Dichlorido[2-({[3-(cyclo­hexyl­aza­nium­yl)prop­yl]imino}­meth­yl)-5-meth­oxy­phenolate]zinc

Wang, C.-Y.

doi:10.1107/S1600536811027085

Dichlorido[2-({[3-(cyclohexylazaniumyl)propyl]imino}methyl)-5-methoxyphenolate]zinc

The title mononuclear zinc complex, [ZnCl₂(C₁₇H₂₆N₂O₂)], was obtained by the reaction of 2-hydroxy-4-methoxybenzaldehyde, N-cyclohexylpropane-1,3-diamine and zinc chloride in methanol. The Zn^II atom is four-coordinated by the phenolate O atom and imine N atom of the bidentate zwitterionic Schiff base ligand 2-{[3-(cyclohexylamino)propyl]iminomethyl}-5-methoxyphenol, and by two chloride ions, generating a distorted ZnONCl₂ tetrahedral geometry. In the crystal, molecules are linked by N—H

O hydrogen bonds, forming chains along the c-axis direction.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811027085/hb5943sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811027085/hb5943Isup2.hkl Contains datablock I

CCDC reference: 841030

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.029
wR factor = 0.075
Data-to-parameter ratio = 18.8

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....          ?
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          8

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ...          1

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   2 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

As part of our investigations into Schiff base complexes (Wang & Ye, 2011; Wang, 2009), we have synthesized the title compound, a new mononuclear zinc(II) complex, Fig. 1. The Zn atom in the complex is four-coordinated by one phenolate O and one imine N atoms of the Schiff base ligand 2-[(3-cyclohexylaminopropylimino)methyl]-5-methoxyphenol, and by two Cl atoms, generating a distorted tetrahedral geometry. The Zn—O, Zn—N, and Zn—Cl bond lengths (Table 1) are comparable with those observed in other similar zinc(II) complexes (Zhu, 2008; Wang, 2007; Ikmal Hisham et al., 2011; Datta et al., 2009). In the crystal, molecules are linked via intermolecular N—H···O hydrogen bonds (Table 2), forming chains along the c direction (Fig. 2)

Related literature top

For the Schiff base complexes we reported previously, see: Wang (2009); Wang & Ye (2011). For similar zinc(II) complexes, see: Zhu (2008); Wang (2007); Ikmal Hisham et al. (2011); Datta et al. (2009).

Experimental top

2-Hydroxy-4-methoxybenzaldehyde (1.0 mmol, 0.152 g), N-cyclohexylpropane-1,3-diamine (1.0 mmol, 0.156 g), and zinc chloride (1.0 mmol, 0.137 g) were dissolved in MeOH (30 ml). The mixture was stirred at room temperature for 10 min to give a clear colorless solution. After keeping the solution in air for several days, colorless block-shaped crystals were formed at the bottom of the vessel.

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

	Fig. 1. The molecular structure of the title complex, showing displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The molecular packing of the title complex, viewed along the a axis. Hydrogen bonds are drawn as dashed lines. H atoms not related to the hydrogen bonding are omitted.

Dichlorido[2-({[3-(cyclohexylazaniumyl)propyl]imino}methyl)-5- methoxyphenolate]zinc top

Crystal data top

[ZnCl₂(C₁₇H₂₆N₂O₂)]	F(000) = 1776
M_r = 426.67	D_x = 1.428 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 25.118 (2) Å	Cell parameters from 3616 reflections
b = 10.543 (1) Å	θ = 2.5–26.9°
c = 14.992 (2) Å	µ = 1.52 mm⁻¹
β = 91.435 (1)°	T = 298 K
V = 3968.9 (7) Å³	Block, colorless
Z = 8	0.33 × 0.30 × 0.29 mm

Data collection top

Bruker SMART CCD diffractometer	4104 independent reflections
Radiation source: fine-focus sealed tube	3101 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ω scans	θ_max = 26.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −31→30
T_min = 0.634, T_max = 0.667	k = −8→13
10824 measured reflections	l = −18→18

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.075	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0333P)² + 1.6888P] where P = (F_o² + 2F_c²)/3
4104 reflections	(Δ/σ)_max < 0.001
218 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[ZnCl₂(C₁₇H₂₆N₂O₂)]	V = 3968.9 (7) Å³
M_r = 426.67	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 25.118 (2) Å	µ = 1.52 mm⁻¹
b = 10.543 (1) Å	T = 298 K
c = 14.992 (2) Å	0.33 × 0.30 × 0.29 mm
β = 91.435 (1)°

Data collection top

Bruker SMART CCD diffractometer	4104 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3101 reflections with I > 2σ(I)
T_min = 0.634, T_max = 0.667	R_int = 0.021
10824 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.075	H-atom parameters constrained
S = 1.03	Δρ_max = 0.21 e Å⁻³
4104 reflections	Δρ_min = −0.29 e Å⁻³
218 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 > 2sigma(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	0.159066 (10)	0.50173 (2)	0.107303 (15)	0.04105 (9)
Cl1	0.08297 (2)	0.50677 (5)	0.18660 (4)	0.04897 (14)
Cl2	0.19579 (3)	0.68984 (6)	0.08640 (4)	0.06432 (18)
N1	0.20745 (6)	0.36504 (17)	0.15451 (10)	0.0402 (4)
N2	0.11696 (6)	0.38198 (15)	0.37490 (10)	0.0352 (4)
H2A	0.0999	0.4227	0.3298	0.042*
H2B	0.1262	0.4405	0.4162	0.042*
O1	0.14586 (6)	0.42308 (13)	−0.00928 (8)	0.0435 (3)
O2	0.12094 (6)	0.07054 (15)	−0.20497 (11)	0.0587 (4)
C1	0.15368 (7)	0.30174 (18)	−0.02645 (12)	0.0344 (4)
C2	0.13357 (7)	0.25212 (19)	−0.10742 (13)	0.0381 (5)
H2	0.1160	0.3056	−0.1477	0.046*
C3	0.13941 (8)	0.1257 (2)	−0.12835 (14)	0.0429 (5)
C4	0.16610 (10)	0.0448 (2)	−0.06927 (17)	0.0562 (6)
H4	0.1695	−0.0409	−0.0826	0.067*
C5	0.18707 (9)	0.0919 (2)	0.00792 (16)	0.0553 (6)
H5	0.2055	0.0371	0.0462	0.066*
C6	0.18229 (8)	0.2201 (2)	0.03293 (13)	0.0399 (5)
C7	0.09238 (12)	0.1469 (3)	−0.26836 (17)	0.0747 (8)
H7A	0.0606	0.1786	−0.2421	0.112*
H7B	0.0831	0.0968	−0.3199	0.112*
H7C	0.1143	0.2169	−0.2858	0.112*
C8	0.20912 (8)	0.2578 (2)	0.11472 (14)	0.0443 (5)
H8	0.2304	0.1963	0.1422	0.053*
C9	0.23994 (8)	0.3838 (2)	0.23653 (13)	0.0476 (5)
H9A	0.2670	0.4472	0.2260	0.057*
H9B	0.2577	0.3050	0.2525	0.057*
C10	0.20563 (8)	0.4261 (2)	0.31269 (13)	0.0431 (5)
H10A	0.1861	0.5017	0.2948	0.052*
H10B	0.2284	0.4479	0.3636	0.052*
C11	0.16647 (8)	0.3247 (2)	0.34013 (14)	0.0416 (5)
H11A	0.1576	0.2716	0.2891	0.050*
H11B	0.1829	0.2715	0.3858	0.050*
C12	0.07854 (7)	0.29055 (19)	0.41592 (13)	0.0377 (4)
H12	0.0977	0.2403	0.4615	0.045*
C13	0.05542 (8)	0.2016 (2)	0.34577 (15)	0.0494 (5)
H13A	0.0838	0.1523	0.3201	0.059*
H13B	0.0383	0.2506	0.2983	0.059*
C14	0.01487 (10)	0.1127 (2)	0.38684 (19)	0.0663 (7)
H14A	−0.0010	0.0598	0.3404	0.080*
H14B	0.0329	0.0575	0.4297	0.080*
C15	−0.02850 (9)	0.1850 (2)	0.43294 (18)	0.0616 (7)
H15A	−0.0520	0.1258	0.4619	0.074*
H15B	−0.0494	0.2324	0.3890	0.074*
C16	−0.00489 (9)	0.2753 (3)	0.50150 (17)	0.0676 (8)
H16A	0.0127	0.2271	0.5488	0.081*
H16B	−0.0332	0.3243	0.5276	0.081*
C17	0.03513 (8)	0.3651 (2)	0.46006 (15)	0.0511 (6)
H17A	0.0171	0.4186	0.4162	0.061*
H17B	0.0507	0.4194	0.5060	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.04827 (15)	0.04339 (15)	0.03132 (13)	0.00342 (11)	−0.00238 (10)	−0.00043 (10)
Cl1	0.0447 (3)	0.0621 (4)	0.0400 (3)	0.0052 (3)	−0.0005 (2)	0.0051 (3)
Cl2	0.0750 (4)	0.0583 (4)	0.0596 (4)	−0.0202 (3)	0.0004 (3)	−0.0009 (3)
N1	0.0339 (9)	0.0555 (11)	0.0311 (9)	0.0034 (8)	0.0014 (7)	0.0037 (8)
N2	0.0375 (9)	0.0386 (9)	0.0292 (8)	−0.0036 (7)	−0.0023 (7)	−0.0006 (7)
O1	0.0626 (9)	0.0365 (8)	0.0311 (7)	0.0094 (7)	−0.0061 (6)	−0.0007 (6)
O2	0.0749 (11)	0.0453 (9)	0.0555 (10)	−0.0138 (8)	−0.0046 (8)	−0.0102 (8)
C1	0.0317 (10)	0.0370 (11)	0.0348 (10)	0.0020 (8)	0.0068 (8)	0.0028 (8)
C2	0.0362 (10)	0.0412 (11)	0.0371 (11)	−0.0016 (9)	0.0029 (8)	0.0010 (9)
C3	0.0406 (11)	0.0427 (12)	0.0456 (12)	−0.0061 (10)	0.0064 (9)	−0.0047 (10)
C4	0.0659 (15)	0.0373 (12)	0.0655 (16)	0.0064 (11)	−0.0001 (13)	−0.0046 (12)
C5	0.0576 (14)	0.0468 (14)	0.0611 (15)	0.0142 (11)	−0.0058 (12)	0.0048 (12)
C6	0.0345 (10)	0.0442 (12)	0.0411 (11)	0.0065 (9)	0.0006 (9)	0.0017 (9)
C7	0.098 (2)	0.0668 (17)	0.0577 (16)	−0.0215 (16)	−0.0208 (15)	−0.0052 (14)
C8	0.0368 (11)	0.0531 (14)	0.0432 (12)	0.0113 (10)	0.0016 (9)	0.0088 (11)
C9	0.0319 (11)	0.0718 (16)	0.0389 (11)	−0.0018 (10)	−0.0018 (9)	0.0049 (11)
C10	0.0385 (11)	0.0552 (13)	0.0353 (11)	−0.0071 (10)	−0.0018 (9)	−0.0021 (10)
C11	0.0406 (11)	0.0445 (12)	0.0401 (11)	0.0029 (9)	0.0071 (9)	−0.0012 (9)
C12	0.0353 (10)	0.0423 (11)	0.0354 (10)	−0.0025 (9)	−0.0010 (8)	0.0064 (9)
C13	0.0473 (12)	0.0404 (12)	0.0607 (14)	−0.0069 (10)	0.0071 (11)	−0.0095 (11)
C14	0.0581 (15)	0.0444 (14)	0.097 (2)	−0.0137 (12)	0.0108 (14)	0.0005 (14)
C15	0.0444 (13)	0.0591 (15)	0.0817 (18)	−0.0114 (12)	0.0087 (12)	0.0103 (14)
C16	0.0505 (14)	0.089 (2)	0.0642 (16)	−0.0095 (13)	0.0186 (12)	−0.0027 (14)
C17	0.0425 (12)	0.0611 (15)	0.0501 (13)	−0.0067 (11)	0.0076 (10)	−0.0128 (11)

Geometric parameters (Å, º) top

Zn1—O1	1.9554 (13)	C8—H8	0.9300
Zn1—N1	2.0029 (17)	C9—C10	1.515 (3)
Zn1—Cl2	2.2129 (8)	C9—H9A	0.9700
Zn1—Cl1	2.2767 (7)	C9—H9B	0.9700
N1—C8	1.279 (3)	C10—C11	1.516 (3)
N1—C9	1.472 (2)	C10—H10A	0.9700
N2—C11	1.488 (2)	C10—H10B	0.9700
N2—C12	1.506 (2)	C11—H11A	0.9700
N2—H2A	0.9000	C11—H11B	0.9700
N2—H2B	0.9000	C12—C17	1.510 (3)
O1—C1	1.320 (2)	C12—C13	1.514 (3)
O2—C3	1.359 (2)	C12—H12	0.9800
O2—C7	1.426 (3)	C13—C14	1.526 (3)
C1—C2	1.404 (3)	C13—H13A	0.9700
C1—C6	1.421 (3)	C13—H13B	0.9700
C2—C3	1.378 (3)	C14—C15	1.511 (3)
C2—H2	0.9300	C14—H14A	0.9700
C3—C4	1.390 (3)	C14—H14B	0.9700
C4—C5	1.354 (3)	C15—C16	1.511 (3)
C4—H4	0.9300	C15—H15A	0.9700
C5—C6	1.408 (3)	C15—H15B	0.9700
C5—H5	0.9300	C16—C17	1.525 (3)
C6—C8	1.440 (3)	C16—H16A	0.9700
C7—H7A	0.9600	C16—H16B	0.9700
C7—H7B	0.9600	C17—H17A	0.9700
C7—H7C	0.9600	C17—H17B	0.9700

O1—Zn1—N1	95.66 (6)	H9A—C9—H9B	108.1
O1—Zn1—Cl2	108.39 (5)	C9—C10—C11	112.44 (18)
N1—Zn1—Cl2	116.33 (5)	C9—C10—H10A	109.1
O1—Zn1—Cl1	110.54 (5)	C11—C10—H10A	109.1
N1—Zn1—Cl1	110.01 (5)	C9—C10—H10B	109.1
Cl2—Zn1—Cl1	114.29 (3)	C11—C10—H10B	109.1
C8—N1—C9	118.95 (18)	H10A—C10—H10B	107.8
C8—N1—Zn1	119.85 (14)	N2—C11—C10	111.25 (17)
C9—N1—Zn1	121.17 (14)	N2—C11—H11A	109.4
C11—N2—C12	115.66 (16)	C10—C11—H11A	109.4
C11—N2—H2A	108.4	N2—C11—H11B	109.4
C12—N2—H2A	108.4	C10—C11—H11B	109.4
C11—N2—H2B	108.4	H11A—C11—H11B	108.0
C12—N2—H2B	108.4	N2—C12—C17	108.84 (17)
H2A—N2—H2B	107.4	N2—C12—C13	110.56 (16)
C1—O1—Zn1	124.22 (12)	C17—C12—C13	110.99 (16)
C3—O2—C7	118.51 (18)	N2—C12—H12	108.8
O1—C1—C2	118.52 (17)	C17—C12—H12	108.8
O1—C1—C6	122.71 (17)	C13—C12—H12	108.8
C2—C1—C6	118.77 (18)	C12—C13—C14	110.40 (19)
C3—C2—C1	121.28 (19)	C12—C13—H13A	109.6
C3—C2—H2	119.4	C14—C13—H13A	109.6
C1—C2—H2	119.4	C12—C13—H13B	109.6
O2—C3—C2	124.8 (2)	C14—C13—H13B	109.6
O2—C3—C4	115.2 (2)	H13A—C13—H13B	108.1
C2—C3—C4	120.1 (2)	C15—C14—C13	111.7 (2)
C5—C4—C3	119.4 (2)	C15—C14—H14A	109.3
C5—C4—H4	120.3	C13—C14—H14A	109.3
C3—C4—H4	120.3	C15—C14—H14B	109.3
C4—C5—C6	123.1 (2)	C13—C14—H14B	109.3
C4—C5—H5	118.5	H14A—C14—H14B	107.9
C6—C5—H5	118.5	C14—C15—C16	110.7 (2)
C5—C6—C1	117.37 (19)	C14—C15—H15A	109.5
C5—C6—C8	116.79 (19)	C16—C15—H15A	109.5
C1—C6—C8	125.77 (19)	C14—C15—H15B	109.5
O2—C7—H7A	109.5	C16—C15—H15B	109.5
O2—C7—H7B	109.5	H15A—C15—H15B	108.1
H7A—C7—H7B	109.5	C15—C16—C17	111.4 (2)
O2—C7—H7C	109.5	C15—C16—H16A	109.3
H7A—C7—H7C	109.5	C17—C16—H16A	109.3
H7B—C7—H7C	109.5	C15—C16—H16B	109.3
N1—C8—C6	128.39 (19)	C17—C16—H16B	109.3
N1—C8—H8	115.8	H16A—C16—H16B	108.0
C6—C8—H8	115.8	C12—C17—C16	110.3 (2)
N1—C9—C10	110.81 (16)	C12—C17—H17A	109.6
N1—C9—H9A	109.5	C16—C17—H17A	109.6
C10—C9—H9A	109.5	C12—C17—H17B	109.6
N1—C9—H9B	109.5	C16—C17—H17B	109.6
C10—C9—H9B	109.5	H17A—C17—H17B	108.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.90	2.35	3.2106 (17)	160
N2—H2B···O1ⁱ	0.90	1.88	2.776 (2)	173

Symmetry code: (i) x, −y+1, z+1/2.

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₁₇H₂₆N₂O₂)]
M_r	426.67
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	25.118 (2), 10.543 (1), 14.992 (2)
β (°)	91.435 (1)
V (Å³)	3968.9 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.52
Crystal size (mm)	0.33 × 0.30 × 0.29

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.634, 0.667
No. of measured, independent and observed [I > 2σ(I)] reflections	10824, 4104, 3101
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.075, 1.03
No. of reflections	4104
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.29

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

Selected bond lengths (Å) top

Zn1—O1	1.9554 (13)	Zn1—Cl2	2.2129 (8)
Zn1—N1	2.0029 (17)	Zn1—Cl1	2.2767 (7)