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metal-organic compounds
Bis{2-[(1H-pyrrol-2-yl)methyliminomethyl]phenolato-κ2N,O}zinc(II)
aEngineering Research Center for Clean Production of Textile Dyeing and Printing, Ministry of Education, Wuhan 430073, People's Republic of China
*Correspondence e-mail: qiangqiang_wang@163.com
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
).
Experimental
Crystal data
|
Refinement
|
|
|
Data collection: SMART (Bruker, 2007); cell 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.
Supporting information
10.1107/S1600536809034217/hy2222sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809034217/hy2222Isup2.hkl
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%).
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).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).[Zn(C12H11N2O)2] | Z = 1 |
Mr = 463.83 | F(000) = 240 |
Triclinic, P1 | Dx = 1.526 Mg m−3 |
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 mm−1 |
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 |
Bruker SMART APEX CCD diffractometer | 2455 independent reflections |
Radiation source: fine-focus sealed tube | 2432 reflections with I > 2σ(I) |
Graphite monochromator | 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 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 Å−3 |
0 restraints | Δρmin = −0.73 e Å−3 |
[Zn(C12H11N2O)2] | γ = 100.126 (1)° |
Mr = 463.83 | V = 504.58 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.3443 (4) Å | Mo Kα radiation |
b = 9.8669 (8) Å | µ = 1.25 mm−1 |
c = 10.1392 (8) Å | T = 200 K |
α = 104.108 (1)° | 0.30 × 0.30 × 0.20 mm |
β = 95.830 (1)° |
Bruker SMART APEX CCD diffractometer | 2455 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2432 reflections with I > 2σ(I) |
Tmin = 0.706, Tmax = 0.789 | Rint = 0.047 |
6063 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.11 | Δρmax = 1.07 e Å−3 |
2455 reflections | Δρmin = −0.73 e Å−3 |
142 parameters |
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) |
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) |
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 code: (i) −x+1, −y+2, −z+1. |
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. |
Experimental details
Crystal data | |
Chemical formula | [Zn(C12H11N2O)2] |
Mr | 463.83 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 200 |
a, b, c (Å) | 5.3443 (4), 9.8669 (8), 10.1392 (8) |
α, β, γ (°) | 104.108 (1), 95.830 (1), 100.126 (1) |
V (Å3) | 504.58 (7) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.25 |
Crystal size (mm) | 0.30 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.706, 0.789 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6063, 2455, 2432 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.144, 1.11 |
No. of reflections | 2455 |
No. of parameters | 142 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.07, −0.73 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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. |
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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.