1-Chloro-methyl-1,4-diazo-niabicyclo-[2.2.2]octane bis-(hexa-fluoro-phosphate).

In the crystal structure of the title compound, C(7)H(15)ClN(2) (2+)·2PF(6) (-), the cations and anions are linked by inter-molecular N-H⋯F hydrogen bonds.

Related literature

For general background to ferroelectric metal-organic frameworks, see: Fu et al. (2009 ▶); Ye et al. (2006 ▶); Zhang et al. (2008 ▶, 2010 ▶).

Experimental

Crystal data

C7H15ClN2 2+·2PF6 −

M = 452.6

Orthorhombic,

a = 14.414 (8) Å

b = 12.976 (7) Å

c = 16.115 (9) Å

V = 3014 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.60 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.836, T max = 0.888

30798 measured reflections

3447 independent reflections

3197 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.146

S = 1.24

3447 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.46 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811000390/fj2377sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000390/fj2377Isup2.hkl

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

C7H15ClN22+·2PF6−	F(000) = 1808
Mr = 452.6	Dx = 1.995 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6697 reflections
a = 14.414 (8) Å	θ = 2.5–27.5°
b = 12.976 (7) Å	µ = 0.60 mm−1
c = 16.115 (9) Å	T = 293 K
V = 3014 (3) Å3	Prism, colorless
Z = 8	0.30 × 0.25 × 0.20 mm

Rigaku SCXmini diffractometer	3447 independent reflections
Radiation source: fine-focus sealed tube	3197 reflections with I > 2σ(I)
graphite	Rint = 0.050
CCD Profile fitting scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −18→18
Tmin = 0.836, Tmax = 0.888	k = −16→16
30798 measured reflections	l = −20→20

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.056	H-atom parameters constrained
wR(F2) = 0.146	w = 1/[σ2(Fo2) + (0.0625P)2 + 3.8206P] where P = (Fo2 + 2Fc2)/3
S = 1.24	(Δ/σ)max < 0.001
3447 reflections	Δρmax = 0.58 e Å−3
217 parameters	Δρmin = −0.46 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (1)

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
P1	0.10243 (5)	0.80778 (6)	0.38500 (5)	0.01982 (19)
P2	0.25717 (5)	0.96221 (6)	0.14312 (5)	0.01997 (19)
F8	0.19471 (13)	0.87588 (16)	0.38218 (13)	0.0359 (5)
F9	0.06202 (13)	0.87478 (14)	0.30870 (11)	0.0293 (4)
F11	0.05718 (12)	0.88833 (14)	0.44911 (11)	0.0268 (4)
F10	0.00885 (13)	0.74127 (15)	0.38738 (13)	0.0331 (4)
F7	0.14303 (13)	0.74224 (16)	0.46061 (11)	0.0343 (5)
F12	0.14650 (13)	0.72793 (15)	0.32030 (12)	0.0322 (4)
F3	0.15177 (12)	1.00058 (16)	0.15861 (13)	0.0347 (5)
F1	0.23000 (15)	0.92628 (16)	0.05253 (11)	0.0363 (5)
F4	0.28151 (16)	0.99851 (17)	0.23639 (13)	0.0430 (6)
F2	0.36096 (14)	0.92349 (19)	0.13078 (16)	0.0479 (6)
F5	0.22953 (16)	0.85130 (15)	0.17743 (14)	0.0421 (5)
F6	0.28287 (17)	1.07397 (16)	0.11115 (15)	0.0465 (6)
Cl1	0.09951 (6)	0.45726 (7)	0.44115 (7)	0.0419 (3)
N1	0.05494 (16)	0.26975 (18)	0.37949 (15)	0.0189 (5)
N2	0.11243 (16)	0.10322 (19)	0.31629 (15)	0.0206 (5)
H2C	0.1332	0.0434	0.2933	0.025*
C5	−0.02655 (19)	0.2006 (2)	0.35656 (18)	0.0207 (6)
H5A	−0.0654	0.1896	0.4049	0.025*
H5B	−0.0638	0.2336	0.3141	0.025*
C1	0.1107 (2)	0.2924 (2)	0.30230 (19)	0.0224 (6)
H1A	0.1657	0.3316	0.3168	0.027*
H1B	0.0740	0.3333	0.2641	0.027*
C3	0.1568 (2)	0.1167 (2)	0.39967 (18)	0.0278 (7)
H3A	0.2234	0.1239	0.3935	0.033*
H3B	0.1446	0.0569	0.4341	0.033*
C7	0.0138 (2)	0.3663 (2)	0.4162 (2)	0.0266 (6)
H7A	−0.0207	0.3486	0.4660	0.032*
H7B	−0.0293	0.3964	0.3769	0.032*
C2	0.1390 (2)	0.1914 (2)	0.2609 (2)	0.0280 (7)
H2A	0.1080	0.1847	0.2077	0.034*
H2B	0.2054	0.1908	0.2513	0.034*
C4	0.1162 (2)	0.2138 (2)	0.44068 (18)	0.0232 (6)
H4A	0.0804	0.1946	0.4892	0.028*
H4B	0.1662	0.2588	0.4584	0.028*
C6	0.0090 (2)	0.0978 (3)	0.3247 (3)	0.0364 (8)
H6A	−0.0078	0.0434	0.3631	0.044*
H6B	−0.0188	0.0825	0.2713	0.044*

	U11	U22	U33	U12	U13	U23
P1	0.0173 (4)	0.0238 (4)	0.0184 (4)	0.0025 (3)	0.0000 (3)	0.0006 (3)
P2	0.0181 (4)	0.0220 (4)	0.0198 (4)	−0.0001 (3)	0.0000 (3)	−0.0018 (3)
F8	0.0217 (9)	0.0451 (12)	0.0410 (11)	−0.0067 (8)	0.0054 (8)	−0.0014 (9)
F9	0.0340 (10)	0.0322 (10)	0.0218 (9)	0.0108 (8)	−0.0020 (7)	0.0035 (7)
F11	0.0282 (9)	0.0286 (9)	0.0235 (9)	0.0024 (7)	0.0050 (7)	−0.0028 (7)
F10	0.0264 (9)	0.0311 (10)	0.0419 (11)	−0.0074 (8)	0.0020 (8)	−0.0041 (9)
F7	0.0372 (10)	0.0422 (11)	0.0235 (9)	0.0133 (9)	−0.0027 (8)	0.0073 (8)
F12	0.0367 (10)	0.0335 (10)	0.0265 (10)	0.0142 (8)	0.0038 (8)	−0.0031 (8)
F3	0.0199 (9)	0.0403 (11)	0.0440 (11)	0.0016 (8)	0.0030 (8)	−0.0162 (9)
F1	0.0466 (12)	0.0429 (11)	0.0195 (9)	0.0112 (10)	−0.0053 (8)	−0.0082 (8)
F4	0.0560 (14)	0.0420 (12)	0.0310 (11)	0.0127 (10)	−0.0191 (10)	−0.0121 (9)
F2	0.0208 (10)	0.0539 (14)	0.0690 (16)	0.0064 (9)	−0.0004 (10)	−0.0187 (12)
F5	0.0614 (14)	0.0256 (10)	0.0392 (11)	−0.0020 (10)	0.0077 (10)	0.0035 (9)
F6	0.0572 (14)	0.0280 (10)	0.0544 (14)	−0.0099 (10)	0.0148 (11)	0.0055 (10)
Cl1	0.0285 (4)	0.0331 (4)	0.0641 (6)	−0.0071 (3)	0.0121 (4)	−0.0250 (4)
N1	0.0164 (11)	0.0205 (11)	0.0199 (11)	−0.0001 (9)	0.0005 (9)	−0.0011 (9)
N2	0.0191 (12)	0.0200 (11)	0.0227 (12)	0.0001 (9)	0.0003 (9)	−0.0010 (10)
C5	0.0159 (13)	0.0237 (14)	0.0225 (14)	−0.0027 (10)	−0.0020 (10)	−0.0003 (11)
C1	0.0218 (14)	0.0202 (13)	0.0252 (14)	−0.0011 (11)	0.0051 (11)	0.0007 (11)
C3	0.0348 (17)	0.0266 (15)	0.0220 (14)	0.0078 (13)	−0.0052 (12)	0.0007 (12)
C7	0.0204 (14)	0.0213 (14)	0.0382 (17)	0.0025 (11)	0.0046 (12)	−0.0076 (13)
C2	0.0377 (17)	0.0239 (15)	0.0223 (15)	0.0035 (13)	0.0074 (13)	0.0043 (12)
C4	0.0200 (13)	0.0294 (15)	0.0201 (13)	0.0005 (12)	−0.0014 (11)	−0.0014 (11)
C6	0.0190 (15)	0.0282 (16)	0.062 (2)	−0.0040 (13)	−0.0030 (15)	−0.0145 (16)

P1—F7	1.597 (2)	N2—C2	1.501 (4)
P1—F8	1.598 (2)	N2—H2C	0.9100
P1—F12	1.601 (2)	C5—C6	1.518 (4)
P1—F10	1.602 (2)	C5—H5A	0.9700
P1—F11	1.6079 (19)	C5—H5B	0.9700
P1—F9	1.6147 (19)	C1—C2	1.527 (4)
P2—F1	1.582 (2)	C1—H1A	0.9700
P2—F6	1.583 (2)	C1—H1B	0.9700
P2—F2	1.591 (2)	C3—C4	1.538 (4)
P2—F5	1.592 (2)	C3—H3A	0.9700
P2—F4	1.614 (2)	C3—H3B	0.9700
P2—F3	1.618 (2)	C7—H7A	0.9700
Cl1—C7	1.756 (3)	C7—H7B	0.9700
N1—C7	1.507 (4)	C2—H2A	0.9700
N1—C4	1.510 (4)	C2—H2B	0.9700
N1—C1	1.510 (4)	C4—H4A	0.9700
N1—C5	1.524 (3)	C4—H4B	0.9700
N2—C6	1.498 (4)	C6—H6A	0.9700
N2—C3	1.498 (4)	C6—H6B	0.9700
F7—P1—F8	90.65 (12)	C6—C5—N1	109.8 (2)
F7—P1—F12	90.40 (11)	C6—C5—H5A	109.7
F8—P1—F12	90.53 (12)	N1—C5—H5A	109.7
F7—P1—F10	90.19 (12)	C6—C5—H5B	109.7
F8—P1—F10	178.98 (12)	N1—C5—H5B	109.7
F12—P1—F10	90.06 (11)	H5A—C5—H5B	108.2
F7—P1—F11	90.26 (11)	N1—C1—C2	109.6 (2)
F8—P1—F11	89.79 (11)	N1—C1—H1A	109.8
F12—P1—F11	179.26 (11)	C2—C1—H1A	109.8
F10—P1—F11	89.62 (11)	N1—C1—H1B	109.8
F7—P1—F9	179.52 (13)	C2—C1—H1B	109.8
F8—P1—F9	88.90 (11)	H1A—C1—H1B	108.2
F12—P1—F9	89.75 (11)	N2—C3—C4	108.6 (2)
F10—P1—F9	90.26 (11)	N2—C3—H3A	110.0
F11—P1—F9	89.59 (10)	C4—C3—H3A	110.0
F1—P2—F6	91.58 (13)	N2—C3—H3B	110.0
F1—P2—F2	91.39 (12)	C4—C3—H3B	110.0
F6—P2—F2	91.64 (14)	H3A—C3—H3B	108.3
F1—P2—F5	89.54 (12)	N1—C7—Cl1	111.8 (2)
F6—P2—F5	178.30 (13)	N1—C7—H7A	109.3
F2—P2—F5	89.61 (13)	Cl1—C7—H7A	109.3
F1—P2—F4	178.20 (13)	N1—C7—H7B	109.3
F6—P2—F4	89.13 (13)	Cl1—C7—H7B	109.3
F2—P2—F4	90.24 (13)	H7A—C7—H7B	107.9
F5—P2—F4	89.71 (13)	N2—C2—C1	109.1 (2)
F1—P2—F3	90.03 (11)	N2—C2—H2A	109.9
F6—P2—F3	89.32 (13)	C1—C2—H2A	109.9
F2—P2—F3	178.26 (14)	N2—C2—H2B	109.9
F5—P2—F3	89.40 (12)	C1—C2—H2B	109.9
F4—P2—F3	88.32 (11)	H2A—C2—H2B	108.3
C7—N1—C4	111.9 (2)	N1—C4—C3	109.6 (2)
C7—N1—C1	111.8 (2)	N1—C4—H4A	109.8
C4—N1—C1	108.7 (2)	C3—C4—H4A	109.8
C7—N1—C5	106.3 (2)	N1—C4—H4B	109.8
C4—N1—C5	109.0 (2)	C3—C4—H4B	109.8
C1—N1—C5	109.0 (2)	H4A—C4—H4B	108.2
C6—N2—C3	110.4 (3)	N2—C6—C5	109.0 (2)
C6—N2—C2	110.1 (3)	N2—C6—H6A	109.9
C3—N2—C2	109.6 (2)	C5—C6—H6A	109.9
C6—N2—H2C	108.9	N2—C6—H6B	109.9
C3—N2—H2C	108.9	C5—C6—H6B	109.9
C2—N2—H2C	108.9	H6A—C6—H6B	108.3

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···F3i	0.91	2.26	2.924 (3)	130
N2—H2C···F4i	0.91	2.40	3.073 (3)	131
N2—H2C···F9i	0.91	2.43	3.055 (3)	126

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯F3i	0.91	2.26	2.924 (3)	130
N2—H2C⋯F4i	0.91	2.40	3.073 (3)	131
N2—H2C⋯F9i	0.91	2.43	3.055 (3)	126

Symmetry code: (i) .