The copper(II) environments for tetrakis(1-ethyl-1,2,4-triazole)dinitratocopper(II), [Cu(NO3)2(C4H7N3)4], and tetrakis(1-propyl-1,2,4-triazole)dinitratocopper(II), [Cu(NO3)2(C5H9N3)4], are distorted square bipyramidal. Both structures are centrosymmetric, with the copper(II) ions located at inversion centers coordinated by four N atoms of four triazole molecules and by two O atoms of two nitrate ions in an elongated octahedral geometry. This elongation is a result of the Jahn-Teller effect. The largest distortion is that of the N-Cu-O angles, which differ from 90° by 5.68 (10)° in the ethyl and 5.59 (8)° in the propyl derivative.
Supporting information
CCDC references: 268089; 268090
1-Ethyl-1,2,4-triazole (m.p. 451 K) and 1-propyl-1,2,4-triazole (m.p. 462–463 K) were synthesized in the Walocha–Nowak Chemical Laboratory in Cracow (Poland). Other chemicals were procured from POCh–Gliwice (Poland). Generally, the complexes were formed during the reaction of ethanol solutions of the ligands with Cu(NO3)2. A solution of Cu(NO3)2 (5 mmol) in anhydrous ethanol (30 ml) with ethyl orthoformate (2 ml) was added to a solution of the ligand (35 mmol) in anhydrous ethanol (60 ml) with stirring. Blue complexes of CuII were formed. The products were digested on a water-bath for 1 h, washed repeatedly with anhydrous ethanol and ethyl ether, and dried in vacuum desiccators.
H atoms were treated as riding atoms [C—H = 0.93 (CH), 0.96 (CH2) and 0.97 Å (CH3), and Uiso(H) = 1.5Ueq(C) (methyl) or 1.2Ueq(C) (other H atoms)].
For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
Crystal data top
[Cu(NO3)2(C4H7N3)4] | F(000) = 598 |
Mr = 576.06 | Dx = 1.561 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 7990 reflections |
a = 9.703 (2) Å | θ = 3.3–26.0° |
b = 15.288 (3) Å | µ = 0.96 mm−1 |
c = 8.386 (2) Å | T = 100 K |
β = 99.97 (1)° | Plate, blue |
V = 1225.2 (5) Å3 | 0.2 × 0.2 × 0.1 mm |
Z = 2 | |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 1339 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.085 |
Graphite monochromator | θmax = 26.0°, θmin = 3.3° |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | h = −11→11 |
ω scans | k = −18→18 |
7990 measured reflections | l = −8→10 |
2384 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.83 | w = 1/[σ2(Fo2) + (0.023P)2] where P = (Fo2 + 2Fc2)/3 |
2386 reflections | (Δ/σ)max < 0.001 |
215 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.62 e Å−3 |
Crystal data top
[Cu(NO3)2(C4H7N3)4] | V = 1225.2 (5) Å3 |
Mr = 576.06 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.703 (2) Å | µ = 0.96 mm−1 |
b = 15.288 (3) Å | T = 100 K |
c = 8.386 (2) Å | 0.2 × 0.2 × 0.1 mm |
β = 99.97 (1)° | |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 1339 reflections with I > 2σ(I) |
7990 measured reflections | Rint = 0.085 |
2384 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.089 | H-atom parameters constrained |
S = 0.83 | Δρmax = 0.47 e Å−3 |
2386 reflections | Δρmin = −0.62 e Å−3 |
215 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 | x | y | z | Uiso*/Ueq | |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.01769 (19) | |
N21 | 0.6212 (4) | 0.7040 (2) | 0.4341 (4) | 0.0215 (8) | |
O1 | 0.6394 (3) | 0.62915 (16) | 0.4990 (3) | 0.0246 (7) | |
O2 | 0.7199 (3) | 0.73969 (17) | 0.3834 (4) | 0.0382 (8) | |
O3 | 0.5052 (3) | 0.74097 (17) | 0.4226 (3) | 0.0313 (7) | |
N4 | 0.4129 (3) | 0.5061 (2) | 0.2633 (3) | 0.0151 (6) | |
C5 | 0.3603 (4) | 0.4406 (2) | 0.1653 (4) | 0.0177 (9) | |
H5A | 0.3572 | 0.3823 | 0.1963 | 0.021* | |
N1 | 0.3140 (3) | 0.47056 (19) | 0.0193 (3) | 0.0172 (8) | |
N2 | 0.3337 (4) | 0.5592 (2) | 0.0123 (4) | 0.0248 (9) | |
C3 | 0.3919 (4) | 0.5766 (3) | 0.1629 (4) | 0.0207 (9) | |
H3A | 0.4168 | 0.6331 | 0.1980 | 0.025* | |
C6 | 0.2467 (4) | 0.4229 (2) | −0.1258 (4) | 0.0238 (10) | |
H6A | 0.2639 | 0.3608 | −0.1094 | 0.029* | |
H6B | 0.2888 | 0.4410 | −0.2174 | 0.029* | |
C7 | 0.0929 (4) | 0.4384 (3) | −0.1641 (5) | 0.0320 (11) | |
H7A | 0.0537 | 0.4055 | −0.2585 | 0.048* | |
H7B | 0.0753 | 0.4996 | −0.1842 | 0.048* | |
H7C | 0.0505 | 0.4202 | −0.0742 | 0.048* | |
N14 | 0.6643 (3) | 0.43521 (18) | 0.4476 (3) | 0.0158 (7) | |
C15 | 0.6704 (4) | 0.3636 (2) | 0.3554 (4) | 0.0146 (8) | |
H15A | 0.5934 | 0.3341 | 0.2989 | 0.018* | |
N11 | 0.8016 (3) | 0.34183 (19) | 0.3574 (3) | 0.0179 (7) | |
N12 | 0.8900 (3) | 0.3977 (2) | 0.4543 (4) | 0.0246 (8) | |
C13 | 0.8018 (4) | 0.4521 (2) | 0.5038 (4) | 0.0207 (9) | |
H13A | 0.8311 | 0.4989 | 0.5723 | 0.025* | |
C16 | 0.8562 (4) | 0.2685 (2) | 0.2729 (5) | 0.0253 (10) | |
H16A | 0.7865 | 0.2513 | 0.1809 | 0.030* | |
H16B | 0.8732 | 0.2189 | 0.3457 | 0.030* | |
C17 | 0.9891 (5) | 0.2922 (3) | 0.2154 (5) | 0.0382 (12) | |
H17A | 1.0226 | 0.2426 | 0.1633 | 0.057* | |
H17B | 1.0582 | 0.3095 | 0.3062 | 0.057* | |
H17C | 0.9718 | 0.3398 | 0.1399 | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0217 (4) | 0.0154 (3) | 0.0152 (3) | 0.0030 (4) | 0.0011 (3) | −0.0019 (3) |
N21 | 0.030 (2) | 0.0136 (18) | 0.0209 (18) | −0.0007 (16) | 0.0033 (16) | −0.0028 (14) |
O1 | 0.0312 (17) | 0.0107 (14) | 0.0300 (16) | −0.0014 (12) | −0.0004 (13) | 0.0039 (12) |
O2 | 0.042 (2) | 0.0196 (16) | 0.063 (2) | −0.0033 (14) | 0.0348 (17) | 0.0083 (15) |
O3 | 0.0252 (18) | 0.0205 (15) | 0.0469 (18) | 0.0058 (14) | 0.0022 (14) | 0.0072 (13) |
N4 | 0.0187 (16) | 0.0120 (15) | 0.0140 (14) | −0.0002 (15) | 0.0017 (12) | −0.0019 (15) |
C5 | 0.019 (2) | 0.016 (2) | 0.018 (2) | −0.0013 (17) | 0.0033 (17) | −0.0003 (17) |
N1 | 0.025 (2) | 0.0157 (17) | 0.0091 (16) | −0.0026 (14) | −0.0020 (14) | −0.0022 (13) |
N2 | 0.037 (2) | 0.0205 (19) | 0.0144 (18) | 0.0001 (17) | −0.0042 (16) | 0.0023 (15) |
C3 | 0.026 (2) | 0.016 (2) | 0.018 (2) | 0.0024 (18) | −0.0011 (18) | −0.0013 (17) |
C6 | 0.036 (3) | 0.020 (2) | 0.013 (2) | −0.0014 (19) | −0.0023 (18) | −0.0053 (17) |
C7 | 0.032 (3) | 0.034 (3) | 0.027 (2) | −0.006 (2) | −0.004 (2) | −0.003 (2) |
N14 | 0.0215 (19) | 0.0131 (17) | 0.0126 (16) | 0.0019 (14) | 0.0020 (13) | 0.0029 (13) |
C15 | 0.017 (2) | 0.011 (2) | 0.016 (2) | −0.0024 (16) | 0.0034 (16) | 0.0000 (16) |
N11 | 0.0171 (18) | 0.0143 (17) | 0.0212 (18) | 0.0022 (14) | 0.0006 (14) | −0.0033 (14) |
N12 | 0.020 (2) | 0.027 (2) | 0.0260 (19) | 0.0019 (15) | 0.0009 (15) | −0.0084 (15) |
C13 | 0.021 (2) | 0.019 (2) | 0.021 (2) | 0.0028 (18) | −0.0012 (17) | −0.0052 (17) |
C16 | 0.030 (3) | 0.018 (2) | 0.029 (2) | 0.0060 (19) | 0.0085 (19) | −0.0070 (18) |
C17 | 0.051 (3) | 0.022 (2) | 0.049 (3) | 0.006 (2) | 0.031 (2) | −0.007 (2) |
Geometric parameters (Å, º) top
Cu1—N14i | 1.990 (3) | C6—H6B | 0.9700 |
Cu1—N14 | 1.990 (3) | C7—H7A | 0.9600 |
Cu1—N4 | 2.020 (3) | C7—H7B | 0.9600 |
Cu1—N4i | 2.020 (3) | C7—H7C | 0.9600 |
Cu1—O1 | 2.394 (3) | N14—C15 | 1.347 (4) |
Cu1—O1i | 2.394 (3) | N14—C13 | 1.361 (4) |
N21—O2 | 1.239 (4) | C15—N11 | 1.312 (4) |
N21—O3 | 1.248 (4) | C15—H15A | 0.9300 |
N21—O1 | 1.266 (4) | N11—N12 | 1.373 (4) |
N4—C5 | 1.339 (4) | N11—C16 | 1.473 (4) |
N4—C3 | 1.362 (4) | N12—C13 | 1.311 (4) |
C5—N1 | 1.312 (4) | C13—H13A | 0.9300 |
C5—H5A | 0.9300 | C16—C17 | 1.498 (5) |
N1—N2 | 1.371 (4) | C16—H16A | 0.9700 |
N1—C6 | 1.470 (4) | C16—H16B | 0.9700 |
N2—C3 | 1.318 (4) | C17—H17A | 0.9600 |
C3—H3A | 0.9300 | C17—H17B | 0.9600 |
C6—C7 | 1.491 (5) | C17—H17C | 0.9600 |
C6—H6A | 0.9700 | | |
| | | |
N14i—Cu1—N14 | 180.00 | N1—C6—H6B | 109.1 |
N14i—Cu1—N4 | 88.79 (11) | C7—C6—H6B | 109.1 |
N14—Cu1—N4 | 91.21 (11) | H6A—C6—H6B | 107.8 |
N14i—Cu1—N4i | 91.21 (11) | C6—C7—H7A | 109.5 |
N14—Cu1—N4i | 88.79 (11) | C6—C7—H7B | 109.5 |
N4—Cu1—N4i | 180.00 | H7A—C7—H7B | 109.5 |
N14i—Cu1—O1 | 93.74 (11) | C6—C7—H7C | 109.5 |
N14—Cu1—O1 | 86.26 (11) | H7A—C7—H7C | 109.5 |
N4—Cu1—O1 | 95.68 (10) | H7B—C7—H7C | 109.5 |
N4i—Cu1—O1 | 84.32 (10) | C15—N14—C13 | 102.4 (3) |
N14i—Cu1—O1i | 86.26 (11) | C15—N14—Cu1 | 130.4 (3) |
N14—Cu1—O1i | 93.74 (11) | C13—N14—Cu1 | 127.2 (2) |
N4—Cu1—O1i | 84.32 (10) | N11—C15—N14 | 109.7 (3) |
N4i—Cu1—O1i | 95.68 (10) | N11—C15—H15A | 125.1 |
O1—Cu1—O1i | 180.00 | N14—C15—H15A | 125.1 |
O2—N21—O3 | 120.9 (3) | C15—N11—N12 | 110.8 (3) |
O2—N21—O1 | 119.1 (3) | C15—N11—C16 | 128.0 (3) |
O3—N21—O1 | 120.0 (3) | N12—N11—C16 | 121.2 (3) |
N21—O1—Cu1 | 135.2 (2) | C13—N12—N11 | 102.0 (3) |
C5—N4—C3 | 102.3 (3) | N12—C13—N14 | 115.1 (3) |
C5—N4—Cu1 | 128.2 (3) | N12—C13—H13A | 122.5 |
C3—N4—Cu1 | 129.5 (2) | N14—C13—H13A | 122.5 |
N1—C5—N4 | 110.2 (3) | N11—C16—C17 | 111.9 (3) |
N1—C5—H5A | 124.9 | N11—C16—H16A | 109.2 |
N4—C5—H5A | 124.9 | C17—C16—H16A | 109.2 |
C5—N1—N2 | 110.9 (3) | N11—C16—H16B | 109.2 |
C5—N1—C6 | 129.1 (3) | C17—C16—H16B | 109.2 |
N2—N1—C6 | 120.0 (3) | H16A—C16—H16B | 107.9 |
C3—N2—N1 | 101.5 (3) | C16—C17—H17A | 109.5 |
N2—C3—N4 | 115.2 (3) | C16—C17—H17B | 109.5 |
N2—C3—H3A | 122.4 | H17A—C17—H17B | 109.5 |
N4—C3—H3A | 122.4 | C16—C17—H17C | 109.5 |
N1—C6—C7 | 112.6 (3) | H17A—C17—H17C | 109.5 |
N1—C6—H6A | 109.1 | H17B—C17—H17C | 109.5 |
C7—C6—H6A | 109.1 | | |
| | | |
O2—N21—O1—Cu1 | −142.7 (3) | C5—N1—C6—C7 | 104.8 (4) |
O3—N21—O1—Cu1 | 37.6 (5) | N2—N1—C6—C7 | −74.3 (4) |
N14i—Cu1—O1—N21 | −49.2 (3) | N4—Cu1—N14—C15 | −50.2 (3) |
N14—Cu1—O1—N21 | 130.8 (3) | N4i—Cu1—N14—C15 | 129.8 (3) |
N4—Cu1—O1—N21 | 39.9 (3) | O1—Cu1—N14—C15 | −145.8 (3) |
N4i—Cu1—O1—N21 | −140.1 (3) | O1i—Cu1—N14—C15 | 34.2 (3) |
N14i—Cu1—N4—C5 | −111.4 (3) | N4—Cu1—N14—C13 | 132.4 (3) |
N14—Cu1—N4—C5 | 68.6 (3) | N4i—Cu1—N14—C13 | −47.6 (3) |
O1—Cu1—N4—C5 | 155.0 (3) | O1—Cu1—N14—C13 | 36.8 (3) |
O1i—Cu1—N4—C5 | −25.0 (3) | O1i—Cu1—N14—C13 | −143.2 (3) |
N14i—Cu1—N4—C3 | 68.4 (3) | C13—N14—C15—N11 | −0.6 (4) |
O1—Cu1—N4—C3 | −25.2 (3) | Cu1—N14—C15—N11 | −178.5 (2) |
O1i—Cu1—N4—C3 | 154.8 (3) | N14—C15—N11—N12 | 1.0 (4) |
C3—N4—C5—N1 | 0.7 (4) | N14—C15—N11—C16 | −179.6 (3) |
Cu1—N4—C5—N1 | −179.5 (2) | C15—N11—N12—C13 | −0.9 (4) |
N4—C5—N1—N2 | 0.1 (4) | C16—N11—N12—C13 | 179.6 (3) |
N4—C5—N1—C6 | −179.2 (3) | N11—N12—C13—N14 | 0.5 (4) |
C5—N1—N2—C3 | −0.8 (4) | C15—N14—C13—N12 | 0.0 (4) |
C6—N1—N2—C3 | 178.5 (3) | Cu1—N14—C13—N12 | 178.0 (2) |
N1—N2—C3—N4 | 1.2 (5) | C15—N11—C16—C17 | 144.1 (4) |
C5—N4—C3—N2 | −1.2 (4) | N12—N11—C16—C17 | −36.6 (5) |
Cu1—N4—C3—N2 | 179.0 (3) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O3 | 0.93 | 2.54 | 3.382 (5) | 151 |
C5—H5A···O2ii | 0.93 | 2.36 | 3.178 (5) | 146 |
C5—H5A···O1i | 0.93 | 2.56 | 3.010 (4) | 111 |
C15—H15A···O3ii | 0.93 | 2.40 | 3.237 (4) | 149 |
C17—H17A···O2iii | 0.96 | 2.60 | 3.180 (5) | 120 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+2, y−1/2, −z+1/2. |
Crystal data top
[Cu(NO3)2(C5H9N3)4] | Z = 1 |
Mr = 632.18 | F(000) = 331 |
Triclinic, P1 | Dx = 1.465 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.027 (6) Å | Cell parameters from 4840 reflections |
b = 8.523 (5) Å | θ = 3.1–26.0° |
c = 11.672 (5) Å | µ = 0.82 mm−1 |
α = 89.67 (4)° | T = 100 K |
β = 73.50 (5)° | Needle, blue |
γ = 70.19 (6)° | 0.2 × 0.1 × 0.1 mm |
V = 716.7 (8) Å3 | |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 2358 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.019 |
Graphite monochromator | θmax = 26.0°, θmin = 3.1° |
Detector resolution: 1024 x 1024 with blocks 2 x 2 pixels mm-1 | h = −6→9 |
ω scans | k = −9→10 |
4840 measured reflections | l = −14→14 |
2766 independent reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 0.98 | w = 1/[σ2(Fo2) + (0.0368P)2] where P = (Fo2 + 2Fc2)/3 |
2766 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Crystal data top
[Cu(NO3)2(C5H9N3)4] | γ = 70.19 (6)° |
Mr = 632.18 | V = 716.7 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.027 (6) Å | Mo Kα radiation |
b = 8.523 (5) Å | µ = 0.82 mm−1 |
c = 11.672 (5) Å | T = 100 K |
α = 89.67 (4)° | 0.2 × 0.1 × 0.1 mm |
β = 73.50 (5)° | |
Data collection top
Oxford Diffraction Xcalibur diffractometer | 2358 reflections with I > 2σ(I) |
4840 measured reflections | Rint = 0.019 |
2766 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.061 | H-atom parameters constrained |
S = 0.98 | Δρmax = 0.24 e Å−3 |
2766 reflections | Δρmin = −0.27 e Å−3 |
190 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.01388 (10) | |
O1 | 0.81736 (16) | 0.37618 (15) | 0.50323 (11) | 0.0236 (3) | |
N21 | 0.9696 (2) | 0.29666 (18) | 0.42608 (13) | 0.0207 (3) | |
O2 | 1.01924 (17) | 0.35387 (16) | 0.32793 (11) | 0.0291 (3) | |
N4 | 0.54576 (18) | 0.39492 (16) | 0.33527 (12) | 0.0140 (3) | |
C5 | 0.4347 (2) | 0.3318 (2) | 0.30218 (14) | 0.0155 (4) | |
H5A | 0.3269 | 0.3224 | 0.3533 | 0.019* | |
N1 | 0.50020 (18) | 0.28434 (16) | 0.18558 (12) | 0.0140 (3) | |
N2 | 0.66133 (19) | 0.31533 (18) | 0.13708 (12) | 0.0207 (3) | |
C3 | 0.6819 (2) | 0.3817 (2) | 0.23087 (15) | 0.0187 (4) | |
H3A | 0.7812 | 0.4167 | 0.2265 | 0.022* | |
C6 | 0.4183 (2) | 0.2159 (2) | 0.11068 (15) | 0.0175 (4) | |
H6A | 0.3377 | 0.1628 | 0.1602 | 0.021* | |
H6B | 0.5162 | 0.1309 | 0.0506 | 0.021* | |
C7 | 0.3079 (3) | 0.3498 (2) | 0.04882 (16) | 0.0245 (4) | |
H7A | 0.3879 | 0.4048 | 0.0010 | 0.029* | |
H7B | 0.2084 | 0.4334 | 0.1090 | 0.029* | |
C8 | 0.2261 (3) | 0.2797 (3) | −0.03136 (17) | 0.0317 (5) | |
H8A | 0.1567 | 0.3691 | −0.0684 | 0.047* | |
H8B | 0.1452 | 0.2266 | 0.0158 | 0.047* | |
H8C | 0.3242 | 0.1989 | −0.0924 | 0.047* | |
N14 | 0.55475 (18) | 0.69912 (16) | 0.42706 (11) | 0.0136 (3) | |
C15 | 0.7193 (2) | 0.7175 (2) | 0.38918 (14) | 0.0161 (4) | |
H15 | 0.8305 | 0.6400 | 0.3940 | 0.019* | |
N11 | 0.70046 (19) | 0.86345 (16) | 0.34345 (12) | 0.0149 (3) | |
N12 | 0.51968 (19) | 0.94714 (17) | 0.35110 (13) | 0.0191 (3) | |
C13 | 0.4368 (2) | 0.8436 (2) | 0.40219 (14) | 0.0167 (4) | |
H13 | 0.3099 | 0.8671 | 0.4196 | 0.020* | |
C16 | 0.8421 (2) | 0.9377 (2) | 0.29173 (16) | 0.0204 (4) | |
H16A | 0.8416 | 1.0148 | 0.3527 | 0.025* | |
H16B | 0.8109 | 1.0014 | 0.2269 | 0.025* | |
C17 | 1.0343 (2) | 0.8078 (2) | 0.24413 (16) | 0.0217 (4) | |
H17A | 1.0335 | 0.7250 | 0.1879 | 0.026* | |
H17B | 1.0713 | 0.7510 | 0.3099 | 0.026* | |
C18 | 1.17267 (18) | 0.88935 (16) | 0.18175 (11) | 0.0300 (5) | |
H18A | 1.2940 | 0.8051 | 0.1519 | 0.045* | |
H18B | 1.1748 | 0.9700 | 0.2379 | 0.045* | |
H18C | 1.1367 | 0.9445 | 0.1161 | 0.045* | |
O31 | 1.09477 (18) | 0.18000 (16) | 0.44575 (11) | 0.0263 (7) | 0.55 |
O32 | 1.04184 (18) | 0.14614 (16) | 0.45335 (11) | 0.0339 (10) | 0.45 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.01790 (17) | 0.01193 (16) | 0.01352 (16) | −0.00748 (13) | −0.00460 (12) | 0.00282 (11) |
O1 | 0.0125 (6) | 0.0279 (7) | 0.0244 (7) | −0.0022 (5) | −0.0022 (5) | 0.0066 (6) |
N21 | 0.0201 (8) | 0.0176 (8) | 0.0253 (9) | −0.0016 (7) | −0.0138 (7) | −0.0036 (6) |
O2 | 0.0219 (7) | 0.0352 (8) | 0.0255 (7) | −0.0102 (6) | −0.0001 (6) | 0.0018 (6) |
N4 | 0.0164 (7) | 0.0116 (7) | 0.0146 (7) | −0.0058 (6) | −0.0048 (6) | 0.0025 (6) |
C5 | 0.0160 (9) | 0.0145 (9) | 0.0151 (9) | −0.0069 (7) | −0.0011 (7) | 0.0014 (7) |
N1 | 0.0158 (7) | 0.0135 (7) | 0.0146 (7) | −0.0073 (6) | −0.0048 (6) | 0.0030 (6) |
N2 | 0.0220 (8) | 0.0269 (8) | 0.0166 (8) | −0.0152 (7) | −0.0027 (6) | 0.0034 (6) |
C3 | 0.0198 (9) | 0.0225 (9) | 0.0177 (9) | −0.0126 (8) | −0.0054 (7) | 0.0041 (7) |
C6 | 0.0224 (9) | 0.0177 (9) | 0.0151 (9) | −0.0104 (8) | −0.0055 (7) | −0.0008 (7) |
C7 | 0.0308 (11) | 0.0210 (10) | 0.0251 (10) | −0.0090 (8) | −0.0136 (9) | 0.0039 (8) |
C8 | 0.0400 (12) | 0.0328 (11) | 0.0298 (11) | −0.0146 (10) | −0.0198 (10) | 0.0063 (9) |
N14 | 0.0157 (7) | 0.0118 (7) | 0.0124 (7) | −0.0045 (6) | −0.0031 (6) | 0.0006 (6) |
C15 | 0.0173 (9) | 0.0128 (8) | 0.0185 (9) | −0.0057 (7) | −0.0054 (7) | 0.0033 (7) |
N11 | 0.0175 (7) | 0.0118 (7) | 0.0155 (7) | −0.0064 (6) | −0.0032 (6) | 0.0025 (6) |
N12 | 0.0174 (8) | 0.0149 (7) | 0.0231 (8) | −0.0043 (6) | −0.0048 (6) | 0.0052 (6) |
C13 | 0.0172 (9) | 0.0144 (9) | 0.0176 (9) | −0.0052 (7) | −0.0045 (7) | 0.0026 (7) |
C16 | 0.0232 (10) | 0.0153 (9) | 0.0233 (10) | −0.0106 (8) | −0.0030 (8) | 0.0043 (7) |
C17 | 0.0221 (10) | 0.0218 (10) | 0.0228 (10) | −0.0103 (8) | −0.0062 (8) | 0.0022 (8) |
C18 | 0.0265 (11) | 0.0392 (12) | 0.0247 (11) | −0.0180 (9) | −0.0006 (9) | 0.0028 (9) |
O31 | 0.0233 (14) | 0.0186 (14) | 0.0312 (17) | 0.0009 (13) | −0.0095 (12) | 0.0066 (12) |
O32 | 0.042 (2) | 0.0110 (17) | 0.034 (2) | 0.0087 (16) | −0.0118 (17) | −0.0002 (14) |
Geometric parameters (Å, º) top
Cu1—N4 | 2.007 (2) | C7—H7A | 0.9700 |
Cu1—N4i | 2.007 (2) | C7—H7B | 0.9700 |
Cu1—N14i | 2.019 (2) | C8—H8A | 0.9600 |
Cu1—N14 | 2.018 (2) | C8—H8B | 0.9600 |
Cu1—O1 | 2.416 (2) | C8—H8C | 0.9600 |
Cu1—O1i | 2.416 (2) | N14—C15 | 1.331 (2) |
O1—N21 | 1.259 (2) | N14—C13 | 1.363 (2) |
N21—O31 | 1.226 (2) | C15—N11 | 1.329 (2) |
N21—O2 | 1.255 (2) | C15—H15 | 0.9300 |
N21—O32 | 1.296 (2) | N11—N12 | 1.359 (2) |
N4—C5 | 1.325 (2) | N11—C16 | 1.467 (2) |
N4—C3 | 1.361 (2) | N12—C13 | 1.320 (2) |
C5—N1 | 1.322 (2) | C13—H13 | 0.9300 |
C5—H5A | 0.9300 | C16—C17 | 1.509 (3) |
N1—N2 | 1.370 (2) | C16—H16A | 0.9700 |
N1—C6 | 1.459 (2) | C16—H16B | 0.9700 |
N2—C3 | 1.311 (2) | C17—C18 | 1.518 (2) |
C3—H3A | 0.9300 | C17—H17A | 0.9700 |
C6—C7 | 1.509 (3) | C17—H17B | 0.9700 |
C6—H6A | 0.9700 | C18—H18A | 0.9600 |
C6—H6B | 0.9700 | C18—H18B | 0.9600 |
C7—C8 | 1.512 (3) | C18—H18C | 0.9600 |
| | | |
N4—Cu1—N4i | 180.00 | C8—C7—H7A | 109.1 |
N4—Cu1—N14i | 90.18 (7) | C6—C7—H7B | 109.1 |
N4i—Cu1—N14i | 89.82 (7) | C8—C7—H7B | 109.1 |
N4—Cu1—N14 | 89.82 (7) | H7A—C7—H7B | 107.9 |
N4i—Cu1—N14 | 90.18 (7) | C7—C8—H8A | 109.5 |
N14i—Cu1—N14 | 180.00 | C7—C8—H8B | 109.5 |
N4—Cu1—O1 | 95.59 (8) | H8A—C8—H8B | 109.5 |
N4i—Cu1—O1 | 84.41 (8) | C7—C8—H8C | 109.5 |
N14i—Cu1—O1 | 89.98 (8) | H8A—C8—H8C | 109.5 |
N14—Cu1—O1 | 90.02 (8) | H8B—C8—H8C | 109.5 |
N4—Cu1—O1i | 84.41 (8) | C15—N14—C13 | 103.41 (15) |
N4i—Cu1—O1i | 95.59 (8) | C15—N14—Cu1 | 127.24 (12) |
N14i—Cu1—O1i | 90.02 (8) | C13—N14—Cu1 | 129.33 (12) |
N14—Cu1—O1i | 89.98 (8) | N11—C15—N14 | 109.67 (16) |
O1—Cu1—O1i | 180.00 | N11—C15—H15 | 125.2 |
N21—O1—Cu1 | 134.70 (11) | N14—C15—H15 | 125.2 |
O31—N21—O2 | 113.35 (16) | C15—N11—N12 | 110.25 (14) |
O31—N21—O1 | 124.75 (16) | C15—N11—C16 | 129.21 (15) |
O2—N21—O1 | 120.47 (15) | N12—N11—C16 | 120.53 (14) |
O2—N21—O32 | 127.05 (15) | C13—N12—N11 | 102.91 (14) |
O1—N21—O32 | 111.38 (16) | N12—C13—N14 | 113.75 (16) |
C5—N4—C3 | 103.30 (14) | N12—C13—H13 | 123.1 |
C5—N4—Cu1 | 125.78 (12) | N14—C13—H13 | 123.1 |
C3—N4—Cu1 | 130.73 (12) | N11—C16—C17 | 112.60 (15) |
N1—C5—N4 | 109.81 (15) | N11—C16—H16A | 109.1 |
N1—C5—H5A | 125.1 | C17—C16—H16A | 109.1 |
N4—C5—H5A | 125.1 | N11—C16—H16B | 109.1 |
C5—N1—N2 | 110.27 (14) | C17—C16—H16B | 109.1 |
C5—N1—C6 | 128.36 (15) | H16A—C16—H16B | 107.8 |
N2—N1—C6 | 121.31 (14) | C16—C17—C18 | 110.53 (15) |
C3—N2—N1 | 102.27 (14) | C16—C17—H17A | 109.5 |
N2—C3—N4 | 114.36 (15) | C18—C17—H17A | 109.5 |
N2—C3—H3A | 122.8 | C16—C17—H17B | 109.5 |
N4—C3—H3A | 122.8 | C18—C17—H17B | 109.5 |
N1—C6—C7 | 111.89 (14) | H17A—C17—H17B | 108.1 |
N1—C6—H6A | 109.2 | C17—C18—H18A | 109.5 |
C7—C6—H6A | 109.2 | C17—C18—H18B | 109.5 |
N1—C6—H6B | 109.2 | H18A—C18—H18B | 109.5 |
C7—C6—H6B | 109.2 | C17—C18—H18C | 109.5 |
H6A—C6—H6B | 107.9 | H18A—C18—H18C | 109.5 |
C6—C7—C8 | 112.37 (16) | H18B—C18—H18C | 109.5 |
C6—C7—H7A | 109.1 | | |
| | | |
N4—Cu1—O1—N21 | 10.75 (15) | N1—C6—C7—C8 | 178.67 (15) |
N4i—Cu1—O1—N21 | −169.25 (15) | N4—Cu1—N14—C15 | −88.88 (15) |
N14i—Cu1—O1—N21 | 100.93 (15) | N4i—Cu1—N14—C15 | 91.12 (15) |
N14—Cu1—O1—N21 | −79.07 (15) | O1—Cu1—N14—C15 | 6.70 (14) |
Cu1—O1—N21—O31 | −143.37 (14) | O1i—Cu1—N14—C15 | −173.30 (14) |
Cu1—O1—N21—O2 | 51.2 (2) | N4—Cu1—N14—C13 | 89.55 (15) |
Cu1—O1—N21—O32 | −117.58 (15) | N4i—Cu1—N14—C13 | −90.45 (15) |
N14i—Cu1—N4—C5 | 49.57 (14) | O1—Cu1—N14—C13 | −174.87 (14) |
N14—Cu1—N4—C5 | −130.43 (14) | O1i—Cu1—N14—C13 | 5.13 (14) |
O1—Cu1—N4—C5 | 139.57 (14) | C13—N14—C15—N11 | −0.59 (18) |
O1i—Cu1—N4—C5 | −40.43 (14) | Cu1—N14—C15—N11 | 178.16 (10) |
N14i—Cu1—N4—C3 | −136.25 (15) | N14—C15—N11—N12 | 0.54 (19) |
N14—Cu1—N4—C3 | 43.75 (15) | N14—C15—N11—C16 | 179.65 (15) |
O1—Cu1—N4—C3 | −46.25 (15) | C15—N11—N12—C13 | −0.23 (17) |
O1i—Cu1—N4—C3 | 133.75 (15) | C16—N11—N12—C13 | −179.43 (14) |
C3—N4—C5—N1 | −0.12 (18) | N11—N12—C13—N14 | −0.15 (18) |
Cu1—N4—C5—N1 | 175.35 (10) | C15—N14—C13—N12 | 0.46 (19) |
N4—C5—N1—N2 | 0.15 (18) | Cu1—N14—C13—N12 | −178.25 (11) |
N4—C5—N1—C6 | −176.86 (14) | C15—N11—C16—C17 | 24.6 (2) |
C5—N1—N2—C3 | −0.11 (18) | N12—N11—C16—C17 | −156.41 (15) |
C6—N1—N2—C3 | 177.14 (14) | N11—C16—C17—C18 | 174.92 (13) |
N1—N2—C3—N4 | 0.04 (19) | O2—N21—O31—O32 | −127.46 (13) |
C5—N4—C3—N2 | 0.05 (19) | O1—N21—O31—O32 | 66.23 (15) |
Cu1—N4—C3—N2 | −175.10 (11) | O2—N21—O32—O31 | 65.95 (16) |
C5—N1—C6—C7 | 95.8 (2) | O1—N21—O32—O31 | −126.15 (13) |
N2—N1—C6—C7 | −80.9 (2) | | |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O2 | 0.93 | 2.43 | 3.158 (3) | 135 |
C15—H15···O1 | 0.93 | 2.60 | 3.139 (3) | 118 |
C15—H15···O2 | 0.93 | 2.39 | 3.147 (4) | 139 |
C5—H5A···O2ii | 0.93 | 2.49 | 3.202 (3) | 133 |
C5—H5A···O31ii | 0.93 | 2.55 | 3.420 (3) | 157 |
C13—H13···O32iii | 0.93 | 2.55 | 3.234 (4) | 131 |
Symmetry codes: (ii) x−1, y, z; (iii) x−1, y+1, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | [Cu(NO3)2(C4H7N3)4] | [Cu(NO3)2(C5H9N3)4] |
Mr | 576.06 | 632.18 |
Crystal system, space group | Monoclinic, P21/c | Triclinic, P1 |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 9.703 (2), 15.288 (3), 8.386 (2) | 8.027 (6), 8.523 (5), 11.672 (5) |
α, β, γ (°) | 90, 99.97 (1), 90 | 89.67 (4), 73.50 (5), 70.19 (6) |
V (Å3) | 1225.2 (5) | 716.7 (8) |
Z | 2 | 1 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.96 | 0.82 |
Crystal size (mm) | 0.2 × 0.2 × 0.1 | 0.2 × 0.1 × 0.1 |
|
Data collection |
Diffractometer | Oxford Diffraction Xcalibur diffractometer | Oxford Diffraction Xcalibur diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7990, 2384, 1339 | 4840, 2766, 2358 |
Rint | 0.085 | 0.019 |
(sin θ/λ)max (Å−1) | 0.617 | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.089, 0.83 | 0.026, 0.061, 0.98 |
No. of reflections | 2386 | 2766 |
No. of parameters | 215 | 190 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.62 | 0.24, −0.27 |
Selected geometric parameters (Å, º) for (I) topCu1—N14 | 1.990 (3) | N21—O2 | 1.239 (4) |
Cu1—N4 | 2.020 (3) | N21—O3 | 1.248 (4) |
Cu1—O1 | 2.394 (3) | N21—O1 | 1.266 (4) |
| | | |
N14—Cu1—N4 | 91.21 (11) | O2—N21—O1 | 119.1 (3) |
N14—Cu1—O1 | 86.26 (11) | O3—N21—O1 | 120.0 (3) |
N4—Cu1—O1 | 95.68 (10) | N21—O1—Cu1 | 135.2 (2) |
O2—N21—O3 | 120.9 (3) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O3 | 0.93 | 2.54 | 3.382 (5) | 151 |
C5—H5A···O2i | 0.93 | 2.36 | 3.178 (5) | 146 |
C5—H5A···O1ii | 0.93 | 2.56 | 3.010 (4) | 111 |
C15—H15A···O3i | 0.93 | 2.40 | 3.237 (4) | 149 |
C17—H17A···O2iii | 0.96 | 2.60 | 3.180 (5) | 120 |
Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, y−1/2, −z+1/2. |
Selected geometric parameters (Å, º) for (II) topCu1—N4 | 2.007 (2) | N21—O31 | 1.226 (2) |
Cu1—N14 | 2.018 (2) | N21—O2 | 1.255 (2) |
Cu1—O1 | 2.416 (2) | N21—O32 | 1.296 (2) |
O1—N21 | 1.259 (2) | | |
| | | |
N4—Cu1—N14i | 90.18 (7) | O31—N21—O2 | 113.35 (16) |
N4—Cu1—N14 | 89.82 (7) | O31—N21—O1 | 124.75 (16) |
N4—Cu1—O1 | 95.59 (8) | O2—N21—O1 | 120.47 (15) |
N14—Cu1—O1 | 90.02 (8) | O2—N21—O32 | 127.05 (15) |
N21—O1—Cu1 | 134.70 (11) | O1—N21—O32 | 111.38 (16) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O2 | 0.93 | 2.43 | 3.158 (3) | 135 |
C15—H15···O1 | 0.93 | 2.60 | 3.139 (3) | 118 |
C15—H15···O2 | 0.93 | 2.39 | 3.147 (4) | 139 |
C5—H5A···O2ii | 0.93 | 2.49 | 3.202 (3) | 133 |
C5—H5A···O31ii | 0.93 | 2.55 | 3.420 (3) | 157 |
C13—H13···O32iii | 0.93 | 2.55 | 3.234 (4) | 131 |
Symmetry codes: (ii) x−1, y, z; (iii) x−1, y+1, z. |
The complexing behaviour of 1-alkyl-1,2,4-triazoles has been investigated in aqueous solution by means of pH-metric and spectrophotometric methods (Gabryszewski, 1992). It has been concluded that the bulk of the alkyl group does not influence significantly the stability of complexes of 1-alkyl-1,2,4-triazoles. The stability of such complexes is approximately equal to that of unsubstituted 1,2,4-triazole (Gabryszewski, 1992). This fact suggested coordination of ligands through the N atom in the 4-position, since it is the N atom furthest from the alkyl group and thus the least sterically affected.
The coordination complexes tetrakis(1-ethyl-1,2,4-triazole)bis(nitrato)copper(II), (I), and tetrakis(1-propyl-1,2,4-triazole)bis(nitrato)copper(II), (II), were prepared in the solid state and initially characterized using IR, far-IR and visible spectroscopy, and magnetic susceptibility data (Gabryszewski & Wieczorek, 2000). These methods indicated that the ligands are monodentate and form complexes with distorted octahedral environments. However, in order to determine the donor N atoms of the ligands, the X-ray single-crystal diffraction method was used.
The molecular structure of (I) is shown in Fig. 1, while (II) is presented in Fig. 2. Selected geometric parameters are listed in Tables 1 and 3. Both complexes possess a distorted octahedral geometry, with the copper(II) ions located on centers of inversion coordinated by four N atoms of the triazole rings and two O atoms from the nitrate ions. The N atoms form a rectangular plane containing the copper ion at the center. The two nitrate ligands are positioned trans to one another, above and below the CuN4 plane, thus completing the tetragonally distorted octahedral coordination of the copper ion. This elongation is a result of the Jahn–Teller effect for Cu2+. Similar elongated octahedral coordination of CuII atoms is found in other molecules with CuN4O2 environments, e.g. bis(2-aminomethylpyridine-N,N')bis(nitrato-O)copper(II) (Kooijman et al., 1997), bis(dibenzene-1,2-diamine)bis(nitrato)copper(II) (Suprija & Das, 2003) and bis(di-2-pyridilamine)dinitratocopper(II) (Munoz et al., 1993). The Cu—N bond lengths in those compounds are between 1.998 (1) and 2.019 (1) Å, very close to those found in (I) and (II). The Cu—O bond lengths range between 2.477 (2) Å (Munoz et al., 1993) and 2.543 (1) Å (Kooijman et al., 1997), and are significantly longer than those found in (I) and (II).
The N—Cu—N angles in (I) and (II) are all close to the ideal in a regular octahedron. The trans angles are equal to 180°, as required by symmetry, while the cis angles differ only slightly from 90°. For (II), the difference is 0.18 (7)°, whereas for (I), it is 1.21 (11)°. The largest angular distortions of the octahedron occur in the N—Cu—O angles. They differ from 90° by 3.74 (11) and 5.68 (10)° in (I), and 0.02 (8) and 5.59 (8)° in (II).
Examples of complexes containing four 1,2,4-triazoles, coordinating through atoms N4, are tetrakis[3,3-dimethyl-1-(1 H-1,2,4-triazolyl)-2-butanone]copper(II) diperchlorate (Jiansheng et al., 1997), which shows square-planar coordination of copper(II), and tetrakis[1-(3-chloropropyl)-1,2,4-triazole]bis(tetrafluoroborato) copper(II) (Mills et al., 2002), which has a distorted octahedral coordination. In those structures, the N—Cu bond lengths are similar to those found in (I) and (II). The cis N—Cu—N angles also do not differ from 90° by more than 1.5°, while the trans N—Cu—N angles differ from 180° by not more than 3.5°.
The N1/N2/C3/N4/C5 plane of the triazole ring is tilted by 47.06 (1)° for (I) and 68.64 (14)° for (II) with respected to the CuN4 coordination plane, whereas the N11/N12/C13/N14/C15 plane is tilted with respect to the CuN4 plane by 85.43 (8)° for (I) and 74.25 (14)° for (II).
The packing diagrams of structures (I) and (II) are presented in Figs. 2 and 4. The copper(II) centers of the complexes are well separated, the closest distance being 8.386 (1) Å in (I) and 8.027 (1) Å in (II).
In both structures there are only weak C—H···O hydrogen bonds, the closest C···O distances being between 3.010 (4) and 3.382 (5) Å in (I), and 3.139 (3) and 3.420 (3) Å in (II) (Tables 2 and 4). The NO3 group in (II) is disordered. Atom O3 atom has two positions occupied at 50%, denoted O31 and O32. We first measured the structures of both (I) and (II) at room temperature. Since the displacement ellipsoid of atom O3 for (II) was very large, we decided to measure both structures at 100 K. We have found that the distortion of atom O3 is also present at 100 K, therefore it was split into the O31 and O32 positions. The apparent reason for disorder comes from the fact that there is a possibility of forming hydrogen bonds at both positions, C5–H5A···O31i and C13–H13A···O32ii [symmetry codes: (i) x − 1, y, z; (ii) x − 1, 1 + y, z].