2,2'-Bipyridinium fluoro­trioxochromate(VI)

A facile synthesis of 2,2'-bipyridinium fluoro­chromate(VI), (C₁₀H₉N₂)[CrO₃F], was developed by reacting CrO₃ with HF in the presence of 2,2'-bipyridine. The structure of the title compound consists of discrete cations and anions. The coordination around Cr is distorted tetra­hedral.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in main residue
• R factor = 0.033
• wR factor = 0.086
• Data-to-parameter ratio = 6.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT111_ALERT_2_B ADDSYM Detects (Pseudo) Centre of Symmetry .....         81 PerFi
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        Cr1

Alert level C
STRVA01_ALERT_4_C           Flack test results are ambiguous.
           From the CIF: _refine_ls_abs_structure_Flack    0.480
           From the CIF: _refine_ls_abs_structure_Flack_su    0.070
PLAT033_ALERT_2_C Flack Parameter Value Deviates from Zero .......       0.48
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.75 mm
PLAT089_ALERT_3_C Poor Data / Parameter Ratio (Zmax .LT. 18) .....       6.78
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _reflns_number_total               1118
           Count of symmetry unique reflns         1119
           Completeness (_total/calc)             99.91%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   2 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
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

2,2'-Bipyridinium fluorotrioxochromate(VI)

Crystal data

(C10H9N2)[CrFO3]	F(000) = 280
Mr = 276.19	Dx = 1.633 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 14782 reflections
a = 5.9765 (5) Å	θ = 2.8–28.0°
b = 13.1069 (10) Å	µ = 1.03 mm^−1
c = 7.2760 (6) Å	T = 293 K
β = 99.829 (7)°	Prism, orange
V = 561.59 (8) Å^3	0.75 × 0.62 × 0.53 mm
Z = 2

Data collection

Stoe IPDSII diffractometer	1118 independent reflections
Radiation source: fine-focus sealed tube	1109 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 3.1°
ω scans	h = −7→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −16→16
Tmin = 0.299, Tmax = 0.478	l = −8→8
6730 measured reflections

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)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.086	w = 1/[σ^2(Fo^2) + (0.0673P)^2 + 0.0279P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1118 reflections	Δρmax = 0.25 e Å^−3
165 parameters	Δρmin = −0.46 e Å^−3
2 restraints	Absolute structure: Flack (1983), with 10584 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.48 (7)

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	Occ. (<1)
C7	0.6086 (6)	0.4409 (3)	0.8399 (6)	0.0576 (8)
H7	0.4755	0.4114	0.8652	0.069*
C8	0.6338 (8)	0.5461 (3)	0.8357 (7)	0.0669 (9)
H8	0.5182	0.5887	0.8606	0.080*
C9	0.8310 (8)	0.5867 (3)	0.7944 (6)	0.0636 (10)
H9	0.8518	0.6570	0.7915	0.076*
C1	0.9531 (7)	0.1165 (3)	0.7336 (6)	0.0585 (9)
H1	1.0661	0.0856	0.6796	0.070*
C2	0.8047 (10)	0.0586 (3)	0.8096 (6)	0.0681 (11)
H2	0.8145	−0.0122	0.8084	0.082*
C3	0.6377 (8)	0.1068 (4)	0.8893 (7)	0.0676 (10)
H3	0.5345	0.0683	0.9423	0.081*
C4	0.6254 (8)	0.2124 (3)	0.8896 (6)	0.0590 (8)
H4	0.5135	0.2452	0.9422	0.071*
C5	0.7801 (5)	0.2685 (2)	0.8113 (4)	0.0459 (6)
C6	0.7880 (5)	0.3810 (2)	0.8051 (4)	0.0458 (6)
C10	0.9977 (7)	0.5208 (3)	0.7572 (6)	0.0601 (8)
H10	1.1295	0.5486	0.7262	0.072*
Cr1	0.33459 (11)	0.81211 (3)	0.84145 (14)	0.0524 (2)
F1	0.2722 (6)	0.7390 (2)	1.0097 (4)	0.0865 (7)
N1	0.9361 (5)	0.2185 (2)	0.7366 (4)	0.0486 (6)
H1A	1.0319	0.2536	0.6872	0.058*
N2	0.9805 (5)	0.4196 (2)	0.7632 (5)	0.0523 (6)
O1	0.2247 (8)	0.7542 (5)	0.6408 (5)	0.1069 (15)
O2	0.6080 (6)	0.8160 (2)	0.8528 (6)	0.0702 (8)
O3A	0.236 (2)	0.9228 (10)	0.844 (5)	0.128 (7)	0.62 (7)
O3B	0.272 (6)	0.9291 (12)	0.912 (6)	0.116 (10)	0.38 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C7	0.0487 (18)	0.0567 (18)	0.0676 (19)	0.0021 (14)	0.0104 (15)	−0.0058 (15)
C8	0.067 (2)	0.0556 (19)	0.076 (2)	0.0149 (17)	0.0038 (19)	−0.0097 (17)
C9	0.065 (2)	0.0464 (14)	0.074 (2)	−0.0021 (16)	−0.003 (2)	−0.0041 (13)
C1	0.067 (2)	0.0466 (17)	0.0620 (19)	0.0067 (15)	0.0123 (17)	−0.0011 (13)
C2	0.086 (3)	0.0471 (15)	0.069 (3)	−0.0045 (18)	0.006 (2)	0.0050 (15)
C3	0.066 (2)	0.063 (2)	0.074 (2)	−0.0143 (18)	0.0129 (19)	0.0154 (18)
C4	0.060 (2)	0.0633 (17)	0.0579 (19)	−0.0038 (18)	0.0210 (16)	0.0040 (16)
C5	0.0466 (17)	0.0502 (16)	0.0406 (13)	−0.0010 (11)	0.0066 (11)	−0.0018 (11)
C6	0.0429 (17)	0.0474 (15)	0.0467 (15)	−0.0008 (11)	0.0065 (11)	−0.0020 (10)
C10	0.0537 (19)	0.0540 (18)	0.071 (2)	−0.0079 (15)	0.0066 (15)	0.0005 (15)
Cr1	0.0505 (3)	0.0456 (3)	0.0636 (3)	0.0007 (2)	0.0166 (2)	0.0054 (2)
F1	0.097 (2)	0.0874 (17)	0.0798 (16)	−0.0073 (15)	0.0295 (14)	0.0094 (13)
N1	0.0516 (15)	0.0461 (13)	0.0487 (13)	−0.0013 (12)	0.0106 (11)	0.0014 (10)
N2	0.0468 (15)	0.0497 (14)	0.0609 (15)	−0.0021 (11)	0.0106 (12)	0.0001 (11)
O1	0.088 (3)	0.169 (4)	0.0619 (17)	−0.046 (3)	0.0070 (16)	−0.006 (2)
O2	0.0546 (17)	0.0720 (19)	0.087 (2)	−0.0053 (11)	0.0200 (15)	−0.0030 (13)
O3A	0.100 (6)	0.055 (5)	0.231 (19)	0.039 (5)	0.033 (11)	0.018 (7)
O3B	0.152 (18)	0.041 (5)	0.19 (2)	−0.008 (8)	0.131 (17)	0.007 (7)

Geometric parameters (Å, º)

C7—C6	1.387 (5)	C4—C5	1.379 (5)
C7—C8	1.389 (6)	C4—H4	0.9300
C7—H7	0.9300	C5—N1	1.329 (4)
C8—C9	1.372 (7)	C5—C6	1.477 (4)
C8—H8	0.9300	C6—N2	1.339 (4)
C9—C10	1.380 (6)	C10—N2	1.331 (5)
C9—H9	0.9300	C10—H10	0.9300
C1—N1	1.341 (5)	Cr1—F1	1.647 (3)
C1—C2	1.354 (7)	Cr1—O1	1.677 (4)
C1—H1	0.9300	Cr1—O2	1.623 (4)
C2—C3	1.389 (8)	Cr1—O3A	1.568 (11)
C2—H2	0.9300	Cr1—O3B	1.68 (2)
C3—C4	1.386 (6)	N1—H1A	0.8600
C3—H3	0.9300
C6—C7—C8	117.9 (4)	N1—C5—C6	116.8 (3)
C6—C7—H7	121.1	C4—C5—C6	124.9 (3)
C8—C7—H7	121.1	N2—C6—C7	123.3 (3)
C9—C8—C7	119.4 (4)	N2—C6—C5	114.7 (3)
C9—C8—H8	120.3	C7—C6—C5	122.0 (3)
C7—C8—H8	120.3	N2—C10—C9	123.7 (4)
C8—C9—C10	118.5 (4)	N2—C10—H10	118.2
C8—C9—H9	120.8	C9—C10—H10	118.2
C10—C9—H9	120.8	O3A—Cr1—O2	110.4 (6)
N1—C1—C2	119.7 (4)	O3A—Cr1—F1	113.4 (11)
N1—C1—H1	120.2	O2—Cr1—F1	109.5 (2)
C2—C1—H1	120.2	O3A—Cr1—O1	109.6 (13)
C1—C2—C3	118.9 (4)	O2—Cr1—O1	107.4 (2)
C1—C2—H2	120.5	F1—Cr1—O1	106.2 (2)
C3—C2—H2	120.5	O3A—Cr1—O3B	17.8 (15)
C4—C3—C2	119.8 (4)	O2—Cr1—O3B	103.4 (11)
C4—C3—H3	120.1	F1—Cr1—O3B	102.3 (8)
C2—C3—H3	120.1	O1—Cr1—O3B	127.1 (17)
C5—C4—C3	119.5 (4)	C5—N1—C1	123.9 (3)
C5—C4—H4	120.3	C5—N1—H1A	118.0
C3—C4—H4	120.3	C1—N1—H1A	118.0
N1—C5—C4	118.2 (3)	C10—N2—C6	117.3 (3)
C6—C7—C8—C9	1.2 (6)	C4—C5—C6—N2	165.1 (3)
C7—C8—C9—C10	0.4 (6)	N1—C5—C6—C7	165.5 (3)
N1—C1—C2—C3	0.0 (6)	C4—C5—C6—C7	−15.0 (5)
C1—C2—C3—C4	0.1 (6)	C8—C9—C10—N2	−1.6 (6)
C2—C3—C4—C5	−0.3 (6)	C4—C5—N1—C1	−0.4 (5)
C3—C4—C5—N1	0.5 (5)	C6—C5—N1—C1	179.1 (3)
C3—C4—C5—C6	−179.0 (3)	C2—C1—N1—C5	0.2 (6)
C8—C7—C6—N2	−1.8 (5)	C9—C10—N2—C6	1.1 (6)
C8—C7—C6—C5	178.3 (3)	C7—C6—N2—C10	0.7 (5)
N1—C5—C6—N2	−14.4 (4)	C5—C6—N2—C10	−179.5 (3)