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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2009 Aug 29;65(Pt 9):m1151. doi: 10.1107/S1600536809034217

Bis{2-[(1H-pyrrol-2-yl)methyl­imino­meth­yl]phenolato-κ2 N,O}zinc(II)

Yong-Ming Cui a, Xian Zhang a, Lian Liu a, Qiang Wang a,*
PMCID: PMC2969913  PMID: 21577484

Abstract

In the title compound, [Zn(C12H11N2O)2], the ZnII atom, lying on an inversion center, is coordinated by two O atoms and two N atoms from two salicylal Schiff base ligands in a distorted square-planar geometry. A three-dimensional network is formed by inter­molecular C—H⋯N hydrogen bonds and C—H⋯π contacts.

Related literature

For general background to Schiff base complexes, see: Qiu et al. (2006); Shi et al. (2007); Xiao et al. (2007a ,b , 2008); You et al. (2006). For related structures, see: Qiu et al. (2004); You et al. (2004).graphic file with name e-65-m1151-scheme1.jpg

Experimental

Crystal data

  • [Zn(C12H11N2O)2]

  • M r = 463.83

  • Triclinic, Inline graphic

  • a = 5.3443 (4) Å

  • b = 9.8669 (8) Å

  • c = 10.1392 (8) Å

  • α = 104.108 (1)°

  • β = 95.830 (1)°

  • γ = 100.126 (1)°

  • V = 504.58 (7) Å3

  • Z = 1

  • Mo Kα radiation

  • μ = 1.25 mm−1

  • T = 200 K

  • 0.30 × 0.30 × 0.20 mm

Data collection

  • Bruker SMART APEX CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.706, T max = 0.789

  • 6063 measured reflections

  • 2455 independent reflections

  • 2432 reflections with I > 2σ(I)

  • R int = 0.047

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050

  • wR(F 2) = 0.144

  • S = 1.11

  • 2455 reflections

  • 142 parameters

  • H-atom parameters constrained

  • Δρmax = 1.07 e Å−3

  • Δρmin = −0.73 e Å−3

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034217/hy2222sup1.cif

e-65-m1151-sup1.cif (16KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034217/hy2222Isup2.hkl

e-65-m1151-Isup2.hkl (120.6KB, hkl)

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

Table 1. Selected bond lengths (Å).

Zn1—O1 1.8967 (19)
Zn1—N1 2.001 (2)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A DA D—H⋯A
C8—H8A⋯O1i 0.99 2.26 2.770 (3) 111
C7—H7⋯N2ii 0.95 2.51 3.453 (3) 170
C6—H6⋯Cg1iii 0.95 2.73 3.624 (3) 158
C11—H11⋯Cg2iv 0.95 2.81 3.615 (3) 143

Symmetry codes: (i) Inline graphic; (ii) Inline graphic; (iii) Inline graphic; (iv) Inline graphic. Cg1 and Cg2 are the centroids of the N2,C9–C12 and C1–C6 rings, respectively.

supplementary crystallographic information

Comment

In preparing metal complexes, Schiff base ligands have been frequently employed (Qiu et al., 2004, 2006; Shi et al., 2007; Xiao et al., 2007a,b; Xiao et al., 2008; You et al., 2006). Zinc derivatives are particularly interesting owing to their essential importance in several biological processes (You et al., 2004, 2006; Xiao et al., 2007a,b; Xiao et al., 2008). We have reported the structures of a few zinc(II) complexes (You et al., 2004; Qiu et al., 2004). As an extension of our work, we report here the structure of a zinc(II) complex with salicylal Schiff base ligands.

The title compound consists of a ZnII atom, lying on an inversion center, and two bidentate salicylal Schiff base ligands. The central ZnII atom is coordinated by two N atoms from the pyrrole groups and two O atoms from the phenolate groups, forming a slightly distorted square-planar geometry (Fig. 1). The distortion arises from the difference between Zn—O and Zn—N bonds (Table 1). The six-membered ring (Zn1, N1, C7, C2, C1, O1) and the benzene ring are almost co-planar with a mean deviation of 0.046 (1) Å.

Intramolecular C—H···O hydrogen bond occours between H8A and O1 (Fig. 1 and Table 2). C—H···π contacts involving C6—H6···Cg1iii [Cg1 is the centroid of N2, C9–C12 ring; symmetry code: (iii) 2-x, 2-y, 1-z] and C11—H11···Cg2iv [Cg2 is the centroid of C1–C6 ring; (iv) x, y, 1+z] are observed (Fig. 3). These interactions as well as intermolecular C—H···N hydrogen bond (Fig. 2) connect the molecules into a three-dimensional network.

Experimental

Zinc oxide (0.5 mmol), salicylaldehyde (1 mmol) and (1H-pyrrol-yl)methanamine (1 mmol) were dissolved in 10 ml of methanol. After 3 ml ammonia was added, the resulting solution was heated to 423 K for 10 h. The reactor was cooled to room temperature at a rate of 10 K h-1. The mixture was filtered and held at room temperature for 10 d. Colorless block crystals were isolated (yield 38%).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 (CH), 0.99 (CH2) Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N).

Figures

Fig. 1.

Fig. 1.

Molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate hydrogen bonds. [Symmetry code: (i) 1-x, 2-y, 1-z.]

Fig. 2.

Fig. 2.

Packing diagram of the title compound. Dashed lines indicate C—H···N hydrogen bonds.

Fig. 3.

Fig. 3.

C—H···π interactions in the title compound (dashed lines).

Crystal data

[Zn(C12H11N2O)2] Z = 1
Mr = 463.83 F(000) = 240
Triclinic, P1 Dx = 1.526 Mg m3
Hall symbol: -P 1 Mo Kα radiation, λ = 0.71073 Å
a = 5.3443 (4) Å Cell parameters from 2361 reflections
b = 9.8669 (8) Å θ = 2.7–26.6°
c = 10.1392 (8) Å µ = 1.25 mm1
α = 104.108 (1)° T = 200 K
β = 95.830 (1)° Block, colorless
γ = 100.126 (1)° 0.30 × 0.30 × 0.20 mm
V = 504.58 (7) Å3

Data collection

Bruker SMART APEX CCD diffractometer 2455 independent reflections
Radiation source: fine-focus sealed tube 2432 reflections with I > 2σ(I)
graphite Rint = 0.047
φ and ω scans θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) h = −7→7
Tmin = 0.706, Tmax = 0.789 k = −13→13
6063 measured reflections l = −13→13

Refinement

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)] = 0.050 Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.144 H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0948P)2 + 0.2435P] where P = (Fo2 + 2Fc2)/3
2455 reflections (Δ/σ)max < 0.001
142 parameters Δρmax = 1.07 e Å3
0 restraints Δρmin = −0.73 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
C1 0.8616 (5) 0.9132 (3) 0.3153 (2) 0.0297 (5)
C2 0.7761 (5) 0.7658 (3) 0.3046 (2) 0.0306 (5)
C3 0.8882 (6) 0.6636 (3) 0.2175 (3) 0.0379 (6)
H3 0.8295 0.5648 0.2088 0.045*
C4 1.0792 (6) 0.7055 (3) 0.1461 (3) 0.0392 (6)
H4 1.1518 0.6367 0.0880 0.047*
C5 1.1647 (6) 0.8508 (4) 0.1602 (3) 0.0403 (6)
H5 1.2984 0.8804 0.1120 0.048*
C6 1.0611 (5) 0.9518 (3) 0.2417 (3) 0.0363 (5)
H6 1.1246 1.0500 0.2491 0.044*
C7 0.5899 (5) 0.7143 (3) 0.3816 (3) 0.0320 (5)
H7 0.5492 0.6139 0.3688 0.038*
C8 0.2983 (5) 0.7075 (3) 0.5401 (3) 0.0331 (5)
H8A 0.1403 0.7464 0.5483 0.040*
H8B 0.2478 0.6061 0.4866 0.040*
C9 0.4297 (5) 0.7175 (3) 0.6791 (3) 0.0290 (5)
C10 0.3985 (5) 0.7807 (4) 0.8078 (3) 0.0398 (6)
H10 0.2724 0.8349 0.8336 0.048*
C11 0.5913 (6) 0.7507 (4) 0.8987 (3) 0.0447 (7)
H11 0.6185 0.7811 0.9964 0.054*
C12 0.7259 (6) 0.6713 (3) 0.8190 (3) 0.0405 (6)
H12 0.8665 0.6354 0.8519 0.049*
N1 0.4708 (4) 0.7890 (2) 0.4666 (2) 0.0297 (4)
N2 0.6319 (4) 0.6496 (2) 0.6837 (2) 0.0291 (4)
H2A 0.6901 0.6011 0.6127 0.035*
O1 0.7656 (4) 1.0126 (2) 0.3902 (2) 0.0346 (4)
Zn1 0.5000 1.0000 0.5000 0.02730 (17)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
C1 0.0298 (11) 0.0310 (11) 0.0267 (10) 0.0055 (9) −0.0013 (8) 0.0079 (9)
C2 0.0311 (11) 0.0325 (12) 0.0263 (10) 0.0053 (9) −0.0014 (8) 0.0075 (9)
C3 0.0413 (14) 0.0378 (13) 0.0334 (12) 0.0112 (11) 0.0002 (10) 0.0074 (10)
C4 0.0384 (14) 0.0478 (15) 0.0307 (12) 0.0177 (11) 0.0042 (10) 0.0035 (11)
C5 0.0349 (13) 0.0527 (17) 0.0340 (13) 0.0124 (11) 0.0044 (10) 0.0110 (12)
C6 0.0331 (12) 0.0405 (13) 0.0353 (12) 0.0057 (10) 0.0047 (9) 0.0118 (10)
C7 0.0370 (12) 0.0265 (11) 0.0300 (11) 0.0048 (9) 0.0000 (9) 0.0062 (9)
C8 0.0350 (12) 0.0292 (11) 0.0318 (11) −0.0022 (9) −0.0009 (9) 0.0108 (9)
C9 0.0282 (11) 0.0285 (11) 0.0320 (11) 0.0050 (8) 0.0041 (8) 0.0123 (9)
C10 0.0311 (12) 0.0613 (18) 0.0306 (12) 0.0152 (12) 0.0082 (9) 0.0140 (12)
C11 0.0368 (14) 0.069 (2) 0.0317 (13) 0.0110 (13) 0.0041 (10) 0.0206 (13)
C12 0.0392 (14) 0.0448 (15) 0.0402 (14) 0.0106 (11) −0.0011 (11) 0.0182 (12)
N1 0.0334 (10) 0.0272 (9) 0.0269 (9) 0.0031 (7) 0.0000 (7) 0.0085 (7)
N2 0.0327 (10) 0.0275 (9) 0.0292 (9) 0.0129 (8) 0.0035 (7) 0.0074 (7)
O1 0.0368 (9) 0.0299 (9) 0.0384 (9) 0.0067 (7) 0.0114 (7) 0.0096 (7)
Zn1 0.0300 (2) 0.0258 (2) 0.0259 (2) 0.00531 (15) 0.00390 (14) 0.00714 (15)

Geometric parameters (Å, °)

C1—O1 1.302 (3) C8—N1 1.491 (3)
C1—C6 1.413 (4) C8—H8A 0.9900
C1—C2 1.419 (4) C8—H8B 0.9900
C2—C7 1.425 (4) C9—C10 1.344 (4)
C2—C3 1.429 (4) C9—N2 1.371 (3)
C3—C4 1.373 (4) C10—C11 1.430 (4)
C3—H3 0.9500 C10—H10 0.9500
C4—C5 1.393 (5) C11—C12 1.339 (5)
C4—H4 0.9500 C11—H11 0.9500
C5—C6 1.367 (4) C12—N2 1.363 (3)
C5—H5 0.9500 C12—H12 0.9500
C6—H6 0.9500 N2—H2A 0.8800
C7—N1 1.287 (3) Zn1—O1 1.8967 (19)
C7—H7 0.9500 Zn1—N1 2.001 (2)
C8—C9 1.481 (3)
O1—C1—C6 119.4 (2) H8A—C8—H8B 108.1
O1—C1—C2 122.8 (2) C10—C9—N2 109.4 (2)
C6—C1—C2 117.8 (3) C10—C9—C8 134.5 (2)
C1—C2—C7 123.0 (2) N2—C9—C8 116.1 (2)
C1—C2—C3 119.1 (2) C9—C10—C11 106.9 (3)
C7—C2—C3 117.8 (2) C9—C10—H10 126.6
C4—C3—C2 121.3 (3) C11—C10—H10 126.6
C4—C3—H3 119.4 C12—C11—C10 106.5 (3)
C2—C3—H3 119.4 C12—C11—H11 126.8
C3—C4—C5 118.8 (3) C10—C11—H11 126.8
C3—C4—H4 120.6 C11—C12—N2 110.1 (2)
C5—C4—H4 120.6 C11—C12—H12 124.9
C6—C5—C4 121.7 (3) N2—C12—H12 124.9
C6—C5—H5 119.2 C7—N1—C8 115.6 (2)
C4—C5—H5 119.2 C7—N1—Zn1 124.25 (18)
C5—C6—C1 121.3 (3) C8—N1—Zn1 120.09 (17)
C5—C6—H6 119.3 C12—N2—C9 107.1 (2)
C1—C6—H6 119.3 C12—N2—H2A 126.4
N1—C7—C2 127.1 (2) C9—N2—H2A 126.4
N1—C7—H7 116.4 C1—O1—Zn1 130.68 (18)
C2—C7—H7 116.4 O1i—Zn1—O1 180.000 (1)
C9—C8—N1 110.58 (19) O1i—Zn1—N1 88.44 (9)
C9—C8—H8A 109.5 O1—Zn1—N1 91.56 (9)
N1—C8—H8A 109.5 O1i—Zn1—N1i 91.56 (9)
C9—C8—H8B 109.5 O1—Zn1—N1i 88.44 (9)
N1—C8—H8B 109.5 N1—Zn1—N1i 180.00 (12)
O1—C1—C2—C7 −4.2 (4) C9—C10—C11—C12 −0.1 (4)
C6—C1—C2—C7 175.2 (2) C10—C11—C12—N2 0.3 (4)
O1—C1—C2—C3 178.6 (2) C2—C7—N1—C8 −176.0 (2)
C6—C1—C2—C3 −2.0 (3) C2—C7—N1—Zn1 5.3 (4)
C1—C2—C3—C4 1.1 (4) C9—C8—N1—C7 98.0 (3)
C7—C2—C3—C4 −176.3 (2) C9—C8—N1—Zn1 −83.2 (2)
C2—C3—C4—C5 0.4 (4) C11—C12—N2—C9 −0.4 (3)
C3—C4—C5—C6 −0.8 (4) C10—C9—N2—C12 0.3 (3)
C4—C5—C6—C1 −0.1 (4) C8—C9—N2—C12 179.9 (2)
O1—C1—C6—C5 −179.0 (2) C6—C1—O1—Zn1 179.70 (17)
C2—C1—C6—C5 1.6 (4) C2—C1—O1—Zn1 −0.9 (4)
C1—C2—C7—N1 1.6 (4) C1—O1—Zn1—N1 5.4 (2)
C3—C2—C7—N1 178.9 (2) C1—O1—Zn1—N1i −174.6 (2)
N1—C8—C9—C10 111.4 (3) C7—N1—Zn1—O1i 172.7 (2)
N1—C8—C9—N2 −68.1 (3) C8—N1—Zn1—O1i −5.97 (17)
N2—C9—C10—C11 −0.1 (3) C7—N1—Zn1—O1 −7.3 (2)
C8—C9—C10—C11 −179.6 (3) C8—N1—Zn1—O1 174.03 (17)

Symmetry codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A
C8—H8A···O1i 0.99 2.26 2.770 (3) 111
C7—H7···N2ii 0.95 2.51 3.453 (3) 170
C6—H6···Cg1iii 0.95 2.73 3.624 (3) 158
C11—H11···Cg2iv 0.95 2.81 3.615 (3) 143

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y+2, −z+1; (iv) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2222).

References

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034217/hy2222sup1.cif

e-65-m1151-sup1.cif (16KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034217/hy2222Isup2.hkl

e-65-m1151-Isup2.hkl (120.6KB, hkl)

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


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