Bis{2-[(2-oxidoeth­yl)imino­meth­yl]phenolato-κ³O,N,O′}manganese(IV) hemihydrate

The crystal structure of the title complex, [Mn(C₉H₉NO₂)₂]·0.5H₂O, contains two Mn^IV units related by a twofold rotation axis and linked by inter­molecular hydrogen bonds to a water mol­ecule lying on this twofold axis.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.030
• wR factor = 0.090
• Data-to-parameter ratio = 16.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O1
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O2
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          2
            O3  -MN1 -O1  -C1    -45.10  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            O4  -MN1 -O2  -C10     3.60  0.60   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         12
            O1  -MN1 -O3  -C9     48.10  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         18
            O2  -MN1 -O4  -C18    27.80  0.60   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         25
            N2  -MN1 -N1  -C7   -109.00  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         30
            N2  -MN1 -N1  -C8     65.40  0.50   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         35
            N1  -MN1 -N2  -C16  -151.60  0.40   1.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         40
            N1  -MN1 -N2  -C17    30.80  0.50   1.555   1.555   1.555   1.555

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

   3 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
   0 ALERT type 3 Indicator that the structure quality may be low
   9 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: APEXII (Bruker, 2004); cell refinement: APEXII; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1995); software used to prepare material for publication: SHELXTL.

Bis{2-[(2-oxidoethyl)iminomethyl]phenolato-κ³O,N,O'}manganese(IV) hemihydrate

Crystal data

[Mn(C9H9NO2)2]·0.5H2O	Dx = 1.511 Mg m^−3
Mr = 390.29	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 7973 reflections
a = 27.6765 (16) Å	θ = 2.7–28.2°
b = 10.6137 (6) Å	µ = 0.80 mm^−1
c = 11.6820 (7) Å	T = 291 K
V = 3431.6 (3) Å^3	Block, yellow
Z = 8	0.39 × 0.28 × 0.21 mm
F(000) = 1616

Data collection

Bruker SMART APEXII CCD diffractometer	3929 independent reflections
Radiation source: fine-focus sealed tube	3255 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 27.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −35→35
Tmin = 0.745, Tmax = 0.850	k = −13→10
19518 measured reflections	l = −15→15

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0512P)^2 + 0.8471P] where P = (Fo^2 + 2Fc^2)/3
3929 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.25 e Å^−3
1 restraint	Δρmin = −0.43 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
Mn1	0.389820 (8)	0.243586 (19)	0.05803 (2)	0.03659 (9)
O1	0.33645 (5)	0.25834 (11)	−0.04270 (12)	0.0556 (3)
O2	0.36968 (5)	0.39703 (10)	0.13019 (11)	0.0547 (3)
O3	0.43686 (4)	0.22539 (11)	0.17066 (11)	0.0512 (3)
O4	0.41377 (5)	0.10557 (10)	−0.02148 (11)	0.0528 (3)
O5	0.5000	0.40762 (16)	0.2500	0.0492 (4)
N1	0.35156 (5)	0.13215 (12)	0.15893 (11)	0.0445 (3)
N2	0.43331 (4)	0.33915 (12)	−0.04313 (11)	0.0375 (3)
C1	0.29807 (5)	0.18642 (16)	−0.05277 (14)	0.0424 (3)
C2	0.26748 (6)	0.20344 (18)	−0.14771 (15)	0.0510 (4)
H2	0.2753	0.2635	−0.2026	0.061*
C3	0.22622 (6)	0.13267 (19)	−0.16069 (16)	0.0555 (4)
H3	0.2064	0.1459	−0.2239	0.067*
C4	0.21380 (7)	0.0416 (2)	−0.08049 (17)	0.0679 (6)
H4	0.1861	−0.0067	−0.0904	0.081*
C5	0.24250 (7)	0.0237 (2)	0.01281 (17)	0.0649 (5)
H5	0.2339	−0.0369	0.0665	0.078*
C6	0.28486 (6)	0.09487 (16)	0.02991 (14)	0.0462 (4)
C7	0.31193 (6)	0.07614 (15)	0.13311 (14)	0.0481 (4)
H7	0.2998	0.0186	0.1858	0.058*
C8	0.37685 (8)	0.10942 (18)	0.26816 (15)	0.0586 (5)
H8A	0.3687	0.0271	0.2987	0.070*
H8B	0.3684	0.1732	0.3242	0.070*
C9	0.42993 (7)	0.11663 (16)	0.23790 (16)	0.0564 (5)
H9A	0.4493	0.1215	0.3070	0.068*
H9B	0.4395	0.0422	0.1955	0.068*
C10	0.38168 (5)	0.51374 (14)	0.10880 (13)	0.0401 (3)
C11	0.36176 (7)	0.61057 (16)	0.17575 (16)	0.0559 (4)
H11	0.3421	0.5899	0.2376	0.067*
C12	0.37065 (8)	0.73504 (16)	0.15193 (18)	0.0586 (5)
H12	0.3564	0.7968	0.1971	0.070*
C13	0.40055 (8)	0.77109 (17)	0.06178 (17)	0.0575 (5)
H13	0.4058	0.8557	0.0453	0.069*
C14	0.42201 (7)	0.67829 (15)	−0.00189 (15)	0.0501 (4)
H14	0.4428	0.7010	−0.0610	0.060*
C15	0.41357 (5)	0.54915 (14)	0.01943 (13)	0.0377 (3)
C16	0.43807 (5)	0.45894 (15)	−0.05036 (12)	0.0394 (3)
H16	0.4592	0.4897	−0.1056	0.047*
C17	0.46109 (7)	0.25490 (16)	−0.11987 (16)	0.0501 (4)
H17A	0.4938	0.2859	−0.1303	0.060*
H17B	0.4456	0.2483	−0.1941	0.060*
C18	0.46126 (7)	0.12953 (17)	−0.05965 (18)	0.0569 (5)
H18A	0.4717	0.0637	−0.1117	0.068*
H18B	0.4833	0.1316	0.0049	0.068*
H1W	0.4777 (6)	0.3585 (17)	0.2193 (17)	0.075 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.03734 (15)	0.02975 (14)	0.04268 (15)	−0.00303 (8)	−0.00346 (9)	0.00415 (8)
O1	0.0405 (6)	0.0588 (8)	0.0676 (8)	−0.0149 (5)	−0.0123 (6)	0.0315 (6)
O2	0.0653 (8)	0.0333 (6)	0.0654 (8)	0.0018 (5)	0.0296 (6)	0.0074 (5)
O3	0.0571 (7)	0.0432 (6)	0.0533 (7)	−0.0049 (5)	−0.0197 (6)	0.0008 (5)
O4	0.0616 (8)	0.0361 (6)	0.0606 (7)	−0.0059 (5)	−0.0041 (6)	−0.0119 (5)
O5	0.0463 (9)	0.0439 (9)	0.0576 (10)	0.000	0.0011 (8)	0.000
N1	0.0553 (8)	0.0350 (7)	0.0430 (7)	−0.0051 (6)	−0.0035 (6)	0.0088 (5)
N2	0.0339 (6)	0.0379 (7)	0.0407 (7)	−0.0013 (5)	0.0006 (5)	−0.0026 (5)
C1	0.0337 (7)	0.0436 (9)	0.0498 (9)	−0.0013 (6)	0.0023 (6)	0.0062 (7)
C2	0.0401 (8)	0.0579 (10)	0.0549 (10)	−0.0017 (8)	−0.0021 (7)	0.0100 (8)
C3	0.0421 (9)	0.0705 (12)	0.0539 (10)	−0.0036 (8)	−0.0031 (8)	−0.0080 (9)
C4	0.0562 (11)	0.0854 (15)	0.0621 (11)	−0.0327 (10)	0.0024 (9)	−0.0089 (11)
C5	0.0699 (12)	0.0702 (13)	0.0547 (11)	−0.0355 (10)	0.0056 (9)	0.0029 (9)
C6	0.0468 (9)	0.0459 (9)	0.0460 (8)	−0.0120 (7)	0.0057 (7)	0.0014 (7)
C7	0.0608 (10)	0.0391 (8)	0.0444 (9)	−0.0129 (7)	0.0067 (7)	0.0076 (7)
C8	0.0826 (13)	0.0497 (10)	0.0436 (9)	−0.0058 (9)	−0.0127 (9)	0.0128 (8)
C9	0.0733 (12)	0.0410 (9)	0.0547 (10)	0.0044 (8)	−0.0230 (9)	0.0016 (7)
C10	0.0444 (8)	0.0342 (7)	0.0417 (8)	0.0011 (6)	0.0047 (6)	0.0048 (6)
C11	0.0680 (12)	0.0441 (9)	0.0556 (10)	0.0061 (8)	0.0193 (9)	−0.0001 (8)
C12	0.0745 (13)	0.0396 (9)	0.0618 (12)	0.0068 (8)	0.0059 (10)	−0.0084 (8)
C13	0.0756 (13)	0.0332 (8)	0.0636 (12)	−0.0041 (8)	−0.0002 (9)	0.0015 (7)
C14	0.0605 (10)	0.0386 (9)	0.0512 (10)	−0.0093 (7)	0.0069 (8)	0.0063 (7)
C15	0.0399 (8)	0.0336 (7)	0.0397 (8)	−0.0029 (6)	−0.0002 (6)	0.0034 (6)
C16	0.0374 (7)	0.0420 (8)	0.0388 (8)	−0.0061 (6)	0.0031 (6)	0.0039 (6)
C17	0.0456 (9)	0.0541 (10)	0.0507 (10)	0.0017 (7)	0.0062 (7)	−0.0134 (7)
C18	0.0568 (11)	0.0441 (9)	0.0699 (12)	0.0082 (8)	0.0004 (9)	−0.0171 (8)

Geometric parameters (Å, º)

Mn1—O4	1.8569 (12)	C6—C7	1.433 (2)
Mn1—O3	1.8611 (12)	C7—H7	0.9300
Mn1—O1	1.8950 (13)	C8—C9	1.513 (3)
Mn1—O2	1.9166 (11)	C8—H8A	0.9700
Mn1—N2	1.9682 (12)	C8—H8B	0.9700
Mn1—N1	1.9771 (13)	C9—H9A	0.9700
O1—C1	1.3132 (19)	C9—H9B	0.9700
O2—C10	1.3067 (18)	C10—C11	1.404 (2)
O3—C9	1.409 (2)	C10—C15	1.418 (2)
O4—C18	1.411 (2)	C11—C12	1.372 (2)
O5—H1W	0.884 (9)	C11—H11	0.9300
N1—C7	1.284 (2)	C12—C13	1.393 (3)
N1—C8	1.475 (2)	C12—H12	0.9300
N2—C16	1.281 (2)	C13—C14	1.370 (3)
N2—C17	1.481 (2)	C13—H13	0.9300
C1—C2	1.407 (2)	C14—C15	1.413 (2)
C1—C6	1.418 (2)	C14—H14	0.9300
C2—C3	1.375 (2)	C15—C16	1.429 (2)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.389 (3)	C17—C18	1.505 (3)
C3—H3	0.9300	C17—H17A	0.9700
C4—C5	1.362 (3)	C17—H17B	0.9700
C4—H4	0.9300	C18—H18A	0.9700
C5—C6	1.409 (2)	C18—H18B	0.9700
C5—H5	0.9300
O4—Mn1—O3	91.26 (6)	N1—C8—C9	104.49 (14)
O4—Mn1—O1	91.88 (6)	N1—C8—H8A	110.9
O3—Mn1—O1	173.16 (6)	C9—C8—H8A	110.9
O4—Mn1—O2	173.79 (5)	N1—C8—H8B	110.9
O3—Mn1—O2	88.89 (6)	C9—C8—H8B	110.9
O1—Mn1—O2	88.64 (6)	H8A—C8—H8B	108.9
O4—Mn1—N2	83.56 (5)	O3—C9—C8	107.69 (14)
O3—Mn1—N2	92.88 (5)	O3—C9—H9A	110.2
O1—Mn1—N2	93.51 (5)	C8—C9—H9A	110.2
O2—Mn1—N2	90.23 (5)	O3—C9—H9B	110.2
O4—Mn1—N1	91.00 (6)	C8—C9—H9B	110.2
O3—Mn1—N1	83.75 (6)	H9A—C9—H9B	108.5
O1—Mn1—N1	90.12 (5)	O2—C10—C11	119.18 (14)
O2—Mn1—N1	95.18 (5)	O2—C10—C15	123.39 (14)
N2—Mn1—N1	173.55 (6)	C11—C10—C15	117.43 (14)
C1—O1—Mn1	129.65 (10)	C12—C11—C10	121.42 (17)
C10—O2—Mn1	130.36 (10)	C12—C11—H11	119.3
C9—O3—Mn1	112.57 (10)	C10—C11—H11	119.3
C18—O4—Mn1	110.39 (10)	C11—C12—C13	121.61 (17)
C7—N1—C8	122.20 (14)	C11—C12—H12	119.2
C7—N1—Mn1	126.49 (11)	C13—C12—H12	119.2
C8—N1—Mn1	111.07 (11)	C14—C13—C12	118.07 (16)
C16—N2—C17	120.39 (13)	C14—C13—H13	121.0
C16—N2—Mn1	127.88 (11)	C12—C13—H13	121.0
C17—N2—Mn1	111.69 (10)	C13—C14—C15	122.04 (17)
O1—C1—C2	118.86 (14)	C13—C14—H14	119.0
O1—C1—C6	123.08 (15)	C15—C14—H14	119.0
C2—C1—C6	118.02 (15)	C14—C15—C10	119.34 (14)
C3—C2—C1	121.10 (17)	C14—C15—C16	118.11 (14)
C3—C2—H2	119.5	C10—C15—C16	122.56 (13)
C1—C2—H2	119.5	N2—C16—C15	125.35 (14)
C2—C3—C4	120.73 (17)	N2—C16—H16	117.3
C2—C3—H3	119.6	C15—C16—H16	117.3
C4—C3—H3	119.6	N2—C17—C18	104.62 (14)
C5—C4—C3	119.51 (17)	N2—C17—H17A	110.8
C5—C4—H4	120.2	C18—C17—H17A	110.8
C3—C4—H4	120.2	N2—C17—H17B	110.8
C4—C5—C6	121.61 (18)	C18—C17—H17B	110.8
C4—C5—H5	119.2	H17A—C17—H17B	108.9
C6—C5—H5	119.2	O4—C18—C17	107.71 (15)
C5—C6—C1	119.03 (17)	O4—C18—H18A	110.2
C5—C6—C7	118.68 (15)	C17—C18—H18A	110.2
C1—C6—C7	122.23 (14)	O4—C18—H18B	110.2
N1—C7—C6	125.45 (14)	C17—C18—H18B	110.2
N1—C7—H7	117.3	H18A—C18—H18B	108.5
C6—C7—H7	117.3
O4—Mn1—O1—C1	72.17 (16)	Mn1—O1—C1—C6	13.7 (3)
O3—Mn1—O1—C1	−45.1 (5)	O1—C1—C2—C3	−178.37 (17)
O2—Mn1—O1—C1	−114.02 (16)	C6—C1—C2—C3	−0.6 (3)
N2—Mn1—O1—C1	155.84 (16)	C1—C2—C3—C4	−0.4 (3)
N1—Mn1—O1—C1	−18.83 (16)	C2—C3—C4—C5	1.0 (3)
O4—Mn1—O2—C10	3.6 (6)	C3—C4—C5—C6	−0.4 (3)
O3—Mn1—O2—C10	95.14 (16)	C4—C5—C6—C1	−0.6 (3)
O1—Mn1—O2—C10	−91.25 (16)	C4—C5—C6—C7	176.5 (2)
N2—Mn1—O2—C10	2.26 (16)	O1—C1—C6—C5	178.78 (18)
N1—Mn1—O2—C10	178.75 (15)	C2—C1—C6—C5	1.1 (3)
O4—Mn1—O3—C9	−69.24 (12)	O1—C1—C6—C7	1.7 (3)
O1—Mn1—O3—C9	48.1 (5)	C2—C1—C6—C7	−175.93 (16)
O2—Mn1—O3—C9	116.97 (12)	C8—N1—C7—C6	178.82 (17)
N2—Mn1—O3—C9	−152.86 (12)	Mn1—N1—C7—C6	−7.4 (3)
N1—Mn1—O3—C9	21.63 (12)	C5—C6—C7—N1	178.46 (19)
O3—Mn1—O4—C18	−63.57 (12)	C1—C6—C7—N1	−4.5 (3)
O1—Mn1—O4—C18	122.51 (12)	C7—N1—C8—C9	144.26 (17)
O2—Mn1—O4—C18	27.8 (6)	Mn1—N1—C8—C9	−30.37 (16)
N2—Mn1—O4—C18	29.18 (12)	Mn1—O3—C9—C8	−44.69 (17)
N1—Mn1—O4—C18	−147.34 (12)	N1—C8—C9—O3	47.14 (18)
O4—Mn1—N1—C7	−76.46 (15)	Mn1—O2—C10—C11	−179.55 (14)
O3—Mn1—N1—C7	−167.62 (16)	Mn1—O2—C10—C15	1.5 (3)
O1—Mn1—N1—C7	15.43 (16)	O2—C10—C11—C12	−175.57 (19)
O2—Mn1—N1—C7	104.07 (15)	C15—C10—C11—C12	3.5 (3)
N2—Mn1—N1—C7	−109.0 (5)	C10—C11—C12—C13	−1.3 (3)
O4—Mn1—N1—C8	97.89 (12)	C11—C12—C13—C14	−1.4 (3)
O3—Mn1—N1—C8	6.73 (12)	C12—C13—C14—C15	1.8 (3)
O1—Mn1—N1—C8	−170.23 (12)	C13—C14—C15—C10	0.5 (3)
O2—Mn1—N1—C8	−81.59 (12)	C13—C14—C15—C16	−179.13 (17)
N2—Mn1—N1—C8	65.4 (5)	O2—C10—C15—C14	175.96 (16)
O4—Mn1—N2—C16	175.64 (14)	C11—C10—C15—C14	−3.0 (2)
O3—Mn1—N2—C16	−93.41 (14)	O2—C10—C15—C16	−4.5 (2)
O1—Mn1—N2—C16	84.14 (14)	C11—C10—C15—C16	176.55 (16)
O2—Mn1—N2—C16	−4.51 (14)	C17—N2—C16—C15	−179.45 (15)
N1—Mn1—N2—C16	−151.6 (4)	Mn1—N2—C16—C15	3.1 (2)
O4—Mn1—N2—C17	−1.96 (11)	C14—C15—C16—N2	−178.34 (16)
O3—Mn1—N2—C17	88.98 (11)	C10—C15—C16—N2	2.1 (2)
O1—Mn1—N2—C17	−93.47 (11)	C16—N2—C17—C18	159.20 (15)
O2—Mn1—N2—C17	177.89 (11)	Mn1—N2—C17—C18	−22.99 (16)
N1—Mn1—N2—C17	30.8 (5)	Mn1—O4—C18—C17	−50.27 (16)
Mn1—O1—C1—C2	−168.65 (13)	N2—C17—C18—O4	45.79 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H1W···O3	0.88 (1)	1.90 (1)	2.7666 (16)	168 (2)