Di­azido­bis­(1,7 phenanthroline)zinc(II)

metal-organic papers

Acta Cryst.(2005). E61, m1099–m1100 doi:10.1107/S1600536805014108 Sun and Du _[Zn(N

3)2(C12H8N2)2]

m1099

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

Diazidobis(1,7-phenanthroline)zinc(II)

Bai-Wang Suna* and Lin Dub

a_{Department of Chemistry and Chemical}

Engineering, Southeast University, Nanjing 210096, People’s Republic of China, and

b_{Department of Chemistry, Yunnan University,}

Kunming 650091, People’s Republic of China

Correspondence e-mail: chmsunbw@seu.edu.cn

Key indicators

Single-crystal X-ray study

T= 223 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.045

wRfactor = 0.123

Data-to-parameter ratio = 20.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

The title complex, [Zn(N3)2(C12H8N2)2], possesses C2 symmetry. The Zn2+ion has a distorted tetrahedral coordina-tion environment and is coordinated by two N atoms from two 1,7-phenanthroline ligands and by two N atoms of end-on-coordinated azides. In the crystal structure, the molecules stack up the c axis via – interactions between the 1,7-phenanthroline ligands.

Comment

The synthesis of new organic–inorganic hybrid compounds is a relatively new research area that has developed rapidly (Ciurtinet al., 2001). A large number of complexes with azido ligands, from dimers to three-dimensional networks, have been structurally and magnetically characterized in recent years (Monfort et al., 2000). Azido-bridged complexes have attracted considerable attention due to their structural diver-sity (Liet al., 2002). They may coordinate as1,3-N3 (end-to-end, EE) or 1,1-N3 (end-on, EO), or in even more exotic modes, such as1,1,3-N3or1,1,1-N3(Goheret al., 2000; Ribas

et al., 1994). Recently, we have synthesized the title compound, (I), and its structure is reported here.

The molecular structure of (I) is illustrated in Fig. 1 and selected bond distances and angles are given in Table 1. The Zn2+ion is situated on a twofold axis and assumes a distorted tetrahedral geometry. It is coordinated by two terminal N atoms of two N

3 ligands, and by two N atoms of two 1,7-phenanthroline ligands. Non-linear coordination of the N3

ligands to the Zn2+centre is apparent from the Zn1—N1—N2 bond angles of 115.8 (2). The bond distances and angles in the 1,7-phenanthroline ligands are normal. They are nearly planar, with the largest deviation of any atom from the 1,7-phen mean-plane being 0.0162 A˚ for C9. The dihedral angle of the two phenanthroline ligands, which coordinate to the Zn2+ ion, is 80.56 (2)_.

The three-dimensional crystal structure of (I) can be regarded as being constructedvia–stacking interactions, as

shown in Fig. 2. The interacting 1,7-phenanthroline ligands are nearly parallel to one another and are separated by a distance ofca3.36 A˚ .

Experimental

To an aqueous solution (5 ml) of Zn(OAc)2H2O (219.22 mg, 1 mmol)

was added 1,7-phenanthroline (182.22 mg, 1 mmol) dissolved in methanol (5 ml). This mixture was then added to an aqueous solution (10 ml) of NaN3(130.03 mg, 2 mmol). The resulting clear solution

was left to stand undisturbed at room temperature. After two weeks, X-ray quality crystals of (I) were obtained by slow evaporation. These were filtered, washed with water and air dried. The yield was 55%. Analysis calculated for C24H16N10Zn: C 56.68, H 3.17, N

27.56%; found: C 56.36, H 3.56, N 27.21%. IR (KBr disk):

(N N N) 2072 cm1_.

Crystal data

[Zn(N3)2(C12H8N2)2] Mr= 509.84

Orthorhombic,Ibca a= 13.7823 (13) A˚

b= 17.5908 (17) A˚

c= 18.1368 (18) A˚

V= 4397.1 (7) A˚3 Z= 8

Dx= 1.540 Mg m

3

MoKradiation

Cell parameters from 18 030 reflections

= 2.3–30.0 = 1.15 mm1 T= 223 (2) K Polyhedron, colourless 0.260.220.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.748,Tmax= 0.812

18 030 measured reflections

3214 independent reflections 2346 reflections withI> 2(I)

Rint= 0.054

max= 30.0

h=19!16

k=24!24

l=25!24

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.045} wR(F2_{) = 0.123} S= 1.02

w= 1/[2_(F

o2) + (0.0691P)2

+ 1.193P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

Table 1

Selected geometric parameters (A˚ ,_).

Zn1—N1i

1.954 (2) Zn1—N4 2.0403 (16)

N1—N2 1.179 (3)

N2—N3 1.138 (3)

N4—C8 1.329 (3)

N4—C9 1.367 (2)

N5—C5 1.319 (3)

N5—C11 1.357 (2)

N1i

—Zn1—N1 115.98 (15) N1i

—Zn1—N4 101.76 (8) N1—Zn1—N4 108.41 (8) N4—Zn1—N4i

121.29 (9) N2—N1—Zn1 122.60 (18)

N3—N2—N1 177.4 (3) C8—N4—C9 118.58 (17) C8—N4—Zn1 116.33 (13) C9—N4—Zn1 124.61 (13)

Symmetry code: (i)xþ1 2;y;zþ1.

H atoms were placed in calculated positions and treated as riding, with C—H = 0.94 A˚ andUiso(H) = 1.2Ueq(C).

Data collection:SMART(Bruker, 2002); cell refinement:SAINT

(Bruker, 2002); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 2002); software used to prepare material for publication:SHELXTL.

References

Bruker (2002). SMART (Version 5.628), SAINT (Version 6.02) and

SHELXTL(Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA. Ciurtin, D. M, Dong, Y. B., Smith, M. D., Barclay, T. & ZurLoye, H. C. (2001).

Inorg. Chem.40, 2425–2434.

Goher, M . A . S., Cano, J., Journaux, Y., Abu-Youssef, M. A. M., Mautner, F. A., Escuer, A. & Vicente , R. (2000).Chem. Eur. J.6, 778–784. Li, L. C., Liao, D. Z., Jiang, Z. H. & Yan, S. P. (2002).Inorg. Chem.41, 1019–

2021.

Monfort, M., Resino, I., Ribas, J. & Stoeckli-Evans, H. (2000).Angew. Chem. Int. Ed.39, 191–193.

Ribas, J., Monfort, M., Solans, X. & Drillon, M. (1994).Inorg. Chem.33, 742– 745.

Figure 1

The molecular structure of (I), showing the atom-labelling scheme and 30% probability displacement ellipsoids. [Symmetry code: (A)1

2x,y, 1

z.]

Figure 2

supporting information

sup-1

Acta Cryst. (2005). E61, m1099–m1100

supporting information

Acta Cryst. (2005). E61, m1099–m1100 [https://doi.org/10.1107/S1600536805014108]

Diazidobis(1,7-phenanthroline)zinc(II)

Bai-Wang Sun and Lin Du

Diazidobis(1,7-phenanthroline)zinc(II)

Crystal data

[Zn(N3)2(C12H8N2)2] Mr = 509.84

Orthorhombic, Ibca

Hall symbol: -I 2b 2c

a = 13.7823 (13) Å

b = 17.5908 (17) Å

c = 18.1368 (18) Å

V = 4397.1 (7) Å3 Z = 8

F(000) = 2080

Dx = 1.540 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 18030 reflections

θ = 2.3–30.0°

µ = 1.15 mm−1 T = 223 K

Polyhedron, colourless 0.26 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.748, Tmax = 0.812

18030 measured reflections 3214 independent reflections 2346 reflections with I > 2σ(I)

Rint = 0.054

θmax = 30.0°, θmin = 2.3° h = −19→16

k = −24→24

l = −25→24

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.045} wR(F2_{) = 0.123} S = 1.02 3214 reflections 159 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0691P)2 + 1.193P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.49 e Å−3

Δρmin = −0.28 e Å−3

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Zn1 0.2500 0.186831 (18) 0.5000 0.03046 (13)

N1 0.28503 (16) 0.24571 (13) 0.41260 (13) 0.0556 (6)

N2 0.22804 (14) 0.26275 (12) 0.36704 (12) 0.0455 (5)

N3 0.1759 (2) 0.27972 (19) 0.32123 (16) 0.0891 (9)

N4 0.12407 (11) 0.12997 (9) 0.47862 (9) 0.0275 (3)

N5 −0.07213 (12) −0.04606 (10) 0.34128 (11) 0.0352 (4)

C1 0.20011 (13) 0.04145 (12) 0.39642 (12) 0.0322 (4)

H1A 0.2610 0.0624 0.4079 0.039*

C2 0.19409 (14) −0.01845 (12) 0.34947 (12) 0.0343 (4)

H2A 0.2513 −0.0388 0.3293 0.041*

C3 0.09528 (16) −0.11401 (11) 0.28265 (12) 0.0371 (5)

H3A 0.1510 −0.1374 0.2632 0.044*

C4 0.00450 (16) −0.14043 (13) 0.26537 (12) 0.0403 (5)

H4A −0.0032 −0.1820 0.2333 0.048*

C5 −0.07613 (15) −0.10478 (12) 0.29613 (13) 0.0407 (5)

H5A −0.1377 −0.1239 0.2839 0.049*

C6 −0.05925 (14) 0.07644 (11) 0.44182 (12) 0.0321 (4)

H6A −0.1216 0.0597 0.4285 0.039*

C7 −0.04867 (15) 0.13272 (13) 0.49300 (11) 0.0351 (5)

H7A −0.1031 0.1543 0.5161 0.042*

C8 0.04435 (16) 0.15738 (13) 0.51017 (11) 0.0330 (4)

H8A 0.0513 0.1955 0.5461 0.040*

C9 0.11483 (13) 0.07261 (10) 0.42825 (11) 0.0261 (4)

C10 0.10300 (14) −0.05116 (10) 0.33011 (11) 0.0299 (4)

C11 0.01741 (13) −0.01922 (10) 0.35832 (11) 0.0273 (4)

C12 0.02268 (13) 0.04355 (10) 0.40913 (11) 0.0263 (4)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Zn1 0.02720 (19) 0.02784 (19) 0.0363 (2) 0.000 −0.01262 (13) 0.000

N1 0.0437 (11) 0.0627 (14) 0.0605 (14) −0.0178 (10) −0.0223 (10) 0.0301 (11)

N2 0.0431 (10) 0.0443 (11) 0.0492 (12) 0.0018 (9) −0.0082 (9) 0.0117 (9)

N3 0.0705 (17) 0.127 (2) 0.0702 (18) 0.0125 (17) −0.0255 (15) 0.0412 (17)

N4 0.0232 (8) 0.0267 (8) 0.0326 (8) 0.0026 (6) −0.0056 (6) −0.0019 (6)

N5 0.0238 (8) 0.0377 (9) 0.0441 (10) −0.0057 (7) −0.0069 (7) −0.0015 (8)

C1 0.0181 (9) 0.0389 (11) 0.0397 (11) 0.0004 (8) −0.0049 (7) −0.0055 (8)

C2 0.0224 (9) 0.0407 (11) 0.0398 (11) 0.0038 (8) −0.0024 (8) −0.0071 (9)

C3 0.0365 (11) 0.0321 (10) 0.0425 (12) 0.0033 (8) −0.0030 (9) −0.0056 (9)

supporting information

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Acta Cryst. (2005). E61, m1099–m1100

C5 0.0313 (11) 0.0386 (12) 0.0520 (13) −0.0093 (9) −0.0107 (9) −0.0042 (10)

C6 0.0196 (9) 0.0346 (10) 0.0421 (12) 0.0004 (7) −0.0025 (8) 0.0017 (8)

C7 0.0246 (9) 0.0379 (11) 0.0430 (12) 0.0070 (8) 0.0015 (8) −0.0024 (8)

C8 0.0317 (11) 0.0296 (10) 0.0376 (12) 0.0055 (8) −0.0038 (8) −0.0041 (8)

C9 0.0214 (8) 0.0279 (9) 0.0289 (9) 0.0002 (7) −0.0045 (7) 0.0007 (7)

C10 0.0252 (9) 0.0307 (10) 0.0338 (10) 0.0004 (7) −0.0048 (8) −0.0023 (8)

C11 0.0203 (8) 0.0292 (9) 0.0325 (10) −0.0021 (7) −0.0045 (7) 0.0003 (7)

C12 0.0197 (8) 0.0279 (9) 0.0313 (10) −0.0003 (7) −0.0023 (7) 0.0020 (7)

Geometric parameters (Å, º)

Zn1—N1i _{1.954 (2) C3—C4 1.371 (3)}

Zn1—N1 1.954 (2) C3—C10 1.405 (3)

Zn1—N4 2.0403 (16) C3—H3A 0.9400

Zn1—N4i _{2.0403 (16) C4—C5 1.393 (3)}

N1—N2 1.179 (3) C4—H4A 0.9400

N2—N3 1.138 (3) C5—H5A 0.9400

N4—C8 1.329 (3) C6—C7 1.365 (3)

N4—C9 1.367 (2) C6—C12 1.400 (3)

N5—C5 1.319 (3) C6—H6A 0.9400

N5—C11 1.357 (2) C7—C8 1.389 (3)

C1—C2 1.357 (3) C7—H7A 0.9400

C1—C9 1.420 (3) C8—H8A 0.9400

C1—H1A 0.9400 C9—C12 1.412 (2)

C2—C10 1.425 (3) C10—C11 1.403 (3)

C2—H2A 0.9400 C11—C12 1.440 (3)

N1i_{—Zn1—N1 115.98 (15) N5—C5—C4 124.61 (19)}

N1i_{—Zn1—N4 101.76 (8) N5—C5—H5A 117.7}

N1—Zn1—N4 108.41 (8) C4—C5—H5A 117.7

N1i_—Zn1—N4i _{108.41 (8) C7—C6—C12 120.10 (18)}

N1—Zn1—N4i _{101.76 (8) C7—C6—H6A 119.9}

N4—Zn1—N4i _{121.29 (9) C12—C6—H6A 119.9}

N2—N1—Zn1 122.60 (18) C6—C7—C8 118.53 (19)

N3—N2—N1 177.4 (3) C6—C7—H7A 120.7

C8—N4—C9 118.58 (17) C8—C7—H7A 120.7

C8—N4—Zn1 116.33 (13) N4—C8—C7 123.58 (19)

C9—N4—Zn1 124.61 (13) N4—C8—H8A 118.2

C5—N5—C11 116.86 (18) C7—C8—H8A 118.2

C2—C1—C9 120.28 (17) N4—C9—C12 120.99 (17)

C2—C1—H1A 119.9 N4—C9—C1 118.66 (16)

C9—C1—H1A 119.9 C12—C9—C1 120.33 (17)

C1—C2—C10 121.46 (18) C11—C10—C3 118.34 (17)

C1—C2—H2A 119.3 C11—C10—C2 119.29 (17)

C10—C2—H2A 119.3 C3—C10—C2 122.36 (19)

C4—C3—C10 118.4 (2) N5—C11—C10 122.83 (17)

C4—C3—H3A 120.8 N5—C11—C12 117.29 (17)

C3—C4—C5 118.9 (2) C6—C12—C9 118.14 (17)

C3—C4—H4A 120.5 C6—C12—C11 123.17 (17)

C5—C4—H4A 120.5 C9—C12—C11 118.69 (17)