cis-Di­chloro­bis(4,5-di­aza­fluoren-9-one-κ²N,N′)­manganese(II) ethanol solvate

In the title compound, [MnCl₂(C₁₁H₆N₂O)₂]·C₂H₅OH, the Mn atom is located on a twofold axis and chelated by two di­aza­fluorenone (dafone) ligands. Two cis Cl⁻ anions coordinate to the Mn atom to complete the octahedral coordination. The long Mn—N bond distances [2.323 (2) and 2.445 (2) Å] observed may be due to the large N...N separation within dafone.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• H-atom completeness 67%
• Disorder in solvent or counterion
• R factor = 0.030
• wR factor = 0.073
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT773_ALERT_2_A Suspect C-C Bond in CIF:      C13    -C13     ..       1.73 Ang.

Alert level C
CHEMW01_ALERT_1_C  The ratio of given/expected molecular weight as calculated
            from the _chemical_formula_sum lies outside
            the range 0.99 <> 1.01
            Calculated formula weight =   536.2752
            Formula weight given      =   530.2600
CHEMW01_ALERT_1_C  The difference between the given and expected weight for
            compound is greater 1 mass unit. Check that all hydrogen
            atoms have been taken into account.
DENSD01_ALERT_1_C  The ratio of the submitted crystal density and that
            calculated from the formula is outside the range 0.99 <> 1.01
            Crystal density given    =      1.517
            Calculated crystal density =      1.499
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT044_ALERT_1_C Calculated and Reported Dx Differ ..............          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT046_ALERT_1_C Reported Z, MW and D(calc) are Inconsistent ....       1.50
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT309_ALERT_2_C Single Bonded Oxygen (C-O .GT. 1.3 Ang) ........         O2
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.25 Ratio

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C24 H18 Cl2 Mn1 N4 O3
            Atom count from the _atom_site data:  C24 H12 Cl2 Mn1 N4 O3
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    4
           From the CIF: _chemical_formula_sum  C24 H18 Cl2 Mn N4 O3
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C         96.00     96.00    0.00
           H         72.00     48.00   24.00
           Cl         8.00      8.00    0.00
           Mn         4.00      4.00    0.00
           N         16.00     16.00    0.00
           O         12.00     12.00    0.00
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           27.40
           From the CIF: _reflns_number_total               2649
           Count of symmetry unique reflns         1523
           Completeness (_total/calc)            173.93%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1126
           Fraction of Friedel pairs measured     0.739
           Are heavy atom types Z>Si present          yes

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

  11 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 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
   3 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1992); cell refinement: MSC/AFCDiffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1985); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(I)

Crystal data

[MnCl2(C11H6N2O)2]·C2H6O	F(000) = 1092
Mr = 530.26	Dx = 1.517 Mg m^−3
Orthorhombic, C2221	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 20 reflections
a = 7.7376 (2) Å	θ = 3.5–8.8°
b = 13.5917 (4) Å	µ = 0.82 mm^−1
c = 22.3338 (8) Å	T = 295 K
V = 2348.78 (12) Å^3	Prism, yellow
Z = 4	0.46 × 0.42 × 0.36 mm

Data collection

Rigaku AFC-7S diffractometer	2161 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0
Graphite monochromator	θmax = 27.4°, θmin = 1.8°
ω/2θ scans	h = −9→10
Absorption correction: ψ scan (North et al., 1968)	k = −16→17
Tmin = 0.685, Tmax = 0.735	l = −28→28
2649 measured reflections	3 standard reflections every 150 reflections
2649 independent reflections	intensity decay: 0.6%

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)] = 0.030	H-atom parameters constrained
wR(F^2) = 0.073	w = 1/[σ^2(Fo^2) + (0.0364P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
2649 reflections	Δρmax = 0.33 e Å^−3
153 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Absolute structure: Flack (1983); 1136 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (3)

Special details

Experimental. The C, H and N content were analysed using a Carlo-Erba 1160 instrument.

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	Occ. (<1)
Mn	0.5000	0.48675 (3)	0.2500	0.04199 (14)
Cl	0.68120 (9)	0.59750 (5)	0.19244 (3)	0.05375 (18)
O1	0.3149 (4)	0.21295 (15)	0.02549 (10)	0.0725 (6)
N1	0.2810 (3)	0.44891 (13)	0.18264 (9)	0.0410 (5)
N2	0.6127 (3)	0.34629 (14)	0.19383 (11)	0.0485 (5)
C1	0.1216 (3)	0.48590 (17)	0.17037 (12)	0.0462 (6)
H1	0.0783	0.5357	0.1947	0.055*
C2	0.0221 (4)	0.45317 (18)	0.12383 (13)	0.0521 (6)
H2	−0.0859	0.4813	0.1174	0.062*
C3	0.0787 (3)	0.37943 (19)	0.08635 (14)	0.0531 (7)
H3	0.0123	0.3576	0.0543	0.064*
C4	0.2389 (3)	0.33951 (16)	0.09878 (12)	0.0439 (6)
C5	0.3486 (4)	0.26078 (17)	0.06989 (12)	0.0512 (7)
C6	0.5113 (4)	0.25695 (14)	0.10644 (11)	0.0458 (5)
C7	0.6611 (4)	0.20175 (16)	0.10341 (14)	0.0559 (7)
H7	0.6784	0.1553	0.0734	0.067*
C8	0.7837 (4)	0.21878 (19)	0.14695 (15)	0.0606 (8)
H8	0.8853	0.1823	0.1471	0.073*
C9	0.7566 (4)	0.2903 (2)	0.19080 (16)	0.0578 (7)
H9	0.8422	0.3000	0.2194	0.069*
C10	0.4972 (4)	0.32634 (13)	0.15193 (10)	0.0414 (5)
C11	0.3308 (3)	0.37752 (15)	0.14670 (11)	0.0401 (5)
O2	0.5091 (13)	0.5302 (5)	0.0649 (4)	0.130 (2)*	0.50
C12	0.6029 (11)	0.5033 (10)	0.0168 (4)	0.106 (3)*	0.50
C13	0.4936 (17)	0.4556 (6)	−0.0278 (5)	0.101 (2)*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0399 (3)	0.0476 (2)	0.0385 (3)	0.000	−0.0055 (3)	0.000
Cl	0.0469 (3)	0.0594 (3)	0.0549 (4)	0.0040 (3)	0.0060 (3)	0.0118 (3)
O1	0.0803 (15)	0.0801 (11)	0.0571 (13)	−0.0058 (12)	0.0033 (13)	−0.0277 (11)
N1	0.0413 (13)	0.0419 (8)	0.0399 (12)	0.0026 (8)	0.0013 (10)	−0.0034 (9)
N2	0.0428 (12)	0.0544 (10)	0.0482 (13)	0.0045 (9)	−0.0045 (11)	0.0044 (11)
C1	0.0413 (14)	0.0497 (11)	0.0476 (15)	0.0049 (10)	0.0048 (11)	−0.0044 (12)
C2	0.0317 (15)	0.0654 (12)	0.0591 (16)	0.0038 (11)	−0.0032 (14)	0.0024 (13)
C3	0.0425 (14)	0.0710 (14)	0.0458 (16)	−0.0075 (12)	−0.0067 (13)	−0.0041 (14)
C4	0.0445 (14)	0.0490 (11)	0.0382 (14)	−0.0041 (10)	0.0003 (11)	−0.0025 (11)
C5	0.0588 (18)	0.0530 (12)	0.0418 (15)	−0.0072 (12)	0.0028 (13)	−0.0059 (12)
C6	0.0493 (14)	0.0421 (9)	0.0461 (14)	0.0010 (13)	0.0073 (16)	0.0042 (10)
C7	0.0611 (18)	0.0454 (11)	0.0612 (19)	0.0122 (13)	0.0166 (17)	0.0047 (13)
C8	0.0498 (18)	0.0543 (12)	0.078 (2)	0.0157 (12)	0.0108 (16)	0.0114 (15)
C9	0.0425 (15)	0.0641 (13)	0.0669 (19)	0.0059 (11)	−0.0078 (15)	0.0129 (15)
C10	0.0411 (12)	0.0414 (8)	0.0416 (12)	−0.0002 (12)	0.0009 (16)	0.0019 (9)
C11	0.0389 (13)	0.0440 (10)	0.0375 (13)	−0.0021 (10)	0.0004 (12)	0.0006 (10)

Geometric parameters (Å, º)

Mn—N1	2.323 (2)	C4—C5	1.510 (4)
Mn—N1^i	2.323 (2)	C5—C6	1.502 (4)
Mn—Cl^i	2.4257 (7)	C6—C7	1.382 (4)
Mn—Cl	2.4257 (7)	C6—C10	1.391 (3)
Mn—N2	2.445 (2)	C7—C8	1.378 (4)
Mn—N2^i	2.445 (2)	C7—H7	0.93
O1—C5	1.214 (3)	C8—C9	1.396 (4)
N1—C11	1.317 (3)	C8—H8	0.93
N1—C1	1.360 (3)	C9—H9	0.93
N2—C10	1.322 (4)	C10—C11	1.469 (4)
N2—C9	1.350 (3)	O2—C13^ii	0.860 (10)
C1—C2	1.368 (4)	O2—C12	1.348 (11)
C1—H1	0.93	C12—C12^ii	0.754 (19)
C2—C3	1.377 (4)	C12—C13^ii	1.043 (13)
C2—H2	0.93	C12—C13	1.458 (13)
C3—C4	1.382 (3)	C13—O2^ii	0.860 (10)
C3—H3	0.93	C13—C12^ii	1.043 (13)
C4—C11	1.385 (3)	C13—C13^ii	1.731 (19)
N1—Mn—N1^i	154.42 (9)	C2—C3—H3	121.7
N1—Mn—Cl^i	93.38 (5)	C4—C3—H3	121.7
N1^i—Mn—Cl^i	102.46 (5)	C3—C4—C11	118.0 (2)
N1—Mn—Cl	102.46 (5)	C3—C4—C5	134.2 (3)
N1^i—Mn—Cl	93.38 (5)	C11—C4—C5	107.8 (2)
Cl^i—Mn—Cl	103.29 (3)	O1—C5—C6	127.2 (3)
N1—Mn—N2	75.82 (7)	O1—C5—C4	127.4 (3)
N1^i—Mn—N2	84.22 (7)	C6—C5—C4	105.3 (2)
Cl^i—Mn—N2	164.27 (5)	C7—C6—C10	118.0 (3)
Cl—Mn—N2	90.37 (5)	C7—C6—C5	134.1 (2)
N1—Mn—N2^i	84.22 (7)	C10—C6—C5	107.9 (2)
N1^i—Mn—N2^i	75.82 (7)	C8—C7—C6	116.8 (2)
Cl^i—Mn—N2^i	90.37 (5)	C8—C7—H7	121.6
Cl—Mn—N2^i	164.27 (5)	C6—C7—H7	121.6
N2—Mn—N2^i	77.34 (10)	C7—C8—C9	120.6 (3)
C11—N1—C1	114.5 (2)	C7—C8—H8	119.7
C11—N1—Mn	110.16 (16)	C9—C8—H8	119.7
C1—N1—Mn	135.25 (16)	N2—C9—C8	123.5 (3)
C10—N2—C9	114.0 (2)	N2—C9—H9	118.3
C10—N2—Mn	106.39 (16)	C8—C9—H9	118.3
C9—N2—Mn	139.4 (2)	N2—C10—C6	127.1 (3)
N1—C1—C2	122.9 (2)	N2—C10—C11	123.5 (2)
N1—C1—H1	118.5	C6—C10—C11	109.4 (2)
C2—C1—H1	118.5	N1—C11—C4	126.6 (2)
C1—C2—C3	121.3 (3)	N1—C11—C10	123.8 (2)
C1—C2—H2	119.3	C4—C11—C10	109.6 (2)
C3—C2—H2	119.3	O2—C12—C13	110.7 (8)
C2—C3—C4	116.7 (3)

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