Reinvestigation of hydrazinium tetra­fluoro­borate

The single-crystal X-ray study of hydrazinium tetra­fluoro­borate, N₂H₅⁺·BF₄⁻, confirms the previous structure determinations in the space group C2/c [Conant, Corrigan & Sparks (1964). Acta Cryst. 17, 1085; Conant & Roof (1970). Acta Cryst. B26, 1928–1932]. The present study includes the determination of the H-atom parameters, which reveal an extensively hydrogen-bonded structure, as expected. Several inter­ionic hydrogen bonds are found, involving short N...F distances [2.929 (3)–2.989 (3) Å] and a short N...N distance [2.916 (3) Å].

Key indicators

• Single-crystal X-ray study
• T = 200 K
• Mean [sigma](F-B) = 0.003 Å
• R factor = 0.050
• wR factor = 0.121
• Data-to-parameter ratio = 11.3

checkCIF/PLATON results

No syntax errors found



Alert level B
CHEMS01_ALERT_1_B  The sum formula contains elements in the wrong order.
            H  precedes B
            Sequence must be C, H, then alphabetical.
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for          B

Alert level C
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2     ..  F1      ..       2.56 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H4     ..  F4      ..       2.63 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          1
              H5 N2

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   6 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
   1 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
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); 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: SHELXL97.

hydrazinium tetrafluoroborate

Crystal data

N2H5^+·BF4^−	F(000) = 480
Mr = 119.87	Dx = 1.914 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.8644 (5) Å	Cell parameters from 2082 reflections
b = 5.3233 (2) Å	θ = 3.1–27.5°
c = 12.2334 (4) Å	µ = 0.25 mm^−1
β = 112.8848 (16)°	T = 200 K
V = 831.81 (5) Å^3	Square prism, colourless
Z = 8	0.24 × 0.08 × 0.04 mm

Data collection

Nonius KappaCCD area-detector diffractometer	752 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 27.5°, θmin = 3.2°
Detector resolution: 9 pixels mm^-1	h = −18→17
φ and ω scans	k = −6→6
1779 measured reflections	l = −15→15
953 independent reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	All H-atom parameters refined
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0411P)^2 + 1.8993P] where P = (Fo^2 + 2Fc^2)/3
953 reflections	(Δ/σ)max < 0.001
84 parameters	Δρmax = 0.45 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Special details

Experimental. The following faces (with distances from a common point in mm) were indexed: 1 0 0, 0.03; 1 0 0, 0.02; 0 1 0, 0.04; 0 1 0, 0.04; 0 0 1, 0.12; 0 0 1, 0.10.

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
B	0.10960 (18)	0.0706 (4)	0.9215 (2)	0.0257 (5)
F1	0.06696 (13)	0.3029 (3)	0.92718 (15)	0.0548 (5)
F2	0.19255 (14)	0.0268 (4)	1.02518 (16)	0.0796 (8)
F3	0.14208 (13)	0.0761 (3)	0.82854 (14)	0.0495 (5)
F4	0.03750 (13)	−0.1189 (3)	0.90527 (14)	0.0551 (5)
N1	0.15635 (14)	−0.5875 (3)	1.22935 (16)	0.0273 (4)
H1	0.100 (2)	−0.685 (6)	1.190 (3)	0.049 (8)*
H2	0.138 (2)	−0.511 (5)	1.285 (3)	0.042 (7)*
N2	0.15703 (15)	−0.3931 (4)	1.14727 (16)	0.0286 (4)
H3	0.213 (2)	−0.284 (6)	1.185 (3)	0.051 (8)*
H4	0.097 (2)	−0.311 (6)	1.119 (2)	0.042 (7)*
H5	0.174 (3)	−0.470 (7)	1.085 (3)	0.068 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
B	0.0234 (10)	0.0263 (11)	0.0257 (11)	−0.0028 (9)	0.0075 (8)	−0.0004 (9)
F1	0.0585 (10)	0.0439 (9)	0.0718 (11)	0.0126 (7)	0.0361 (9)	−0.0070 (8)
F2	0.0589 (11)	0.0756 (13)	0.0601 (11)	−0.0258 (10)	−0.0249 (9)	0.0393 (10)
F3	0.0706 (10)	0.0393 (8)	0.0605 (10)	−0.0057 (7)	0.0494 (9)	−0.0074 (7)
F4	0.0551 (10)	0.0628 (11)	0.0464 (9)	−0.0366 (8)	0.0185 (7)	−0.0093 (8)
N1	0.0278 (9)	0.0242 (9)	0.0278 (9)	−0.0032 (7)	0.0086 (7)	0.0006 (7)
N2	0.0267 (9)	0.0289 (9)	0.0263 (9)	−0.0001 (8)	0.0060 (7)	0.0031 (7)

Geometric parameters (Å, º)

B—F2	1.361 (3)	N1—H1	0.91 (3)
B—F3	1.377 (3)	N1—H2	0.91 (3)
B—F4	1.379 (3)	N2—H3	0.93 (3)
B—F1	1.384 (3)	N2—H4	0.89 (3)
N1—N2	1.445 (2)	N2—H5	0.97 (4)
F2—B—F3	110.1 (2)	H1—N1—H2	103 (2)
F2—B—F4	108.12 (19)	N1—N2—H3	109.4 (19)
F3—B—F4	110.38 (19)	N1—N2—H4	111.3 (18)
F2—B—F1	109.2 (2)	H3—N2—H4	111 (3)
F3—B—F1	107.84 (18)	N1—N2—H5	108 (2)
F4—B—F1	111.16 (19)	H3—N2—H5	104 (3)
N2—N1—H1	106.0 (19)	H4—N2—H5	112 (3)
N2—N1—H2	106.3 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F4^i	0.91 (3)	2.08 (3)	2.989 (2)	175 (3)
N1—H2···F3^ii	0.91 (3)	2.37 (3)	3.019 (2)	128 (2)
N1—H2···F1^ii	0.91 (3)	2.56 (3)	3.467 (3)	174 (2)
N2—H3···N1^iii	0.93 (3)	2.00 (3)	2.929 (3)	173 (3)
N2—H4···F1^iv	0.89 (3)	2.12 (3)	2.916 (3)	150 (3)
N2—H4···F4	0.89 (3)	2.63 (3)	3.135 (2)	118 (2)
N2—H5···F1^v	0.97 (4)	2.27 (4)	2.969 (3)	128 (3)

Symmetry codes: (i) −x, −y−1, −z+2; (ii) x, −y, z+1/2; (iii) −x+1/2, y+1/2, −z+5/2; (iv) −x, −y, −z+2; (v) x, y−1, z.