metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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Di­chlorido{2-[(2-iso­propyl­ammonio­ethyl)imino­meth­yl]-5-meth­oxy­phenolato}zinc(II)

aApplied Technical College, Qiqihar University, Qiqihar 161006, People's Republic of China, bQiqihar Environmental Monitoring Central Station, Qiqihar 161005, People's Republic of China, and cCollege of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar 161006, People's Republic of China
*Correspondence e-mail: zhenquan_han@126.com

(Received 19 March 2010; accepted 24 March 2010; online 31 March 2010)

The ZnII atom in the title compound, [ZnCl2(C13H20N2O2)], is four-coordinated by the imine N and phenolate O atoms of the zwitterionic Schiff base ligand, and by two choride ions in a distorted tetra­hedral coordination. In the crystal structure, mol­ecules are linked through inter­molecular N—H⋯O and N—H⋯Cl hydrogen bonds along [010].

Related literature

For a nickel(II) complex with the 3-ethoxy­salicylaldehyde ligand, see: Han (2008[Han, Z.-Q. (2008). Acta Cryst. E64, m592.]). For similar zinc(II) complexes with Schiff bases, see: Ali et al. (2008[Ali, H. M., Mohamed Mustafa, M. I., Rizal, M. R. & Ng, S. W. (2008). Acta Cryst. E64, m718-m719.]); Wang (2007[Wang, S.-X. (2007). Acta Cryst. E63, m706-m707.]); Zhang et al. (2008[Zhang, D.-F., Zhou, M.-H. & Yuan, C.-J. (2008). Acta Cryst. E64, m825-m826.]); Zhu et al. (2009[Zhu, X.-W., Yang, X.-Z., Zhang, C.-X., Li, G.-S. & Yin, Z.-G. (2009). Acta Cryst. E65, m1332-m1333.]).

[Scheme 1]

Experimental

Crystal data
  • [ZnCl2(C13H20N2O2)]

  • Mr = 372.58

  • Monoclinic, P 21 /n

  • a = 6.2915 (9) Å

  • b = 11.8990 (18) Å

  • c = 22.115 (4) Å

  • β = 96.518 (4)°

  • V = 1644.9 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.82 mm−1

  • T = 298 K

  • 0.18 × 0.18 × 0.18 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.735, Tmax = 0.735

  • 9437 measured reflections

  • 3557 independent reflections

  • 2515 reflections with I > 2σ(I)

  • Rint = 0.042

Refinement
  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.086

  • S = 1.01

  • 3557 reflections

  • 184 parameters

  • H-atom parameters constrained

  • Δρmax = 0.46 e Å−3

  • Δρmin = −0.31 e Å−3

Table 1
Selected geometric parameters (Å, °)

Zn1—O1 1.9425 (19)
Zn1—N1 1.997 (2)
Zn1—Cl2 2.2290 (9)
Zn1—Cl1 2.2554 (10)
O1—Zn1—N1 97.16 (9)
O1—Zn1—Cl2 107.02 (6)
N1—Zn1—Cl2 113.82 (7)
O1—Zn1—Cl1 111.15 (7)
N1—Zn1—Cl1 110.44 (7)
Cl2—Zn1—Cl1 115.64 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H2A⋯Cl2i 0.90 2.62 3.357 (2) 140
N2—H2B⋯O1i 0.90 1.91 2.782 (3) 162
N2—H2A⋯Cl1 0.90 2.97 3.483 (2) 118
Symmetry code: (i) [-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: SMART (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1998[Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Recently, we have reported a nickel(II) complex with the ligand 3-ethoxysalicylaldehyde (Han, 2008). We report here a new zinc(II) complex derived from the Schiff base ligand 2-[(2-isopropylammonioethylimino)methyl]-5-methoxyphenol, which was formed by the condensation reaction of 4-methoxysalicylaldehyde with N-isopropylethane-1,2-diamine in a methanol solution.The ZnII atom is four-coordinated by the imine N and phenolate O atoms of the Schiff base ligand, and by two choride ions in a distorted tetrahedral coordination. In the crystal structure, molecules are linked through intermolecular N—H··· O and N—H ···O and hydrogen bonds along [010], (Fig. 2). The geometric parameters are comparable to those in similar zinc(II) complexes with Schiff bases (Wang, 2007; Ali et al., 2008; Zhang et al., 2008; Zhu et al., 2009) as representative examples.

Related literature top

For a nickel(II) complex with the 3-ethoxysalicylaldehyde ligand, see: Han (2008). For similar zinc(II) complexes with Schiff bases, see: Ali et al. (2008); Wang (2007); Zhang et al. (2008); Zhu et al. (2009).

Experimental top

All the chemicals were of AR grade. 4-Methoxysalicylaldehyde (30.4 mg, 0.2 mmol) and N-isopropylethane-1,2-diamine (20.4 mg, 0.2 mmol) were stirred in a methanol solution for 2 h at reflux. Then the zinc(II) chloride (27.5 mg, 0.2 mmol) was added to the mixture. The mixture was further stirred at reflux for 1 h. The mixture was cooled to room temperature and filtered. After keeping the filtrate in air for a week, yielding colorless block crystals suitable for X-ray analysis.

Refinement top

H atoms were placed in idealized positions and constrained to ride on their parent atoms with C–H distances in the range 0.93-0.97 Å, N–H distances of 0.90 Å, and with Uiso(H) set at 1.2Ueq(C,N) and 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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).

Figures top
[Figure 1] Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Molecular packing of the title complex.
Dichlorido{2-[(2-isopropylammonioethyl)iminomethyl]-5-methoxyphenolato}zinc(II) top
Crystal data top
[ZnCl2(C13H20N2O2)]F(000) = 768
Mr = 372.58Dx = 1.504 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 6.2915 (9) ÅCell parameters from 1935 reflections
b = 11.8990 (18) Åθ = 2.5–24.5°
c = 22.115 (4) ŵ = 1.82 mm1
β = 96.518 (4)°T = 298 K
V = 1644.9 (4) Å3Block, colourless
Z = 40.18 × 0.18 × 0.18 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
3557 independent reflections
Radiation source: fine-focus sealed tube2515 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.042
ω scansθmax = 27.0°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 78
Tmin = 0.735, Tmax = 0.735k = 1315
9437 measured reflectionsl = 2728
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)] = 0.038Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0339P)2 + 0.3384P]
where P = (Fo2 + 2Fc2)/3
3557 reflections(Δ/σ)max = 0.001
184 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.31 e Å3
Crystal data top
[ZnCl2(C13H20N2O2)]V = 1644.9 (4) Å3
Mr = 372.58Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.2915 (9) ŵ = 1.82 mm1
b = 11.8990 (18) ÅT = 298 K
c = 22.115 (4) Å0.18 × 0.18 × 0.18 mm
β = 96.518 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3557 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2515 reflections with I > 2σ(I)
Tmin = 0.735, Tmax = 0.735Rint = 0.042
9437 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.086H-atom parameters constrained
S = 1.01Δρmax = 0.46 e Å3
3557 reflectionsΔρmin = 0.31 e Å3
184 parameters
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Zn10.75702 (6)0.83340 (3)0.763592 (16)0.03646 (12)
Cl10.56343 (14)0.81826 (7)0.67166 (4)0.0519 (2)
Cl21.00002 (12)0.97048 (6)0.77248 (4)0.0497 (2)
N10.8725 (4)0.68364 (18)0.79167 (11)0.0336 (6)
N20.9034 (4)0.58914 (18)0.66336 (10)0.0329 (6)
H2A0.77880.59590.67940.039*
H2B0.94120.51620.66580.039*
O10.5732 (3)0.85623 (15)0.82740 (9)0.0399 (5)
O20.0900 (4)0.7411 (2)0.95938 (11)0.0652 (7)
C10.6016 (5)0.6635 (2)0.86232 (13)0.0360 (7)
C20.5081 (5)0.7727 (2)0.85973 (13)0.0336 (7)
C30.3364 (5)0.7916 (2)0.89406 (14)0.0397 (7)
H30.27350.86250.89310.048*
C40.2582 (5)0.7086 (3)0.92900 (14)0.0449 (8)
C50.3475 (6)0.6021 (3)0.93171 (16)0.0524 (9)
H50.29560.54600.95540.063*
C60.5158 (5)0.5815 (3)0.89822 (15)0.0483 (8)
H60.57520.50990.89950.058*
C70.7806 (5)0.6282 (2)0.83109 (13)0.0367 (7)
H70.83530.55710.84080.044*
C81.0626 (5)0.6333 (3)0.76875 (14)0.0417 (8)
H8A1.06220.55280.77580.050*
H8B1.19070.66400.79130.050*
C91.0685 (5)0.6552 (2)0.70159 (14)0.0374 (7)
H9A1.04540.73460.69350.045*
H9B1.20890.63580.69060.045*
C100.8660 (6)0.6211 (3)0.59723 (15)0.0513 (9)
H100.81150.69830.59520.062*
C110.6940 (6)0.5472 (3)0.56592 (17)0.0732 (12)
H11A0.74280.47070.56690.110*
H11B0.66130.57090.52440.110*
H11C0.56790.55260.58640.110*
C121.0658 (7)0.6201 (4)0.56802 (18)0.0780 (13)
H12A1.12820.54650.57150.117*
H12B1.16430.67380.58780.117*
H12C1.03460.63940.52580.117*
C130.0014 (7)0.6613 (3)0.99717 (18)0.0725 (12)
H13A0.04950.59740.97320.109*
H13B0.11550.69491.01500.109*
H13C0.10920.63761.02880.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Zn10.0419 (2)0.02734 (18)0.0413 (2)0.00185 (15)0.00994 (15)0.00074 (15)
Cl10.0564 (5)0.0489 (5)0.0486 (5)0.0057 (4)0.0021 (4)0.0049 (4)
Cl20.0413 (5)0.0393 (4)0.0687 (6)0.0057 (4)0.0072 (4)0.0064 (4)
N10.0342 (14)0.0289 (13)0.0369 (14)0.0010 (10)0.0005 (11)0.0047 (10)
N20.0353 (14)0.0291 (12)0.0351 (14)0.0002 (10)0.0076 (11)0.0013 (10)
O10.0491 (13)0.0260 (10)0.0477 (13)0.0021 (9)0.0186 (11)0.0011 (9)
O20.0748 (18)0.0618 (15)0.0661 (17)0.0106 (13)0.0389 (15)0.0050 (13)
C10.0391 (17)0.0321 (15)0.0365 (17)0.0011 (13)0.0028 (13)0.0009 (13)
C20.0367 (17)0.0316 (16)0.0320 (17)0.0050 (13)0.0018 (13)0.0046 (13)
C30.0457 (19)0.0347 (16)0.0399 (18)0.0030 (14)0.0095 (15)0.0069 (14)
C40.047 (2)0.051 (2)0.0370 (18)0.0116 (16)0.0082 (15)0.0074 (15)
C50.061 (2)0.048 (2)0.050 (2)0.0107 (17)0.0151 (18)0.0073 (16)
C60.055 (2)0.0361 (17)0.054 (2)0.0002 (15)0.0057 (18)0.0081 (15)
C70.0444 (18)0.0255 (14)0.0384 (18)0.0035 (13)0.0035 (15)0.0021 (13)
C80.0338 (17)0.0439 (18)0.046 (2)0.0068 (14)0.0002 (14)0.0072 (14)
C90.0297 (15)0.0320 (16)0.051 (2)0.0015 (13)0.0076 (14)0.0029 (14)
C100.069 (2)0.0459 (19)0.039 (2)0.0039 (18)0.0056 (18)0.0044 (15)
C110.085 (3)0.084 (3)0.046 (2)0.011 (2)0.014 (2)0.005 (2)
C120.085 (3)0.095 (3)0.058 (3)0.002 (3)0.025 (2)0.011 (2)
C130.082 (3)0.080 (3)0.062 (3)0.020 (2)0.035 (2)0.000 (2)
Geometric parameters (Å, º) top
Zn1—O11.9425 (19)C5—H50.9300
Zn1—N11.997 (2)C6—H60.9300
Zn1—Cl22.2290 (9)C7—H70.9300
Zn1—Cl12.2554 (10)C8—C91.513 (4)
N1—C71.282 (3)C8—H8A0.9700
N1—C81.478 (3)C8—H8B0.9700
N2—C91.487 (4)C9—H9A0.9700
N2—C101.504 (4)C9—H9B0.9700
N2—H2A0.9000C10—C121.477 (5)
N2—H2B0.9000C10—C111.502 (5)
O1—C21.317 (3)C10—H100.9800
O2—C41.372 (4)C11—H11A0.9600
O2—C131.420 (4)C11—H11B0.9600
C1—C61.404 (4)C11—H11C0.9600
C1—C21.425 (4)C12—H12A0.9600
C1—C71.448 (4)C12—H12B0.9600
C2—C31.408 (4)C12—H12C0.9600
C3—C41.379 (4)C13—H13A0.9600
C3—H30.9300C13—H13B0.9600
C4—C51.385 (4)C13—H13C0.9600
C5—C61.381 (4)
O1—Zn1—N197.16 (9)C1—C7—H7116.2
O1—Zn1—Cl2107.02 (6)N1—C8—C9112.2 (2)
N1—Zn1—Cl2113.82 (7)N1—C8—H8A109.2
O1—Zn1—Cl1111.15 (7)C9—C8—H8A109.2
N1—Zn1—Cl1110.44 (7)N1—C8—H8B109.2
Cl2—Zn1—Cl1115.64 (3)C9—C8—H8B109.2
C7—N1—C8118.0 (2)H8A—C8—H8B107.9
C7—N1—Zn1119.60 (19)N2—C9—C8111.9 (2)
C8—N1—Zn1122.37 (19)N2—C9—H9A109.2
C9—N2—C10116.2 (2)C8—C9—H9A109.2
C9—N2—H2A108.2N2—C9—H9B109.2
C10—N2—H2A108.2C8—C9—H9B109.2
C9—N2—H2B108.2H9A—C9—H9B107.9
C10—N2—H2B108.2C12—C10—C11113.4 (3)
H2A—N2—H2B107.4C12—C10—N2112.1 (3)
C2—O1—Zn1122.43 (17)C11—C10—N2109.0 (3)
C4—O2—C13118.4 (3)C12—C10—H10107.3
C6—C1—C2118.2 (3)C11—C10—H10107.3
C6—C1—C7116.0 (3)N2—C10—H10107.3
C2—C1—C7125.8 (3)C10—C11—H11A109.5
O1—C2—C3118.5 (2)C10—C11—H11B109.5
O1—C2—C1123.9 (2)H11A—C11—H11B109.5
C3—C2—C1117.6 (3)C10—C11—H11C109.5
C4—C3—C2122.1 (3)H11A—C11—H11C109.5
C4—C3—H3118.9H11B—C11—H11C109.5
C2—C3—H3118.9C10—C12—H12A109.5
O2—C4—C3114.6 (3)C10—C12—H12B109.5
O2—C4—C5124.6 (3)H12A—C12—H12B109.5
C3—C4—C5120.8 (3)C10—C12—H12C109.5
C6—C5—C4118.1 (3)H12A—C12—H12C109.5
C6—C5—H5121.0H12B—C12—H12C109.5
C4—C5—H5121.0O2—C13—H13A109.5
C5—C6—C1123.2 (3)O2—C13—H13B109.5
C5—C6—H6118.4H13A—C13—H13B109.5
C1—C6—H6118.4O2—C13—H13C109.5
N1—C7—C1127.6 (3)H13A—C13—H13C109.5
N1—C7—H7116.2H13B—C13—H13C109.5
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl2i0.902.623.357 (2)140
N2—H2B···O1i0.901.912.782 (3)162
N2—H2A···Cl10.902.973.483 (2)118
Symmetry code: (i) x+3/2, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formula[ZnCl2(C13H20N2O2)]
Mr372.58
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)6.2915 (9), 11.8990 (18), 22.115 (4)
β (°) 96.518 (4)
V3)1644.9 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.82
Crystal size (mm)0.18 × 0.18 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.735, 0.735
No. of measured, independent and
observed [I > 2σ(I)] reflections
9437, 3557, 2515
Rint0.042
(sin θ/λ)max1)0.639
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.086, 1.01
No. of reflections3557
No. of parameters184
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.46, 0.31

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Zn1—O11.9425 (19)Zn1—Cl22.2290 (9)
Zn1—N11.997 (2)Zn1—Cl12.2554 (10)
O1—Zn1—N197.16 (9)O1—Zn1—Cl1111.15 (7)
O1—Zn1—Cl2107.02 (6)N1—Zn1—Cl1110.44 (7)
N1—Zn1—Cl2113.82 (7)Cl2—Zn1—Cl1115.64 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···Cl2i0.902.623.357 (2)139.7
N2—H2B···O1i0.901.912.782 (3)161.8
N2—H2A···Cl10.902.973.483 (2)118.0
Symmetry code: (i) x+3/2, y1/2, z+3/2.
 

Acknowledgements

The authors acknowledge Qiqihar University for a research grant.

References

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