Ammonium 4,4-difluoro-1,3,2-dithia-zetin-2-ide 1,1,3,3-tetra-oxide.

The asymmetric unit of the title compound, NH(4) (+)·CF(2)NO(4)S(2) (-), consists of two crystallographically independent ammonium cations and two 4,4-difluoro-1,3,2-dithia-zetin-2-ide 1,1,3,3-tetra-oxide anions all located in general positions. The S-C-S-N rings of both crystallographically independent anions are almost planar, with the N atom bent out of the plane by 9.82 (5) and 12.82 (4)°. The structure was determined from a crystal twinned by inversion, with refined components in the ratio 0.73 (4):0.27 (4). Anions and cations are connected via hydrogen bonds (N-H⋯O and N-H⋯N) to form a three-dimensional framework. This framework is composed of two different layers parallel to the ab plane, which are built by the ammonium cations on the one hand and the complex cyclic anions on the other.

Related literature

For general aspects of the chemistry of fluorinated sulfonimides and their salts, see: Antoniotti et al. (2010 ▶); Foropoulos & DesMarteau (1984 ▶); Popov et al. (2011 ▶); Vij et al. (1997 ▶); DesMarteau (1995 ▶). For the synthesis and chemistry of the title compound, see: Jüschke et al. (1997 ▶). For related structures, see: DesMarteau et al. (1992 ▶); Davidson et al. (2003 ▶). For similar layered ammonium salts, see: Reiss (2002 ▶); Plizko & Meyer (1998 ▶); Bucholz & Mattes (1988 ▶).

Experimental

Crystal data

NH4 +·CF2NO4S2 −

M = 210.18

Orthorhombic,

a = 11.28642 (13) Å

b = 10.98496 (14) Å

c = 10.58826 (12) Å

V = 1312.74 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.82 mm−1

T = 100 K

0.30 × 0.25 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T min = 0.922, T max = 1.000

25817 measured reflections

3823 independent reflections

3778 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.049

S = 1.00

3823 reflections

227 parameters

9 restraints

All H-atom parameters refined

Δρmax = 0.42 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack (1983 ▶), 1816 Friedel pairs

Flack parameter: 0.27 (4)

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2011 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812024221/pk2414sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812024221/pk2414Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

NH4+·CF2NO4S2−	F(000) = 848
Mr = 210.18	Dx = 2.127 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 21999 reflections
a = 11.28642 (13) Å	θ = 3.2–33.6°
b = 10.98496 (14) Å	µ = 0.82 mm−1
c = 10.58826 (12) Å	T = 100 K
V = 1312.74 (3) Å3	Block, colourless
Z = 8	0.30 × 0.25 × 0.20 mm

Oxford Diffraction Xcalibur Eos diffractometer	3823 independent reflections
Radiation source: fine-focus sealed tube	3778 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 16.2711 pixels mm-1	θmax = 30.0°, θmin = 3.2°
ω scans	h = −15→15
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −15→15
Tmin = 0.922, Tmax = 1.000	l = −14→14
25817 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.019	All H-atom parameters refined
wR(F2) = 0.049	w = 1/[σ2(Fo2) + (0.027P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
3823 reflections	Δρmax = 0.42 e Å−3
227 parameters	Δρmin = −0.23 e Å−3
9 restraints	Absolute structure: Flack (1983), 1816 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.27 (4)

Experimental. Absorption correction: CrysAlisPro, Oxford Diffraction Ltd., Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
S1	0.48379 (3)	0.87892 (3)	0.65469 (3)	0.00949 (7)
S2	0.35058 (3)	0.70690 (3)	0.59946 (3)	0.00899 (7)
O1	0.51045 (10)	0.92154 (11)	0.77958 (11)	0.0153 (2)
O2	0.53141 (10)	0.94654 (10)	0.55027 (12)	0.0180 (2)
O3	0.28692 (10)	0.63106 (11)	0.68639 (12)	0.0188 (2)
O4	0.32923 (10)	0.68643 (11)	0.46733 (11)	0.0141 (2)
C1	0.51223 (12)	0.71376 (13)	0.63358 (13)	0.0101 (3)
F1	0.58461 (8)	0.68458 (9)	0.53906 (9)	0.01534 (18)
F2	0.54517 (8)	0.65524 (9)	0.73788 (9)	0.01670 (18)
N1	0.34538 (11)	0.84878 (11)	0.63851 (13)	0.0126 (2)
S3	0.48620 (3)	0.31465 (3)	0.55319 (3)	0.00837 (6)
S4	0.67564 (3)	0.29184 (3)	0.67001 (3)	0.00808 (6)
O6	0.40654 (9)	0.22416 (10)	0.50504 (11)	0.0135 (2)
O5	0.45653 (9)	0.43993 (9)	0.52553 (10)	0.0129 (2)
O7	0.73598 (9)	0.40480 (10)	0.69468 (10)	0.0126 (2)
O8	0.73416 (9)	0.18093 (10)	0.70717 (11)	0.0128 (2)
F3	0.47997 (8)	0.20036 (8)	0.77901 (9)	0.01355 (17)
F4	0.49019 (8)	0.39790 (9)	0.79297 (9)	0.01288 (17)
N2	0.62391 (11)	0.28395 (11)	0.52747 (12)	0.0104 (2)
C2	0.51915 (12)	0.30127 (13)	0.72413 (14)	0.0095 (2)
N1A	0.72362 (11)	0.99695 (12)	0.91184 (12)	0.0122 (2)
H1	0.6585 (14)	0.9597 (19)	0.895 (3)	0.030 (3)*
H2	0.7758 (17)	0.9398 (16)	0.916 (2)	0.030 (3)*
H3	0.715 (2)	1.034 (2)	0.9834 (15)	0.030 (3)*
H4	0.739 (2)	1.0475 (18)	0.8532 (18)	0.030 (3)*
N2A	0.22203 (11)	0.44588 (12)	0.41410 (12)	0.0132 (2)
H5	0.2919 (14)	0.449 (2)	0.448 (2)	0.041 (4)*
H6	0.201 (2)	0.3720 (13)	0.426 (3)	0.041 (4)*
H7	0.173 (2)	0.496 (2)	0.449 (2)	0.041 (4)*
H8	0.230 (2)	0.461 (2)	0.3348 (12)	0.041 (4)*

	U11	U22	U33	U12	U13	U23
S1	0.00951 (13)	0.00917 (14)	0.00979 (15)	−0.00032 (10)	−0.00095 (11)	−0.00005 (12)
S2	0.00864 (13)	0.00925 (14)	0.00907 (14)	−0.00050 (11)	0.00066 (11)	0.00012 (12)
O1	0.0149 (5)	0.0167 (5)	0.0143 (5)	0.0003 (4)	−0.0040 (4)	−0.0052 (4)
O2	0.0186 (5)	0.0171 (5)	0.0183 (5)	−0.0020 (4)	0.0028 (4)	0.0068 (5)
O3	0.0179 (5)	0.0187 (5)	0.0199 (6)	−0.0036 (4)	0.0056 (4)	0.0072 (4)
O4	0.0128 (5)	0.0177 (5)	0.0117 (5)	0.0013 (4)	−0.0028 (4)	−0.0041 (4)
C1	0.0096 (6)	0.0106 (6)	0.0101 (6)	0.0015 (4)	−0.0002 (4)	−0.0011 (5)
F1	0.0108 (4)	0.0203 (4)	0.0149 (4)	0.0023 (3)	0.0030 (3)	−0.0056 (3)
F2	0.0204 (4)	0.0158 (4)	0.0139 (4)	0.0033 (4)	−0.0070 (4)	0.0036 (3)
N1	0.0098 (5)	0.0098 (5)	0.0183 (6)	0.0008 (4)	−0.0019 (4)	−0.0037 (5)
S3	0.00810 (13)	0.00965 (14)	0.00735 (14)	0.00008 (11)	−0.00006 (11)	−0.00046 (11)
S4	0.00836 (13)	0.00801 (14)	0.00787 (14)	0.00020 (10)	−0.00012 (11)	0.00033 (11)
O6	0.0124 (5)	0.0157 (5)	0.0123 (5)	−0.0035 (4)	−0.0003 (4)	−0.0038 (4)
O5	0.0141 (5)	0.0111 (5)	0.0133 (5)	0.0026 (4)	−0.0019 (4)	0.0013 (4)
O7	0.0142 (4)	0.0115 (5)	0.0122 (5)	−0.0040 (4)	0.0006 (4)	−0.0013 (4)
O8	0.0129 (4)	0.0121 (5)	0.0133 (5)	0.0035 (4)	0.0008 (4)	0.0036 (4)
F3	0.0140 (4)	0.0138 (4)	0.0128 (4)	−0.0027 (3)	0.0018 (3)	0.0048 (3)
F4	0.0151 (4)	0.0135 (4)	0.0100 (4)	0.0037 (3)	0.0004 (3)	−0.0041 (3)
N2	0.0083 (5)	0.0149 (6)	0.0079 (5)	0.0011 (4)	0.0001 (4)	−0.0009 (4)
C2	0.0103 (6)	0.0091 (6)	0.0091 (6)	−0.0001 (4)	0.0004 (5)	0.0002 (5)
N1A	0.0136 (6)	0.0116 (5)	0.0114 (6)	−0.0006 (4)	0.0000 (4)	0.0007 (4)
N2A	0.0113 (5)	0.0150 (6)	0.0133 (6)	−0.0003 (4)	−0.0009 (5)	0.0037 (5)

S1—O1	1.4347 (12)	S4—O7	1.4394 (11)
S1—O2	1.4363 (12)	S4—O8	1.4406 (11)
S1—N1	1.6060 (12)	S4—N2	1.6206 (12)
S1—C1	1.8559 (14)	S4—C2	1.8596 (15)
S2—O3	1.4344 (12)	F3—C2	1.3274 (16)
S2—O4	1.4373 (12)	F4—C2	1.3285 (16)
S2—N1	1.6135 (13)	N1A—H1	0.860 (11)
S2—C1	1.8614 (14)	N1A—H2	0.862 (11)
C1—F2	1.3308 (16)	N1A—H3	0.865 (11)
C1—F1	1.3311 (16)	N1A—H4	0.852 (12)
S3—O6	1.4340 (11)	N2A—H5	0.866 (12)
S3—O5	1.4463 (11)	N2A—H6	0.855 (12)
S3—N2	1.6135 (12)	N2A—H7	0.862 (12)
S3—C2	1.8535 (15)	N2A—H8	0.860 (12)
O1—S1—O2	117.53 (7)	O7—S4—O8	117.55 (7)
O1—S1—N1	111.69 (7)	O7—S4—N2	112.68 (7)
O2—S1—N1	112.86 (7)	O8—S4—N2	111.98 (7)
O1—S1—C1	113.18 (7)	O7—S4—C2	110.21 (6)
O2—S1—C1	110.37 (7)	O8—S4—C2	113.48 (6)
N1—S1—C1	87.36 (6)	N2—S4—C2	87.01 (6)
O3—S2—O4	116.73 (7)	S3—N2—S4	100.29 (7)
O3—S2—N1	112.23 (7)	F3—C2—F4	110.19 (12)
O4—S2—N1	113.23 (7)	F3—C2—S3	115.27 (10)
O3—S2—C1	112.95 (7)	F4—C2—S3	115.03 (10)
O4—S2—C1	111.07 (6)	F3—C2—S4	113.88 (10)
N1—S2—C1	86.95 (6)	F4—C2—S4	116.57 (10)
F2—C1—F1	109.64 (11)	S3—C2—S4	83.92 (6)
F2—C1—S1	114.87 (10)	H1—N1A—H2	104 (2)
F1—C1—S1	115.60 (10)	H1—N1A—H3	108 (2)
F2—C1—S2	114.54 (10)	H2—N1A—H3	112 (2)
F1—C1—S2	116.48 (10)	H1—N1A—H4	110 (2)
S1—C1—S2	83.88 (6)	H2—N1A—H4	112 (2)
S1—N1—S2	101.01 (7)	H3—N1A—H4	111 (2)
O6—S3—O5	116.26 (7)	H5—N2A—H6	103 (3)
O6—S3—N2	113.52 (7)	H5—N2A—H7	113 (3)
O5—S3—N2	112.81 (6)	H6—N2A—H7	112 (3)
O6—S3—C2	114.71 (7)	H5—N2A—H8	108 (2)
O5—S3—C2	108.64 (6)	H6—N2A—H8	111 (3)
N2—S3—C2	87.42 (7)	H7—N2A—H8	111 (2)
N1—S1—C1—S2	6.25 (6)	C2—S3—N2—S4	−9.52 (7)
N1—S2—C1—S1	−6.22 (6)	C2—S4—N2—S3	9.49 (7)
C1—S1—N1—S2	−7.31 (7)	N2—S3—C2—S4	8.20 (6)
C1—S2—N1—S1	7.29 (7)	N2—S4—C2—S3	−8.17 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1···O1	0.86 (1)	2.11 (2)	2.9044 (17)	153 (2)
N1A—H3···N1i	0.87 (1)	2.20 (1)	3.0395 (19)	165 (2)
N1A—H4···O8ii	0.85 (1)	2.13 (1)	2.9657 (17)	166 (2)
N2A—H5···O5	0.87 (1)	2.04 (1)	2.8985 (16)	175 (3)
N2A—H6···N2iii	0.86 (1)	2.20 (2)	3.0068 (18)	157 (3)
N2A—H7···O2iv	0.86 (1)	2.03 (2)	2.8467 (17)	158 (3)
N2A—H8···O7v	0.86 (1)	2.13 (2)	2.8832 (17)	146 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1⋯O1	0.86 (1)	2.11 (2)	2.9044 (17)	153 (2)
N1A—H3⋯N1i	0.87 (1)	2.20 (1)	3.0395 (19)	165 (2)
N1A—H4⋯O8ii	0.85 (1)	2.13 (1)	2.9657 (17)	166 (2)
N2A—H5⋯O5	0.87 (1)	2.04 (1)	2.8985 (16)	175 (3)
N2A—H6⋯N2iii	0.86 (1)	2.20 (2)	3.0068 (18)	157 (3)
N2A—H7⋯O2iv	0.86 (1)	2.03 (2)	2.8467 (17)	158 (3)
N2A—H8⋯O7v	0.86 (1)	2.13 (2)	2.8832 (17)	146 (2)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .