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

Hong, Z.

doi:10.1107/S1600536809009568

metal-organic compounds

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Volume 65| Part 4| April 2009| Page m419

doi:10.1107/S1600536809009568

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

Zhe Hong ^a ^*

^aCollege of Chemical Engineering and Materials Science, Liaodong University, Dandong 118003, People's Republic of China
^*Correspondence e-mail: hongzhe57@126.com

(Received 16 February 2009; accepted 16 March 2009; online 19 March 2009)

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 ).

Experimental

Crystal data

[Zn(NCS)₂(C₁₂H₁₈N₂O)]
M_r = 387.81
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.036
wR(F²) = 0.089
S = 1.03
4067 reflections
205 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.891 (10)	1.855 (11)	2.737 (2)	170 (2)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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

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

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

checkCIF report

Comment top

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.

Related literature top

For related literature, see: Cai et al. (2006).

Experimental top

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.

Computing details top

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

	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.

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

Crystal data top

[Zn(NCS)₂(C₁₂H₁₈N₂O)]	F(000) = 800
M_r = 387.81	D_x = 1.454 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3352 reflections
a = 9.850 (2) Å	θ = 2.3–25.5°
b = 14.931 (3) Å	µ = 1.63 mm⁻¹
c = 12.290 (3) Å	T = 298 K
β = 101.450 (2)°	Block, colorless
V = 1771.5 (7) Å³	0.23 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4067 independent reflections
Radiation source: fine-focus sealed tube	3048 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
T_min = 0.706, T_max = 0.737	k = −19→15
10464 measured reflections	l = −15→15

Refinement top

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.039P)² + 0.5P] where P = (F_o² + 2F_c²)/3
4067 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.59 e Å⁻³
1 restraint	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Zn(NCS)₂(C₁₂H₁₈N₂O)]	V = 1771.5 (7) Å³
M_r = 387.81	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.850 (2) Å	µ = 1.63 mm⁻¹
b = 14.931 (3) Å	T = 298 K
c = 12.290 (3) Å	0.23 × 0.20 × 0.20 mm
β = 101.450 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4067 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3048 reflections with I > 2σ(I)
T_min = 0.706, T_max = 0.737	R_int = 0.026
10464 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.59 e Å⁻³
4067 reflections	Δρ_min = −0.49 e Å⁻³
205 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Zn1	0.85499 (3)	0.192204 (19)	0.33421 (2)	0.04580 (11)
S1	1.05230 (8)	0.47887 (5)	0.33292 (6)	0.0647 (2)
S2	0.62695 (9)	0.21786 (8)	0.63228 (6)	0.0849 (3)
O1	0.98390 (17)	0.09278 (11)	0.33954 (13)	0.0506 (4)
N1	0.72661 (19)	0.15862 (14)	0.19440 (16)	0.0444 (4)
N2	0.7435 (2)	0.38001 (14)	−0.03594 (16)	0.0473 (5)
N3	0.9446 (3)	0.30791 (16)	0.3333 (2)	0.0607 (6)
N4	0.7670 (3)	0.19029 (16)	0.4625 (2)	0.0660 (6)
C1	0.8647 (2)	0.02717 (16)	0.16587 (19)	0.0448 (5)
C2	0.9731 (2)	0.03075 (15)	0.26025 (19)	0.0431 (5)
C3	1.0747 (3)	−0.03634 (17)	0.2697 (2)	0.0558 (7)
H3	1.1456	−0.0368	0.3321	0.067*
C4	1.0736 (3)	−0.10103 (18)	0.1908 (3)	0.0637 (7)
H4	1.1444	−0.1432	0.1997	0.076*
C5	0.9690 (3)	−0.1042 (2)	0.0987 (3)	0.0708 (8)
H5	0.9685	−0.1479	0.0446	0.085*
C6	0.8654 (3)	−0.0416 (2)	0.0880 (2)	0.0650 (8)
H6	0.7927	−0.0449	0.0269	0.078*
C7	0.7495 (2)	0.08861 (17)	0.14064 (19)	0.0483 (6)
H7	0.6836	0.0757	0.0773	0.058*
C8	0.6009 (3)	0.21127 (19)	0.1489 (2)	0.0556 (7)
H8A	0.5460	0.2186	0.2057	0.067*
H8B	0.5454	0.1791	0.0872	0.067*
C9	0.6387 (3)	0.30309 (17)	0.1095 (2)	0.0518 (6)
H9A	0.5547	0.3354	0.0777	0.062*
H9B	0.6877	0.3372	0.1724	0.062*
C10	0.7288 (3)	0.29423 (15)	0.0237 (2)	0.0464 (6)
H10A	0.8200	0.2737	0.0600	0.056*
H10B	0.6892	0.2491	−0.0302	0.056*
C11	0.7994 (3)	0.45391 (19)	0.0407 (2)	0.0682 (8)
H11A	0.8824	0.4343	0.0897	0.102*
H11B	0.7319	0.4708	0.0836	0.102*
H11C	0.8199	0.5045	−0.0014	0.102*
C12	0.8300 (3)	0.3647 (2)	−0.1207 (2)	0.0707 (8)
H12A	0.8385	0.4196	−0.1594	0.106*
H12B	0.7871	0.3201	−0.1726	0.106*
H12C	0.9203	0.3445	−0.0847	0.106*
C13	0.9883 (2)	0.37954 (18)	0.33335 (18)	0.0448 (5)
C14	0.7095 (3)	0.20301 (17)	0.5332 (2)	0.0497 (6)
H2	0.6584 (14)	0.3946 (16)	−0.0715 (18)	0.052 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.04936 (18)	0.04294 (18)	0.04378 (16)	0.00497 (12)	0.00605 (12)	0.00177 (12)
S1	0.0756 (5)	0.0494 (4)	0.0688 (4)	−0.0091 (3)	0.0139 (4)	−0.0034 (3)
S2	0.0603 (5)	0.1489 (9)	0.0473 (4)	0.0125 (5)	0.0153 (3)	0.0184 (5)
O1	0.0508 (9)	0.0474 (10)	0.0470 (9)	0.0101 (8)	−0.0062 (7)	−0.0092 (7)
N1	0.0383 (10)	0.0463 (12)	0.0463 (10)	−0.0015 (9)	0.0030 (8)	0.0095 (9)
N2	0.0446 (12)	0.0429 (12)	0.0504 (11)	0.0003 (9)	−0.0003 (9)	0.0070 (9)
N3	0.0709 (15)	0.0498 (14)	0.0631 (14)	−0.0065 (12)	0.0173 (12)	−0.0009 (11)
N4	0.0793 (17)	0.0650 (16)	0.0590 (14)	0.0083 (12)	0.0263 (13)	0.0087 (12)
C1	0.0465 (13)	0.0402 (13)	0.0451 (12)	−0.0050 (10)	0.0026 (10)	0.0010 (10)
C2	0.0444 (13)	0.0360 (12)	0.0466 (13)	−0.0043 (10)	0.0035 (10)	−0.0007 (10)
C3	0.0513 (15)	0.0421 (15)	0.0670 (16)	0.0036 (11)	−0.0050 (13)	−0.0076 (12)
C4	0.0609 (17)	0.0443 (16)	0.085 (2)	0.0042 (12)	0.0124 (15)	−0.0132 (14)
C5	0.081 (2)	0.0522 (18)	0.0759 (19)	−0.0022 (15)	0.0075 (17)	−0.0234 (15)
C6	0.0702 (19)	0.0597 (18)	0.0571 (16)	−0.0072 (15)	−0.0063 (14)	−0.0140 (14)
C7	0.0447 (13)	0.0534 (16)	0.0425 (12)	−0.0083 (11)	−0.0022 (10)	0.0070 (11)
C8	0.0402 (13)	0.0674 (18)	0.0574 (15)	0.0064 (12)	0.0050 (11)	0.0153 (13)
C9	0.0471 (14)	0.0537 (16)	0.0516 (14)	0.0128 (11)	0.0025 (11)	0.0081 (12)
C10	0.0467 (13)	0.0396 (14)	0.0503 (13)	0.0033 (10)	0.0035 (11)	0.0054 (10)
C11	0.080 (2)	0.0461 (16)	0.0701 (18)	−0.0098 (14)	−0.0063 (15)	0.0001 (14)
C12	0.0704 (19)	0.076 (2)	0.0696 (18)	0.0019 (16)	0.0240 (15)	0.0154 (16)
C13	0.0457 (13)	0.0513 (15)	0.0373 (11)	0.0069 (11)	0.0077 (10)	0.0003 (11)
C14	0.0475 (14)	0.0519 (16)	0.0472 (13)	−0.0006 (11)	0.0035 (11)	0.0143 (12)

Geometric parameters (Å, º) top

Zn1—O1	1.946 (2)	C4—C5	1.372 (4)
Zn1—N1	1.985 (2)	C4—H4	0.9300
Zn1—N3	1.941 (2)	C5—C6	1.371 (4)
Zn1—N4	1.945 (2)	C5—H5	0.9300
S1—C13	1.612 (3)	C6—H6	0.9300
S2—C14	1.608 (3)	C7—H7	0.9300
O1—C2	1.333 (3)	C8—C9	1.524 (4)
N1—C7	1.280 (3)	C8—H8A	0.9700
N1—C8	1.479 (3)	C8—H8B	0.9700
N2—C11	1.484 (3)	C9—C10	1.513 (4)
N2—C12	1.489 (3)	C9—H9A	0.9700
N2—C10	1.497 (3)	C9—H9B	0.9700
N2—H2	0.891 (10)	C10—H10A	0.9700
N3—C13	1.153 (3)	C10—H10B	0.9700
N4—C14	1.142 (3)	C11—H11A	0.9600
C1—C6	1.405 (3)	C11—H11B	0.9600
C1—C2	1.413 (3)	C11—H11C	0.9600
C1—C7	1.444 (3)	C12—H12A	0.9600
C2—C3	1.404 (3)	C12—H12B	0.9600
C3—C4	1.367 (4)	C12—H12C	0.9600
C3—H3	0.9300

N3—Zn1—N4	107.10 (10)	N1—C7—C1	128.3 (2)
N3—Zn1—O1	112.62 (9)	N1—C7—H7	115.9
N4—Zn1—O1	110.76 (9)	C1—C7—H7	115.9
N3—Zn1—N1	115.61 (9)	N1—C8—C9	111.1 (2)
N4—Zn1—N1	112.86 (10)	N1—C8—H8A	109.4
O1—Zn1—N1	97.80 (8)	C9—C8—H8A	109.4
C2—O1—Zn1	123.25 (14)	N1—C8—H8B	109.4
C7—N1—C8	117.3 (2)	C9—C8—H8B	109.4
C7—N1—Zn1	120.38 (16)	H8A—C8—H8B	108.0
C8—N1—Zn1	122.30 (18)	C10—C9—C8	110.9 (2)
C11—N2—C12	111.5 (2)	C10—C9—H9A	109.5
C11—N2—C10	112.6 (2)	C8—C9—H9A	109.5
C12—N2—C10	109.6 (2)	C10—C9—H9B	109.5
C11—N2—H2	108.9 (16)	C8—C9—H9B	109.5
C12—N2—H2	107.9 (16)	H9A—C9—H9B	108.1
C10—N2—H2	106.1 (16)	N2—C10—C9	113.16 (19)
C13—N3—Zn1	174.8 (2)	N2—C10—H10A	108.9
C14—N4—Zn1	169.0 (2)	C9—C10—H10A	108.9
C6—C1—C2	118.8 (2)	N2—C10—H10B	108.9
C6—C1—C7	115.3 (2)	C9—C10—H10B	108.9
C2—C1—C7	125.8 (2)	H10A—C10—H10B	107.8
O1—C2—C3	118.9 (2)	N2—C11—H11A	109.5
O1—C2—C1	124.3 (2)	N2—C11—H11B	109.5
C3—C2—C1	116.8 (2)	H11A—C11—H11B	109.5
C4—C3—C2	122.7 (2)	N2—C11—H11C	109.5
C4—C3—H3	118.6	H11A—C11—H11C	109.5
C2—C3—H3	118.6	H11B—C11—H11C	109.5
C3—C4—C5	120.6 (3)	N2—C12—H12A	109.5
C3—C4—H4	119.7	N2—C12—H12B	109.5
C5—C4—H4	119.7	H12A—C12—H12B	109.5
C6—C5—C4	118.6 (3)	N2—C12—H12C	109.5
C6—C5—H5	120.7	H12A—C12—H12C	109.5
C4—C5—H5	120.7	H12B—C12—H12C	109.5
C5—C6—C1	122.5 (3)	N3—C13—S1	178.9 (2)
C5—C6—H6	118.7	N4—C14—S2	178.3 (3)
C1—C6—H6	118.7

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.89 (1)	1.86 (1)	2.737 (2)	170 (2)

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

Experimental details

Crystal data
Chemical formula	[Zn(NCS)₂(C₁₂H₁₈N₂O)]
M_r	387.81
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	9.850 (2), 14.931 (3), 12.290 (3)
β (°)	101.450 (2)
V (Å³)	1771.5 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.63
Crystal size (mm)	0.23 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.706, 0.737
No. of measured, independent and observed [I > 2σ(I)] reflections	10464, 4067, 3048
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.089, 1.03
No. of reflections	4067
No. of parameters	205
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.49

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.891 (10)	1.855 (11)	2.737 (2)	170 (2)

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

Acknowledgements

The author acknowledges Liaodong University for funding this study.

References

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

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

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