Bis[(2-amino­phen­yl)methanol-κ2O,N]bis­(nitrato-κO)manganese(II)

Esmhosseini, M.; Maleki, S.

doi:10.1107/S1600536810030114

metal-organic compounds

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Volume 66| Part 9| September 2010| Page m1052

https://doi.org/10.1107/S1600536810030114

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Bis[(2-aminophenyl)methanol-κ²O,N]bis(nitrato-κO)manganese(II)

Majid Esmhosseini ^a ^* and Shahrzad Maleki ^a

^aDepartment of Chemistry, University of Urmiyeh, Urmyieh, Iran
^*Correspondence e-mail: m.esmhosseini@urmia.ac.ir

(Received 17 July 2010; accepted 28 July 2010; online 4 August 2010)

In the title compound, [Mn(NO₃)₂(C₇H₉NO)₂], the Mn^II atom (site symmetry 2) is coordinated by two N,O-bidentate (2-aminophenyl)methanol ligands and two monodentate nitrate anions in a distorted cis-MnN₂O₄ octahedral coordination geometry. In the crystal, N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds help to establish the packing.

Related literature

For structures involving the same ligand with other metal ions, see: Bandoli et al. (2002 ); Lewiriski et al. (1998 ).

Experimental

Crystal data

[Mn(NO₃)₂(C₇H₉NO)₂]
M_r = 425.26
Orthorhombic, P b c n
a = 23.374 (2) Å
b = 10.1929 (12) Å
c = 7.3336 (6) Å
V = 1747.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 120 K
0.40 × 0.10 × 0.06 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ) T_min = 0.907, T_max = 0.955
6668 measured reflections
2335 independent reflections
1928 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.071
S = 1.10
2335 reflections
135 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Selected bond lengths (Å)

Mn1—N1	2.2469 (15)
Mn1—O1	2.2041 (13)
Mn1—O2	2.2203 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O3ⁱ	0.87 (2)	2.16 (2)	2.9775 (19)	156 (2)
N1—H1D⋯O4ⁱⁱ	0.90 (3)	2.15 (3)	3.037 (2)	169 (2)
O1—H1E⋯O2ⁱⁱⁱ	0.82 (3)	1.88 (3)	2.6937 (17)	176 (3)
C1—H1B⋯O4ⁱⁱ	0.97	2.60	3.479 (2)	151
Symmetry codes: (i) $[x, -y, z-{\script{1\over 2}}]$ ; (ii) x, y, z-1; (iii) $[x, -y+1, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810030114/hb5561sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030114/hb5561Isup2.hkl

checkCIF report

Comment top

(2-Aminophenyl)methanol is a bidentate ligand ligand. There are only two complexes with this ligand that have been prepared: those of Re (Bandoli et al., 2002) and Al (Lewiriski et al. 1998). We report herein the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of the title compound, Fig. 1, contains half molecule. The Mn^II atom is six-coordinated in distorted hexagonal configurations by two N and two O atoms from two (2-aminophenyl)methanol ligand and two O atoms from two nitrate anions. The Mn—O and Mn—N bond lengths and angles are collected in Table 1.

Intermolecular N—H···O, O—H···O and C—H···O hydrogen bonding may stabilize the structure, (Table 2, Fig. 2).

Related literature top

For structures involving the same ligand with other metal ions, see: Bandoli et al. (2002); Lewiriski et al. (1998).

Experimental top

A solution of (2-aminophenyl)methanol (0.25 g, 2.00 mmol) in methanol (10 ml) was added to a solution of Mn(NO₃)₂.4H₂O (0.25 g, 1.00 mmol) in methanol (10 ml) and the resulting colorless solution was stirred for 20 min at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colorless needles of (I) were isolated (yield 0.33 g, 77.6%).

Structure description top

Intermolecular N—H···O, O—H···O and C—H···O hydrogen bonding may stabilize the structure, (Table 2, Fig. 2).

For structures involving the same ligand with other metal ions, see: Bandoli et al. (2002); Lewiriski et al. (1998).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level. Atoms with suffix a are generated by (1–x, y, 1/2–z).
	Fig. 2. Unit-cell packing diagram for (I). Hydrogen bonds are shown as dashed lines.

Bis[(2-aminophenyl)methanol-κ²O,N]bis(nitrato- κO)manganese(II) top

Crystal data top

[Mn(NO₃)₂(C₇H₉NO)₂]	F(000) = 876
M_r = 425.26	D_x = 1.617 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 1154 reflections
a = 23.374 (2) Å	θ = 2.2–29.2°
b = 10.1929 (12) Å	µ = 0.81 mm⁻¹
c = 7.3336 (6) Å	T = 120 K
V = 1747.2 (3) Å³	Block, colorless
Z = 4	0.40 × 0.10 × 0.06 mm

Data collection top

Bruker SMART CCD diffractometer	2335 independent reflections
Radiation source: fine-focus sealed tube	1928 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
phi and ω scans	θ_max = 29.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −31→23
T_min = 0.907, T_max = 0.955	k = −13→10
6668 measured reflections	l = −9→9

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ²(F_o²) + (0.017P)² + 1.3224P] where P = (F_o² + 2F_c²)/3
2335 reflections	(Δ/σ)_max = 0.007
135 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Mn(NO₃)₂(C₇H₉NO)₂]	V = 1747.2 (3) Å³
M_r = 425.26	Z = 4
Orthorhombic, Pbcn	Mo Kα radiation
a = 23.374 (2) Å	µ = 0.81 mm⁻¹
b = 10.1929 (12) Å	T = 120 K
c = 7.3336 (6) Å	0.40 × 0.10 × 0.06 mm

Data collection top

Bruker SMART CCD diffractometer	2335 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1928 reflections with I > 2σ(I)
T_min = 0.907, T_max = 0.955	R_int = 0.046
6668 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.31 e Å⁻³
2335 reflections	Δρ_min = −0.32 e Å⁻³
135 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
C1	0.61659 (7)	0.43167 (16)	0.1127 (2)	0.0177 (3)
H1A	0.6380	0.5132	0.1158	0.021*
H1B	0.6137	0.4033	−0.0132	0.021*
C2	0.64736 (7)	0.32879 (16)	0.2234 (2)	0.0160 (3)
C3	0.69730 (8)	0.36086 (18)	0.3180 (2)	0.0208 (3)
H3	0.7119	0.4455	0.3095	0.025*
C4	0.72554 (8)	0.26846 (19)	0.4247 (3)	0.0248 (4)
H4	0.7586	0.2911	0.4876	0.030*
C5	0.70376 (8)	0.14206 (19)	0.4363 (3)	0.0248 (4)
H5	0.7221	0.0802	0.5087	0.030*
C6	0.65484 (8)	0.10717 (17)	0.3408 (2)	0.0197 (3)
H6	0.6411	0.0217	0.3473	0.024*
C7	0.62624 (7)	0.20036 (16)	0.2348 (2)	0.0162 (3)
N1	0.57317 (7)	0.16868 (14)	0.1479 (2)	0.0168 (3)
H1D	0.5731 (10)	0.194 (2)	0.030 (4)	0.033 (6)*
H1C	0.5657 (10)	0.085 (2)	0.156 (3)	0.027 (6)*
N2	0.55303 (6)	0.21326 (14)	0.61414 (18)	0.0165 (3)
O1	0.55977 (5)	0.45233 (12)	0.18714 (17)	0.0181 (2)
H1E	0.5502 (11)	0.522 (3)	0.141 (4)	0.046 (8)*
O2	0.53386 (6)	0.31604 (10)	0.53077 (16)	0.0184 (3)
O3	0.53757 (6)	0.10431 (11)	0.55841 (18)	0.0241 (3)
O4	0.58609 (6)	0.22845 (13)	0.74423 (18)	0.0249 (3)
Mn1	0.5000	0.29131 (3)	0.2500	0.01412 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0222 (8)	0.0131 (7)	0.0179 (8)	−0.0029 (6)	0.0022 (7)	0.0018 (6)
C2	0.0186 (7)	0.0156 (7)	0.0137 (8)	0.0016 (6)	0.0017 (6)	−0.0019 (6)
C3	0.0197 (8)	0.0212 (8)	0.0216 (8)	−0.0015 (7)	0.0024 (7)	−0.0055 (7)
C4	0.0196 (8)	0.0306 (10)	0.0243 (8)	0.0028 (8)	−0.0040 (7)	−0.0056 (8)
C5	0.0244 (9)	0.0276 (10)	0.0224 (8)	0.0090 (8)	−0.0023 (7)	0.0006 (8)
C6	0.0237 (8)	0.0152 (7)	0.0203 (8)	0.0043 (7)	0.0000 (7)	−0.0005 (7)
C7	0.0191 (7)	0.0151 (7)	0.0143 (7)	0.0014 (6)	0.0016 (6)	−0.0017 (6)
N1	0.0230 (7)	0.0109 (6)	0.0165 (7)	−0.0018 (5)	−0.0026 (6)	−0.0005 (5)
N2	0.0213 (7)	0.0139 (6)	0.0144 (6)	0.0013 (6)	0.0004 (5)	0.0012 (5)
O1	0.0204 (6)	0.0102 (5)	0.0238 (6)	−0.0002 (5)	−0.0008 (5)	0.0045 (5)
O2	0.0288 (6)	0.0087 (5)	0.0177 (6)	0.0011 (5)	−0.0042 (5)	0.0014 (4)
O3	0.0316 (7)	0.0103 (5)	0.0305 (7)	−0.0017 (5)	−0.0047 (6)	0.0007 (5)
O4	0.0308 (6)	0.0276 (7)	0.0163 (6)	0.0021 (5)	−0.0072 (6)	0.0004 (6)
Mn1	0.01774 (16)	0.00979 (14)	0.01484 (16)	0.000	−0.00214 (14)	0.000

Geometric parameters (Å, º) top

C1—O1	1.451 (2)	C7—N1	1.431 (2)
C1—C2	1.509 (2)	Mn1—N1	2.2469 (15)
C1—H1A	0.9700	N1—H1D	0.90 (3)
C1—H1B	0.9700	N1—H1C	0.87 (2)
C2—C3	1.397 (2)	N2—O3	1.2372 (19)
C2—C7	1.402 (2)	N2—O4	1.2375 (18)
C3—C4	1.391 (3)	N2—O2	1.2931 (18)
C3—H3	0.9300	Mn1—O1	2.2041 (13)
C4—C5	1.388 (3)	O1—H1E	0.82 (3)
C4—H4	0.9300	Mn1—O2	2.2203 (12)
C5—C6	1.387 (3)	Mn1—O1ⁱ	2.2041 (13)
C5—H5	0.9300	Mn1—O2ⁱ	2.2202 (12)
C6—C7	1.398 (2)	Mn1—N1ⁱ	2.2469 (15)
C6—H6	0.9300

O1—C1—C2	109.56 (13)	Mn1—N1—H1D	99.2 (16)
O1—C1—H1A	109.8	C7—N1—H1C	111.3 (15)
C2—C1—H1A	109.8	Mn1—N1—H1C	111.6 (15)
O1—C1—H1B	109.8	H1D—N1—H1C	110 (2)
C2—C1—H1B	109.8	O3—N2—O4	123.32 (14)
H1A—C1—H1B	108.2	O3—N2—O2	118.03 (13)
C3—C2—C7	118.92 (15)	O4—N2—O2	118.65 (14)
C3—C2—C1	120.20 (15)	C1—O1—Mn1	123.42 (10)
C7—C2—C1	120.88 (15)	C1—O1—H1E	102.7 (19)
C4—C3—C2	121.16 (17)	Mn1—O1—H1E	124.1 (19)
C4—C3—H3	119.4	N2—O2—Mn1	118.03 (10)
C2—C3—H3	119.4	O1ⁱ—Mn1—O1	83.74 (7)
C5—C4—C3	119.26 (17)	O1ⁱ—Mn1—O2ⁱ	83.31 (5)
C5—C4—H4	120.4	O1—Mn1—O2ⁱ	86.99 (5)
C3—C4—H4	120.4	O1ⁱ—Mn1—O2	86.99 (5)
C6—C5—C4	120.63 (17)	O1—Mn1—O2	83.31 (5)
C6—C5—H5	119.7	O2ⁱ—Mn1—O2	166.96 (6)
C4—C5—H5	119.7	O1ⁱ—Mn1—N1ⁱ	82.07 (5)
C5—C6—C7	120.05 (17)	O1—Mn1—N1ⁱ	165.12 (5)
C5—C6—H6	120.0	O2ⁱ—Mn1—N1ⁱ	95.79 (5)
C7—C6—H6	120.0	O2—Mn1—N1ⁱ	91.45 (5)
C6—C7—C2	119.96 (15)	O1ⁱ—Mn1—N1	165.11 (5)
C6—C7—N1	120.58 (15)	O1—Mn1—N1	82.07 (5)
C2—C7—N1	119.31 (14)	O2ⁱ—Mn1—N1	91.45 (5)
C7—N1—Mn1	112.68 (10)	O2—Mn1—N1	95.79 (5)
C7—N1—H1D	111.3 (16)	N1ⁱ—Mn1—N1	112.40 (8)

O1—C1—C2—C3	−117.48 (17)	O4—N2—O2—Mn1	159.69 (11)
O1—C1—C2—C7	61.89 (19)	C1—O1—Mn1—O1ⁱ	−175.17 (15)
C7—C2—C3—C4	−1.1 (3)	C1—O1—Mn1—O2ⁱ	−91.58 (12)
C1—C2—C3—C4	178.31 (16)	C1—O1—Mn1—O2	97.15 (12)
C2—C3—C4—C5	0.4 (3)	C1—O1—Mn1—N1ⁱ	167.15 (17)
C3—C4—C5—C6	0.9 (3)	C1—O1—Mn1—N1	0.31 (12)
C4—C5—C6—C7	−1.4 (3)	N2—O2—Mn1—O1ⁱ	148.15 (12)
C5—C6—C7—C2	0.7 (2)	N2—O2—Mn1—O1	−127.80 (12)
C5—C6—C7—N1	−174.78 (16)	N2—O2—Mn1—O2ⁱ	−169.96 (11)
C3—C2—C7—C6	0.5 (2)	N2—O2—Mn1—N1ⁱ	66.17 (12)
C1—C2—C7—C6	−178.84 (15)	N2—O2—Mn1—N1	−46.52 (12)
C3—C2—C7—N1	176.07 (15)	C7—N1—Mn1—O1ⁱ	69.1 (2)
C1—C2—C7—N1	−3.3 (2)	C7—N1—Mn1—O1	51.34 (11)
C6—C7—N1—Mn1	117.00 (14)	C7—N1—Mn1—O2ⁱ	138.10 (11)
C2—C7—N1—Mn1	−58.50 (17)	C7—N1—Mn1—O2	−31.05 (12)
C2—C1—O1—Mn1	−49.35 (17)	C7—N1—Mn1—N1ⁱ	−125.03 (12)
O3—N2—O2—Mn1	−19.78 (18)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3ⁱⁱ	0.87 (2)	2.16 (2)	2.9775 (19)	156 (2)
N1—H1D···O4ⁱⁱⁱ	0.90 (3)	2.15 (3)	3.037 (2)	169 (2)
O1—H1E···O2^iv	0.82 (3)	1.88 (3)	2.6937 (17)	176 (3)
C1—H1B···O4ⁱⁱⁱ	0.97	2.60	3.479 (2)	151

Symmetry codes: (ii) x, −y, z−1/2; (iii) x, y, z−1; (iv) x, −y+1, z−1/2.

Experimental details

Crystal data
Chemical formula	[Mn(NO₃)₂(C₇H₉NO)₂]
M_r	425.26
Crystal system, space group	Orthorhombic, Pbcn
Temperature (K)	120
a, b, c (Å)	23.374 (2), 10.1929 (12), 7.3336 (6)
V (Å³)	1747.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.40 × 0.10 × 0.06

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.907, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	6668, 2335, 1928
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.071, 1.10
No. of reflections	2335
No. of parameters	135
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.32

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXTL (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Mn1—N1	2.2469 (15)	Mn1—O2	2.2203 (12)
Mn1—O1	2.2041 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3ⁱ	0.87 (2)	2.16 (2)	2.9775 (19)	156 (2)
N1—H1D···O4ⁱⁱ	0.90 (3)	2.15 (3)	3.037 (2)	169 (2)
O1—H1E···O2ⁱⁱⁱ	0.82 (3)	1.88 (3)	2.6937 (17)	176 (3)
C1—H1B···O4ⁱⁱ	0.97	2.60	3.479 (2)	151

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

Acknowledgements

We are grateful to the University of Urmiyeh for financial support.

References

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