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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
CCDC reference: 170737
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (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
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
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
[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).
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
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.
Crystal data top
[Cu(NO2)2(C12H8N2)] | Dx = 1.763 Mg m−3 |
Mr = 335.76 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbcn | Cell parameters from 25 reflections |
a = 9.773 (1) Å | θ = 20.2–22.9° |
b = 17.404 (2) Å | µ = 1.75 mm−1 |
c = 7.440 (1) Å | T = 295 K |
V = 1265.4 (3) Å3 | Plate, green |
Z = 4 | 0.50 × 0.50 × 0.08 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.019 |
θ/2θ scans | θmax = 23.0° |
Absorption correction: ψ scan (MolEN; Fair, 1990) | h = 0→10 |
Tmin = 0.445, Tmax = 0.875 | k = 0→19 |
1054 measured reflections | l = 0→8 |
875 independent reflections | 1 standard reflections every 167 min |
813 reflections with I > 2σ(I) | intensity decay: 0.3% |
Refinement top
Refinement on F2 | H-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 = 1.15 | Δρmax = 0.31 e Å−3 |
875 reflections | Δρmin = −0.29 e Å−3 |
96 parameters | |
Crystal data top
[Cu(NO2)2(C12H8N2)] | V = 1265.4 (3) Å3 |
Mr = 335.76 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 9.773 (1) Å | µ = 1.75 mm−1 |
b = 17.404 (2) Å | T = 295 K |
c = 7.440 (1) Å | 0.50 × 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 = 0.875 | θmax = 23.0° |
1054 measured reflections | 1 standard reflections every 167 min |
875 independent reflections | intensity decay: 0.3% |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | 96 parameters |
wR(F2) = 0.109 | H-atom parameters constrained |
S = 1.15 | Δρmax = 0.31 e Å−3 |
875 reflections | Δρmin = −0.29 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu | 0.5000 | 0.71045 (3) | 0.2500 | 0.0510 (3) | |
O1 | 0.3632 (3) | 0.79139 (13) | 0.1925 (5) | 0.0793 (8) | |
O2 | 0.4682 (4) | 0.7684 (2) | −0.0416 (5) | 0.1065 (10) | |
N1 | 0.3700 (2) | 0.62416 (14) | 0.2029 (3) | 0.0460 (6) | |
N2 | 0.3842 (4) | 0.80593 (18) | 0.0326 (6) | 0.0833 (10) | |
C1 | 0.2404 (3) | 0.62665 (19) | 0.1528 (5) | 0.0567 (8) | |
H1A | 0.2003 | 0.6763 | 0.1334 | 0.080* | |
C2 | 0.1643 (3) | 0.5600 (2) | 0.1228 (5) | 0.0643 (9) | |
H2A | 0.0699 | 0.5634 | 0.0873 | 0.080* | |
C3 | 0.2229 (3) | 0.4903 (2) | 0.1439 (4) | 0.0608 (9) | |
H3A | 0.1727 | 0.4439 | 0.1216 | 0.080* | |
C4 | 0.3608 (3) | 0.48441 (16) | 0.1971 (4) | 0.0476 (7) | |
C5 | 0.4332 (4) | 0.41433 (19) | 0.2244 (4) | 0.0594 (9) | |
H5A | 0.3774 | 0.3699 | 0.2028 | 0.080* | |
C6 | 0.4295 (3) | 0.55400 (16) | 0.2238 (3) | 0.0416 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu | 0.0507 (5) | 0.0292 (4) | 0.0731 (5) | 0.000 | 0.0010 (2) | 0.000 |
O1 | 0.078 (2) | 0.0480 (16) | 0.112 (2) | 0.0169 (12) | 0.0033 (19) | −0.0030 (14) |
O2 | 0.143 (3) | 0.089 (2) | 0.087 (2) | −0.007 (2) | 0.017 (2) | 0.014 (2) |
N1 | 0.0418 (15) | 0.0362 (14) | 0.0601 (15) | 0.0018 (11) | 0.0059 (11) | −0.0040 (11) |
N2 | 0.111 (3) | 0.0518 (17) | 0.087 (3) | 0.0098 (18) | −0.006 (2) | 0.0109 (18) |
C1 | 0.0487 (18) | 0.0509 (19) | 0.070 (2) | 0.0061 (14) | 0.0014 (16) | −0.0048 (15) |
C2 | 0.0447 (17) | 0.074 (2) | 0.074 (2) | −0.0056 (16) | −0.0009 (15) | −0.0115 (17) |
C3 | 0.058 (2) | 0.055 (2) | 0.070 (2) | −0.0166 (16) | −0.0008 (15) | −0.0086 (16) |
C4 | 0.0570 (18) | 0.0385 (17) | 0.0473 (16) | −0.0061 (13) | 0.0065 (14) | −0.0050 (12) |
C5 | 0.080 (2) | 0.0354 (17) | 0.063 (2) | −0.0107 (17) | 0.0047 (17) | −0.0045 (14) |
C6 | 0.0451 (16) | 0.0351 (16) | 0.0448 (16) | 0.0011 (14) | 0.0082 (11) | 0.0005 (11) |
Geometric parameters (Å, º) top
Cu—O1 | 1.987 (3) | C1—H1A | 0.9600 |
Cu—N1 | 1.997 (2) | C2—C3 | 1.349 (5) |
Cu—O2 | 2.410 (4) | C2—H2A | 0.9600 |
O1—N2 | 1.231 (5) | C3—C4 | 1.407 (5) |
O2—N2 | 1.184 (5) | C3—H3A | 0.9600 |
N1—C1 | 1.319 (4) | C4—C6 | 1.398 (4) |
N1—C6 | 1.361 (4) | C4—C5 | 1.424 (5) |
C1—C2 | 1.395 (5) | C5—H5A | 0.9600 |
| | | |
O1—Cu—N1 | 93.91 (12) | C3—C2—C1 | 120.2 (3) |
O1—Cu—O2 | 54.79 (15) | C3—C2—H2A | 119.6 |
N1—Cu—O2 | 94.32 (12) | C1—C2—H2A | 120.2 |
N2—O1—Cu | 104.0 (2) | C2—C3—C4 | 120.3 (3) |
N2—O2—Cu | 84.3 (3) | C2—C3—H3A | 121.3 |
C1—N1—C6 | 118.1 (3) | C4—C3—H3A | 118.4 |
C1—N1—Cu | 129.4 (2) | C6—C4—C3 | 115.8 (3) |
C6—N1—Cu | 112.53 (19) | C6—C4—C5 | 118.9 (3) |
O2—N2—O1 | 116.8 (4) | C3—C4—C5 | 125.3 (3) |
N1—C1—C2 | 121.9 (3) | C4—C5—H5A | 112.6 |
N1—C1—H1A | 117.6 | N1—C6—C4 | 123.8 (3) |
C2—C1—H1A | 120.5 | | |
Experimental details
Crystal data |
Chemical formula | [Cu(NO2)2(C12H8N2)] |
Mr | 335.76 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 295 |
a, b, c (Å) | 9.773 (1), 17.404 (2), 7.440 (1) |
V (Å3) | 1265.4 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.75 |
Crystal size (mm) | 0.50 × 0.50 × 0.08 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (MolEN; Fair, 1990) |
Tmin, Tmax | 0.445, 0.875 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1054, 875, 813 |
Rint | 0.019 |
θmax (°) | 23.0 |
(sin θ/λ)max (Å−1) | 0.550 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.109, 1.15 |
No. of reflections | 875 |
No. of parameters | 96 |
No. of restraints | ? |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.29 |
Selected geometric parameters (Å, º) topCu—O1 | 1.987 (3) | O1—N2 | 1.231 (5) |
Cu—N1 | 1.997 (2) | O2—N2 | 1.184 (5) |
Cu—O2 | 2.410 (4) | | |
| | | |
O1—Cu—N1 | 93.91 (12) | N2—O2—Cu | 84.3 (3) |
O1—Cu—O2 | 54.79 (15) | C1—N1—Cu | 129.4 (2) |
N1—Cu—O2 | 94.32 (12) | C6—N1—Cu | 112.53 (19) |
N2—O1—Cu | 104.0 (2) | | |
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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.