Hemi{tris­(picolinic acid-κ²N,O)iron(II)/tris­(picolinato-κ²N,O)iron(II)} hemi(tetra­fluoro­borate)

The crystal structure of the title compound, [Fe(C₆H₄NO₂)(C₆H_4.5NO₂)(C₆H₅NO₂)](BF₄)_0.5, is regarded as consisting of disordered mononuclear [Fe^II(C₆H_4.5NO₂)₃]^0.5+ cations and tetra­fluoro­borate anions. The N,O-chelated Fe lies on a special position of site symmetry 3 and the acid H atom on a special position of site symmetry . The B atom is located on a special position of site symmetry . The disordered mononuclear units are linked through the acid H atom into a layer motif.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.008 Å
• Disorder in solvent or counterion
• R factor = 0.065
• wR factor = 0.154
• Data-to-parameter ratio = 11.6

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of expected to reported Tmax/Tmin(RR') is < 0.75
            Tmin and Tmax reported:      0.437     0.920
            Tmin(prime) and Tmax expected:      0.862     0.919
            RR(prime) =      0.506
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_B Tmax/Tmin Range Test RR' too Large .............       0.50

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
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.39
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      57.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...          8
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.31 Ratio

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C18 H13.5 B0.5 F2 Fe1 N3 O6
            Atom count from _chemical_formula_moiety:

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

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

---

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXL97.

Hemi{tris(picolinic acid-κ²N,O)iron(II)/tris(picolinato- κ²N,O)iron(II)} hemi(tetrafluoroborate)

Crystal data

[Fe(C6H4NO2)(C6H4.5NO2)(C6H5NO2)](BF4)0.5	Dx = 1.620 Mg m^−3
Mr = 467.07	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P3	Cell parameters from 724 reflections
Hall symbol: -P 3	θ = 3.0–23.4°
a = 13.564 (2) Å	µ = 0.85 mm^−1
c = 6.0108 (9) Å	T = 295 K
V = 957.7 (2) Å^3	Block, orange
Z = 2	0.17 × 0.15 × 0.10 mm
F(000) = 474

Data collection

Bruker APEX area-detector diffractometer	1128 independent reflections
Radiation source: fine-focus sealed tube	1055 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
φ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→16
Tmin = 0.437, Tmax = 0.920	k = −16→7
4988 measured reflections	l = −7→6

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.154	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.0655P)^2 + 1.2441P] where P = (Fo^2 + 2Fc^2)/3
1128 reflections	(Δ/σ)max = 0.001
97 parameters	Δρmax = 0.74 e Å^−3
6 restraints	Δρmin = −0.31 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.6667	0.3333	0.08941 (16)	0.0306 (4)
F1	0.0971 (8)	0.0162 (7)	0.3730 (18)	0.168 (4)	0.67
O1	0.6008 (2)	0.1833 (2)	0.2873 (5)	0.0378 (7)
O2	0.4535 (3)	0.0092 (2)	0.3321 (5)	0.0484 (9)
N1	0.5135 (3)	0.2122 (3)	−0.0838 (5)	0.0306 (8)
C1	0.5068 (4)	0.1033 (3)	0.2321 (7)	0.033 (1)
C2	0.4500 (4)	0.1171 (3)	0.0300 (7)	0.036 (1)
C3	0.3413 (4)	0.0387 (4)	−0.0314 (8)	0.053 (1)
C4	0.2961 (5)	0.0588 (5)	−0.221 (1)	0.061 (2)
C5	0.3621 (5)	0.1533 (4)	−0.3428 (8)	0.053 (1)
C6	0.4707 (4)	0.2298 (4)	−0.2692 (7)	0.042 (1)
B1	0.0000	0.0000	0.5000	0.20 (1)
H2o	0.4891	0.0105	0.4433	0.058*	0.50
H3	0.2986	−0.0267	0.0526	0.063*
H4	0.2217	0.0081	−0.2640	0.074*
H5	0.3347	0.1667	−0.4745	0.064*
H6	0.5153	0.2954	−0.3516	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0288 (4)	0.0288 (4)	0.0340 (6)	0.0144 (2)	0.000	0.000
F1	0.136 (7)	0.083 (5)	0.279 (12)	0.051 (6)	−0.010 (7)	−0.009 (7)
O1	0.038 (2)	0.035 (2)	0.038 (2)	0.016 (1)	−0.006 (1)	0.005 (1)
O2	0.051 (2)	0.031 (2)	0.050 (2)	0.010 (2)	−0.010 (2)	0.012 (1)
N1	0.036 (2)	0.030 (2)	0.029 (2)	0.019 (2)	−0.002 (1)	0.002 (1)
C1	0.036 (2)	0.028 (2)	0.034 (2)	0.015 (2)	−0.002 (2)	0.002 (2)
C2	0.040 (2)	0.030 (2)	0.036 (2)	0.016 (2)	−0.007 (2)	−0.003 (2)
C3	0.045 (3)	0.037 (3)	0.064 (3)	0.011 (2)	−0.015 (2)	0.002 (2)
C4	0.048 (3)	0.052 (3)	0.073 (4)	0.016 (3)	−0.025 (3)	−0.011 (3)
C5	0.067 (3)	0.059 (3)	0.045 (3)	0.040 (3)	−0.023 (2)	−0.010 (2)
C6	0.057 (3)	0.042 (3)	0.035 (2)	0.031 (2)	−0.003 (2)	0.003 (2)
B1	0.20 (1)	0.20 (1)	0.20 (2)	0.099 (5)	0.000	0.000

Geometric parameters (Å, º)

Fe1—O1	2.130 (3)	C2—C3	1.368 (6)
Fe1—O1^i	2.130 (3)	C3—C4	1.383 (7)
Fe1—O1^ii	2.130 (3)	C4—C5	1.354 (8)
Fe1—N1	2.165 (3)	C5—C6	1.384 (7)
Fe1—N1^i	2.165 (3)	B1—F1^iii	1.441 (9)
Fe1—N1^ii	2.165 (3)	B1—F1^iv	1.441 (9)
F1—B1	1.441 (9)	B1—F1^v	1.441 (9)
O1—C1	1.236 (5)	B1—F1^vi	1.441 (9)
O2—C1	1.261 (5)	B1—F1^vii	1.441 (9)
O2—H2o	0.8200	C3—H3	0.9300
N1—C2	1.327 (5)	C4—H4	0.9300
N1—C6	1.331 (5)	C5—H5	0.9300
C1—C2	1.500 (6)	C6—H6	0.9300
O1—Fe1—O1^i	91.9 (1)	C4—C5—C6	119.2 (4)
O1—Fe1—O1^ii	91.9 (1)	N1—C6—C5	122.0 (4)
O1—Fe1—N1	76.0 (1)	F1^iii—B1—F1^iv	94.5 (6)
O1^ii—Fe1—N1	94.3 (1)	F1^iii—B1—F1^v	180.0 (7)
O1—Fe1—N1^ii	166.5 (1)	F1^iv—B1—F1^v	85.5 (6)
O1^i—Fe1—O1^ii	91.9 (1)	F1^iii—B1—F1	85.5 (6)
O1^i—Fe1—N1^i	76.0 (1)	F1^iv—B1—F1	85.5 (6)
O1—Fe1—N1^i	94.3 (1)	F1^v—B1—F1	94.5 (6)
O1^ii—Fe1—N1^i	166.5 (1)	F1^iii—B1—F1^vi	85.5 (6)
O1^i—Fe1—N1	166.5 (1)	F1^iv—B1—F1^vi	180.000 (1)
O1^i—Fe1—N1^ii	94.3 (1)	F1^v—B1—F1^vi	94.5 (6)
O1^ii—Fe1—N1^ii	76.0 (1)	F1—B1—F1^vi	94.5 (6)
N1—Fe1—N1^i	98.8 (1)	F1^iii—B1—F1^vii	94.5 (6)
N1—Fe1—N1^ii	98.8 (1)	F1^iv—B1—F1^vii	94.5 (6)
N1^i—Fe1—N1^ii	98.8 (1)	F1^v—B1—F1^vii	85.5 (6)
C1—O1—Fe1	116.4 (2)	F1—B1—F1^vii	180.0 (4)
C2—N1—C6	118.4 (4)	F1^vi—B1—F1^vii	85.5 (6)
C2—N1—Fe1	113.6 (2)	C1—O2—H2o	109.5
C6—N1—Fe1	127.2 (3)	C2—C3—H3	120.6
O1—C1—O2	125.4 (4)	C4—C3—H3	120.6
O1—C1—C2	118.4 (4)	C5—C4—H4	120.5
O2—C1—C2	116.2 (4)	C3—C4—H4	120.5
N1—C2—C3	122.6 (4)	C4—C5—H5	120.4
N1—C2—C1	114.5 (3)	C6—C5—H5	120.4
C3—C2—C1	122.9 (4)	N1—C6—H6	119.0
C2—C3—C4	118.7 (5)	C5—C6—H6	119.0
C5—C4—C3	118.9 (5)
O1^i—Fe1—O1—C1	−180.0 (3)	Fe1—O1—C1—C2	1.9 (5)
O1^ii—Fe1—O1—C1	88.1 (4)	C6—N1—C2—C3	−2.4 (6)
N1^i—Fe1—O1—C1	−103.9 (3)	Fe1—N1—C2—C3	168.4 (4)
N1—Fe1—O1—C1	−5.9 (3)	C6—N1—C2—C1	178.2 (4)
N1^ii—Fe1—O1—C1	62.9 (6)	Fe1—N1—C2—C1	−11.1 (4)
O1^i—Fe1—N1—C2	35.2 (7)	O1—C1—C2—N1	6.4 (6)
O1—Fe1—N1—C2	9.2 (3)	O2—C1—C2—N1	−173.4 (4)
O1^ii—Fe1—N1—C2	−81.6 (3)	O1—C1—C2—C3	−173.0 (4)
N1^i—Fe1—N1—C2	101.5 (3)	O2—C1—C2—C3	7.2 (6)
N1^ii—Fe1—N1—C2	−158.1 (3)	N1—C2—C3—C4	0.7 (7)
O1^i—Fe1—N1—C6	−155.0 (5)	C1—C2—C3—C4	−179.9 (5)
O1—Fe1—N1—C6	179.0 (4)	C2—C3—C4—C5	2.0 (8)
O1^ii—Fe1—N1—C6	88.2 (4)	C3—C4—C5—C6	−2.9 (8)
N1^i—Fe1—N1—C6	−88.8 (3)	C2—N1—C6—C5	1.4 (6)
N1^ii—Fe1—N1—C6	11.7 (4)	Fe1—N1—C6—C5	−168.0 (3)
Fe1—O1—C1—O2	−178.3 (3)	C4—C5—C6—N1	1.3 (7)

Symmetry codes: (i) −y+1, x−y, z; (ii) −x+y+1, −x+1, z; (iii) x−y, x, −z+1; (iv) y, −x+y, −z+1; (v) −x+y, −x, z; (vi) −y, x−y, z; (vii) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2o···O2^viii	0.82	1.65	2.459 (6)	171

Symmetry code: (viii) −x+1, −y, −z+1.