Buy article online - an online subscription or single-article purchase is required to access this article.
Download citation
Download citation
link to html
The title complex, [Cu(Me2phen)(N3)2]2, is disposed about an inversion centre; Me2phen is 4,7-di­methyl-1,10-phenanthroline (C14H12N2). The structure features μ2-bridging and terminal azide ligands, chelating Me2phen and the Cu atom in a distorted square pyramidal geometry.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803015861/lh6087sup1.cif
Contains datablocks general, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803015861/lh6087Isup2.hkl
Contains datablock I

CCDC reference: 222797

Key indicators

  • Single-crystal X-ray study
  • T = 223 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.037
  • wR factor = 0.101
  • Data-to-parameter ratio = 20.3

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT230_ALERT_2_C Hirshfeld Test Diff for N1 - N2 = 6.28 su
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Azide-bridged copper(II) complexes involving combinations of chelating 1,10-phenanthroline (phen) ligands with end-on (µ1,1) and/or end-to-end (µ1,3) azides have been structurally determined. For example, [Cu(phen)(N3)2]n adopts a chain motif (Li et al., 2000) and [Cu(phen)(N3)3]2·2N3·4H2O is dimeric and features lattice azide (Cheng et al., 2002). In order to determine the affect of steric hindrance in the phen ligand by introducing methyl groups at the 4- and 7-positions, so as to generate Me2phen, we synthesized the complex [Cu(Me2phen)(N3)2]2, (I).

The dinuclear structure of [Cu(Me2phen)(N3)2]2 (Fig. 1) is situated about a twofold axis of symmetry and features µ2-bridging and terminal azides as well as chelating Me2phen ligands. The bridges are effectively symmetric (Table 1) and, as expected, the bridging Cu—Nazide distances are longer than the terminal Cu—Nazide distance. The Cu···Cui separation within the dimer is 3.1616 (3) Å [symmetry code: (i) −x + 1/2, −y + 1/2, −z]. The coordination geometry for Cu is based on a square pyramid. Thus, azide atoms N1, N4 and N1i and the Me2phen N7 atom define the basal plane and have deviations of 0.040 (2), 0.022 (3), −0.015 (3) and −0.060 (2) Å, respectively, from their least-squares plane. The Cu atom lies 0.2449 (3) Å out of this plane in the direction of atom N8. This arrangement introduces some of the disparity in the Cu—Nchelate bond distances with the axial Cu—N8 distance being significantly longer than the basal Cu—N distance. Within the molecule, the disposition of the Me2phen methyl groups are such so as to place one of the methyl-H atoms directly above the N1 atom with C14—H···N1i = 2.55 Å, C14···N1i = 3.494 (3) Å and the angle subtended at H = 164°. The most significant contact in the lattice is also of the type C—H···N so that C3—H···N6ii = 2.42 Å, C3···N6ii = 3.305 (3) Å and the angle at H = 157° [symmetry code: (ii) −x, y, 1/2 − z]. Such associations, as described, lead to the formation of weakly associated chains comprising complex molecules.

There is one closely related structure available in the literature available for comparison, namely that of di-µ2-azido-bis[azido(N,N-diethylethylenediamine)copper(II)] (Casagrande et al., 1989). This is centrosymmetric in contrast to the title complex but features essentially the same pattern of bond distances.

Experimental top

A single-crystal of (I) was grown in aqueous solution by slow diffusion using an H-double-tube glass vessel. Methanol solutions of Cu(Me2phen)(NO3)2 (0.01 M) and NaN3 (0.02 M) were placed in separate arms. After two months, brown crystals had separated.

Refinement top

The C—H atoms were included in the riding-model approximation, with C—H distances of 0.94 Å (0.97 Å for methyl), Uiso(phenyl-H) = 1.2Ueq(C) and Uiso(methyl-H) = 1.5Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SHELXTL (Bruker, 2000); program(s) used to solve structure: PATTY in DIRDIF92 (Beurskens et al., 1992); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHEXLTL.

Figures top
[Figure 1] Fig. 1. The molecular structure and crystallographic numbering scheme for (I). The other half of the molecule is generated by the symmetry operation (1/2 − x, 1/2 − y, −z). Displacement ellipsoids are drawn at the 50% probability level (Johnson, 1976).
(I) top
Crystal data top
[Cu2(N3)4(C14H12N2)2]F(000) = 1448
Mr = 711.72Dx = 1.611 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -C 2ycCell parameters from 3661 reflections
a = 13.3691 (5) Åθ = 2.4–30.0°
b = 11.2648 (5) ŵ = 1.50 mm1
c = 19.5792 (9) ÅT = 223 K
β = 95.565 (2)°Block, brown
V = 2934.7 (2) Å30.49 × 0.16 × 0.16 mm
Z = 4
Data collection top
Bruker AXS SMART CCD
diffractometer
4259 independent reflections
Radiation source: fine-focus sealed tube3450 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ω scansθmax = 30.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2000; Blessing, 1995)
h = 1818
Tmin = 0.750, Tmax = 0.787k = 1415
11979 measured reflectionsl = 2719
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0584P)2 + 0.0245P]
where P = (Fo2 + 2Fc2)/3
4259 reflections(Δ/σ)max = 0.001
210 parametersΔρmax = 0.62 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
[Cu2(N3)4(C14H12N2)2]V = 2934.7 (2) Å3
Mr = 711.72Z = 4
Monoclinic, C2/cMo Kα radiation
a = 13.3691 (5) ŵ = 1.50 mm1
b = 11.2648 (5) ÅT = 223 K
c = 19.5792 (9) Å0.49 × 0.16 × 0.16 mm
β = 95.565 (2)°
Data collection top
Bruker AXS SMART CCD
diffractometer
4259 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000; Blessing, 1995)
3450 reflections with I > 2σ(I)
Tmin = 0.750, Tmax = 0.787Rint = 0.032
11979 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 1.04Δρmax = 0.62 e Å3
4259 reflectionsΔρmin = 0.33 e Å3
210 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
xyzUiso*/Ueq
Cu0.152642 (16)0.259903 (18)0.039472 (11)0.02300 (9)
N10.30477 (13)0.26186 (14)0.05616 (9)0.0285 (3)
N20.35279 (13)0.23119 (15)0.10891 (9)0.0309 (4)
N30.39785 (17)0.2044 (2)0.15878 (10)0.0558 (6)
N40.01649 (13)0.29821 (17)0.00094 (9)0.0348 (4)
N50.05016 (12)0.33126 (16)0.03205 (8)0.0327 (4)
N60.11857 (16)0.3630 (2)0.05827 (10)0.0570 (6)
N70.13577 (11)0.31505 (13)0.13648 (7)0.0233 (3)
N80.13538 (11)0.08577 (13)0.09397 (8)0.0253 (3)
C10.13146 (14)0.42862 (16)0.15577 (10)0.0271 (4)
C20.12784 (15)0.45956 (18)0.22500 (11)0.0331 (4)
H20.12490.53990.23760.040*
C30.12863 (15)0.37389 (19)0.27385 (10)0.0338 (4)
H30.12730.39490.32020.041*
C40.13139 (15)0.25342 (16)0.25485 (10)0.0283 (4)
C50.13421 (14)0.22804 (16)0.18496 (10)0.0236 (4)
C60.13254 (13)0.10597 (16)0.16216 (9)0.0248 (4)
C70.12679 (15)0.01531 (18)0.21068 (10)0.0306 (4)
C80.12536 (15)0.0440 (2)0.28141 (11)0.0372 (5)
H80.12240.01740.31370.045*
C90.12818 (15)0.1579 (2)0.30287 (10)0.0357 (5)
H90.12800.17480.34990.043*
C100.12010 (17)0.10215 (18)0.18507 (11)0.0388 (5)
H100.11480.16640.21510.047*
C110.12147 (17)0.12118 (18)0.11668 (12)0.0391 (5)
H110.11590.19900.09940.047*
C120.13115 (14)0.02539 (16)0.07126 (10)0.0292 (4)
C130.12982 (17)0.52244 (17)0.10197 (11)0.0365 (5)
H13A0.14200.48660.05850.055*
H13B0.18170.58060.11490.055*
H13C0.06470.56110.09750.055*
C140.13416 (17)0.04688 (18)0.00341 (11)0.0372 (5)
H14A0.14220.02810.02660.056*
H14B0.07200.08420.02190.056*
H14C0.19030.09860.01050.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.02508 (13)0.02718 (13)0.01676 (13)0.00025 (8)0.00218 (8)0.00196 (8)
N10.0278 (8)0.0404 (9)0.0174 (8)0.0011 (6)0.0023 (6)0.0043 (6)
N20.0300 (9)0.0406 (9)0.0223 (8)0.0018 (7)0.0037 (7)0.0004 (7)
N30.0514 (13)0.0852 (16)0.0289 (11)0.0056 (12)0.0052 (9)0.0127 (11)
N40.0298 (9)0.0499 (10)0.0239 (8)0.0066 (8)0.0007 (7)0.0004 (8)
N50.0329 (9)0.0443 (9)0.0201 (8)0.0030 (7)0.0012 (6)0.0071 (7)
N60.0469 (12)0.0960 (18)0.0296 (10)0.0245 (12)0.0105 (9)0.0077 (11)
N70.0240 (7)0.0264 (7)0.0193 (7)0.0014 (6)0.0020 (5)0.0004 (6)
N80.0257 (7)0.0255 (7)0.0248 (8)0.0015 (6)0.0025 (6)0.0013 (6)
C10.0260 (9)0.0293 (9)0.0257 (9)0.0013 (7)0.0015 (7)0.0020 (7)
C20.0340 (10)0.0336 (10)0.0318 (10)0.0008 (8)0.0041 (8)0.0066 (8)
C30.0321 (10)0.0473 (11)0.0224 (9)0.0006 (9)0.0041 (7)0.0089 (8)
C40.0238 (9)0.0406 (11)0.0206 (9)0.0012 (7)0.0029 (7)0.0025 (7)
C50.0208 (8)0.0307 (8)0.0196 (9)0.0012 (7)0.0029 (6)0.0039 (7)
C60.0216 (8)0.0292 (9)0.0234 (9)0.0002 (7)0.0012 (6)0.0050 (7)
C70.0262 (9)0.0353 (10)0.0299 (10)0.0009 (8)0.0015 (7)0.0111 (8)
C80.0353 (11)0.0481 (12)0.0284 (11)0.0012 (9)0.0053 (8)0.0153 (9)
C90.0365 (11)0.0519 (12)0.0190 (9)0.0005 (9)0.0045 (8)0.0079 (9)
C100.0441 (12)0.0296 (10)0.0417 (12)0.0026 (8)0.0007 (10)0.0134 (9)
C110.0458 (12)0.0273 (9)0.0431 (12)0.0031 (8)0.0022 (10)0.0053 (8)
C120.0284 (9)0.0275 (9)0.0313 (10)0.0012 (7)0.0006 (8)0.0023 (8)
C130.0501 (12)0.0250 (9)0.0338 (11)0.0013 (8)0.0007 (9)0.0014 (8)
C140.0467 (12)0.0280 (9)0.0371 (11)0.0032 (9)0.0045 (9)0.0038 (8)
Geometric parameters (Å, º) top
Cu—N12.0285 (17)C4—C91.432 (3)
Cu—N41.9499 (17)C5—C61.445 (3)
Cu—N72.0316 (15)C6—C71.402 (2)
Cu—N82.2554 (15)C7—C101.415 (3)
Cu—N1i2.0240 (17)C7—C81.424 (3)
N1—N21.212 (2)C8—C91.350 (3)
N2—N31.137 (2)C8—H80.9400
N4—N51.187 (2)C9—H90.9400
N5—N61.149 (2)C10—C111.358 (3)
N7—C11.337 (2)C10—H100.9400
N7—C51.366 (2)C11—C121.412 (3)
N8—C121.328 (2)C11—H110.9400
N8—C61.359 (2)C12—C141.486 (3)
C1—C21.405 (3)C13—H13A0.9700
C1—C131.491 (3)C13—H13B0.9700
C2—C31.358 (3)C13—H13C0.9700
C2—H20.9400C14—H14A0.9700
C3—C41.409 (3)C14—H14B0.9700
C3—H30.9400C14—H14C0.9700
C4—C51.402 (3)
N1—Cu—N4160.67 (7)N7—C5—C6117.96 (16)
N1—Cu—N792.67 (6)C4—C5—C6119.64 (16)
N1—Cu—N894.60 (6)N8—C6—C7123.54 (17)
N1—Cu—N1i77.45 (7)N8—C6—C5117.51 (15)
N4—Cu—N796.31 (7)C7—C6—C5118.94 (17)
N4—Cu—N8103.95 (7)C6—C7—C10116.54 (18)
N4—Cu—N1i90.27 (7)C6—C7—C8120.03 (18)
N7—Cu—N878.34 (6)C10—C7—C8123.41 (18)
N7—Cu—N1i165.60 (6)C9—C8—C7121.06 (19)
N8—Cu—N1i112.53 (6)C9—C8—H8119.5
Cu—N1—N2125.03 (14)C7—C8—H8119.5
Cui—N1—N2125.47 (14)C8—C9—C4120.76 (18)
Cu—N1—Cui102.55 (7)C8—C9—H9119.6
N1—N2—N3178.8 (2)C4—C9—H9119.6
Cu—N4—N5126.15 (14)C11—C10—C7119.39 (18)
N4—N5—N6175.6 (2)C11—C10—H10120.3
C1—N7—C5119.11 (16)C7—C10—H10120.3
C1—N7—Cu124.64 (12)C10—C11—C12120.74 (19)
C5—N7—Cu116.16 (12)C10—C11—H11119.6
C12—N8—C6118.85 (16)C12—C11—H11119.6
C12—N8—Cu131.65 (13)N8—C12—C11120.88 (18)
C6—N8—Cu109.46 (11)N8—C12—C14118.58 (17)
N7—C1—C2121.09 (17)C11—C12—C14120.52 (17)
N7—C1—C13118.49 (17)C1—C13—H13A109.5
C2—C1—C13120.42 (17)C1—C13—H13B109.5
C3—C2—C1120.31 (18)H13A—C13—H13B109.5
C3—C2—H2119.8C1—C13—H13C109.5
C1—C2—H2119.8H13A—C13—H13C109.5
C2—C3—C4119.81 (18)H13B—C13—H13C109.5
C2—C3—H3120.1C12—C14—H14A109.5
C4—C3—H3120.1C12—C14—H14B109.5
C5—C4—C3117.27 (17)H14A—C14—H14B109.5
C5—C4—C9119.53 (17)C12—C14—H14C109.5
C3—C4—C9123.16 (18)H14A—C14—H14C109.5
N7—C5—C4122.38 (16)H14B—C14—H14C109.5
Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula[Cu2(N3)4(C14H12N2)2]
Mr711.72
Crystal system, space groupMonoclinic, C2/c
Temperature (K)223
a, b, c (Å)13.3691 (5), 11.2648 (5), 19.5792 (9)
β (°) 95.565 (2)
V3)2934.7 (2)
Z4
Radiation typeMo Kα
µ (mm1)1.50
Crystal size (mm)0.49 × 0.16 × 0.16
Data collection
DiffractometerBruker AXS SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000; Blessing, 1995)
Tmin, Tmax0.750, 0.787
No. of measured, independent and
observed [I > 2σ(I)] reflections
11979, 4259, 3450
Rint0.032
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.101, 1.04
No. of reflections4259
No. of parameters210
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.62, 0.33

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), PATTY in DIRDIF92 (Beurskens et al., 1992), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHEXLTL.

Selected geometric parameters (Å, º) top
Cu—N12.0285 (17)N1—N21.212 (2)
Cu—N41.9499 (17)N2—N31.137 (2)
Cu—N72.0316 (15)N4—N51.187 (2)
Cu—N82.2554 (15)N5—N61.149 (2)
Cu—N1i2.0240 (17)
N1—Cu—N4160.67 (7)N7—Cu—N1i165.60 (6)
N1—Cu—N792.67 (6)N8—Cu—N1i112.53 (6)
N1—Cu—N894.60 (6)Cu—N1—N2125.03 (14)
N1—Cu—N1i77.45 (7)Cui—N1—N2125.47 (14)
N4—Cu—N796.31 (7)Cu—N1—Cui102.55 (7)
N4—Cu—N8103.95 (7)N1—N2—N3178.8 (2)
N4—Cu—N1i90.27 (7)Cu—N4—N5126.15 (14)
N7—Cu—N878.34 (6)N4—N5—N6175.6 (2)
Symmetry code: (i) x+1/2, y+1/2, z.
 

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

The full text of this article is available to subscribers to the journal.

If you have already registered and are using a computer listed in your registration details, please email support@iucr.org for assistance.

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.
E-mail address* 
Repeat e-mail address* 
(for error checking) 

Format*   PDF (US $40)
   HTML (US $40)
   PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number 
(non-UK EC countries only) 
Country* 
 

Terms and conditions of use
Contact us

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds