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

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.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.038
• wR factor = 0.071
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    --  N1      ..       7.36 su
PLAT430_ALERT_2_C Short Inter D...A Contact  O3     ..  O3      ..       2.89 Ang.
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         10
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          3
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          6

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

(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

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

S2. Experimental

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%).

S3. Refinement

The N- and O-bound H atoms were located in a difference map and freely refined. All C-bound H atoms were positioned geometrically, with C—H = 0.93Å and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Computing details

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

	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)

Crystal data

[Mn(NO3)2(C7H9NO)2]	F(000) = 876
Mr = 425.26	Dx = 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) Å^3	Block, colorless
Z = 4	0.40 × 0.10 × 0.06 mm

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	w = 1/[σ^2(Fo^2) + (0.017P)^2 + 1.3224P] where P = (Fo^2 + 2Fc^2)/3
2335 reflections	(Δ/σ)max = 0.007
135 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

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 > 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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—O1^i	2.2041 (13)
C5—H5	0.9300	Mn1—O2^i	2.2202 (12)
C6—C7	1.398 (2)	Mn1—N1^i	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	O1^i—Mn1—O1	83.74 (7)
C5—C4—C3	119.26 (17)	O1^i—Mn1—O2^i	83.31 (5)
C5—C4—H4	120.4	O1—Mn1—O2^i	86.99 (5)
C3—C4—H4	120.4	O1^i—Mn1—O2	86.99 (5)
C6—C5—C4	120.63 (17)	O1—Mn1—O2	83.31 (5)
C6—C5—H5	119.7	O2^i—Mn1—O2	166.96 (6)
C4—C5—H5	119.7	O1^i—Mn1—N1^i	82.07 (5)
C5—C6—C7	120.05 (17)	O1—Mn1—N1^i	165.12 (5)
C5—C6—H6	120.0	O2^i—Mn1—N1^i	95.79 (5)
C7—C6—H6	120.0	O2—Mn1—N1^i	91.45 (5)
C6—C7—C2	119.96 (15)	O1^i—Mn1—N1	165.11 (5)
C6—C7—N1	120.58 (15)	O1—Mn1—N1	82.07 (5)
C2—C7—N1	119.31 (14)	O2^i—Mn1—N1	91.45 (5)
C7—N1—Mn1	112.68 (10)	O2—Mn1—N1	95.79 (5)
C7—N1—H1D	111.3 (16)	N1^i—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—O1^i	−175.17 (15)
C7—C2—C3—C4	−1.1 (3)	C1—O1—Mn1—O2^i	−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—N1^i	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—O1^i	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—O2^i	−169.96 (11)
C3—C2—C7—C6	0.5 (2)	N2—O2—Mn1—N1^i	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—O1^i	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—O2^i	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—N1^i	−125.03 (12)
O3—N2—O2—Mn1	−19.78 (18)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O3^ii	0.87 (2)	2.16 (2)	2.9775 (19)	156 (2)
N1—H1D···O4^iii	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···O4^iii	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.