Literature DB >> 23468758

(Nitrato-κ(2) O,O')bis-(1,10-phenanthroline-κ(2) N,N')copper(II) tricyano-methanide.

Katarína Lacková1, Ivan Potočňák.   

Abstract

The title compound, [class="Chemical">Cu(<class="Chemical">span class="Chemical">NO3)(C12H8N2)2][C(CN)3], is formed of discrete [Cu(NO3)(phen)2](+) complex cations (phen is 1,10-phenanthroline) and C(CN)3(-) counter-anions. The Cu(II) atom has an asymmetric tetragonal-bipyramidal (4 + 1+1) stereochemistry with a pseudo-C2 symmetry axis bis-ecting the nitrate ligand and passing through the Cu(II) atom between the two phen ligands. The four N atoms of the phen ligands coordinate to the Cu(II) atom with Cu-N distances in the range 1.974 (2)-2.126 (2) Å, while the two O atoms coordinate at substanti-ally different distances [2.154 (2) and 2.586 (2) Å]. The structure is stabilized by C-H⋯O hydrogen bonds and weak π-π inter-actions between nearly parallel benzene and pyridine rings of two adjacent phen mol-ecules, with centroid-centroid distances of 3.684 (2) and 3.6111 (2) Å, and between π-electrons of the tricyano-methanide anion and the pyridine or benzene rings [N⋯(ring centroid) distances = 3.553 (3)-3.875 (3) Å].

Entities:  

Year:  2012        PMID： 23468758      PMCID： PMC3588793          DOI： 10.1107/S1600536812047757

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For five-coordinate class="Chemical">CuII in [<class="Chemical">span class="Chemical">Cu(L)2 X]Y complexes [L = 1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy); X = N(CN)2 − or ONC(CN)2 −, Y = 1− anion], see: Potočňák et al. (2005 ▶, 2008 ▶). For complexes containing [Cu(NO3)(phen)2]+ cations, see: van Meerssche et al. (1981 ▶); Marsh (1997 ▶); Chen et al. (2005 ▶); Ovens et al. (2010 ▶). For complexes containing [Cu(bpy)2NO3]+ cations, see: Prasad et al. (1999 ▶); Marjani et al. (2005 ▶). For π–π inter­actions, see: Janiak (2000 ▶). For a description of the properties of the tricyano­methanide (tcm or C(CN)3 −) anion, see: Golub et al. (1986 ▶). For [Cu(L)2 Y]tcm (Y = Cl− or Br−), see: Lacková (2012 ▶).

Experimental

Crystal data

[class="Chemical">Cu(<class="Chemical">span class="Chemical">NO3)(C12H8N2)2](C4N3) M = 576.03 Monoclinic, a = 13.3011 (4) Å b = 10.1155 (3) Å c = 19.5597 (6) Å β = 103.997 (3)° V = 2553.56 (13) Å3 Z = 4 Mo Kα radiation μ = 0.90 mm−1 T = 183 K 0.38 × 0.31 × 0.26 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer Absorption correction: analytical [CrysAlis class="Disease">RED (Oxford Diffraction, 2007 ▶), based on expressions derived from Clark & Reid (1995 ▶)] T min = 0.777, T max = 0.825 10675 measuclass="Disease">red reflections 5283 independent reflections 4034 reflections with I > 2σ(I) R int = 0.024

Refinement

R[F 2 > 2σ(F 2)] = 0.040 wR(F 2) = 0.097 S = 1.01 5283 reflections 361 parameters H-atom parameters constrained Δρmax = 0.40 e Å−3 Δρmin = −0.43 e Å−3 Data collection: CrysAlis class="Disease">CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis <class="Chemical">span class="Disease">RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: SHELXL97. Click here for additional data file. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812047757/gk2531sup1.cif Click here for additional data file. Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047757/gk2531Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
[Cu(NO3)(C12H8N2)2](C4N3)F(000) = 1172
Mr = 576.03Dx = 1.498 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 4424 reflections
a = 13.3011 (4) Åθ = 2.9–29.4°
b = 10.1155 (3) ŵ = 0.90 mm−1
c = 19.5597 (6) ÅT = 183 K
β = 103.997 (3)°Prism, green
V = 2553.56 (13) Å30.38 × 0.31 × 0.26 mm
Z = 4
Oxford Diffraction Xcalibur Sapphire2 diffractometer5283 independent reflections
Radiation source: fine-focus sealed tube4034 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
Detector resolution: 8.3438 pixels mm-1θmax = 26.5°, θmin = 2.9°
ω scansh = −16→9
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007), based on expressions derived from Clark & Reid (1995)]k = −11→12
Tmin = 0.777, Tmax = 0.825l = −22→24
10675 measured reflections
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0384P)2 + 1.6904P] where P = (Fo2 + 2Fc2)/3
5283 reflections(Δ/σ)max = 0.001
361 parametersΔρmax = 0.40 e Å−3
0 restraintsΔρmin = −0.43 e Å−3
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.
xyzUiso*/Ueq
Cu10.23397 (2)0.23042 (3)0.492800 (16)0.02860 (11)
N100.20297 (15)0.0829 (2)0.42426 (10)0.0279 (5)
N200.37950 (15)0.2104 (2)0.47543 (10)0.0254 (4)
N300.27128 (15)0.3747 (2)0.56231 (10)0.0269 (5)
N400.12822 (15)0.3762 (2)0.43990 (10)0.0273 (5)
O10.12472 (15)0.1517 (2)0.54749 (10)0.0456 (5)
O20.27099 (14)0.0638 (2)0.59615 (12)0.0480 (5)
O30.13425 (17)0.0080 (2)0.62999 (11)0.0535 (6)
N40.17688 (15)0.07347 (19)0.59182 (11)0.0251 (5)
C110.28763 (18)0.0376 (2)0.40462 (12)0.0247 (5)
C120.1122 (2)0.0234 (3)0.39845 (13)0.0326 (6)
H120.05380.05420.41170.039*
C130.1022 (2)−0.0837 (3)0.35220 (14)0.0358 (6)
H130.0376−0.12160.33400.043*
C140.1878 (2)−0.1322 (3)0.33397 (13)0.0341 (6)
H140.1820−0.20530.30450.041*
C150.2850 (2)−0.0715 (2)0.35975 (12)0.0280 (6)
C160.3793 (2)−0.1106 (3)0.34200 (13)0.0316 (6)
H160.3789−0.18410.31340.038*
C210.38273 (18)0.1067 (2)0.43158 (12)0.0236 (5)
C220.46619 (19)0.2782 (3)0.49966 (13)0.0302 (6)
H220.46480.34950.52940.036*
C230.5594 (2)0.2471 (3)0.48255 (13)0.0320 (6)
H230.61860.29710.50070.038*
C240.5630 (2)0.1427 (3)0.43896 (13)0.0319 (6)
H240.62480.12090.42730.038*
C250.47279 (19)0.0682 (2)0.41169 (12)0.0251 (5)
C260.4683 (2)−0.0431 (3)0.36593 (13)0.0311 (6)
H260.5277−0.06940.35250.037*
C310.21763 (18)0.4890 (2)0.54394 (12)0.0240 (5)
C320.3421 (2)0.3704 (3)0.62327 (13)0.0327 (6)
H320.37800.29190.63650.039*
C330.3646 (2)0.4792 (3)0.66803 (14)0.0350 (6)
H330.41530.47350.71010.042*
C340.3117 (2)0.5938 (3)0.64957 (13)0.0327 (6)
H340.32650.66730.67890.039*
C350.23491 (19)0.6016 (2)0.58662 (13)0.0267 (5)
C360.1738 (2)0.7169 (3)0.56400 (14)0.0322 (6)
H360.18470.79240.59200.039*
C410.14034 (18)0.4896 (2)0.47829 (13)0.0252 (5)
C420.0572 (2)0.3760 (3)0.37912 (13)0.0348 (6)
H420.04840.29980.35170.042*
C43−0.0048 (2)0.4860 (3)0.35470 (14)0.0378 (7)
H43−0.05380.48210.31180.045*
C440.0065 (2)0.5983 (3)0.39360 (14)0.0351 (6)
H44−0.03520.67130.37780.042*
C450.08147 (18)0.6040 (3)0.45786 (13)0.0282 (6)
C460.1005 (2)0.7181 (3)0.50269 (15)0.0340 (6)
H460.06150.79430.48930.041*
C10.3205 (3)0.4583 (3)0.34844 (17)0.0488 (8)
C20.4051 (2)0.3074 (3)0.28228 (14)0.0384 (7)
C30.2207 (2)0.2859 (3)0.27295 (14)0.0408 (7)
C40.3157 (2)0.3509 (3)0.30173 (14)0.0381 (7)
N10.3254 (3)0.5442 (3)0.38713 (17)0.0772 (10)
N20.4774 (2)0.2697 (3)0.26576 (13)0.0481 (7)
N30.1445 (2)0.2311 (3)0.25020 (14)0.0594 (8)
U11U22U33U12U13U23
Cu10.02404 (17)0.02999 (18)0.02883 (17)0.00306 (14)0.00066 (12)−0.00604 (14)
N100.0248 (11)0.0302 (12)0.0268 (11)0.0005 (9)0.0026 (9)−0.0015 (9)
N200.0246 (10)0.0265 (11)0.0233 (10)−0.0003 (9)0.0026 (9)0.0008 (9)
N300.0253 (11)0.0267 (11)0.0268 (11)0.0050 (9)0.0027 (9)−0.0008 (9)
N400.0210 (10)0.0315 (12)0.0270 (11)0.0020 (9)0.0007 (9)0.0003 (9)
O10.0396 (11)0.0472 (12)0.0433 (11)0.0154 (10)−0.0029 (9)−0.0071 (10)
O20.0230 (10)0.0497 (13)0.0711 (14)0.0028 (9)0.0111 (10)−0.0105 (11)
O30.0639 (15)0.0471 (13)0.0574 (14)−0.0118 (11)0.0298 (12)−0.0044 (11)
N40.0220 (11)0.0207 (11)0.0337 (11)−0.0005 (9)0.0092 (9)−0.0091 (9)
C110.0266 (13)0.0253 (13)0.0203 (12)0.0015 (11)0.0019 (10)0.0032 (10)
C120.0279 (13)0.0373 (15)0.0305 (14)−0.0031 (12)0.0032 (11)−0.0003 (12)
C130.0337 (15)0.0374 (16)0.0332 (14)−0.0103 (13)0.0018 (12)−0.0005 (12)
C140.0465 (17)0.0266 (14)0.0267 (13)−0.0054 (12)0.0038 (12)−0.0056 (11)
C150.0355 (14)0.0257 (13)0.0210 (12)0.0002 (11)0.0030 (11)0.0025 (10)
C160.0454 (16)0.0263 (13)0.0233 (12)0.0063 (12)0.0090 (12)−0.0021 (11)
C210.0279 (13)0.0232 (12)0.0181 (11)0.0019 (10)0.0024 (10)0.0055 (10)
C220.0309 (14)0.0302 (14)0.0281 (13)−0.0042 (12)0.0044 (11)−0.0029 (11)
C230.0262 (13)0.0402 (16)0.0284 (13)−0.0071 (12)0.0040 (11)0.0023 (12)
C240.0263 (13)0.0414 (16)0.0286 (13)0.0031 (12)0.0080 (11)0.0068 (12)
C250.0295 (13)0.0248 (13)0.0206 (11)0.0047 (11)0.0051 (10)0.0056 (10)
C260.0343 (14)0.0351 (15)0.0258 (13)0.0088 (12)0.0108 (11)0.0052 (11)
C310.0200 (12)0.0276 (13)0.0256 (12)0.0012 (10)0.0077 (10)0.0016 (10)
C320.0324 (14)0.0326 (15)0.0285 (13)0.0049 (12)−0.0017 (11)0.0014 (11)
C330.0356 (15)0.0374 (16)0.0274 (13)−0.0011 (12)−0.0014 (12)−0.0038 (12)
C340.0370 (15)0.0298 (14)0.0301 (13)−0.0030 (12)0.0057 (12)−0.0075 (11)
C350.0246 (13)0.0276 (13)0.0298 (13)−0.0013 (11)0.0102 (11)0.0004 (11)
C360.0343 (14)0.0248 (13)0.0397 (15)0.0014 (11)0.0131 (12)−0.0024 (12)
C410.0199 (12)0.0292 (13)0.0277 (13)−0.0010 (10)0.0080 (10)0.0030 (11)
C420.0300 (14)0.0417 (16)0.0296 (14)−0.0020 (12)0.0013 (11)−0.0009 (12)
C430.0268 (14)0.0500 (18)0.0313 (14)0.0018 (13)−0.0032 (12)0.0086 (13)
C440.0264 (14)0.0384 (16)0.0389 (15)0.0052 (12)0.0046 (12)0.0114 (13)
C450.0213 (12)0.0323 (14)0.0327 (13)0.0039 (11)0.0097 (11)0.0064 (11)
C460.0306 (14)0.0277 (14)0.0458 (16)0.0088 (12)0.0132 (13)0.0065 (13)
C10.055 (2)0.0455 (19)0.0450 (17)−0.0154 (16)0.0094 (15)−0.0067 (16)
C20.0484 (18)0.0380 (17)0.0226 (13)−0.0190 (15)−0.0033 (13)0.0032 (12)
C30.0483 (18)0.0447 (17)0.0283 (14)−0.0067 (15)0.0072 (13)−0.0054 (13)
C40.0443 (17)0.0364 (16)0.0299 (14)−0.0098 (13)0.0015 (13)−0.0003 (12)
N10.086 (2)0.062 (2)0.085 (2)−0.0259 (18)0.025 (2)−0.0363 (19)
N20.0455 (16)0.0587 (17)0.0381 (14)−0.0186 (14)0.0064 (12)−0.0048 (13)
N30.0510 (17)0.075 (2)0.0492 (16)−0.0219 (15)0.0059 (14)−0.0160 (15)
Cu1—N101.981 (2)C23—H230.9300
Cu1—N202.055 (2)C24—C251.409 (3)
Cu1—N301.974 (2)C24—H240.9300
Cu1—N402.126 (2)C25—C261.431 (3)
Cu1—O12.154 (2)C26—H260.9300
Cu1—O22.586 (2)C31—C351.398 (3)
O1—N41.253 (3)C31—C411.438 (3)
O2—N41.238 (3)C32—C331.393 (4)
O3—N41.234 (3)C32—H320.9300
N10—C111.354 (3)C33—C341.359 (4)
N10—C121.334 (3)C33—H330.9300
N20—C211.362 (3)C34—C351.399 (3)
N20—C221.326 (3)C34—H340.9300
N30—C311.361 (3)C35—C361.429 (3)
N30—C321.330 (3)C36—C461.351 (4)
N40—C411.359 (3)C36—H360.9300
N40—C421.327 (3)C41—C451.401 (3)
C11—C151.405 (3)C42—C431.400 (4)
C11—C211.430 (3)C42—H420.9300
C12—C131.397 (4)C43—C441.355 (4)
C12—H120.9300C43—H430.9300
C13—C141.364 (4)C44—C451.404 (3)
C13—H130.9300C44—H440.9300
C14—C151.410 (4)C45—C461.434 (4)
C14—H140.9300C46—H460.9300
C15—C161.435 (4)C1—N11.144 (4)
C16—C261.349 (4)C1—C41.411 (4)
C16—H160.9300C2—N21.151 (4)
C21—C251.401 (3)C2—C41.404 (4)
C22—C231.396 (4)C3—N31.147 (4)
C22—H220.9300C3—C41.415 (4)
C23—C241.366 (4)
N10—Cu1—N30177.46 (8)C23—C22—H22118.5
N10—Cu1—N40100.85 (8)C24—C23—C22119.4 (2)
N20—Cu1—N1082.20 (8)C24—C23—H23120.3
N20—Cu1—N3095.54 (8)C22—C23—H23120.3
N20—Cu1—N40121.78 (8)C23—C24—C25119.7 (2)
N30—Cu1—N4081.31 (8)C23—C24—H24120.2
N10—Cu1—O190.15 (8)C25—C24—H24120.2
N20—Cu1—O1145.22 (8)C21—C25—C24117.0 (2)
N30—Cu1—O191.07 (8)C21—C25—C26118.9 (2)
N40—Cu1—O192.97 (8)C24—C25—C26124.1 (2)
N10—Cu1—O290.41 (8)C16—C26—C25121.1 (2)
N20—Cu1—O293.23 (7)C16—C26—H26119.5
N30—Cu1—O288.55 (7)C25—C26—H26119.5
N40—Cu1—O2144.19 (7)N30—C31—C35122.3 (2)
O1—Cu1—O252.76 (6)N30—C31—C41117.1 (2)
C12—N10—C11118.6 (2)C35—C31—C41120.6 (2)
C12—N10—Cu1128.10 (18)N30—C32—C33122.4 (2)
C11—N10—Cu1113.29 (15)N30—C32—H32118.8
C22—N20—C21117.7 (2)C33—C32—H32118.8
C22—N20—Cu1131.50 (18)C34—C33—C32119.2 (2)
C21—N20—Cu1110.75 (16)C34—C33—H33120.4
C32—N30—C31118.5 (2)C32—C33—H33120.4
C32—N30—Cu1126.82 (17)C33—C34—C35120.2 (2)
C31—N30—Cu1114.70 (15)C33—C34—H34119.9
C42—N40—C41117.4 (2)C35—C34—H34119.9
C42—N40—Cu1132.69 (18)C31—C35—C34117.3 (2)
C41—N40—Cu1109.91 (15)C31—C35—C36118.8 (2)
N4—O1—Cu1104.48 (15)C34—C35—C36123.9 (2)
N4—O2—Cu184.07 (15)C46—C36—C35121.1 (2)
O3—N4—O2121.4 (2)C46—C36—H36119.5
O3—N4—O1120.0 (2)C35—C36—H36119.5
O2—N4—O1118.6 (2)N40—C41—C45123.8 (2)
N10—C11—C15123.1 (2)N40—C41—C31117.0 (2)
N10—C11—C21116.9 (2)C45—C41—C31119.2 (2)
C15—C11—C21120.0 (2)N40—C42—C43122.5 (3)
N10—C12—C13122.1 (3)N40—C42—H42118.8
N10—C12—H12119.0C43—C42—H42118.8
C13—C12—H12119.0C44—C43—C42119.9 (2)
C14—C13—C12119.6 (2)C44—C43—H43120.0
C14—C13—H13120.2C42—C43—H43120.0
C12—C13—H13120.2C43—C44—C45119.7 (2)
C13—C14—C15120.1 (2)C43—C44—H44120.1
C13—C14—H14120.0C45—C44—H44120.1
C15—C14—H14120.0C41—C45—C44116.6 (2)
C11—C15—C14116.6 (2)C41—C45—C46119.1 (2)
C11—C15—C16118.5 (2)C44—C45—C46124.2 (2)
C14—C15—C16124.9 (2)C36—C46—C45121.2 (2)
C26—C16—C15121.4 (2)C36—C46—H46119.4
C26—C16—H16119.3C45—C46—H46119.4
C15—C16—H16119.3N1—C1—C4178.9 (4)
N20—C21—C25123.2 (2)N2—C2—C4178.7 (3)
N20—C21—C11116.7 (2)N3—C3—C4178.8 (4)
C25—C21—C11120.1 (2)C1—C4—C2120.6 (3)
N20—C22—C23123.0 (2)C2—C4—C3118.7 (3)
N20—C22—H22118.5C3—C4—C1120.8 (3)
D—H···AD—HH···AD···AD—H···A
C12—H12···O3i0.932.523.206 (3)131
C24—H24···O2ii0.932.443.231 (3)144
C36—H36···O3iii0.932.453.307 (3)153
C46—H46···O1iv0.932.473.201 (3)136
Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A D—HH⋯A D⋯A D—H⋯A
C12—H12⋯O3i 0.932.523.206 (3)131
C24—H24⋯O2ii 0.932.443.231 (3)144
C36—H36⋯O3iii 0.932.453.307 (3)153
C46—H46⋯O1iv 0.932.473.201 (3)136

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .

  2 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  The use of polarizable [AuX2(CN)2]- (X = Br, I) building blocks toward the formation of birefringent coordination polymers.

Authors:  Jeffrey S Ovens; Andrew R Geisheimer; Alexei A Bokov; Zuo-Guang Ye; Daniel B Leznoff
Journal:  Inorg Chem       Date:  2010-10-18       Impact factor: 5.165
  2 in total

北京卡尤迪生物科技股份有限公司 © 2022-2023.