Aqua-(azido)[N-(pyridin-2-ylcarbon-yl)pyridine-2-carboxamido-κ(3) N,N',N'']copper(II).

The title compound, [Cu(C12H8N3O2)(N3)(H2O)], was formed by the air oxidation of 2-(amino-meth-yl)pyridine in 95% ethanol in the presence of copper(II) nitrate and sodium azide with condensation of the resulting picolinamide mol-ecules 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 mol-ecule [Cu-O = 2.319 (4) Å]. The crystal structure is stabilized by hydrogen-bonding inter-actions between the water mol-ecules and carbonyl O atoms. The inversion-related square-pyramidal complex molecules pack base-to-base with long Cu⋯Npy contact distances of 3.537 (9) Å, preventing coordination of a sixth ligand.

Related literature

For magneto-structural relationships in CuII 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 = 349.80

Triclinic,

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[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.105

S = 1.17

2258 reflections

205 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.69 e Å−3

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 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813027499/sj5358sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C12H8N3O2)(N3)(H2O)]	Z = 2
Mr = 349.80	F(000) = 354
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0191P)2 + 2.3778P] where P = (Fo2 + 2Fc2)/3
2258 reflections	(Δ/σ)max = 0.001
205 parameters	Δρmax = 0.50 e Å−3
2 restraints	Δρmin = −0.69 e Å−3

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
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*

	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)

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)

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)

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) ; (ii) .