Bis(μ-azido-κ²N,N)bis­({2-[3-(dimethyl­amino)­propyl­iminometh­yl]-4-nitro­phenolato-κ³O,N,N′}copper(II))

The title complex, [Cu₂(N₃)₂(C₁₂H₁₆N₃O₃)₂], is an azide-bridged dinuclear copper(II) complex. There is a crystallographic inversion centre at the mid-point of the Cu...Cu vector. Each Cu atom is coordinated by one O and two N atoms of one Schiff base ligand and two bridging N atoms from two azide ligands, forming a trigonal–bipyramidal geometry. The Cu...Cu distance is 3.327 (2) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.074
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.95
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3     -   N4      ..       6.86 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N4     -   N5      ..       5.25 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   O1      ..       7.56 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   N3_a    ..       6.79 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       1.97

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

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

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S1. Comment

Many azide-bridged polynuclear complexes have been reported previously (Zhao et al., 2003; Cai et al., 2007; Yu et al., 2006; Zhang et al., 2006; Zhu et al., 2004; Li et al., 2007). These complexes have interesting structures. We report herein the new copper(II) complex, (I), derived from the Schiff base ligand 4-nitro-2-[(3-dimethylaminopropylimino)methyl]phenol with azide bridges.

Complex (I) is an azide-bridged dinuclear copper(II) complex (Fig. 1). There is a crystallographic inversion centre at the midpoint of the two copper atoms in the complex. Each Cu atom is coordinated by one O and two N atoms of one Schiff base ligand and two briding N atoms from two azide ligands, forming a trigonal-bipyramidal geometry. The Cu···Cu distance is 3.327 (2) Å.

Related literature

For related literature, see: Cai et al. (2007); Li et al. (2007); Yu et al. (2006); Zhang et al. (2006); Zhao et al. (2003); Zhu et al. (2004).

S2. Experimental

5-Nitro-2-hydroxybenzaldehyde (0.2 mmol, 33.5 mg), N,N-dimethylpropane-1,3-diamine (0.2 mmol, 20.5 mg), NaN₃ (0.2 mmol, 6.5 mg), and Cu(CH₃COO)₂.H₂O (0.2 mmol, 40.0 mg) were mixed in a methanol solution. The mixture was stirred at 325 K for 30 min to give a transparent blue solution. Blue crystals were obtained by slow evaporation of the solution in air.

S3. Refinement

H atoms were positioned geometrically and refined as riding atoms, with C–H distances in the range 0.93–0.97Å and U_iso(H) set at 1.2U_eq(C) and 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), with anisotropic displacement ellipsoids drawn at the 30% probability level.

Bis(µ-azido-κ²N,N)bis({2- [3-(dimethylamino)propyliminomethyl]-4-nitrophenolato- κ³O,N,N'}copper(II))

Crystal data

[Cu2(N3)2(C12H16N3O3)2]	F(000) = 732
Mr = 711.70	Dx = 1.584 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.7410 (17) Å	Cell parameters from 3793 reflections
b = 14.846 (3) Å	θ = 2.2–27.3°
c = 11.775 (2) Å	µ = 1.49 mm^−1
β = 102.43 (3)°	T = 293 K
V = 1492.2 (5) Å^3	Block, blue
Z = 2	0.40 × 0.38 × 0.35 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	3239 independent reflections
Radiation source: fine-focus sealed tube	2706 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
ω scans	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
Tmin = 0.588, Tmax = 0.624	k = −18→18
12293 measured reflections	l = −15→15

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.074	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0349P)^2 + 0.1139P] where P = (Fo^2 + 2Fc^2)/3
3239 reflections	(Δ/σ)max < 0.001
201 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

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
Cu1	0.94961 (3)	0.106755 (14)	0.014558 (19)	0.02791 (9)
O1	1.14184 (17)	0.17565 (9)	0.07071 (14)	0.0480 (4)
O2	1.42356 (19)	0.55892 (11)	0.08461 (15)	0.0562 (5)
O3	1.2338 (2)	0.57421 (11)	−0.06657 (16)	0.0573 (4)
N1	0.85117 (18)	0.21807 (10)	−0.07976 (14)	0.0312 (4)
N2	0.7638 (2)	0.10303 (11)	0.10393 (15)	0.0374 (4)
N3	0.90672 (19)	0.00703 (11)	−0.10862 (15)	0.0371 (4)
N4	0.7826 (2)	−0.00746 (11)	−0.17324 (15)	0.0359 (4)
N5	0.6652 (2)	−0.02203 (14)	−0.23562 (18)	0.0557 (6)
N6	1.3106 (2)	0.52861 (12)	0.01293 (17)	0.0416 (4)
C1	1.1769 (2)	0.25787 (13)	0.05229 (17)	0.0328 (4)
C2	1.3234 (2)	0.29231 (14)	0.11226 (18)	0.0371 (5)
H2	1.3917	0.2542	0.1616	0.044*
C3	1.3673 (2)	0.37865 (14)	0.10029 (19)	0.0388 (5)
H3	1.4635	0.3996	0.1417	0.047*
C4	1.2658 (2)	0.43592 (13)	0.02469 (18)	0.0343 (5)
C5	1.1238 (2)	0.40603 (12)	−0.03678 (18)	0.0333 (5)
H5	1.0589	0.4448	−0.0875	0.040*
C6	1.0759 (2)	0.31767 (13)	−0.02370 (16)	0.0295 (4)
C7	0.9186 (2)	0.29377 (13)	−0.08454 (17)	0.0314 (4)
H7	0.8614	0.3379	−0.1315	0.038*
C8	0.6851 (2)	0.21132 (14)	−0.13842 (18)	0.0376 (5)
H8A	0.6699	0.1597	−0.1902	0.045*
H8B	0.6540	0.2650	−0.1846	0.045*
C9	0.5848 (2)	0.20112 (15)	−0.0484 (2)	0.0428 (5)
H9A	0.6061	0.2516	0.0049	0.051*
H9B	0.4755	0.2048	−0.0880	0.051*
C10	0.6085 (2)	0.11484 (14)	0.0218 (2)	0.0401 (5)
H10A	0.5274	0.1113	0.0664	0.048*
H10B	0.5931	0.0645	−0.0320	0.048*
C11	0.7889 (3)	0.17461 (19)	0.1933 (2)	0.0604 (7)
H11A	0.7017	0.1761	0.2309	0.091*
H11B	0.7979	0.2318	0.1571	0.091*
H11C	0.8834	0.1625	0.2499	0.091*
C12	0.7584 (3)	0.01507 (18)	0.1626 (2)	0.0590 (7)
H12A	0.8537	0.0065	0.2197	0.089*
H12B	0.7470	−0.0325	0.1061	0.089*
H12C	0.6710	0.0142	0.1999	0.089*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02889 (14)	0.01925 (13)	0.03410 (15)	−0.00229 (9)	0.00353 (10)	−0.00002 (9)
O1	0.0389 (8)	0.0283 (8)	0.0686 (11)	−0.0054 (6)	−0.0064 (7)	0.0129 (7)
O2	0.0549 (10)	0.0413 (10)	0.0700 (12)	−0.0213 (8)	0.0078 (9)	−0.0117 (8)
O3	0.0655 (11)	0.0321 (8)	0.0720 (12)	−0.0070 (8)	0.0100 (9)	0.0082 (9)
N1	0.0303 (9)	0.0265 (9)	0.0352 (9)	−0.0001 (7)	0.0035 (7)	0.0009 (7)
N2	0.0352 (9)	0.0385 (10)	0.0377 (10)	−0.0022 (7)	0.0059 (8)	0.0036 (8)
N3	0.0367 (9)	0.0283 (9)	0.0412 (10)	0.0004 (8)	−0.0031 (8)	−0.0044 (7)
N4	0.0454 (10)	0.0247 (9)	0.0349 (10)	0.0028 (8)	0.0028 (8)	−0.0036 (7)
N5	0.0479 (11)	0.0508 (12)	0.0565 (13)	0.0010 (10)	−0.0150 (10)	−0.0132 (10)
N6	0.0439 (10)	0.0312 (10)	0.0536 (12)	−0.0073 (8)	0.0188 (9)	−0.0064 (9)
C1	0.0366 (11)	0.0255 (10)	0.0366 (11)	−0.0018 (8)	0.0086 (9)	0.0002 (8)
C2	0.0310 (11)	0.0369 (12)	0.0414 (12)	0.0006 (9)	0.0034 (9)	0.0050 (9)
C3	0.0310 (11)	0.0420 (13)	0.0428 (12)	−0.0065 (9)	0.0064 (9)	−0.0032 (10)
C4	0.0380 (11)	0.0272 (10)	0.0407 (12)	−0.0075 (9)	0.0153 (9)	−0.0035 (9)
C5	0.0376 (11)	0.0267 (10)	0.0365 (11)	0.0007 (8)	0.0099 (9)	0.0016 (8)
C6	0.0302 (10)	0.0260 (10)	0.0330 (11)	−0.0019 (8)	0.0081 (8)	−0.0006 (8)
C7	0.0356 (11)	0.0260 (10)	0.0316 (10)	0.0006 (8)	0.0053 (8)	0.0036 (8)
C8	0.0338 (11)	0.0327 (11)	0.0421 (12)	−0.0024 (9)	−0.0010 (9)	0.0047 (9)
C9	0.0306 (11)	0.0411 (13)	0.0546 (14)	0.0049 (9)	0.0042 (10)	0.0054 (10)
C10	0.0309 (11)	0.0422 (13)	0.0468 (13)	−0.0029 (9)	0.0072 (9)	0.0018 (10)
C11	0.0541 (15)	0.0777 (19)	0.0489 (15)	−0.0052 (13)	0.0101 (12)	−0.0190 (14)
C12	0.0505 (14)	0.0621 (17)	0.0653 (17)	−0.0008 (12)	0.0145 (13)	0.0314 (14)

Geometric parameters (Å, º)

Cu1—O1	1.9567 (14)	C3—C4	1.401 (3)
Cu1—N3	2.0498 (17)	C3—H3	0.9300
Cu1—N1	2.0720 (16)	C4—C5	1.369 (3)
Cu1—N2	2.1178 (18)	C5—C6	1.396 (3)
Cu1—N3^i	2.2492 (17)	C5—H5	0.9300
O1—C1	1.288 (2)	C6—C7	1.451 (2)
O2—N6	1.237 (2)	C7—H7	0.9300
O3—N6	1.231 (2)	C8—C9	1.522 (3)
N1—C7	1.276 (2)	C8—H8A	0.9700
N1—C8	1.470 (2)	C8—H8B	0.9700
N2—C11	1.478 (3)	C9—C10	1.514 (3)
N2—C12	1.483 (3)	C9—H9A	0.9700
N2—C10	1.498 (3)	C9—H9B	0.9700
N3—N4	1.203 (2)	C10—H10A	0.9700
N3—Cu1^i	2.2492 (17)	C10—H10B	0.9700
N4—N5	1.147 (2)	C11—H11A	0.9600
N6—C4	1.445 (3)	C11—H11B	0.9600
C1—C2	1.417 (3)	C11—H11C	0.9600
C1—C6	1.424 (3)	C12—H12A	0.9600
C2—C3	1.354 (3)	C12—H12B	0.9600
C2—H2	0.9300	C12—H12C	0.9600
O1—Cu1—N3	129.02 (7)	C4—C5—C6	120.39 (19)
O1—Cu1—N1	89.52 (6)	C4—C5—H5	119.8
N3—Cu1—N1	101.84 (7)	C6—C5—H5	119.8
O1—Cu1—N2	122.72 (7)	C5—C6—C1	119.65 (18)
N3—Cu1—N2	106.84 (7)	C5—C6—C7	116.77 (17)
N1—Cu1—N2	90.73 (6)	C1—C6—C7	123.47 (18)
O1—Cu1—N3^i	83.01 (6)	N1—C7—C6	126.24 (18)
N3—Cu1—N3^i	78.68 (7)	N1—C7—H7	116.9
N1—Cu1—N3^i	170.54 (6)	C6—C7—H7	116.9
N2—Cu1—N3^i	98.18 (6)	N1—C8—C9	109.78 (17)
C1—O1—Cu1	131.04 (13)	N1—C8—H8A	109.7
C7—N1—C8	117.25 (16)	C9—C8—H8A	109.7
C7—N1—Cu1	125.72 (14)	N1—C8—H8B	109.7
C8—N1—Cu1	116.84 (12)	C9—C8—H8B	109.7
C11—N2—C12	108.4 (2)	H8A—C8—H8B	108.2
C11—N2—C10	110.51 (17)	C10—C9—C8	115.64 (18)
C12—N2—C10	106.79 (16)	C10—C9—H9A	108.4
C11—N2—Cu1	108.82 (14)	C8—C9—H9A	108.4
C12—N2—Cu1	111.05 (14)	C10—C9—H9B	108.4
C10—N2—Cu1	111.20 (13)	C8—C9—H9B	108.4
N4—N3—Cu1	125.42 (14)	H9A—C9—H9B	107.4
N4—N3—Cu1^i	120.61 (13)	N2—C10—C9	116.75 (17)
Cu1—N3—Cu1^i	101.32 (7)	N2—C10—H10A	108.1
N5—N4—N3	179.1 (2)	C9—C10—H10A	108.1
O3—N6—O2	122.90 (19)	N2—C10—H10B	108.1
O3—N6—C4	118.82 (18)	C9—C10—H10B	108.1
O2—N6—C4	118.27 (19)	H10A—C10—H10B	107.3
O1—C1—C2	118.69 (18)	N2—C11—H11A	109.5
O1—C1—C6	123.94 (18)	N2—C11—H11B	109.5
C2—C1—C6	117.36 (18)	H11A—C11—H11B	109.5
C3—C2—C1	122.37 (19)	N2—C11—H11C	109.5
C3—C2—H2	118.8	H11A—C11—H11C	109.5
C1—C2—H2	118.8	H11B—C11—H11C	109.5
C2—C3—C4	119.07 (19)	N2—C12—H12A	109.5
C2—C3—H3	120.5	N2—C12—H12B	109.5
C4—C3—H3	120.5	H12A—C12—H12B	109.5
C5—C4—C3	121.14 (19)	N2—C12—H12C	109.5
C5—C4—N6	119.42 (19)	H12A—C12—H12C	109.5
C3—C4—N6	119.43 (19)	H12B—C12—H12C	109.5

Symmetry code: (i) −x+2, −y, −z.