Aqua­(azido)[N-(pyridin-2-ylcarbon­yl)pyridine-2-carboxamido-κ3N,N′,N′′]copper(II)

Bruda, S.; Turnbull, M.M.; Wikaira, J.L.

doi:10.1107/S1600536813027499

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Pages m598-m599

doi:10.1107/S1600536813027499

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Aqua(azido)[N-(pyridin-2-ylcarbonyl)pyridine-2-carboxamido-κ³N,N′,N′′]copper(II)

Sandra Bruda,^a Mark M. Turnbull ^a ^* and Jan L. Wikaira ^b

^aDepartment of Chemistry, Clark University, 950 Main St, Worcester, MA 01610, USA, and ^bDepartment of Chemistry, University of Canterbury, Private Bag 4800, Christchurch, New Zealand
^*Correspondence e-mail: mturnbull@clarku.edu

(Received 4 October 2013; accepted 7 October 2013; online 12 October 2013)

The title compound, [Cu(C₁₂H₈N₃O₂)(N₃)(H₂O)], was formed by the air oxidation of 2-(aminomethyl)pyridine in 95% ethanol in the presence of copper(II) nitrate and sodium azide with condensation of the resulting picolinamide molecules to generate the imide moiety. The Cu^II ion has a square-pyramidal coordination sphere, the basal plane being occupied by four N atoms [two pyridine (py) N atoms, the imide N atom and an azide N atom] in a nearly planar array [mean deviation = 0.048 (6) Å] with the Cu^II ion displaced slightly from the plane [0.167 (5) Å] toward the fifth ligand. The apical position is occupied by a coordinating water molecule [Cu—O = 2.319 (4) Å]. The crystal structure is stabilized by hydrogen-bonding interactions between the water molecules and carbonyl O atoms. The inversion-related square-pyramidal complex molecules pack base-to-base with long Cu⋯N_py contact distances of 3.537 (9) Å, preventing coordination of a sixth ligand.

CCDC reference: 949825

Related literature

For magneto-structural relationships in Cu^II complexes, see: Landee & Turnbull (2013 ). For copper(II)-catalysed air-oxidation of 2-aminomethylpyridine, see: Sahu et al. (2010 ); Turnbull et al. (2013 ). For the corresponding dicyanamide complex, see: Vangdal et al. (2002 ) and for the tricyanomethanide complex, see: de Gomes et al. (2008 ). For the bromide complex, see: Zhou et al. (2006 ) and for the fluoride and formate analogues, see: Borras et al. (2007 ). For the cyanate and thiocyanate complexes, see: Dey et al. (2002 ) and Madariaga et al. (1991 ), respectively. For a related 2-aminomethylpyridine structure, see: Bruda et al. (2006 ). For the τ parameter as a geometry predictor in coordination complexes, see: Addison et al. (1984 ).

Experimental

Crystal data

[Cu(C₁₂H₈N₃O₂)(N₃)(H₂O)]
M_r = 349.80
Triclinic, $[P \overline 1]$
a = 7.402 (4) Å
b = 8.900 (5) Å
c = 10.606 (6) Å
α = 78.186 (9)°
β = 84.118 (8)°
γ = 70.040 (7)°
V = 642.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 1.72 mm⁻¹
T = 168 K
0.28 × 0.06 × 0.03 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.854, T_max = 1.000
7577 measured reflections
2258 independent reflections
1837 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.105
S = 1.17
2258 reflections
205 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O9ⁱ	0.85 (2)	2.10 (4)	2.843 (5)	145 (5)
O1—H1B⋯O7ⁱⁱ	0.84 (2)	2.13 (3)	2.922 (5)	157 (5)
O1—H1A⋯O7ⁱ	0.85 (2)	2.45 (4)	3.105 (5)	134 (5)
Symmetry codes: (i) -x, -y+1, -z; (ii) x+1, y, z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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: SHELXL97, enCIFer (Allen et al., 2004 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 949825

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813027499/sj5358sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813027499/sj5358Isup2.hkl

checkCIF report

Comment top

We are interested in the design and synthesis of Cu^II complexes to study magnetostructural relationships in low-dimensional magnetic lattics (Landee and Turnbull, 2013). In this work, a wide variety of heterocyclic amines such as substituted pyrazine and pyridine compounds have been employed both as ligands and as bases. One such compound has been 2-aminomethylpyridine (Bruda et al., 2006). We were attempting the preparation of a series of Cu^II complexes employing the 2-aminomethylpyridine molecule as a blocking agent to limit coordination by other species when we encountered the Cu^II catalyzed air-oxidation and condensation of 2-aminomethylpyridine and resulting in situ formation of a Cu^II nitrate complex of N-(pridin-2-ylcarboyl)pyridine-2-carbamide (bis-picolinimide; bpa) (Turnbull et al., 2013). A similar reaction, in the presence of azide ion, has shown the same oxidation and condensation resulting in the preparation of [(N-(pyridin-2-ylcarboyl)pyridine2-carboxamido)(azido)(aqua)copper(II)] (1).

Crystals of (1) (Figure 1) were produced via slow crystallization in air of an ethanolic solution of Cu(NO₃)₂·3H₂O, 2-aminomethylpyridine and sodium azide. The Cu^II ion is coordinated by one bpa anion, one azide anion and a water molecule to generate a nearly square pyramidal, five-coordinate structure. The basal plane is composed of three nitrogen atoms from the bpa ligand and the coordinated azide ion. The four N-atoms are planar within 0.048 (6) Å and the Cu^II ion is displaced 0.167 (5) Å out of this plane. The O-atom of the water molecule is located in the apical position [Cu—O = 2.319 (4)Å]. The Addison parameter is 0.053, indicating that the geometry is very close to square pyramidal (Addison et al., 1984).

The pyridine rings in the bpa ligand are virtually planar (mean deviation of constituent atoms = 0.0021 (8) N1-ring; 0.003 (2) N15-ring) and the rings themselves are nearly co-planar (2.5 (1)°). The lattice structure of (1) is supported by hydrogen bonds between the coordinated water molecule (donor) and the carbonyl oxygen atoms (acceptor) of adjacent bpa ligands (see Figure 2, Table 1). The five-coordinate nature of the Cu^II ion is stabilized by long intermolecular Cu···N contacts between inversion related molecules [dCu···N15A = 3.537 (9) Å (-x, 2-y, -z)] effectively blocking the basal face of the square pyramidal structure and preventing coordination of a sixth ligand (see Figure 2).

Sahu and co-workers (Sahu et al., 2010) have previously observed the copper catalyzed air-oxidation and condensation of 2-aminomethylpyridine to bpa as well as the corresponding reaction for 2-aminomethylquinoline. Similar structures have been reported with other inorganic anions replacing the azide ion including halides [Br, (Zhou et al., 2006); F, (Borras et al., 2007)], pseudo halides [OCN, (Dey et al., 2002); SCN, (Madariaga, et al., 1991)] and cyanamide derivatives (Vangdal, et al., 2002; de Gomes et al. 2008)].

Experimental top

Cu(NO₃)₂.3H₂O, ethanol and NaN₃ were obtained from VWR Scientific while 2-aminomethylpyridine was purchased from Aldrich Chemical. All were used as received.

Synthesis and crystallization top

Cu(NO₃)₂^.3H₂O (0.241 g, 1.00 mmol), NaN₃ (0.071g, 1.1 mmol) and 2-aminomethylpyridine (0.237 g,2.20 mmol) were dissolved in 20 ml of 95% ethanol in a 50 mL beaker and the beaker covered with parafilm with a couple of small holes in the film. Over the course of 2 weeks, blue needle-shaped crystals of (1) formed, which were isolated by filtration to give (1) 0.082 g (23 %).

Refinement top

All H-atoms bound to carbon were placed in calculated positions (C—H = 0.95 Å) and refined using a riding model with U_iso=1.2U_eq (C). Hydrogen atoms bonded to oxygen atoms were located in the difference map and their positions allowed to refine using anti-bumping restraints (0.85 Å for O—H distances) and fixed isotropic U values [U_iso=1.2U_eq (O)].

Related literature top

For magneto structural relationships in Cu^II complexes, see: Landee & Turnbull (2013). For copper(II)-catalysed air-oxidation of 2-aminomethylpyridine, see: Sahu et al. (2010); Turnbull et al. (2013). For the corresponding dicyanamide complex, see: Vangdal et al. (2002) and for the tricyanomethanide complex, see: de Gomes et al. (2008). For the bromide complex, see: Zhou et al. (2006) and for the fluoride and formate analogues, see: Borras et al. (2007). For the cyanate and thiocyanate complexes, see: Dey et al. (2002) and Madariaga et al. (1991), respectively. For a related 2-aminomethylpyridine structure, see: Bruda et al. (2006). For the Addison parameter as a geometry predictor in coordination complexes, see: Addison et al. (1984).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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: SHELXL97 (Sheldrick, 2008), enCIFer (Allen et al., 2004) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. - Thermal ellipsoid plot (50%) of the molecular unit of (1). Only those H-atoms whose positions were refined are labeled.
	Fig. 2. - Packing diagram of (1) showing hydrogen bonds and short Cu···N intermolecular contacts (dashed lines).

Aqua(azido)[N-(pyridin-2-ylcarbonyl)pyridine-2-carboxamido-κ³N,N',N'']copper(II) top

Crystal data top

[Cu(C₁₂H₈N₃O₂)(N₃)(H₂O)]	Z = 2
M_r = 349.80	F(000) = 354
Triclinic, P1	D_x = 1.808 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.402 (4) Å	Cell parameters from 2526 reflections
b = 8.900 (5) Å	θ = 2.9–26.0°
c = 10.606 (6) Å	µ = 1.72 mm⁻¹
α = 78.186 (9)°	T = 168 K
β = 84.118 (8)°	Needle, blue
γ = 70.040 (7)°	0.28 × 0.06 × 0.03 mm
V = 642.4 (6) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	2258 independent reflections
Radiation source: fine-focus sealed tube	1837 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ & ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.854, T_max = 1.000	k = −9→10
7577 measured reflections	l = −12→12

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0191P)² + 2.3778P] where P = (F_o² + 2F_c²)/3
2258 reflections	(Δ/σ)_max = 0.001
205 parameters	Δρ_max = 0.50 e Å⁻³
2 restraints	Δρ_min = −0.69 e Å⁻³

Crystal data top

[Cu(C₁₂H₈N₃O₂)(N₃)(H₂O)]	γ = 70.040 (7)°
M_r = 349.80	V = 642.4 (6) Å³
Triclinic, P1	Z = 2
a = 7.402 (4) Å	Mo Kα radiation
b = 8.900 (5) Å	µ = 1.72 mm⁻¹
c = 10.606 (6) Å	T = 168 K
α = 78.186 (9)°	0.28 × 0.06 × 0.03 mm
β = 84.118 (8)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2258 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1837 reflections with I > 2σ(I)
T_min = 0.854, T_max = 1.000	R_int = 0.063
7577 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	2 restraints
wR(F²) = 0.105	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.50 e Å⁻³
2258 reflections	Δρ_min = −0.69 e Å⁻³
205 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	U_iso*/U_eq
Cu	0.09830 (10)	0.76976 (9)	0.14071 (7)	0.0155 (2)
N1	−0.0741 (6)	0.7152 (5)	0.2890 (4)	0.0185 (11)
C2	−0.0718 (8)	0.7285 (7)	0.4124 (5)	0.0220 (13)
H2	0.0206	0.7691	0.4361	0.026*
C3	−0.1984 (8)	0.6857 (7)	0.5071 (6)	0.0247 (14)
H3	−0.1926	0.6958	0.5939	0.030*
C4	−0.3340 (8)	0.6274 (7)	0.4709 (6)	0.0263 (14)
H4	−0.4235	0.5976	0.5331	0.032*
C5	−0.3374 (8)	0.6133 (7)	0.3427 (5)	0.0244 (14)
H5	−0.4291	0.5738	0.3167	0.029*
C6	−0.2058 (7)	0.6573 (6)	0.2541 (5)	0.0169 (12)
C7	−0.2052 (8)	0.6497 (6)	0.1132 (5)	0.0180 (12)
O7	−0.3162 (5)	0.5945 (5)	0.0733 (4)	0.0232 (9)
N8	−0.0714 (6)	0.7116 (5)	0.0432 (4)	0.0164 (10)
C9	−0.0375 (7)	0.7206 (6)	−0.0861 (5)	0.0151 (12)
O9	−0.1195 (5)	0.6830 (5)	−0.1644 (4)	0.0227 (9)
C10	0.1237 (7)	0.7882 (6)	−0.1305 (5)	0.0163 (12)
C11	0.1863 (8)	0.8111 (6)	−0.2593 (5)	0.0195 (13)
H11	0.1276	0.7848	−0.3234	0.023*
C12	0.3370 (8)	0.8732 (7)	−0.2914 (5)	0.0237 (13)
H12	0.3830	0.8901	−0.3783	0.028*
C13	0.4194 (8)	0.9104 (7)	−0.1954 (5)	0.0228 (13)
H13	0.5227	0.9528	−0.2159	0.027*
C14	0.3502 (8)	0.8853 (7)	−0.0697 (6)	0.0229 (13)
H14	0.4076	0.9103	−0.0041	0.028*
N15	0.2036 (6)	0.8264 (5)	−0.0380 (4)	0.0165 (10)
N16	0.2400 (7)	0.8814 (6)	0.2117 (5)	0.0241 (12)
N17	0.2333 (6)	0.9146 (6)	0.3164 (5)	0.0206 (11)
N18	0.2343 (8)	0.9525 (7)	0.4143 (5)	0.0365 (14)
O1	0.3387 (5)	0.5191 (5)	0.1809 (4)	0.0217 (9)
H1A	0.305 (8)	0.455 (6)	0.147 (5)	0.026*
H1B	0.440 (5)	0.520 (7)	0.138 (5)	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.0162 (4)	0.0193 (4)	0.0141 (4)	−0.0097 (3)	0.0013 (3)	−0.0040 (3)
N1	0.018 (3)	0.023 (3)	0.016 (3)	−0.008 (2)	−0.001 (2)	−0.004 (2)
C2	0.023 (3)	0.029 (3)	0.020 (3)	−0.015 (3)	0.004 (3)	−0.010 (3)
C3	0.033 (3)	0.029 (4)	0.015 (3)	−0.013 (3)	0.007 (3)	−0.007 (3)
C4	0.027 (3)	0.029 (4)	0.023 (3)	−0.014 (3)	0.008 (3)	−0.004 (3)
C5	0.022 (3)	0.031 (4)	0.027 (3)	−0.016 (3)	0.005 (3)	−0.013 (3)
C6	0.020 (3)	0.010 (3)	0.018 (3)	−0.003 (2)	0.002 (2)	−0.002 (2)
C7	0.020 (3)	0.013 (3)	0.021 (3)	−0.005 (2)	0.000 (2)	−0.006 (2)
O7	0.023 (2)	0.028 (2)	0.026 (2)	−0.0158 (19)	0.0003 (18)	−0.0074 (18)
N8	0.019 (2)	0.019 (3)	0.016 (3)	−0.012 (2)	0.000 (2)	−0.004 (2)
C9	0.016 (3)	0.014 (3)	0.015 (3)	−0.005 (2)	−0.006 (2)	0.001 (2)
O9	0.021 (2)	0.028 (2)	0.021 (2)	−0.0119 (18)	−0.0018 (18)	−0.0023 (18)
C10	0.016 (3)	0.013 (3)	0.019 (3)	−0.005 (2)	0.000 (2)	−0.001 (2)
C11	0.021 (3)	0.022 (3)	0.015 (3)	−0.007 (3)	−0.004 (2)	0.000 (2)
C12	0.024 (3)	0.029 (3)	0.016 (3)	−0.008 (3)	0.005 (2)	−0.002 (3)
C13	0.016 (3)	0.028 (3)	0.025 (3)	−0.012 (3)	0.006 (2)	0.000 (3)
C14	0.020 (3)	0.020 (3)	0.032 (4)	−0.011 (3)	0.001 (3)	−0.005 (3)
N15	0.012 (2)	0.020 (3)	0.019 (3)	−0.007 (2)	−0.0003 (19)	−0.003 (2)
N16	0.026 (3)	0.034 (3)	0.022 (3)	−0.022 (2)	0.001 (2)	−0.009 (2)
N17	0.022 (3)	0.024 (3)	0.020 (3)	−0.014 (2)	−0.005 (2)	−0.001 (2)
N18	0.044 (3)	0.052 (4)	0.024 (3)	−0.026 (3)	−0.004 (3)	−0.011 (3)
O1	0.016 (2)	0.025 (2)	0.025 (2)	−0.0093 (18)	0.0014 (17)	−0.0069 (18)

Geometric parameters (Å, º) top

Cu—N16	1.958 (4)	N8—C9	1.359 (7)
Cu—N8	1.961 (4)	C9—O9	1.235 (6)
Cu—N15	2.007 (4)	C9—C10	1.505 (7)
Cu—N1	2.009 (4)	C10—N15	1.350 (7)
Cu—O1	2.319 (4)	C10—C11	1.393 (7)
N1—C2	1.341 (6)	C11—C12	1.390 (7)
N1—C6	1.359 (6)	C11—H11	0.9500
C2—C3	1.388 (7)	C12—C13	1.386 (8)
C2—H2	0.9500	C12—H12	0.9500
C3—C4	1.393 (8)	C13—C14	1.380 (8)
C3—H3	0.9500	C13—H13	0.9500
C4—C5	1.394 (8)	C14—N15	1.344 (6)
C4—H4	0.9500	C14—H14	0.9500
C5—C6	1.382 (7)	N16—N17	1.198 (6)
C5—H5	0.9500	N17—N18	1.157 (6)
C6—C7	1.509 (7)	O1—H1A	0.85 (2)
C7—O7	1.236 (6)	O1—H1B	0.84 (2)
C7—N8	1.375 (7)

N16—Cu—N8	165.67 (19)	N8—C7—C6	111.0 (4)
N16—Cu—N15	91.65 (19)	C9—N8—C7	124.6 (4)
N8—Cu—N15	80.91 (18)	C9—N8—Cu	118.2 (3)
N16—Cu—N1	103.67 (19)	C7—N8—Cu	116.9 (3)
N8—Cu—N1	82.26 (18)	O9—C9—N8	129.1 (5)
N15—Cu—N1	162.45 (16)	O9—C9—C10	120.3 (5)
N16—Cu—O1	93.76 (18)	N8—C9—C10	110.7 (4)
N8—Cu—O1	98.80 (16)	N15—C10—C11	121.8 (5)
N15—Cu—O1	92.89 (16)	N15—C10—C9	115.9 (4)
N1—Cu—O1	94.57 (16)	C11—C10—C9	122.3 (5)
C2—N1—C6	119.0 (5)	C12—C11—C10	118.3 (5)
C2—N1—Cu	128.2 (4)	C12—C11—H11	120.8
C6—N1—Cu	112.8 (3)	C10—C11—H11	120.8
N1—C2—C3	122.9 (5)	C13—C12—C11	119.4 (5)
N1—C2—H2	118.5	C13—C12—H12	120.3
C3—C2—H2	118.5	C11—C12—H12	120.3
C2—C3—C4	118.0 (5)	C14—C13—C12	119.4 (5)
C2—C3—H3	121.0	C14—C13—H13	120.3
C4—C3—H3	121.0	C12—C13—H13	120.3
C3—C4—C5	119.4 (5)	N15—C14—C13	121.6 (5)
C3—C4—H4	120.3	N15—C14—H14	119.2
C5—C4—H4	120.3	C13—C14—H14	119.2
C6—C5—C4	119.3 (5)	C14—N15—C10	119.5 (5)
C6—C5—H5	120.4	C14—N15—Cu	126.3 (4)
C4—C5—H5	120.4	C10—N15—Cu	114.0 (3)
N1—C6—C5	121.4 (5)	N17—N16—Cu	131.4 (4)
N1—C6—C7	116.6 (4)	N18—N17—N16	175.6 (5)
C5—C6—C7	122.0 (5)	Cu—O1—H1A	106 (4)
O7—C7—N8	127.9 (5)	Cu—O1—H1B	112 (4)
O7—C7—C6	121.1 (5)	H1A—O1—H1B	101 (5)

N16—Cu—N1—C2	−9.4 (5)	O1—Cu—N8—C7	87.4 (4)
N8—Cu—N1—C2	−176.2 (5)	C7—N8—C9—O9	2.8 (9)
N15—Cu—N1—C2	−159.6 (5)	Cu—N8—C9—O9	176.3 (4)
O1—Cu—N1—C2	85.6 (5)	C7—N8—C9—C10	−177.7 (5)
N16—Cu—N1—C6	171.0 (4)	Cu—N8—C9—C10	−4.1 (6)
N8—Cu—N1—C6	4.3 (4)	O9—C9—C10—N15	179.7 (5)
N15—Cu—N1—C6	20.9 (8)	N8—C9—C10—N15	0.1 (6)
O1—Cu—N1—C6	−94.0 (4)	O9—C9—C10—C11	0.0 (8)
C6—N1—C2—C3	0.0 (8)	N8—C9—C10—C11	−179.6 (5)
Cu—N1—C2—C3	−179.5 (4)	N15—C10—C11—C12	0.8 (8)
N1—C2—C3—C4	−0.4 (9)	C9—C10—C11—C12	−179.6 (5)
C2—C3—C4—C5	0.4 (9)	C10—C11—C12—C13	0.0 (8)
C3—C4—C5—C6	0.0 (9)	C11—C12—C13—C14	−0.1 (8)
C2—N1—C6—C5	0.5 (8)	C12—C13—C14—N15	−0.4 (8)
Cu—N1—C6—C5	−179.9 (4)	C13—C14—N15—C10	1.1 (8)
C2—N1—C6—C7	178.3 (5)	C13—C14—N15—Cu	175.7 (4)
Cu—N1—C6—C7	−2.1 (6)	C11—C10—N15—C14	−1.3 (8)
C4—C5—C6—N1	−0.5 (8)	C9—C10—N15—C14	179.1 (5)
C4—C5—C6—C7	−178.2 (5)	C11—C10—N15—Cu	−176.6 (4)
N1—C6—C7—O7	177.9 (5)	C9—C10—N15—Cu	3.8 (6)
C5—C6—C7—O7	−4.3 (8)	N16—Cu—N15—C14	12.8 (5)
N1—C6—C7—N8	−2.6 (7)	N8—Cu—N15—C14	−179.5 (5)
C5—C6—C7—N8	175.2 (5)	N1—Cu—N15—C14	163.8 (5)
O7—C7—N8—C9	−0.7 (9)	O1—Cu—N15—C14	−81.1 (4)
C6—C7—N8—C9	179.9 (5)	N16—Cu—N15—C10	−172.3 (4)
O7—C7—N8—Cu	−174.3 (4)	N8—Cu—N15—C10	−4.6 (4)
C6—C7—N8—Cu	6.3 (6)	N1—Cu—N15—C10	−21.3 (8)
N16—Cu—N8—C9	64.4 (10)	O1—Cu—N15—C10	93.8 (4)
N15—Cu—N8—C9	4.9 (4)	N8—Cu—N16—N17	112.7 (8)
N1—Cu—N8—C9	179.9 (4)	N15—Cu—N16—N17	171.0 (5)
O1—Cu—N8—C9	−86.6 (4)	N1—Cu—N16—N17	−0.4 (6)
N16—Cu—N8—C7	−121.6 (8)	O1—Cu—N16—N17	−96.0 (5)
N15—Cu—N8—C7	179.0 (4)	Cu—N16—N17—N18	−171 (7)
N1—Cu—N8—C7	−6.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O9ⁱ	0.85 (2)	2.10 (4)	2.843 (5)	145 (5)
O1—H1B···O7ⁱⁱ	0.84 (2)	2.13 (3)	2.922 (5)	157 (5)
O1—H1A···O7ⁱ	0.85 (2)	2.45 (4)	3.105 (5)	134 (5)

Symmetry codes: (i) −x, −y+1, −z; (ii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O9ⁱ	0.85 (2)	2.10 (4)	2.843 (5)	145 (5)
O1—H1B···O7ⁱⁱ	0.84 (2)	2.13 (3)	2.922 (5)	157 (5)
O1—H1A···O7ⁱ	0.85 (2)	2.45 (4)	3.105 (5)	134 (5)

Symmetry codes: (i) −x, −y+1, −z; (ii) x+1, y, z.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335–338. Web of Science CrossRef CAS IUCr Journals Google Scholar
Borras, J., Alzuet, G., Gonzalez-Alvarez, M., Garcia-Gimenez, J. L., Macias, B. & Liu-Gonzalez, M. (2007). Eur. J. Inorg. Chem. pp. 822–834. Google Scholar
Bruda, S., Turnbull, M. M., Landee, C. P. & Xu, Q. (2006). Inorg. Chim. Acta, 359, 298–308. Web of Science CSD CrossRef CAS Google Scholar
Dey, S. K., Choudhury, C. R., Dey, S. P., Dey, D. K., Mondal, N., Mahalli, S. O. G., Malik, K. M. A. & Mitra, S. (2002). J. Chem. Res. pp. 496–499. CrossRef Google Scholar
Gomes, D. C. de, Toma, L. M., Stumpf, H. O., Adams, H., Thomas, J. A., Lloret, F. L. & Julve, M. (2008). Polyhedron, 27, 559–573. CAS Google Scholar
Landee, C. P. & Turnbull, M. M. (2013). Eur. J. Inorg. Chem. pp. 2266–2285. Web of Science CrossRef Google Scholar
Madariaga, G., Zuñiga, F.-J., Rojo, T. & Folgado, J.-V. (1991). Acta Cryst. C47, 1632–1634. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sahu, R., Padhi, S. K., Jena, H. S. & Manivannan, V. (2010). Inorg. Chim. Acta, 363, 1448–1454. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemans Analytical X-ray Instruments, Inc. Madison, Wisconsin, USA. Google Scholar
Turnbull, M. M., Bruda, S. & Wikaira, J. L. (2013). Eur. Chem. Bull. 2, 2038–2240. Google Scholar
Vangdal, B., Carranza, J., Lloret, F., Julve, M. & Sletten, J. (2002). J. Chem. Soc. Dalton Trans. pp. 566–574. Web of Science CSD CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhou, X.-P., Li, D., Zheng, S.-L., Zhang, X. & Wu, T. (2006). Inorg. Chem. 45, 7119–7125. Web of Science CSD CrossRef PubMed CAS Google Scholar

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Volume 69| Part 11| November 2013| Pages m598-m599

doi:10.1107/S1600536813027499

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