Chlorido{2,2′-[propane-1,3-diylbis(nitrilo­methyl­idyne)]diphenolato-κ4O,N,N′,O′}manganese(III)

Li, M.-J.; Yan, P.-F.; Li, G.-M.; Li, H.-F.

doi:10.1107/S1600536809005352

Chlorido{2,2′-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N′,O′}manganese(III)

M.-J. Li, P.-F. Yan, G.-M. Li and H.-F. Li

In the title complex, [Mn(C₁₇H₁₆N₂O₂)Cl], the Mn^III ion is coordinated by two O [Mn—O = 1.719 (2) and 1.813 (2) Å] and two N [Mn—N = 1.824 (2) and 1.931 (2) Å] atoms from the tetradentate Schiff base ligand and a chloride anion [Mn—Cl = 2.9634 (16) Å] in a square-pyramidal geometry. In the ligand, the two benzene rings form a dihedral angle of 68.06 (5)°.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809005352/cv2500sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809005352/cv2500Isup2.hkl Contains datablock I

CCDC reference: 722819

checkCIF report

Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.005 Å
R factor = 0.035
wR factor = 0.094
Data-to-parameter ratio = 12.9

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   291.000
            Value of melting point given =     0.000
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT213_ALERT_2_C Atom O1      has ADP max/min Ratio .............       3.60 prola
PLAT213_ALERT_2_C Atom O2      has ADP max/min Ratio .............       3.40 prola
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       3.81
PLAT334_ALERT_2_C Small Average Benzene C-C Dist.  C1     -C6            1.36 Ang.
PLAT334_ALERT_2_C Small Average Benzene C-C Dist.  C12    -C17           1.34 Ang.
PLAT360_ALERT_2_C Short  C(sp3)-C(sp3) Bond  C9     -   C10    ...       1.42 Ang.
PLAT368_ALERT_2_C Short  C(sp2)-C(sp2) Bond  C3     -   C4     ...       1.23 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  Cl1    ..  C8      ..       3.24 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1     ..  C7      ..       3.01 Ang.
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT234_ALERT_4_C Large Hirshfeld Difference C5     --  C6      ..       0.11  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference C14    --  C15     ..       0.10  Ang.

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           24.99
           From the CIF: _reflns_number_total               2689
           Count of symmetry unique reflns         1462
           Completeness (_total/calc)            183.93%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1227
           Fraction of Friedel pairs measured     0.839
           Are heavy atom types Z>Si present        yes
PLAT335_ALERT_2_G Check Large C6 Ring C-C Range .  C1     -C6            0.22 Ang.

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  10 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In the title compound (Fig. 1), the tetradentate Schiff base ligand links Mn atom into a mononuclear complex through two phenolate O atoms and two N atoms with the bond lengths similar to those reported for another manganese complex of the same ligand (Watkinson et al., 1999). The Mn^III center is five-coordinate by two nitrogen atoms and two oxygen atoms from the ligand and one chlorine anion in a square-pyramidal geometry.

Related literature top

For a similar manganese complex of the same Schiff base, see: Watkinson et al. (1999).

Experimental top

The title complex was obtained by the treatment of manganese(III) chloride tetrahydrate with the Schiff base in methanol. The first two reactants were refluxed for 1 h. The reaction mixture was cooled and filtered; Diethyl ether was allowed to diffuse slowly into the solution of the filtrate. Single crystals were obtained after several days. Analysis: calculated for C₁₇H₁₆MnN₂O₂Cl: C, 55.08; H, 4.35; Mn, 14.82; N, 7.56; found: C, 54.98; H, 4.39; N, 7.45; Mn, 14.28%.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids.

Chlorido{2,2'-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato- κ⁴O,N,N',O'}manganese(III) top

Crystal data top

[Mn(C₁₇H₁₆N₂O₂)Cl]	F(000) = 760
M_r = 370.71	D_x = 1.562 Mg m⁻³
Orthorhombic, Pca2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 12324 reflections
a = 10.428 (3) Å	θ = 3.1–27.5°
b = 12.067 (4) Å	µ = 1.02 mm⁻¹
c = 12.530 (5) Å	T = 291 K
V = 1576.6 (10) Å³	Block, black
Z = 4	0.19 × 0.17 × 0.12 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2689 independent reflections
Radiation source: fine-focus sealed tube	2526 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 25.0°, θ_min = 3.1°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −12→12
T_min = 0.830, T_max = 0.889	k = −14→14
11321 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	w = 1/[σ²(F_o²) + (0.0666P)² + 0.1785P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
2689 reflections	Δρ_max = 0.44 e Å⁻³
208 parameters	Δρ_min = −0.31 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1227 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (2)

Crystal data top

[Mn(C₁₇H₁₆N₂O₂)Cl]	V = 1576.6 (10) Å³
M_r = 370.71	Z = 4
Orthorhombic, Pca2₁	Mo Kα radiation
a = 10.428 (3) Å	µ = 1.02 mm⁻¹
b = 12.067 (4) Å	T = 291 K
c = 12.530 (5) Å	0.19 × 0.17 × 0.12 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	2689 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2526 reflections with I > 2σ(I)
T_min = 0.830, T_max = 0.889	R_int = 0.032
11321 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.094	Δρ_max = 0.44 e Å⁻³
S = 1.05	Δρ_min = −0.31 e Å⁻³
2689 reflections	Absolute structure: Flack (1983), 1227 Friedel pairs
208 parameters	Absolute structure parameter: −0.01 (2)
1 restraint

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
C1	0.8363 (3)	0.4885 (3)	0.7136 (3)	0.0330 (8)
C2	0.9063 (3)	0.4297 (3)	0.6323 (3)	0.0383 (8)
H1	0.9918	0.4508	0.6257	0.046*
C3	0.8679 (3)	0.3466 (3)	0.5617 (3)	0.0434 (9)
H2	0.9238	0.3167	0.5115	0.052*
C4	0.7560 (5)	0.3148 (3)	0.5694 (5)	0.0550 (12)
H3	0.7204	0.2607	0.5256	0.066*
C5	0.6881 (3)	0.3678 (3)	0.6502 (4)	0.0506 (11)
H4	0.6045	0.3426	0.6589	0.061*
C6	0.7247 (3)	0.4555 (3)	0.7232 (3)	0.0365 (9)
C7	0.6476 (3)	0.5107 (3)	0.8041 (3)	0.0365 (8)
H5	0.5738	0.4717	0.8224	0.044*
C8	0.5664 (3)	0.6436 (3)	0.9321 (3)	0.0378 (8)
H7	0.6039	0.6538	1.0022	0.045*
H6	0.4934	0.5941	0.9376	0.045*
C9	0.5303 (3)	0.7500 (3)	0.8835 (3)	0.0393 (8)
H8	0.5342	0.7425	0.8065	0.047*
H9	0.4421	0.7665	0.9024	0.047*
C10	0.6086 (3)	0.8410 (3)	0.9145 (3)	0.0397 (9)
H10	0.5632	0.9106	0.9056	0.048*
H11	0.6352	0.8340	0.9884	0.048*
C11	0.7546 (3)	0.9233 (3)	0.8068 (3)	0.0341 (8)
H12	0.7055	0.9853	0.8231	0.041*
C12	0.8596 (3)	0.9429 (3)	0.7439 (3)	0.0342 (8)
C13	0.8794 (3)	1.0423 (3)	0.6866 (4)	0.0468 (10)
H13	0.8180	1.0976	0.6947	0.056*
C14	0.9749 (4)	1.0638 (3)	0.6237 (4)	0.0499 (10)
H14	0.9815	1.1286	0.5839	0.060*
C15	1.0592 (3)	0.9870 (3)	0.6221 (3)	0.0455 (10)
H15	1.1323	0.9960	0.5805	0.055*
C16	1.0440 (3)	0.8901 (3)	0.6812 (3)	0.0422 (9)
H16	1.1107	0.8390	0.6787	0.051*
C17	0.9428 (3)	0.8637 (3)	0.7408 (3)	0.0320 (8)
Cl1	0.82072 (8)	0.70229 (8)	1.06882 (7)	0.0435 (2)
Mn1	0.79832 (4)	0.69247 (3)	0.83324 (5)	0.03055 (16)
N1	0.6603 (2)	0.6027 (2)	0.8558 (2)	0.0319 (7)
N2	0.7160 (2)	0.8353 (2)	0.8449 (3)	0.0303 (6)
O1	0.87583 (19)	0.56992 (19)	0.7799 (2)	0.0435 (6)
O2	0.92804 (19)	0.76783 (19)	0.7896 (2)	0.0457 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0170 (15)	0.0230 (17)	0.059 (2)	0.0016 (12)	−0.0073 (14)	0.0037 (14)
C2	0.0165 (15)	0.0260 (17)	0.072 (3)	0.0026 (13)	−0.0026 (16)	0.0053 (15)
C3	0.0275 (17)	0.0269 (17)	0.076 (3)	0.0054 (14)	−0.0028 (18)	−0.0031 (17)
C4	0.0323 (18)	0.0296 (17)	0.103 (4)	−0.0024 (16)	−0.012 (2)	−0.015 (2)
C5	0.0223 (17)	0.0280 (18)	0.101 (3)	−0.0069 (14)	−0.0072 (19)	0.004 (2)
C6	0.0206 (17)	0.0237 (16)	0.065 (3)	−0.0017 (13)	−0.0096 (15)	0.0087 (15)
C7	0.0142 (13)	0.0296 (17)	0.066 (2)	−0.0035 (12)	−0.0056 (14)	0.0123 (16)
C8	0.0157 (14)	0.044 (2)	0.053 (2)	−0.0016 (13)	0.0046 (14)	0.0005 (16)
C9	0.0135 (14)	0.044 (2)	0.060 (2)	0.0056 (13)	0.0084 (15)	−0.0050 (16)
C10	0.0215 (15)	0.0381 (19)	0.060 (2)	0.0082 (14)	0.0048 (15)	−0.0085 (16)
C11	0.0183 (13)	0.0324 (17)	0.052 (2)	0.0076 (13)	−0.0021 (14)	−0.0019 (14)
C12	0.0198 (15)	0.0224 (15)	0.060 (2)	−0.0009 (12)	−0.0024 (15)	−0.0026 (15)
C13	0.0268 (18)	0.0245 (18)	0.089 (3)	−0.0020 (13)	−0.005 (2)	0.0033 (18)
C14	0.035 (2)	0.0296 (18)	0.085 (3)	−0.0068 (16)	−0.013 (2)	0.0107 (18)
C15	0.0271 (17)	0.040 (2)	0.069 (3)	−0.0159 (16)	−0.0009 (17)	0.0012 (18)
C16	0.0193 (16)	0.0310 (18)	0.076 (3)	−0.0047 (13)	−0.0011 (17)	−0.0065 (18)
C17	0.0171 (15)	0.0253 (17)	0.054 (2)	−0.0036 (12)	−0.0080 (14)	−0.0018 (15)
Cl1	0.0340 (4)	0.0450 (5)	0.0516 (6)	−0.0052 (4)	−0.0144 (4)	0.0071 (4)
Mn1	0.0114 (2)	0.0231 (2)	0.0571 (3)	0.00044 (15)	−0.0008 (2)	0.0015 (3)
N1	0.0106 (10)	0.0306 (14)	0.0544 (19)	0.0022 (9)	−0.0040 (11)	0.0068 (13)
N2	0.0120 (10)	0.0291 (13)	0.0499 (17)	0.0028 (9)	−0.0012 (12)	−0.0002 (15)
O1	0.0079 (9)	0.0278 (12)	0.0949 (18)	0.0026 (8)	−0.0058 (11)	−0.0085 (12)
O2	0.0087 (9)	0.0268 (12)	0.101 (2)	0.0014 (8)	−0.0015 (11)	0.0066 (13)

Geometric parameters (Å, º) top

C1—C6	1.236 (5)	C10—H10	0.9700
C1—O1	1.351 (4)	C10—H11	0.9700
C1—C2	1.439 (5)	C11—N2	1.232 (4)
C2—C3	1.397 (5)	C11—C12	1.370 (5)
C2—H1	0.9300	C11—H12	0.9300
C3—C4	1.232 (6)	C12—C17	1.292 (5)
C3—H2	0.9300	C12—C13	1.413 (5)
C4—C5	1.391 (7)	C13—C14	1.296 (6)
C4—H3	0.9300	C13—H13	0.9300
C5—C6	1.449 (6)	C14—C15	1.277 (5)
C5—H4	0.9300	C14—H14	0.9300
C6—C7	1.456 (5)	C15—C16	1.394 (5)
C7—N1	1.291 (4)	C15—H15	0.9300
C7—H5	0.9300	C16—C17	1.331 (5)
C8—N1	1.455 (4)	C16—H16	0.9300
C8—C9	1.470 (5)	C17—O2	1.317 (4)
C8—H7	0.9700	Cl1—Mn1	2.9634 (16)
C8—H6	0.9700	Mn1—O2	1.719 (2)
C9—C10	1.423 (5)	Mn1—O1	1.813 (2)
C9—H8	0.9700	Mn1—N1	1.824 (2)
C9—H9	0.9700	Mn1—N2	1.931 (2)
C10—N2	1.421 (4)

C6—C1—O1	117.5 (3)	N2—C11—C12	129.3 (3)
C6—C1—C2	112.9 (3)	N2—C11—H12	115.4
O1—C1—C2	129.6 (3)	C12—C11—H12	115.4
C3—C2—C1	131.0 (3)	C17—C12—C11	115.2 (3)
C3—C2—H1	114.5	C17—C12—C13	121.0 (3)
C1—C2—H1	114.5	C11—C12—C13	123.8 (3)
C4—C3—C2	116.5 (4)	C14—C13—C12	126.3 (4)
C4—C3—H2	121.8	C14—C13—H13	116.9
C2—C3—H2	121.8	C12—C13—H13	116.9
C3—C4—C5	113.3 (4)	C15—C14—C13	113.1 (4)
C3—C4—H3	123.3	C15—C14—H14	123.4
C5—C4—H3	123.3	C13—C14—H14	123.4
C4—C5—C6	131.4 (3)	C14—C15—C16	121.5 (4)
C4—C5—H4	114.3	C14—C15—H15	119.3
C6—C5—H4	114.3	C16—C15—H15	119.3
C1—C6—C5	114.9 (4)	C17—C16—C15	126.1 (3)
C1—C6—C7	116.1 (3)	C17—C16—H16	116.9
C5—C6—C7	128.9 (3)	C15—C16—H16	116.9
N1—C7—C6	133.3 (3)	C12—C17—O2	123.9 (3)
N1—C7—H5	113.4	C12—C17—C16	111.8 (3)
C6—C7—H5	113.4	O2—C17—C16	124.3 (3)
N1—C8—C9	101.3 (3)	O2—Mn1—O1	87.90 (11)
N1—C8—H7	111.5	O2—Mn1—N1	169.92 (14)
C9—C8—H7	111.5	O1—Mn1—N1	85.65 (11)
N1—C8—H6	111.5	O2—Mn1—N2	84.35 (11)
C9—C8—H6	111.5	O1—Mn1—N2	162.58 (14)
H7—C8—H6	109.3	N1—Mn1—N2	99.68 (11)
C10—C9—C8	114.5 (3)	O2—Mn1—Cl1	103.51 (11)
C10—C9—H8	108.6	O1—Mn1—Cl1	111.39 (10)
C8—C9—H8	108.6	N1—Mn1—Cl1	86.08 (9)
C10—C9—H9	108.6	N2—Mn1—Cl1	85.64 (10)
C8—C9—H9	108.6	C7—N1—C8	123.5 (3)
H8—C9—H9	107.6	C7—N1—Mn1	120.9 (2)
N2—C10—C9	104.3 (3)	C8—N1—Mn1	115.6 (2)
N2—C10—H10	110.9	C11—N2—C10	117.0 (3)
C9—C10—H10	110.9	C11—N2—Mn1	126.5 (2)
N2—C10—H11	110.9	C10—N2—Mn1	116.1 (2)
C9—C10—H11	110.9	C1—O1—Mn1	133.14 (19)
H10—C10—H11	108.9	C17—O2—Mn1	134.8 (2)

Experimental details

Crystal data
Chemical formula	[Mn(C₁₇H₁₆N₂O₂)Cl]
M_r	370.71
Crystal system, space group	Orthorhombic, Pca2₁
Temperature (K)	291
a, b, c (Å)	10.428 (3), 12.067 (4), 12.530 (5)
V (Å³)	1576.6 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.19 × 0.17 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.830, 0.889
No. of measured, independent and observed [I > 2σ(I)] reflections	11321, 2689, 2526
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.05
No. of reflections	2689
No. of parameters	208
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.31
Absolute structure	Flack (1983), 1227 Friedel pairs
Absolute structure parameter	−0.01 (2)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

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Chlorido{2,2′-[propane-1,3-diylbis(nitrilo­methyl­idyne)]diphenolato-κ4O,N,N′,O′}manganese(III)

Supporting information

Key indicators

checkCIF/PLATON results

Chlorido{2,2′-[propane-1,3-diylbis(nitrilomethylidyne)]diphenolato-κ⁴O,N,N′,O′}manganese(III)