metal-organic compounds
Bis(N-nitroso-N-pentylhydroxylaminato-κ2O,O′)copper(II)
aPeoples' Friendship University of Russia, 6 Miklukho-Mallaya, 117198 Moscow, Russian Federation, bKarpov Institute of Physical Chemistry, 10 Vorontsovo Pole, 105064 Moscow, Russian Federation, and cThe Institute of Problems of Chemical Physics of the Russian Academy of Sciences (IPCP RAS), Academician Semenov Avenue 1, Chernogolovka, Moscow region, 142432, Russian Federation
*Correspondence e-mail: alishkh144@gmail.com
In the centrosymmetric title compound, [Cu(C5H11N2O2)2], the Cu2+ ion, located on an inversion centre (Wyckoff position 2b), is in a square-planar environment, surounded by four O atoms of the N—O groups of two N-nitroso-N-pentylhydroxylaminate ligands [Cu—O = 1.9042 (17) and 1.9095 (16) Å]. The hydroxylaminate monoanions are bidentate chelating ligands. The Cu2+ cations form stacks along [010], with intermolecular Cu⋯N contacts of 3.146 (2) and 3.653 (2) Å.
CCDC reference: 989916
Related literature
The basic procedure for the synthesis of the reported complex is described by Zyuzin et al. (1997). For related structures of copper complexes with the N-nitrosohydroxylamine derivatives, see: Abraham et al. (1987); Kovalchukova et al. (2013, 2014). The synthesis and properties of other metal nitrosohydroxylaminates are given in: Ahmed et al. (1988); Basson et al. (1992); Bolboaca et al. (2000); Kovalchukova et al. (2013); Najafi et al. (2011); Okabe & Tamaki (1995); Parkanyi et al. (1999); Pavel et al. (2000); Tamaki & Okabe (1998); Van der Helm et al. (1965). For applications of N-nitrosohydroxylamine derivatives see: Lundell & Knowles (1920); Buscarons & Canela (1974); Oztekin & Erim (2000); McGill et al. (2000).
Experimental
Crystal data
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Data collection: CAD-4-PC (Enraf–Nonius, 1993); cell CAD-4-PC; data reduction: CAD-4-PC; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXXTL (Sheldrick, 2008); software used to prepare material for publication: CIFTAB97 and SHELXL97.
Supporting information
CCDC reference: 989916
10.1107/S1600536814004978/pj2009sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814004978/pj2009Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814004978/pj2009Isup3.mol
The title compound was obtained in accordance with the previously published procedure (Zyuzin et al., 1997) with some modifications. A solution of n-pentylmagnesium chloride was prepared from magnesium (12.2 g, 0.5 mol) and 1-bromopentane (75.5 g, 0.5 mol) in the dry Et2O (0.5 L). The NO gas was bubbled through the solution under vigorous stirring and cooling at such a rate that NO was almost entirely absorbed. The reaction mixture temperature was maintained in the range 248 to 243 K. After the period of a rapid NO absorption (1 h), stirring was continued in an NO atmosphere for 0.5 h until the NO absorption was completed, with a gradual increase in temperature to 263 K. The reaction mixture was purged with Ar, treated with MeOH (100 mL), poured into ice (300 g) and acidified with 2 M H2SO4. The organic layer was separated, and the aqueous layer was extracted with Et2O (100 mL × 3). The combined extracts were washed with 50 mL 1 M NaOH and 50 mL H2O. The aqueous layer was neutralized with 2 M H2SO4 until pH 4 and treated with 20 per cent CuSO4 solution (120 g, 0.2 mol). The blue precipitate was washed with water, dried and crystallized from EtOH. Yield 42.3 g (52 per cent), blue crystals, m.p. 355–356 K. Analysis calculated for C10H22CuN4O4: Cu 19.50; found: Cu 18.83. Single crystals of C10H22CuN4O4 were grown by the slow evaporation of the ethanol solution of the bis[N-nitroso-N-(n-pentyl)hydroxylaminato] copper(II) powdered sample.
The structure of of C10H22CuN4O4 was solved by direct method and all non-hydrogen atoms were located and refined anisotropically. All the hydrogen atoms added using a riding model.
Data collection: CAD-4-PC (Enraf–Nonius, 1993); cell
CAD-4-PC (Enraf–Nonius, 1993); data reduction: CAD-4-PC (Enraf–Nonius, 1993); 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: CIFTAB97 and SHELXL97 (Sheldrick, 2008).[Cu(C5H11N2O2)2] | F(000) = 342 |
Mr = 325.86 | Dx = 1.402 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 14.325 (3) Å | θ = 9.7–11.9° |
b = 4.776 (1) Å | µ = 1.43 mm−1 |
c = 11.619 (2) Å | T = 293 K |
β = 103.82 (3)° | Plate, blue |
V = 771.9 (3) Å3 | 0.80 × 0.20 × 0.03 mm |
Z = 2 |
Enraf–Nonius CAD-4 diffractometer | 871 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
β-filter monochromator | θmax = 25.5°, θmin = 2.9° |
ω/2τ scans | h = −17→16 |
Absorption correction: part of the (Walker & Stuart, 1983) | model (ΔF) k = −5→0 |
Tmin = 0.202, Tmax = 0.670 | l = 0→13 |
1509 measured reflections | 3 standard reflections every 60 min |
1429 independent reflections | intensity decay: none |
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) = 0.073 | H-atom parameters constrained |
S = 0.88 | w = 1/[σ2(Fo2) + (0.049P)2] where P = (Fo2 + 2Fc2)/3 |
1429 reflections | (Δ/σ)max < 0.001 |
88 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.68 e Å−3 |
[Cu(C5H11N2O2)2] | V = 771.9 (3) Å3 |
Mr = 325.86 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.325 (3) Å | µ = 1.43 mm−1 |
b = 4.776 (1) Å | T = 293 K |
c = 11.619 (2) Å | 0.80 × 0.20 × 0.03 mm |
β = 103.82 (3)° |
Enraf–Nonius CAD-4 diffractometer | 871 reflections with I > 2σ(I) |
Absorption correction: part of the (Walker & Stuart, 1983) | model (ΔF) Rint = 0.030 |
Tmin = 0.202, Tmax = 0.670 | 3 standard reflections every 60 min |
1509 measured reflections | intensity decay: none |
1429 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 0.88 | Δρmax = 0.32 e Å−3 |
1429 reflections | Δρmin = −0.68 e Å−3 |
88 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.5000 | 0.5000 | 0.5000 | 0.04458 (15) | |
O1 | 0.38526 (12) | 0.6395 (4) | 0.39762 (14) | 0.0498 (4) | |
O2 | 0.55742 (13) | 0.7912 (3) | 0.42774 (14) | 0.0498 (4) | |
N1 | 0.40843 (14) | 0.8595 (4) | 0.34077 (15) | 0.0447 (4) | |
N2 | 0.49421 (15) | 0.9440 (4) | 0.35334 (17) | 0.0481 (5) | |
C1 | 0.33006 (17) | 1.0104 (6) | 0.26151 (19) | 0.0506 (5) | |
H11 | 0.3559 | 1.1716 | 0.2288 | 0.061* | |
H12 | 0.2855 | 1.0778 | 0.3063 | 0.061* | |
C2 | 0.2767 (2) | 0.8251 (6) | 0.1611 (2) | 0.0577 (6) | |
H21 | 0.3225 | 0.7366 | 0.1232 | 0.069* | |
H22 | 0.2431 | 0.6788 | 0.1928 | 0.069* | |
C3 | 0.20524 (19) | 0.9925 (7) | 0.0702 (2) | 0.0647 (6) | |
H31 | 0.2394 | 1.1373 | 0.0383 | 0.078* | |
H32 | 0.1606 | 1.0840 | 0.1091 | 0.078* | |
C4 | 0.1491 (3) | 0.8157 (8) | −0.0308 (3) | 0.0848 (10) | |
H41 | 0.1094 | 0.6844 | 0.0000 | 0.102* | |
H42 | 0.1937 | 0.7083 | −0.0641 | 0.102* | |
C5 | 0.0852 (3) | 0.9888 (11) | −0.1285 (3) | 0.1163 (15) | |
H51 | 0.0516 | 0.8669 | −0.1903 | 0.174* | |
H52 | 0.1242 | 1.1171 | −0.1603 | 0.174* | |
H53 | 0.0396 | 1.0918 | −0.0966 | 0.174* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0460 (2) | 0.0446 (2) | 0.0432 (2) | −0.0028 (2) | 0.01086 (14) | 0.0008 (2) |
O1 | 0.0449 (9) | 0.0472 (9) | 0.0562 (9) | −0.0053 (8) | 0.0097 (7) | 0.0084 (8) |
O2 | 0.0473 (10) | 0.0532 (9) | 0.0505 (9) | −0.0062 (8) | 0.0147 (7) | 0.0020 (7) |
N1 | 0.0485 (12) | 0.0428 (11) | 0.0428 (9) | −0.0033 (9) | 0.0112 (8) | −0.0001 (8) |
N2 | 0.0508 (12) | 0.0499 (14) | 0.0448 (10) | −0.0036 (9) | 0.0137 (8) | 0.0016 (8) |
C1 | 0.0521 (13) | 0.0470 (11) | 0.0533 (11) | 0.0052 (14) | 0.0138 (10) | 0.0037 (14) |
C2 | 0.0538 (15) | 0.0578 (16) | 0.0584 (14) | 0.0037 (13) | 0.0073 (12) | −0.0015 (12) |
C3 | 0.0556 (15) | 0.0693 (15) | 0.0641 (14) | 0.0041 (17) | 0.0042 (11) | 0.0016 (17) |
C4 | 0.069 (2) | 0.092 (3) | 0.081 (2) | 0.0044 (19) | −0.0064 (16) | −0.0107 (19) |
C5 | 0.099 (3) | 0.140 (4) | 0.086 (2) | −0.002 (3) | −0.025 (2) | −0.002 (3) |
Cu1—O1 | 1.9042 (17) | C2—H21 | 0.9700 |
Cu1—O1i | 1.9042 (17) | C2—H22 | 0.9700 |
Cu1—O2i | 1.9095 (16) | C3—C4 | 1.512 (4) |
Cu1—O2 | 1.9095 (16) | C3—H31 | 0.9700 |
O1—N1 | 1.325 (3) | C3—H32 | 0.9700 |
O2—N2 | 1.314 (2) | C4—C5 | 1.521 (5) |
N1—N2 | 1.268 (3) | C4—H41 | 0.9700 |
N1—C1 | 1.461 (3) | C4—H42 | 0.9700 |
C1—C2 | 1.518 (4) | C5—H51 | 0.9600 |
C1—H11 | 0.9700 | C5—H52 | 0.9600 |
C1—H12 | 0.9700 | C5—H53 | 0.9600 |
C2—C3 | 1.512 (4) | ||
O1—Cu1—O1i | 180.0 | C3—C2—H22 | 109.4 |
O1—Cu1—O2i | 97.54 (7) | C1—C2—H22 | 109.4 |
O1i—Cu1—O2i | 82.46 (7) | H21—C2—H22 | 108.0 |
O1—Cu1—O2 | 82.46 (7) | C2—C3—C4 | 113.1 (3) |
O1i—Cu1—O2 | 97.54 (7) | C2—C3—H31 | 109.0 |
O2i—Cu1—O2 | 180.0 | C4—C3—H31 | 109.0 |
N1—O1—Cu1 | 107.90 (13) | C2—C3—H32 | 109.0 |
N2—O2—Cu1 | 113.09 (14) | C4—C3—H32 | 109.0 |
N2—N1—O1 | 123.09 (19) | H31—C3—H32 | 107.8 |
N2—N1—C1 | 119.6 (2) | C3—C4—C5 | 112.9 (3) |
O1—N1—C1 | 117.35 (19) | C3—C4—H41 | 109.0 |
N1—N2—O2 | 113.32 (18) | C5—C4—H41 | 109.0 |
N1—C1—C2 | 111.5 (2) | C3—C4—H42 | 109.0 |
N1—C1—H11 | 109.3 | C5—C4—H42 | 109.0 |
C2—C1—H11 | 109.3 | H41—C4—H42 | 107.8 |
N1—C1—H12 | 109.3 | C4—C5—H51 | 109.5 |
C2—C1—H12 | 109.3 | C4—C5—H52 | 109.5 |
H11—C1—H12 | 108.0 | H51—C5—H52 | 109.5 |
C3—C2—C1 | 111.2 (2) | C4—C5—H53 | 109.5 |
C3—C2—H21 | 109.4 | H51—C5—H53 | 109.5 |
C1—C2—H21 | 109.4 | H52—C5—H53 | 109.5 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C5H11N2O2)2] |
Mr | 325.86 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 14.325 (3), 4.776 (1), 11.619 (2) |
β (°) | 103.82 (3) |
V (Å3) | 771.9 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.43 |
Crystal size (mm) | 0.80 × 0.20 × 0.03 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Part of the refinement model (ΔF) (Walker & Stuart, 1983) |
Tmin, Tmax | 0.202, 0.670 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1509, 1429, 871 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.073, 0.88 |
No. of reflections | 1429 |
No. of parameters | 88 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.68 |
Computer programs: CAD-4-PC (Enraf–Nonius, 1993), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CIFTAB97 and SHELXL97 (Sheldrick, 2008).
Acknowledgements
This research was supported by the Russian Foundation for Basic Research (grant 13–03–00079).
References
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The chelate-forming derivatives of N-nitroso hydroxylamines form stable complexes with the metallic ions of various natures but only few of them have been structurally characterized (Abraham et al., 1987; Ahmed et al., 1988; Basson et al., 1992; Bolboaca et al., 2000; Kovalchukova et al., 2013; Najafi et al., 2011; Okabe & Tamaki, 1995; Parkanyi et al., 1999; Pavel et al., 2000; Tamaki & Okabe, 1998; Van der Helm et al., 1965). Their ammonium and potassium salts are reported as good analytical reagents for different purposes (Lundell & Knowles, 1920; Buscarons & Canela, 1974; Oztekin & Erim, 2000). In addition, recently it was reported that many o-substituted N-nitroso-N-oxybenzenamines are good NO donors for both in vitro and in vivo assays (McGill et al., 2000). The title compound C10H22CuN4O4 (Fig. 1) is centrosymmetric with the Cu2+ ion located on the inversion centre (Wyckoff position 2b) in square planar coordination, surounded by four oxo O atoms of the N—O groups of two organic ligands [Cu—O = 1.9042 (17) and 1.90905 (16) Å]. The molecule of the metal complex is completed by the 1-x, 1-y, 1-z symmetry operation. The mean deviation from the plane is 0.0199 Å. The N-nitroso-N-(n-pentyl)hydroxylaminate anions are bidentate chelating ligands. The Cu cations in the columns form stacks in the columns along the [010] direction with intermolecular Cu—N contacts equal to 3.146 (2) and 3.653 (2) Å (Fig. 2). The described coordination type of the central atom correlates with those described previously for the bis(N– nitroso-N-benzyl-hydroxylaminato-o,o) copper(II) (Kovalchukova et al., 2013) and bis(N-nitroso-N-ethyl-hydroxylaminato-o,o) copper(II) (Kovalchukova et al., 2014).