(Azido-κN){(E)-2-[1-(pyridin-2-yl)ethyl­idene­amino]­phenolato-κ³N,N′,O}copper(II)

In the title complex, [Cu(C₁₃H₁₁N₂O)(N₃)], the Cu^II cation is four-coordinated by an N₂O donor set of the tridentate Schiff base ligand and by the terminal N atom of the azide anion, forming a slightly distorted square-planar configuration.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.092
• Data-to-parameter ratio = 13.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......      0.975
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3     --  N4      ..        6.1 su
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ? Do !
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            CU1 -N3  -N4  -N5    166.00  5.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         42
            N4  -N3  -CU1 -N2    -47.40  1.10   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         46
            C6  -N2  -CU1 -N3    -72.00  1.00   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_G Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         47
            C8  -N2  -CU1 -N3    102.50  1.00   1.555   1.555   1.555   1.555
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         58

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

In the title complex, [Cu(C₁₃H₁₁N₂O)(N₃)], the Cu^II ion exhibits a slightly distorted square-planar coordination environment defined by the deprotonated tridentate Schiff base ligand that coordinates via the phenolate O, imine N and pyridyl N atoms and the N atom of azide ion (Fig. 1). The bond angles around Cu^II ion are slightly distorted from those of regular square-planar and range from 81.53 (7) to 175.89 (7)°. The [CuN₃O] square plane and the aryl and pyridyl rings in the Schiff base are almost coplanar. The dihedral angles among these three planes are 3.55 (6)°, 4.70 (5)° and 4.99 (7)°. The bond distances to the central copper [Cu—N_py = 1.9775 (16) Å, Cu—N_imine = 1.9682 (16) Å, Cu—N_azide = 1.9470 (18) Å, Cu—O_phenolic = 1.9133 (14) Å] (Table 1) are similar to those in complexes [Cu(C₁₄H₁₃N₂O₂)(N₃)] and [Cu(C₁₃H₁₀ClN₂O)Cl] (Sun, 2008; Wang et al., 2012). The bond distances and bond angles in azide ion bound to Cu^II ion are similar to those in complexes [Cu(C₁₄H₁₃N₂O₂)(N₃)] and [Cu(C₁₆H₂₃N₂O)(N₃)] (Sun, 2008; Talukder et al., 2004). The N3—N4 bond [1.201 (3) Å] in the complex is longer than the N4—N5 bond [1.157 (3) Å]. The NNN moiety is nearly linear and shows a bent coordination mode with the Cu^II ion [(N3—N4—N5/Cu1—N3—N4 = 177.4 (2)/117.06 (15)°].

Related literature

For related structures, see: Talukder et al. (2004); Sun (2008); Wang et al. (2012); Yu (2012). For the synthesis, see: Shita et al. (2009).

S2. Experimental

The tridentate Schiff base ligand was prepared according to literature procedure (Shita et al., 2009). To a hot methanolic solution (20 ml) of Cu(CCl₃COO)₂.6H₂O (0.484 g, 1.0 mmol), the ligand (1.0 mmol) was added, which produced immediately an intensely green solution. The solution was then heated to boiling and then, an aqueous solution (10 ml) of sodium azide (0.065 g, 1 mmol) was added dropwise slowly over 15 min in hot condition. After the completion of addition of sodium azide, the resulting solution was kept under boiling for another 10 min. On cooling and after slow evaporation of the solution, the dark-green plate-shaped single crystals of the complex were separated out in 3 d. The crystals were filtered off and washed with water and dried in air.

S3. Refinement

H atoms were placed at calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C) and 1.5 Ueq(C)

Computing details

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and WinGX32 (Farrugia, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

Fig. 1. The molecular structure of the title complex, showing displacement ellipsoids at the 50% probability level.

(Azido-κN){(E)-2-[1-(pyridin-2-yl)ethylideneamino]phenolato-κ³N,N',O}copper(II)

Crystal data

[Cu(C13H11CuN2O)(N3)]	F(000) = 644
Mr = 316.81	Dx = 1.712 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ybc	Cell parameters from 2697 reflections
a = 6.5881 (3) Å	θ = 4.4–71.9°
b = 10.1576 (3) Å	µ = 2.54 mm^−1
c = 18.3884 (7) Å	T = 120 K
β = 92.810 (3)°	Plate, green
V = 1229.06 (8) Å^3	0.57 × 0.31 × 0.04 mm
Z = 4

Data collection

Agilent Xcalibur Gemini ultra diffractometer with Eos detector	2357 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	2180 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.021
Detector resolution: 16.1183 pixels mm^-1	θmax = 72.0°, θmin = 4.8°
ω scans	h = −8→6
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −11→12
Tmin = 0.709, Tmax = 1.000	l = −21→22
4723 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0589P)^2 + 0.5226P] where P = (Fo^2 + 2Fc^2)/3
2357 reflections	(Δ/σ)max < 0.001
182 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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 (Ų)

	x	y	z	Uiso*/Ueq
C11	0.1572 (3)	0.7721 (2)	0.10880 (11)	0.0224 (4)
H11	0.1311	0.8364	0.1447	0.027*
C12	0.1511 (3)	0.80806 (19)	0.03531 (13)	0.0238 (4)
H12	0.1217	0.8965	0.0216	0.029*
C13	0.1878 (3)	0.7152 (2)	−0.01764 (11)	0.0214 (4)
H13	0.1842	0.7401	−0.0675	0.026*
N3	0.3338 (3)	0.14937 (18)	0.06852 (10)	0.0267 (4)
N4	0.1971 (3)	0.12200 (16)	0.10667 (9)	0.0225 (4)
N5	0.0684 (3)	0.09080 (19)	0.14363 (10)	0.0300 (4)
C1	0.3018 (3)	0.3279 (2)	−0.13806 (11)	0.0190 (4)
C2	0.3721 (3)	0.1131 (2)	−0.10036 (11)	0.0233 (4)
H2	0.3975	0.0518	−0.0620	0.028*
C3	0.3734 (3)	0.0698 (2)	−0.17231 (12)	0.0270 (4)
H3	0.3992	−0.0201	−0.1829	0.032*
C4	0.3368 (3)	0.1587 (2)	−0.22775 (12)	0.0281 (5)
H4	0.3346	0.1309	−0.2771	0.034*
C5	0.3030 (3)	0.2905 (2)	−0.21045 (11)	0.0250 (4)
H5	0.2809	0.3539	−0.2480	0.030*
C6	0.2590 (3)	0.4639 (2)	−0.11276 (10)	0.0190 (4)
C7	0.2071 (3)	0.5713 (2)	−0.16602 (11)	0.0269 (4)
H7A	0.0753	0.6095	−0.1553	0.040*
H7B	0.2001	0.5351	−0.2155	0.040*
H7C	0.3120	0.6397	−0.1622	0.040*
C8	0.2306 (3)	0.58395 (19)	0.00240 (10)	0.0176 (4)
C9	0.2387 (3)	0.54692 (19)	0.07755 (10)	0.0181 (4)
C10	0.2008 (3)	0.6441 (2)	0.12986 (11)	0.0208 (4)
H10	0.2053	0.6214	0.1800	0.025*
N1	0.3362 (2)	0.23872 (17)	−0.08411 (9)	0.0193 (3)
N2	0.2667 (2)	0.47613 (16)	−0.04273 (9)	0.0172 (3)
O1	0.2789 (2)	0.42425 (13)	0.09719 (7)	0.0201 (3)
Cu1	0.31041 (4)	0.31370 (3)	0.014256 (14)	0.01721 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C11	0.0158 (9)	0.0196 (10)	0.0318 (11)	−0.0014 (7)	0.0007 (8)	−0.0067 (8)
C12	0.0179 (10)	0.0169 (10)	0.0362 (12)	−0.0003 (7)	−0.0015 (8)	−0.0001 (8)
C13	0.0173 (10)	0.0203 (10)	0.0262 (10)	−0.0010 (7)	−0.0023 (8)	0.0030 (8)
N3	0.0297 (10)	0.0213 (8)	0.0294 (9)	0.0053 (7)	0.0047 (8)	0.0048 (7)
N4	0.0305 (9)	0.0141 (8)	0.0221 (8)	0.0025 (7)	−0.0051 (7)	−0.0003 (6)
N5	0.0361 (10)	0.0259 (9)	0.0278 (9)	−0.0051 (8)	0.0021 (8)	0.0035 (8)
C1	0.0107 (9)	0.0248 (10)	0.0213 (9)	0.0000 (7)	0.0001 (7)	0.0001 (8)
C2	0.0186 (9)	0.0242 (10)	0.0271 (10)	0.0020 (8)	0.0013 (7)	−0.0035 (8)
C3	0.0209 (10)	0.0283 (11)	0.0320 (11)	−0.0001 (8)	0.0019 (8)	−0.0091 (9)
C4	0.0211 (10)	0.0381 (12)	0.0253 (10)	−0.0010 (9)	0.0020 (8)	−0.0096 (9)
C5	0.0190 (10)	0.0330 (11)	0.0230 (10)	0.0007 (8)	0.0010 (8)	−0.0004 (9)
C6	0.0117 (8)	0.0239 (10)	0.0215 (9)	0.0010 (7)	0.0015 (7)	0.0035 (8)
C7	0.0322 (11)	0.0283 (11)	0.0202 (9)	0.0067 (9)	0.0017 (8)	0.0039 (8)
C8	0.0117 (8)	0.0191 (9)	0.0220 (9)	−0.0007 (7)	0.0006 (7)	−0.0001 (7)
C9	0.0124 (8)	0.0184 (9)	0.0236 (9)	−0.0006 (7)	0.0017 (7)	−0.0008 (8)
C10	0.0157 (9)	0.0233 (10)	0.0233 (9)	−0.0006 (7)	0.0012 (7)	−0.0021 (8)
N1	0.0139 (7)	0.0221 (8)	0.0218 (8)	0.0013 (6)	0.0016 (6)	−0.0016 (7)
N2	0.0123 (7)	0.0193 (8)	0.0199 (7)	−0.0003 (6)	0.0000 (6)	0.0018 (6)
O1	0.0241 (7)	0.0180 (7)	0.0182 (6)	0.0025 (5)	0.0011 (5)	0.0012 (5)
Cu1	0.0182 (2)	0.01587 (19)	0.01753 (19)	0.00191 (10)	0.00069 (12)	0.00060 (10)

Geometric parameters (Å, º)

C11—C10	1.383 (3)	C3—H3	0.9500
C11—C12	1.399 (3)	C4—C5	1.396 (3)
C11—H11	0.9500	C4—H4	0.9500
C12—C13	1.385 (3)	C5—H5	0.9500
C12—H12	0.9500	C6—N2	1.292 (3)
C13—C8	1.408 (3)	C6—C7	1.495 (3)
C13—H13	0.9500	C7—H7A	0.9800
N3—N4	1.201 (3)	C7—H7B	0.9800
N3—Cu1	1.9470 (18)	C7—H7C	0.9800
N4—N5	1.157 (3)	C8—N2	1.402 (3)
C1—N1	1.354 (3)	C8—C9	1.431 (3)
C1—C5	1.385 (3)	C9—O1	1.320 (2)
C1—C6	1.489 (3)	C9—C10	1.409 (3)
C2—N1	1.334 (3)	C10—H10	0.9500
C2—C3	1.395 (3)	N1—Cu1	1.9775 (16)
C2—H2	0.9500	N2—Cu1	1.9682 (16)
C3—C4	1.375 (3)	O1—Cu1	1.9134 (14)
C10—C11—C12	120.79 (18)	C6—C7—H7A	109.5
C10—C11—H11	119.6	C6—C7—H7B	109.5
C12—C11—H11	119.6	H7A—C7—H7B	109.5
C13—C12—C11	120.23 (19)	C6—C7—H7C	109.5
C13—C12—H12	119.9	H7A—C7—H7C	109.5
C11—C12—H12	119.9	H7B—C7—H7C	109.5
C12—C13—C8	120.02 (19)	N2—C8—C13	128.50 (18)
C12—C13—H13	120.0	N2—C8—C9	111.54 (17)
C8—C13—H13	120.0	C13—C8—C9	119.96 (18)
N4—N3—Cu1	117.06 (14)	O1—C9—C10	120.94 (18)
N5—N4—N3	177.4 (2)	O1—C9—C8	120.65 (17)
N1—C1—C5	120.84 (19)	C10—C9—C8	118.41 (18)
N1—C1—C6	114.76 (17)	C11—C10—C9	120.59 (19)
C5—C1—C6	124.37 (19)	C11—C10—H10	119.7
N1—C2—C3	121.6 (2)	C9—C10—H10	119.7
N1—C2—H2	119.2	C2—N1—C1	120.03 (17)
C3—C2—H2	119.2	C2—N1—Cu1	126.68 (14)
C4—C3—C2	119.1 (2)	C1—N1—Cu1	113.19 (14)
C4—C3—H3	120.4	C6—N2—C8	131.76 (18)
C2—C3—H3	120.4	C6—N2—Cu1	116.57 (14)
C3—C4—C5	119.0 (2)	C8—N2—Cu1	111.37 (12)
C3—C4—H4	120.5	C9—O1—Cu1	111.35 (12)
C5—C4—H4	120.5	O1—Cu1—N3	95.95 (7)
C1—C5—C4	119.3 (2)	O1—Cu1—N2	85.04 (6)
C1—C5—H5	120.3	N3—Cu1—N2	175.89 (7)
C4—C5—H5	120.3	O1—Cu1—N1	166.56 (7)
N2—C6—C1	113.71 (17)	N3—Cu1—N1	97.49 (8)
N2—C6—C7	125.38 (19)	N2—Cu1—N1	81.53 (7)
C1—C6—C7	120.89 (17)
C10—C11—C12—C13	0.3 (3)	C7—C6—N2—C8	0.6 (3)
C11—C12—C13—C8	0.3 (3)	C1—C6—N2—Cu1	−4.7 (2)
Cu1—N3—N4—N5	166 (5)	C7—C6—N2—Cu1	173.67 (15)
N1—C2—C3—C4	0.0 (3)	C13—C8—N2—C6	−4.9 (3)
C2—C3—C4—C5	1.1 (3)	C9—C8—N2—C6	174.29 (18)
N1—C1—C5—C4	1.1 (3)	C13—C8—N2—Cu1	−178.26 (16)
C6—C1—C5—C4	−177.32 (19)	C9—C8—N2—Cu1	0.96 (18)
C3—C4—C5—C1	−1.6 (3)	C10—C9—O1—Cu1	177.20 (14)
N1—C1—C6—N2	1.7 (2)	C8—C9—O1—Cu1	−2.2 (2)
C5—C1—C6—N2	−179.81 (18)	C9—O1—Cu1—N3	−173.93 (13)
N1—C1—C6—C7	−176.72 (17)	C9—O1—Cu1—N2	2.06 (12)
C5—C1—C6—C7	1.7 (3)	C9—O1—Cu1—N1	5.2 (3)
C12—C13—C8—N2	178.35 (18)	N4—N3—Cu1—O1	56.36 (17)
C12—C13—C8—C9	−0.8 (3)	N4—N3—Cu1—N2	−47.4 (11)
N2—C8—C9—O1	0.8 (2)	N4—N3—Cu1—N1	−123.42 (16)
C13—C8—C9—O1	−179.90 (17)	C6—N2—Cu1—O1	−176.11 (14)
N2—C8—C9—C10	−178.59 (16)	C8—N2—Cu1—O1	−1.67 (12)
C13—C8—C9—C10	0.7 (3)	C6—N2—Cu1—N3	−72.0 (10)
C12—C11—C10—C9	−0.4 (3)	C8—N2—Cu1—N3	102.5 (10)
O1—C9—C10—C11	−179.47 (17)	C6—N2—Cu1—N1	4.61 (14)
C8—C9—C10—C11	−0.1 (3)	C8—N2—Cu1—N1	179.05 (13)
C3—C2—N1—C1	−0.6 (3)	C2—N1—Cu1—O1	177.1 (2)
C3—C2—N1—Cu1	175.50 (15)	C1—N1—Cu1—O1	−6.5 (4)
C5—C1—N1—C2	0.1 (3)	C2—N1—Cu1—N3	−3.81 (17)
C6—C1—N1—C2	178.62 (16)	C1—N1—Cu1—N3	172.56 (14)
C5—C1—N1—Cu1	−176.55 (15)	C2—N1—Cu1—N2	−179.78 (17)
C6—C1—N1—Cu1	2.0 (2)	C1—N1—Cu1—N2	−3.41 (13)
C1—C6—N2—C8	−177.73 (17)