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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): m419.
Published online 2009 March 19. doi:  10.1107/S1600536809009568
PMCID: PMC2969054

Redetermination of {2-[3-(dimethyl­ammonio)propyl­imino­meth­yl]phenol­ato}­dithio­cyanato­zinc(II)

Abstract

In comparison with the previous refinement of the title complex, [Zn(NCS)2(C12H18N2O)], the present redetermination reveals a different location of the non-carbon attached H atom. Whereas in the previous refinement this H atom was modelled as part of a phenol OH group, the present study indicates a zwitterionic Schiff base ligand with a deprotonated OH group and a protonated tertiary amine group. The Zn(II) atom is four-coordinated by one O and one imine N atoms of the 2-[3-(dimethyl­ammonio)propyl­imino­meth­yl]phenolate Schiff base ligand, and by two N atoms from two thio­cyanate ligands, forming a distorted tetra­hedral geometry. In the crystal structure, adjacent mol­ecules are linked through inter­molecular N—H(...)O hydrogen bonds, forming a chain in the [101] direction.

Related literature

For a previous refinement of this structure, see: Cai et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m419-scheme1.jpg

Experimental

Crystal data

  • [Zn(NCS)2(C12H18N2O)]
  • M r = 387.81
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m419-efi1.jpg
  • a = 9.850 (2) Å
  • b = 14.931 (3) Å
  • c = 12.290 (3) Å
  • β = 101.450 (2)°
  • V = 1771.5 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.63 mm−1
  • T = 298 K
  • 0.23 × 0.20 × 0.20 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.706, T max = 0.737
  • 10464 measured reflections
  • 4067 independent reflections
  • 3048 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.089
  • S = 1.03
  • 4067 reflections
  • 205 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.59 e Å−3
  • Δρmin = −0.49 e Å−3

Data collection: SMART (Bruker, 2002 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009568/er2062sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009568/er2062Isup2.hkl

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

Acknowledgments

The author acknowledges Liaodong University for funding this study.

supplementary crystallographic information

Comment

Previously, Cai et al. (2006) have reported the crystal structure of the title mononuclear zinc(II) complex, (I), with the non-carbon attached H atom located at the phenolate O atom. The present redetermination of (I) indicates that the H atom should be attached to the amine N atom.

Complex (I) is a mononuclear zinc(II) compound. The Zn atom in (I) is four-coordinated by one O and one imine N atoms of a Schiff base ligand [(3-dimethylammoniopropylimino)methyl]phenolate, and by two N atoms from two thiocyanate ligands, forming a tetrahedral geometry. All the bond lengths and angles are comparable to those observed in the previously reported structure, (II) (Cai et al., 2006). The main difference lies in the positions of the non-carbon attached H atoms. The H2 in (I) is attached to N2, while that in (II) is attached to O1.

In the crystal structure of (I), molecules are linked through intermolecular N—H···O hydrogen bonds (Table 1), forming chains running along the [101] direction (Fig. 2). While that in the crystal structure of (II), a strong hydrogen bond interaction is presented between the phenolic hydroxyl H and the uncoordinated amine N, forming a one-dimensional chain.

Experimental

Salicylaldehyde (1.0 mmol, 122.1 mg), N,N-dimethylpropane-1,3-diamine (1.0 mmol, 102.2 mg), ammonium thiocyanate (2.0 mmol, 152.0 mg) and Zn(CH3COO)2.2H2O (1.0 mmol, 219.5 mg) were dissolved in a methanol solution (30 ml). The mixture was stirred at room temperature for 30 min to give a clear colorless solution. After keeping the solution in air for a few days, colorless block-shaped crystals were formed.

Refinement

H2 was located from a difference Fourier map and refined isotropically, with N—H distance restrained to 0.90 (1) Å. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms with C—H distances of 0.93–0.97 Å, and with Uiso(H) set to 1.2Ueq(C) and 1.5Ueq(methyl C).

Figures

Fig. 1.
The structure of compound (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
Molecular packing of compound (I), viewed perpendicular to the [101] direction. Intermolecular N—H···O hydrogen bonds are shown as dashed lines.

Crystal data

[Zn(NCS)2(C12H18N2O)]F(000) = 800
Mr = 387.81Dx = 1.454 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3352 reflections
a = 9.850 (2) Åθ = 2.3–25.5°
b = 14.931 (3) ŵ = 1.63 mm1
c = 12.290 (3) ÅT = 298 K
β = 101.450 (2)°Block, colorless
V = 1771.5 (7) Å30.23 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer4067 independent reflections
Radiation source: fine-focus sealed tube3048 reflections with I > 2σ(I)
graphiteRint = 0.026
ω scansθmax = 27.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −11→12
Tmin = 0.706, Tmax = 0.737k = −19→15
10464 measured reflectionsl = −15→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.039P)2 + 0.5P] where P = (Fo2 + 2Fc2)/3
4067 reflections(Δ/σ)max < 0.001
205 parametersΔρmax = 0.59 e Å3
1 restraintΔρmin = −0.49 e Å3

Special details

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)

xyzUiso*/Ueq
Zn10.85499 (3)0.192204 (19)0.33421 (2)0.04580 (11)
S11.05230 (8)0.47887 (5)0.33292 (6)0.0647 (2)
S20.62695 (9)0.21786 (8)0.63228 (6)0.0849 (3)
O10.98390 (17)0.09278 (11)0.33954 (13)0.0506 (4)
N10.72661 (19)0.15862 (14)0.19440 (16)0.0444 (4)
N20.7435 (2)0.38001 (14)−0.03594 (16)0.0473 (5)
N30.9446 (3)0.30791 (16)0.3333 (2)0.0607 (6)
N40.7670 (3)0.19029 (16)0.4625 (2)0.0660 (6)
C10.8647 (2)0.02717 (16)0.16587 (19)0.0448 (5)
C20.9731 (2)0.03075 (15)0.26025 (19)0.0431 (5)
C31.0747 (3)−0.03634 (17)0.2697 (2)0.0558 (7)
H31.1456−0.03680.33210.067*
C41.0736 (3)−0.10103 (18)0.1908 (3)0.0637 (7)
H41.1444−0.14320.19970.076*
C50.9690 (3)−0.1042 (2)0.0987 (3)0.0708 (8)
H50.9685−0.14790.04460.085*
C60.8654 (3)−0.0416 (2)0.0880 (2)0.0650 (8)
H60.7927−0.04490.02690.078*
C70.7495 (2)0.08861 (17)0.14064 (19)0.0483 (6)
H70.68360.07570.07730.058*
C80.6009 (3)0.21127 (19)0.1489 (2)0.0556 (7)
H8A0.54600.21860.20570.067*
H8B0.54540.17910.08720.067*
C90.6387 (3)0.30309 (17)0.1095 (2)0.0518 (6)
H9A0.55470.33540.07770.062*
H9B0.68770.33720.17240.062*
C100.7288 (3)0.29423 (15)0.0237 (2)0.0464 (6)
H10A0.82000.27370.06000.056*
H10B0.68920.2491−0.03020.056*
C110.7994 (3)0.45391 (19)0.0407 (2)0.0682 (8)
H11A0.88240.43430.08970.102*
H11B0.73190.47080.08360.102*
H11C0.81990.5045−0.00140.102*
C120.8300 (3)0.3647 (2)−0.1207 (2)0.0707 (8)
H12A0.83850.4196−0.15940.106*
H12B0.78710.3201−0.17260.106*
H12C0.92030.3445−0.08470.106*
C130.9883 (2)0.37954 (18)0.33335 (18)0.0448 (5)
C140.7095 (3)0.20301 (17)0.5332 (2)0.0497 (6)
H20.6584 (14)0.3946 (16)−0.0715 (18)0.052 (7)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Zn10.04936 (18)0.04294 (18)0.04378 (16)0.00497 (12)0.00605 (12)0.00177 (12)
S10.0756 (5)0.0494 (4)0.0688 (4)−0.0091 (3)0.0139 (4)−0.0034 (3)
S20.0603 (5)0.1489 (9)0.0473 (4)0.0125 (5)0.0153 (3)0.0184 (5)
O10.0508 (9)0.0474 (10)0.0470 (9)0.0101 (8)−0.0062 (7)−0.0092 (7)
N10.0383 (10)0.0463 (12)0.0463 (10)−0.0015 (9)0.0030 (8)0.0095 (9)
N20.0446 (12)0.0429 (12)0.0504 (11)0.0003 (9)−0.0003 (9)0.0070 (9)
N30.0709 (15)0.0498 (14)0.0631 (14)−0.0065 (12)0.0173 (12)−0.0009 (11)
N40.0793 (17)0.0650 (16)0.0590 (14)0.0083 (12)0.0263 (13)0.0087 (12)
C10.0465 (13)0.0402 (13)0.0451 (12)−0.0050 (10)0.0026 (10)0.0010 (10)
C20.0444 (13)0.0360 (12)0.0466 (13)−0.0043 (10)0.0035 (10)−0.0007 (10)
C30.0513 (15)0.0421 (15)0.0670 (16)0.0036 (11)−0.0050 (13)−0.0076 (12)
C40.0609 (17)0.0443 (16)0.085 (2)0.0042 (12)0.0124 (15)−0.0132 (14)
C50.081 (2)0.0522 (18)0.0759 (19)−0.0022 (15)0.0075 (17)−0.0234 (15)
C60.0702 (19)0.0597 (18)0.0571 (16)−0.0072 (15)−0.0063 (14)−0.0140 (14)
C70.0447 (13)0.0534 (16)0.0425 (12)−0.0083 (11)−0.0022 (10)0.0070 (11)
C80.0402 (13)0.0674 (18)0.0574 (15)0.0064 (12)0.0050 (11)0.0153 (13)
C90.0471 (14)0.0537 (16)0.0516 (14)0.0128 (11)0.0025 (11)0.0081 (12)
C100.0467 (13)0.0396 (14)0.0503 (13)0.0033 (10)0.0035 (11)0.0054 (10)
C110.080 (2)0.0461 (16)0.0701 (18)−0.0098 (14)−0.0063 (15)0.0001 (14)
C120.0704 (19)0.076 (2)0.0696 (18)0.0019 (16)0.0240 (15)0.0154 (16)
C130.0457 (13)0.0513 (15)0.0373 (11)0.0069 (11)0.0077 (10)0.0003 (11)
C140.0475 (14)0.0519 (16)0.0472 (13)−0.0006 (11)0.0035 (11)0.0143 (12)

Geometric parameters (Å, °)

Zn1—O11.946 (2)C4—C51.372 (4)
Zn1—N11.985 (2)C4—H40.9300
Zn1—N31.941 (2)C5—C61.371 (4)
Zn1—N41.945 (2)C5—H50.9300
S1—C131.612 (3)C6—H60.9300
S2—C141.608 (3)C7—H70.9300
O1—C21.333 (3)C8—C91.524 (4)
N1—C71.280 (3)C8—H8A0.9700
N1—C81.479 (3)C8—H8B0.9700
N2—C111.484 (3)C9—C101.513 (4)
N2—C121.489 (3)C9—H9A0.9700
N2—C101.497 (3)C9—H9B0.9700
N2—H20.891 (10)C10—H10A0.9700
N3—C131.153 (3)C10—H10B0.9700
N4—C141.142 (3)C11—H11A0.9600
C1—C61.405 (3)C11—H11B0.9600
C1—C21.413 (3)C11—H11C0.9600
C1—C71.444 (3)C12—H12A0.9600
C2—C31.404 (3)C12—H12B0.9600
C3—C41.367 (4)C12—H12C0.9600
C3—H30.9300
N3—Zn1—N4107.10 (10)N1—C7—C1128.3 (2)
N3—Zn1—O1112.62 (9)N1—C7—H7115.9
N4—Zn1—O1110.76 (9)C1—C7—H7115.9
N3—Zn1—N1115.61 (9)N1—C8—C9111.1 (2)
N4—Zn1—N1112.86 (10)N1—C8—H8A109.4
O1—Zn1—N197.80 (8)C9—C8—H8A109.4
C2—O1—Zn1123.25 (14)N1—C8—H8B109.4
C7—N1—C8117.3 (2)C9—C8—H8B109.4
C7—N1—Zn1120.38 (16)H8A—C8—H8B108.0
C8—N1—Zn1122.30 (18)C10—C9—C8110.9 (2)
C11—N2—C12111.5 (2)C10—C9—H9A109.5
C11—N2—C10112.6 (2)C8—C9—H9A109.5
C12—N2—C10109.6 (2)C10—C9—H9B109.5
C11—N2—H2108.9 (16)C8—C9—H9B109.5
C12—N2—H2107.9 (16)H9A—C9—H9B108.1
C10—N2—H2106.1 (16)N2—C10—C9113.16 (19)
C13—N3—Zn1174.8 (2)N2—C10—H10A108.9
C14—N4—Zn1169.0 (2)C9—C10—H10A108.9
C6—C1—C2118.8 (2)N2—C10—H10B108.9
C6—C1—C7115.3 (2)C9—C10—H10B108.9
C2—C1—C7125.8 (2)H10A—C10—H10B107.8
O1—C2—C3118.9 (2)N2—C11—H11A109.5
O1—C2—C1124.3 (2)N2—C11—H11B109.5
C3—C2—C1116.8 (2)H11A—C11—H11B109.5
C4—C3—C2122.7 (2)N2—C11—H11C109.5
C4—C3—H3118.6H11A—C11—H11C109.5
C2—C3—H3118.6H11B—C11—H11C109.5
C3—C4—C5120.6 (3)N2—C12—H12A109.5
C3—C4—H4119.7N2—C12—H12B109.5
C5—C4—H4119.7H12A—C12—H12B109.5
C6—C5—C4118.6 (3)N2—C12—H12C109.5
C6—C5—H5120.7H12A—C12—H12C109.5
C4—C5—H5120.7H12B—C12—H12C109.5
C5—C6—C1122.5 (3)N3—C13—S1178.9 (2)
C5—C6—H6118.7N4—C14—S2178.3 (3)
C1—C6—H6118.7

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.89 (1)1.86 (1)2.737 (2)170 (2)

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ER2062).

References

  • Bruker (2002). SAINT and SMART Bruker AXS Inc., Madison, Wisconsin, USA.
  • Cai, W.-X., Wen, Y.-H., Su, H. & Feng, Y.-L. (2006). Chin. J. Struct. Chem.25, 1031–1034.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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