(1-{(E)-2-[(2E,3Z)-4-Oxidopent-3-en-2-ylideneamino]ethyl­imino­meth­yl}­naphthalen-2-olato)manganese(II) methanol solvate

In the title compound, [Mn(C₁₈H₁₈N₂O₂)]·CH₃OH, the Mn atom is coordinated by two N atoms and two O atoms from the asymmetrical Schiff base ligand 1-[2-(4-oxidopent-3-en-2-ylidene­amino)ethyl­imino­meth­yl]naphthalen-2-olate in an approximately square-planar configuration. There is an O—H...O hydrogen-bond inter­action between the complex and the methanol solvent mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.050
• wR factor = 0.152
• Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C16    -   C17     ..       6.30 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   O1      ..       6.76 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    -   N2      ..       5.90 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Mn1
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         11

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.01
           From the CIF: _reflns_number_total               3122
           Count of symmetry unique reflns         1816
           Completeness (_total/calc)            171.92%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1306
           Fraction of Friedel pairs measured     0.719
           Are heavy atom types Z>Si present        yes
PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1         (4)       3.61

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. Comment

Complexes synthesized from manganese and Schiff base ligand have been of great interest for many years. They are very important in the development of coordination chemistry. As an extension of the research on the structural characterization of Mn compounds, we report here the crystal structure of a new mononuclear manganese(II) complex.

The title compound is an electronically neutral mononuclear manganese(II) complex. The Mn^II ion in the compound is four coordinated by two N atoms and two O atoms from the asymmetrical tetradentate Schiff base ligand H₂hemn (H₂hemn= 1-((E)-(2-((E)-((Z)-4-hydroxypent-3-en-2-ylidene)amino)ethylimino)methyl)naphthalen-2-ol) in an approximately square-planar geometry. The Mn—N2 bond distance (1.812 (6) Å) is shorter than Mn—N1(1.836 (5) Å) and the other two Mn—O bonds distance (Mn—O1=1.835 (5) Å, Mn—O2=1.829 (4) Å). There is O—H···O hydrogen bond interaction between the complex and the methanol solvent molecule (Table 1).

Related literature

Complexes with a similar ligand were reported by Yan et al. (2006); in those complexes the ligand was synthesized from the reaction of ethylenediamine, acetylacetone and salicylaldehyde.

S2. Experimental

1. Synthesis of the ligand H₂hemn

To a 250 ml 3-neck round-bottom flask containing a solution of ethylenediamine (0.1 mol, 6.01 g) in ethanol (60 ml) at 50 °C, was added dropwise a solution of acetylacetone (0.1 mol, 10.01 g) in ethanol (60 ml). After the mixture was stirred at 50 °C for 4 h. A suspension of 2-hydroxy-1-naphthaldehyde (0.1 mol, 17.22 g) in ethanol (50 ml) was added into the flask. The resulted mixture was continued being stirred for another 4 h and then cooled down and the crude product was precipitated. The crude product was collected by filtration, washed with ethanol and vacuum dried overnight. The brown product H₂hemn was used without further purification.

2. Synthesis of the complex

To a solution of MnCl₂·4H₂O (1 mmol, 197 mg) in methanol (40 ml) was added ligand H₂hemn (1 mmol, 298 mg). After the resulted brown mixture was stirred at room temperature for 48 h, a brown turbid solution was obtained. The solution was filtered and slow evaporation of the solvent from the filtrate afforded dark brown crystals after 30 d.

S3. Refinement

Methyl H atoms and hydroxyl H atom were placed in calculated positions with C—H = 0.96 Å and O—H = 0.82 Å, and torsion angles were refined, U_iso(H) = 1.5U_eq(C,O). Other H atoms were placed in calculated positions with C—H = 0.93 (aromatic) or 0.97 Å (methylene) and refined in riding mode, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. The atom-numbering scheme of the title complex. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted.
	Fig. 2. The packed diagram for the title compound, viewed down the b axis with hydrogen bonds drawn as dashed lines. H atoms have been omitted.

(1-{(E)-2-[(2E,3Z)-4-Oxidopent-3-en-2- ylideneamino]ethyliminomethyl}naphthalen-2-olato)manganese(II) methanol solvate

Crystal data

[Mn(C18H18N2O2)]·CH4O	F(000) = 796
Mr = 381.33	Dx = 1.431 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	θ = 1.9–25.0°
a = 7.3800 (16) Å	µ = 0.77 mm^−1
b = 10.8935 (14) Å	T = 298 K
c = 22.01 (2) Å	Block, dark brown
V = 1769.6 (18) Å^3	0.48 × 0.32 × 0.29 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3122 independent reflections
Radiation source: fine-focus sealed tube	1863 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.081
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.709, Tmax = 0.808	k = −12→12
9257 measured reflections	l = −12→26

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.050	H-atom parameters constrained
wR(F^2) = 0.152	w = 1/[σ^2(Fo^2) + (0.0806P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.91	(Δ/σ)max = 0.001
3122 reflections	Δρmax = 0.29 e Å^−3
227 parameters	Δρmin = −0.29 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1306 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.14 (4)

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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0.56596 (12)	0.66361 (7)	0.47664 (4)	0.0444 (3)
N1	0.5557 (7)	0.8306 (5)	0.4659 (3)	0.0621 (13)
N2	0.5466 (8)	0.6932 (5)	0.5574 (3)	0.0653 (15)
O1	0.6034 (6)	0.6254 (4)	0.3964 (2)	0.0703 (14)
C1	0.6364 (10)	0.6470 (7)	0.2897 (3)	0.091 (2)
H1A	0.7642	0.6325	0.2856	0.136*
H1B	0.5972	0.7025	0.2584	0.136*
H1C	0.5723	0.5707	0.2858	0.136*
O2	0.5492 (7)	0.4972 (4)	0.48610 (18)	0.0685 (12)
O3	0.3061 (10)	0.4431 (6)	0.3797 (3)	0.140 (3)
H4	0.3692	0.4501	0.4102	0.210*
C2	0.5976 (10)	0.7030 (7)	0.3516 (3)	0.070 (2)
C3	0.5641 (10)	0.8231 (6)	0.3573 (3)	0.0754 (19)
H2	0.5551	0.8686	0.3216	0.090*
C4	0.5406 (9)	0.8882 (6)	0.4136 (4)	0.070 (2)
C5	0.4973 (10)	1.0246 (6)	0.4112 (4)	0.104 (3)
H4A	0.5880	1.0694	0.4332	0.155*
H4B	0.3808	1.0389	0.4292	0.155*
H4C	0.4958	1.0514	0.3697	0.155*
C6	0.5291 (10)	0.9018 (6)	0.5220 (4)	0.077 (2)
H5A	0.4023	0.9231	0.5269	0.093*
H5B	0.5997	0.9768	0.5207	0.093*
C7	0.5913 (10)	0.8210 (6)	0.5734 (3)	0.076 (2)
H6A	0.7209	0.8297	0.5794	0.091*
H6B	0.5305	0.8441	0.6108	0.091*
C8	0.5105 (8)	0.6148 (6)	0.6014 (3)	0.0626 (19)
H7	0.5063	0.6450	0.6409	0.075*
C9	0.4781 (8)	0.4893 (6)	0.5928 (3)	0.0618 (18)
C10	0.4983 (9)	0.4373 (6)	0.5344 (3)	0.067 (2)
C11	0.4626 (12)	0.3081 (6)	0.5271 (3)	0.090 (2)
H10	0.4787	0.2719	0.4893	0.108*
C12	0.4054 (13)	0.2374 (6)	0.5749 (4)	0.092 (3)
H11	0.3757	0.1555	0.5683	0.111*
C13	0.3906 (11)	0.2869 (7)	0.6343 (4)	0.078 (2)
C14	0.4268 (10)	0.4126 (7)	0.6430 (3)	0.0694 (18)
C15	0.4008 (10)	0.4593 (8)	0.7031 (3)	0.087 (2)
H14	0.4212	0.5417	0.7119	0.105*
C16	0.3433 (11)	0.3769 (11)	0.7489 (4)	0.110 (3)
H15	0.3262	0.4074	0.7879	0.132*
C17	0.3113 (14)	0.2542 (10)	0.7389 (5)	0.110 (3)
H16	0.2712	0.2031	0.7700	0.132*
C18	0.3400 (11)	0.2108 (8)	0.6825 (5)	0.097 (3)
H17	0.3256	0.1273	0.6753	0.116*
C19	0.3463 (13)	0.3403 (9)	0.3519 (5)	0.148 (4)
H18A	0.3735	0.3571	0.3100	0.222*
H18B	0.2451	0.2852	0.3542	0.222*
H18C	0.4498	0.3034	0.3710	0.222*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0396 (4)	0.0422 (4)	0.0515 (5)	−0.0011 (4)	0.0017 (5)	−0.0022 (5)
N1	0.047 (3)	0.056 (3)	0.083 (4)	−0.006 (3)	0.003 (4)	−0.002 (3)
N2	0.053 (3)	0.068 (4)	0.075 (4)	−0.004 (3)	0.000 (3)	−0.008 (3)
O1	0.081 (4)	0.059 (3)	0.071 (3)	−0.004 (2)	0.004 (3)	0.006 (2)
C1	0.094 (6)	0.097 (6)	0.081 (5)	0.010 (5)	0.016 (4)	0.011 (5)
O2	0.088 (3)	0.054 (2)	0.064 (3)	0.005 (3)	0.011 (3)	−0.002 (2)
O3	0.144 (6)	0.110 (5)	0.166 (6)	0.018 (4)	−0.034 (5)	−0.036 (5)
C2	0.062 (5)	0.074 (5)	0.075 (5)	−0.009 (4)	0.009 (4)	0.004 (4)
C3	0.073 (5)	0.057 (4)	0.097 (5)	−0.003 (5)	0.000 (5)	0.012 (4)
C4	0.041 (4)	0.058 (4)	0.111 (6)	−0.008 (3)	0.003 (5)	0.014 (4)
C5	0.075 (6)	0.064 (5)	0.172 (9)	0.000 (4)	0.011 (6)	0.028 (6)
C6	0.062 (5)	0.056 (4)	0.113 (6)	−0.008 (3)	0.015 (5)	−0.017 (5)
C7	0.066 (5)	0.075 (5)	0.086 (5)	−0.015 (5)	0.006 (4)	−0.024 (4)
C8	0.051 (4)	0.077 (5)	0.060 (4)	0.000 (3)	−0.002 (3)	0.002 (4)
C9	0.056 (5)	0.063 (4)	0.067 (4)	0.006 (3)	0.004 (3)	0.004 (4)
C10	0.077 (5)	0.047 (4)	0.077 (5)	0.008 (3)	−0.002 (4)	0.004 (4)
C11	0.112 (7)	0.076 (5)	0.083 (5)	0.008 (4)	0.014 (6)	−0.004 (4)
C12	0.111 (7)	0.055 (4)	0.111 (7)	0.001 (5)	0.023 (6)	0.023 (5)
C13	0.070 (6)	0.074 (5)	0.090 (6)	0.012 (4)	0.016 (4)	0.019 (5)
C14	0.054 (4)	0.082 (5)	0.073 (5)	0.011 (5)	0.004 (4)	0.012 (4)
C15	0.072 (6)	0.118 (7)	0.071 (5)	0.010 (5)	−0.004 (4)	0.014 (5)
C16	0.077 (6)	0.184 (11)	0.069 (6)	0.024 (7)	0.004 (5)	0.031 (7)
C17	0.105 (8)	0.106 (8)	0.120 (9)	0.017 (6)	0.008 (7)	0.039 (7)
C18	0.086 (6)	0.085 (6)	0.118 (7)	0.013 (5)	0.013 (6)	0.029 (6)
C19	0.152 (10)	0.120 (8)	0.172 (9)	0.031 (8)	0.003 (8)	−0.078 (8)

Geometric parameters (Å, º)

Mn1—N2	1.812 (6)	C6—H5B	0.9700
Mn1—O2	1.829 (4)	C7—H6A	0.9700
Mn1—O1	1.835 (5)	C7—H6B	0.9700
Mn1—N1	1.836 (5)	C8—C9	1.401 (8)
N1—C4	1.316 (8)	C8—H7	0.9300
N1—C6	1.470 (8)	C9—C10	1.412 (9)
N2—C8	1.319 (7)	C9—C14	1.436 (8)
N2—C7	1.475 (8)	C10—C11	1.441 (9)
O1—C2	1.300 (7)	C11—C12	1.370 (9)
C1—C2	1.521 (10)	C11—H10	0.9300
C1—H1A	0.9600	C12—C13	1.418 (10)
C1—H1B	0.9600	C12—H11	0.9300
C1—H1C	0.9600	C13—C18	1.396 (10)
O2—C10	1.303 (7)	C13—C14	1.408 (10)
O3—C19	1.311 (9)	C14—C15	1.432 (9)
O3—H4	0.8200	C15—C16	1.414 (10)
C2—C3	1.338 (8)	C15—H14	0.9300
C3—C4	1.439 (9)	C16—C17	1.375 (11)
C3—H2	0.9300	C16—H15	0.9300
C4—C5	1.520 (8)	C17—C18	1.346 (11)
C5—H4A	0.9600	C17—H16	0.9300
C5—H4B	0.9600	C18—H17	0.9300
C5—H4C	0.9600	C19—H18A	0.9600
C6—C7	1.506 (9)	C19—H18B	0.9600
C6—H5A	0.9700	C19—H18C	0.9600
N2—Mn1—O2	93.4 (2)	C6—C7—H6A	110.2
N2—Mn1—O1	174.9 (2)	N2—C7—H6B	110.2
O2—Mn1—O1	83.98 (18)	C6—C7—H6B	110.2
N2—Mn1—N1	86.9 (2)	H6A—C7—H6B	108.5
O2—Mn1—N1	173.7 (2)	N2—C8—C9	124.5 (6)
O1—Mn1—N1	96.2 (2)	N2—C8—H7	117.8
C4—N1—C6	118.1 (6)	C9—C8—H7	117.8
C4—N1—Mn1	126.0 (5)	C8—C9—C10	119.8 (6)
C6—N1—Mn1	114.8 (4)	C8—C9—C14	120.6 (6)
C8—N2—C7	118.7 (6)	C10—C9—C14	119.6 (6)
C8—N2—Mn1	128.5 (4)	O2—C10—C9	124.9 (6)
C7—N2—Mn1	112.7 (4)	O2—C10—C11	116.8 (6)
C2—O1—Mn1	125.3 (4)	C9—C10—C11	118.3 (7)
C2—C1—H1A	109.5	C12—C11—C10	121.3 (7)
C2—C1—H1B	109.5	C12—C11—H10	119.3
H1A—C1—H1B	109.5	C10—C11—H10	119.3
C2—C1—H1C	109.5	C11—C12—C13	121.2 (7)
H1A—C1—H1C	109.5	C11—C12—H11	119.4
H1B—C1—H1C	109.5	C13—C12—H11	119.4
C10—O2—Mn1	127.5 (4)	C18—C13—C14	121.6 (8)
C19—O3—H4	109.5	C18—C13—C12	119.7 (8)
O1—C2—C3	124.8 (6)	C14—C13—C12	118.7 (7)
O1—C2—C1	114.5 (6)	C13—C14—C15	116.5 (7)
C3—C2—C1	120.7 (7)	C13—C14—C9	120.7 (7)
C2—C3—C4	125.8 (7)	C15—C14—C9	122.7 (7)
C2—C3—H2	117.1	C16—C15—C14	118.2 (8)
C4—C3—H2	117.1	C16—C15—H14	120.9
N1—C4—C3	120.6 (6)	C14—C15—H14	120.9
N1—C4—C5	120.9 (8)	C17—C16—C15	123.7 (9)
C3—C4—C5	118.4 (7)	C17—C16—H15	118.2
C4—C5—H4A	109.5	C15—C16—H15	118.2
C4—C5—H4B	109.5	C18—C17—C16	117.5 (10)
H4A—C5—H4B	109.5	C18—C17—H16	121.2
C4—C5—H4C	109.5	C16—C17—H16	121.2
H4A—C5—H4C	109.5	C17—C18—C13	122.3 (9)
H4B—C5—H4C	109.5	C17—C18—H17	118.8
N1—C6—C7	106.4 (5)	C13—C18—H17	118.8
N1—C6—H5A	110.4	O3—C19—H18A	109.5
C7—C6—H5A	110.4	O3—C19—H18B	109.5
N1—C6—H5B	110.4	H18A—C19—H18B	109.5
C7—C6—H5B	110.4	O3—C19—H18C	109.5
H5A—C6—H5B	108.6	H18A—C19—H18C	109.5
N2—C7—C6	107.6 (6)	H18B—C19—H18C	109.5
N2—C7—H6A	110.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H4···O2	0.82	2.20	3.008 (9)	171