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The crystal structure of a second form of green [Cu(NO2)2(phen)], where phen is 1,10-phenanthroline (C12H8N2), containing six-coordinate copper(II) with a distorted tetragonal [CuIIN2O4] core is reported. The first form had a crystal symmetry of C2/c [Breneman et al. (1999). Acta Cryst. C55, IUC9900158], while the form reported here is Pbcn. The nitrito ligands are bonded to the central copper through both O atoms, with short Cu-O bond distances of 1.987 (3) Å and longer Cu-O bond distances of 2.410 (4) Å. Both nitrito groups are significantly displaced from the plane defined by the 1,10-phenanthroline and the square-planar arrangement of the ligands around the CuII atom.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801007863/om6023sup1.cif
Contains datablocks [Cu(NO~2~)~2~(phen)]II, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801007863/om6023Isup2.hkl
Contains datablock I

CCDC reference: 170737

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.037
  • wR factor = 0.109
  • Data-to-parameter ratio = 9.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5498
Yellow Alert Alert Level C:
REFNR_01 Alert C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.5498 Proportion of unique data used 1.0000 Ratio reflections to parameters 9.1146
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check

Comment top

The title molecule, (I), in this second form (Fig. 1) is very similar to that in the first form except this second form possesses twofold crystallographic symmetry. Each nitrito group is bonded to the copper(II) by an oxygen, with a short and long distance of 1.999 (3) and 2.056 (2) Å, respectively, in the first form and 1.987 (3) Å for both bonds in the second form. Each remaining O atom of the nitrito groups appears to interact with the copper at longer distances of 2.470 (3) and 2.396 (3) Å in the first form, and 2.410 (4) Å for both bonds in the second form. These two O atoms finish what could be described as a distorted tetragonal coordination around the center copper(II) in both forms. These observed Cu—O distances of 2.470 (3) and 2.396 (3) Å in the first form, and 2.410 (4) Å in the second form are all shorter than the normal non-bonded distance of ca 2.9 Å for CuII. The Cu—N(phen) distances of 1.995 (3) and 2.021 (2) Å in the first form are close to the Cu—N1 bond distance of 1.997 (2) Å in the second form. The planes of the nitrito groups are significantly displaced from the planar arrangement of the Cu and the two N atoms of the 1,10-phenanthroline including the planar ring structure. The two forms differ in their crystal packing with regard to how the phenanthroline rings on adjacent molecules overlap.

Experimental top

[Cu(NO2)2(phen)] was prepared by the slow addition of a 25 ml solution of 1,10-phenanthroline monohydrate (1.01 g, 5.0 mmol) in ethanol to a 20 ml solution of Cu(NO3)2·3H2O (1.20 g, 5.0 mmol) dissolved in water. To the resulting pale green solution, 30 ml of an aqueous solution of NaNO2 (0.69 g, 10.0 mmol) was slowly added with continuous stirring. The product was a green solution from which a single crop of dark-green crystals was produced by evaporation of the solvent. Both prisms and plates were present with prisms being the first form (C2/c symmetry) and the plates being the second form (Pbcn symmetry).

Refinement top

H atoms were set to ride on respective C atoms. C—H bond lengths were constrained to 0.96 Å and H-atom Uiso values to 0.08 Å2

Computing details top

Data collection: CAD-4 Software (Schagen et al., 1989); cell refinement: CAD-4 Software; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXTL/PC (Siemens, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid (50% probablility) plot of [Cu(NO2)2(phen)] showing the atom-numbering scheme. H atoms have been omitted.
(I) top
Crystal data top
[Cu(NO2)2(C12H8N2)]Dx = 1.763 Mg m3
Mr = 335.76Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcnCell parameters from 25 reflections
a = 9.773 (1) Åθ = 20.2–22.9°
b = 17.404 (2) ŵ = 1.75 mm1
c = 7.440 (1) ÅT = 295 K
V = 1265.4 (3) Å3Plate, green
Z = 40.50 × 0.50 × 0.08 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
Rint = 0.019
θ/2θ scansθmax = 23.0°
Absorption correction: ψ scan
(MolEN; Fair, 1990)
h = 010
Tmin = 0.445, Tmax = 0.875k = 019
1054 measured reflectionsl = 08
875 independent reflections1 standard reflections every 167 min
813 reflections with I > 2σ(I) intensity decay: 0.3%
Refinement top
Refinement on F2H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037 w = 1/[σ2(Fo2) + (0.0679P)2 + 0.6552]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.109(Δ/σ)max = 0.001
S = 1.15Δρmax = 0.31 e Å3
875 reflectionsΔρmin = 0.29 e Å3
96 parameters
Crystal data top
[Cu(NO2)2(C12H8N2)]V = 1265.4 (3) Å3
Mr = 335.76Z = 4
Orthorhombic, PbcnMo Kα radiation
a = 9.773 (1) ŵ = 1.75 mm1
b = 17.404 (2) ÅT = 295 K
c = 7.440 (1) Å0.50 × 0.50 × 0.08 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
813 reflections with I > 2σ(I)
Absorption correction: ψ scan
(MolEN; Fair, 1990)
Rint = 0.019
Tmin = 0.445, Tmax = 0.875θmax = 23.0°
1054 measured reflections1 standard reflections every 167 min
875 independent reflections intensity decay: 0.3%
Refinement top
R[F2 > 2σ(F2)] = 0.03796 parameters
wR(F2) = 0.109H-atom parameters constrained
S = 1.15Δρmax = 0.31 e Å3
875 reflectionsΔρmin = 0.29 e Å3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu0.50000.71045 (3)0.25000.0510 (3)
O10.3632 (3)0.79139 (13)0.1925 (5)0.0793 (8)
O20.4682 (4)0.7684 (2)0.0416 (5)0.1065 (10)
N10.3700 (2)0.62416 (14)0.2029 (3)0.0460 (6)
N20.3842 (4)0.80593 (18)0.0326 (6)0.0833 (10)
C10.2404 (3)0.62665 (19)0.1528 (5)0.0567 (8)
H1A0.20030.67630.13340.080*
C20.1643 (3)0.5600 (2)0.1228 (5)0.0643 (9)
H2A0.06990.56340.08730.080*
C30.2229 (3)0.4903 (2)0.1439 (4)0.0608 (9)
H3A0.17270.44390.12160.080*
C40.3608 (3)0.48441 (16)0.1971 (4)0.0476 (7)
C50.4332 (4)0.41433 (19)0.2244 (4)0.0594 (9)
H5A0.37740.36990.20280.080*
C60.4295 (3)0.55400 (16)0.2238 (3)0.0416 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0507 (5)0.0292 (4)0.0731 (5)0.0000.0010 (2)0.000
O10.078 (2)0.0480 (16)0.112 (2)0.0169 (12)0.0033 (19)0.0030 (14)
O20.143 (3)0.089 (2)0.087 (2)0.007 (2)0.017 (2)0.014 (2)
N10.0418 (15)0.0362 (14)0.0601 (15)0.0018 (11)0.0059 (11)0.0040 (11)
N20.111 (3)0.0518 (17)0.087 (3)0.0098 (18)0.006 (2)0.0109 (18)
C10.0487 (18)0.0509 (19)0.070 (2)0.0061 (14)0.0014 (16)0.0048 (15)
C20.0447 (17)0.074 (2)0.074 (2)0.0056 (16)0.0009 (15)0.0115 (17)
C30.058 (2)0.055 (2)0.070 (2)0.0166 (16)0.0008 (15)0.0086 (16)
C40.0570 (18)0.0385 (17)0.0473 (16)0.0061 (13)0.0065 (14)0.0050 (12)
C50.080 (2)0.0354 (17)0.063 (2)0.0107 (17)0.0047 (17)0.0045 (14)
C60.0451 (16)0.0351 (16)0.0448 (16)0.0011 (14)0.0082 (11)0.0005 (11)
Geometric parameters (Å, º) top
Cu—O11.987 (3)C1—H1A0.9600
Cu—N11.997 (2)C2—C31.349 (5)
Cu—O22.410 (4)C2—H2A0.9600
O1—N21.231 (5)C3—C41.407 (5)
O2—N21.184 (5)C3—H3A0.9600
N1—C11.319 (4)C4—C61.398 (4)
N1—C61.361 (4)C4—C51.424 (5)
C1—C21.395 (5)C5—H5A0.9600
O1—Cu—N193.91 (12)C3—C2—C1120.2 (3)
O1—Cu—O254.79 (15)C3—C2—H2A119.6
N1—Cu—O294.32 (12)C1—C2—H2A120.2
N2—O1—Cu104.0 (2)C2—C3—C4120.3 (3)
N2—O2—Cu84.3 (3)C2—C3—H3A121.3
C1—N1—C6118.1 (3)C4—C3—H3A118.4
C1—N1—Cu129.4 (2)C6—C4—C3115.8 (3)
C6—N1—Cu112.53 (19)C6—C4—C5118.9 (3)
O2—N2—O1116.8 (4)C3—C4—C5125.3 (3)
N1—C1—C2121.9 (3)C4—C5—H5A112.6
N1—C1—H1A117.6N1—C6—C4123.8 (3)
C2—C1—H1A120.5

Experimental details

Crystal data
Chemical formula[Cu(NO2)2(C12H8N2)]
Mr335.76
Crystal system, space groupOrthorhombic, Pbcn
Temperature (K)295
a, b, c (Å)9.773 (1), 17.404 (2), 7.440 (1)
V3)1265.4 (3)
Z4
Radiation typeMo Kα
µ (mm1)1.75
Crystal size (mm)0.50 × 0.50 × 0.08
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(MolEN; Fair, 1990)
Tmin, Tmax0.445, 0.875
No. of measured, independent and
observed [I > 2σ(I)] reflections
1054, 875, 813
Rint0.019
θmax (°)23.0
(sin θ/λ)max1)0.550
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.109, 1.15
No. of reflections875
No. of parameters96
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.29

Computer programs: CAD-4 Software (Schagen et al., 1989), CAD-4 Software, MolEN (Fair, 1990), SHELXTL/PC (Siemens, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL/PC, SHELXL97.

Selected geometric parameters (Å, º) top
Cu—O11.987 (3)O1—N21.231 (5)
Cu—N11.997 (2)O2—N21.184 (5)
Cu—O22.410 (4)
O1—Cu—N193.91 (12)N2—O2—Cu84.3 (3)
O1—Cu—O254.79 (15)C1—N1—Cu129.4 (2)
N1—Cu—O294.32 (12)C6—N1—Cu112.53 (19)
N2—O1—Cu104.0 (2)
 

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