

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).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecule structure of the title complex with atom numbering scheme [Symmetry codes: -x + 1,-y + 1,-z + 1]. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.
Bis(N,N-dimethylformamide-κO)bis(2,4,6-trinitrophenolato- κ2O1,O2)copper(II) top
Crystal data top
[Cu(C6H2N3O7)2(C3H7NO)2]Z = 1
Mr = 665.94F(000) = 339
Triclinic, P1Dx = 1.741 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.062 (1) ÅCell parameters from 2174 reflections
b = 8.3361 (11) Åθ = 2.5–27.5°
c = 9.8429 (14) ŵ = 0.96 mm1
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
Data collection top
Siemens SMART 1000 CCD area-detector
diffractometer
2198 independent reflections
Radiation source: fine-focus sealed tube1973 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.020
ϕ and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 99
Tmin = 0.673, Tmax = 0.762k = 96
3320 measured reflectionsl = 1111
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H-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 reflectionsΔρmax = 0.22 e Å3
199 parametersΔρmin = 0.36 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.141 (6)
Crystal data top
[Cu(C6H2N3O7)2(C3H7NO)2]γ = 87.968 (2)°
Mr = 665.94V = 635.25 (15) Å3
Triclinic, P1Z = 1
a = 8.062 (1) ÅMo Kα radiation
b = 8.3361 (11) ŵ = 0.96 mm1
c = 9.8429 (14) ÅT = 298 K
α = 73.945 (1)°0.45 × 0.42 × 0.30 mm
β = 88.796 (2)°
Data collection top
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 = 0.762Rint = 0.020
3320 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.078H-atom parameters constrained
S = 1.08Δρmax = 0.22 e Å3
2198 reflectionsΔρmin = 0.36 e Å3
199 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.50000.50000.02554 (17)
N10.5597 (3)0.5206 (2)0.1667 (2)0.0339 (5)
N20.8515 (3)1.0013 (3)0.1186 (2)0.0407 (5)
N30.5610 (3)1.0497 (2)0.3079 (2)0.0341 (5)
N40.9697 (2)0.3374 (2)0.4240 (2)0.0289 (4)
O10.4863 (2)0.71913 (19)0.36927 (16)0.0332 (4)
O20.4407 (2)0.4683 (2)0.2441 (2)0.0497 (5)
O30.6381 (3)0.4363 (2)0.1017 (2)0.0496 (5)
O40.9214 (3)0.9088 (3)0.1814 (2)0.0587 (6)
O50.8672 (3)1.1525 (3)0.1527 (2)0.0639 (6)
O60.6713 (3)1.1133 (3)0.3553 (2)0.0552 (5)
O70.4137 (3)1.0653 (2)0.3315 (2)0.0556 (5)
O80.72371 (18)0.47226 (19)0.43167 (16)0.0306 (4)
C10.5606 (3)0.7778 (3)0.2512 (2)0.0255 (5)
C20.6088 (3)0.6916 (3)0.1486 (2)0.0265 (5)
C30.7030 (3)0.7633 (3)0.0293 (2)0.0301 (5)
H30.73500.70180.03310.036*
C40.7490 (3)0.9268 (3)0.0041 (2)0.0298 (5)
C50.7014 (3)1.0223 (3)0.0951 (2)0.0287 (5)
H50.73121.13310.07670.034*
C60.6098 (3)0.9480 (3)0.2118 (2)0.0259 (5)
C70.8263 (3)0.3548 (3)0.4840 (2)0.0278 (5)
H70.79890.27740.56870.033*
C81.0134 (3)0.4484 (4)0.2868 (3)0.0434 (6)
H8A0.97570.40340.21340.065*
H8B1.13170.45870.27950.065*
H8C0.96150.55640.27680.065*
C91.0878 (3)0.2028 (3)0.4895 (3)0.0402 (6)
H9A1.04760.14410.58170.060*
H9B1.19330.24890.49790.060*
H9C1.10010.12700.43200.060*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0244 (2)0.0238 (2)0.0255 (2)0.00033 (15)0.00563 (15)0.00252 (15)
N10.0396 (12)0.0273 (11)0.0347 (11)0.0003 (9)0.0077 (9)0.0081 (9)
N20.0390 (12)0.0539 (15)0.0278 (11)0.0100 (11)0.0067 (9)0.0084 (10)
N30.0480 (13)0.0224 (10)0.0299 (10)0.0035 (9)0.0070 (9)0.0051 (8)
N40.0255 (10)0.0290 (10)0.0325 (10)0.0012 (8)0.0019 (8)0.0097 (8)
O10.0358 (9)0.0260 (8)0.0316 (9)0.0026 (7)0.0142 (7)0.0011 (7)
O20.0463 (11)0.0393 (10)0.0610 (12)0.0169 (9)0.0065 (9)0.0085 (9)
O30.0708 (14)0.0310 (10)0.0510 (12)0.0033 (9)0.0010 (10)0.0187 (9)
O40.0601 (13)0.0758 (15)0.0440 (12)0.0094 (11)0.0237 (10)0.0236 (11)
O50.0878 (17)0.0495 (13)0.0479 (12)0.0253 (12)0.0274 (11)0.0019 (10)
O60.0705 (14)0.0512 (12)0.0538 (12)0.0025 (11)0.0067 (10)0.0306 (10)
O70.0498 (13)0.0475 (12)0.0714 (14)0.0092 (9)0.0224 (10)0.0225 (10)
O80.0249 (8)0.0303 (9)0.0318 (9)0.0019 (7)0.0065 (6)0.0015 (7)
C10.0218 (11)0.0253 (11)0.0256 (11)0.0035 (9)0.0002 (9)0.0013 (9)
C20.0273 (12)0.0235 (11)0.0274 (11)0.0003 (9)0.0013 (9)0.0047 (9)
C30.0316 (12)0.0328 (13)0.0262 (12)0.0031 (10)0.0000 (9)0.0088 (9)
C40.0286 (12)0.0348 (13)0.0226 (11)0.0015 (10)0.0024 (9)0.0026 (9)
C50.0300 (12)0.0239 (11)0.0292 (12)0.0041 (9)0.0008 (9)0.0020 (9)
C60.0268 (11)0.0247 (11)0.0259 (11)0.0031 (9)0.0010 (9)0.0069 (9)
C70.0284 (12)0.0273 (12)0.0267 (11)0.0027 (9)0.0025 (9)0.0060 (9)
C80.0360 (14)0.0516 (16)0.0381 (14)0.0010 (12)0.0132 (11)0.0059 (12)
C90.0323 (13)0.0369 (14)0.0517 (16)0.0065 (11)0.0001 (11)0.0135 (12)
Geometric parameters (Å, º) top
Cu1—O1i1.9226 (15)O1—C11.275 (3)
Cu1—O11.9226 (15)O8—C71.261 (3)
Cu1—O81.9401 (15)C1—C61.431 (3)
Cu1—O8i1.9401 (15)C1—C21.432 (3)
Cu1—O22.659 (2)C2—C31.385 (3)
N1—O31.226 (3)C3—C41.379 (3)
N1—O21.228 (3)C3—H30.9300
N1—C21.455 (3)C4—C51.393 (3)
N2—O51.222 (3)C5—C61.361 (3)
N2—O41.230 (3)C5—H50.9300
N2—C41.452 (3)C7—H70.9300
N3—O61.215 (3)C8—H8A0.9600
N3—O71.215 (3)C8—H8B0.9600
N3—C61.474 (3)C8—H8C0.9600
N4—C71.310 (3)C9—H9A0.9600
N4—C81.455 (3)C9—H9B0.9600
N4—C91.459 (3)C9—H9C0.9600
O1i—Cu1—O1180.0C3—C2—N1116.6 (2)
O1i—Cu1—O890.87 (6)C1—C2—N1120.38 (19)
O1—Cu1—O889.13 (6)C4—C3—C2119.3 (2)
O1i—Cu1—O8i89.13 (6)C4—C3—H3120.4
O1—Cu1—O8i90.87 (6)C2—C3—H3120.4
O8—Cu1—O8i180.000 (1)C3—C4—C5121.5 (2)
O1i—Cu1—O2108.49 (7)C3—C4—N2119.6 (2)
O1—Cu1—O271.51 (7)C5—C4—N2118.9 (2)
O8—Cu1—O278.81 (6)C6—C5—C4117.8 (2)
O8i—Cu1—O2101.19 (6)C6—C5—H5121.1
O3—N1—O2123.1 (2)C4—C5—H5121.1
O3—N1—C2118.1 (2)C5—C6—C1125.5 (2)
O2—N1—C2118.8 (2)C5—C6—N3117.3 (2)
O5—N2—O4123.1 (2)C1—C6—N3117.15 (18)
O5—N2—C4118.4 (2)O8—C7—N4122.7 (2)
O4—N2—C4118.5 (2)O8—C7—H7118.7
O6—N3—O7125.3 (2)N4—C7—H7118.7
O6—N3—C6117.4 (2)N4—C8—H8A109.5
O7—N3—C6117.3 (2)N4—C8—H8B109.5
C7—N4—C8120.7 (2)H8A—C8—H8B109.5
C7—N4—C9121.3 (2)N4—C8—H8C109.5
C8—N4—C9117.95 (19)H8A—C8—H8C109.5
C1—O1—Cu1130.29 (14)H8B—C8—H8C109.5
N1—O2—Cu1108.53 (14)N4—C9—H9A109.5
C7—O8—Cu1126.60 (14)N4—C9—H9B109.5
O1—C1—C6119.4 (2)H9A—C9—H9B109.5
O1—C1—C2127.7 (2)N4—C9—H9C109.5
C6—C1—C2112.79 (19)H9A—C9—H9C109.5
C3—C2—C1123.0 (2)H9B—C9—H9C109.5
O8—Cu1—O1—C127.0 (2)N1—C2—C3—C4178.0 (2)
O8i—Cu1—O1—C1153.0 (2)C2—C3—C4—C50.7 (3)
O2—Cu1—O1—C151.52 (19)C2—C3—C4—N2178.4 (2)
O3—N1—O2—Cu1123.9 (2)O5—N2—C4—C3167.6 (2)
C2—N1—O2—Cu157.3 (2)O4—N2—C4—C314.0 (3)
O1i—Cu1—O2—N1115.98 (15)O5—N2—C4—C513.3 (3)
O1—Cu1—O2—N164.02 (15)O4—N2—C4—C5165.1 (2)
O8—Cu1—O2—N128.83 (15)C3—C4—C5—C61.1 (3)
O8i—Cu1—O2—N1151.17 (15)N2—C4—C5—C6177.9 (2)
O1i—Cu1—O8—C78.81 (18)C4—C5—C6—C11.4 (3)
O1—Cu1—O8—C7171.19 (18)C4—C5—C6—N3179.6 (2)
O2—Cu1—O8—C7117.49 (19)O1—C1—C6—C5174.3 (2)
Cu1—O1—C1—C6144.15 (17)C2—C1—C6—C53.9 (3)
Cu1—O1—C1—C233.8 (3)O1—C1—C6—N33.9 (3)
O1—C1—C2—C3173.8 (2)C2—C1—C6—N3177.93 (19)
C6—C1—C2—C34.3 (3)O6—N3—C6—C556.1 (3)
O1—C1—C2—N15.9 (3)O7—N3—C6—C5122.8 (2)
C6—C1—C2—N1176.03 (19)O6—N3—C6—C1122.2 (2)
O3—N1—C2—C319.5 (3)O7—N3—C6—C158.9 (3)
O2—N1—C2—C3159.3 (2)Cu1—O8—C7—N4173.74 (16)
O3—N1—C2—C1160.2 (2)C8—N4—C7—O84.3 (3)
O2—N1—C2—C121.0 (3)C9—N4—C7—O8178.2 (2)
C1—C2—C3—C42.2 (3)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Cu(C6H2N3O7)2(C3H7NO)2]
Mr665.94
Crystal system, space groupTriclinic, 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)
V3)635.25 (15)
Z1
Radiation typeMo Kα
µ (mm1)0.96
Crystal size (mm)0.45 × 0.42 × 0.30
Data collection
DiffractometerSiemens SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.673, 0.762
No. of measured, independent and
observed [I > 2σ(I)] reflections
3320, 2198, 1973
Rint0.020
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.078, 1.08
No. of reflections2198
No. of parameters199
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.36

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds