(1-Aza-4-aziniobi­cyclo­[2.2.2]­octane-N¹)­tri­chlorozinc(II)

Zn(dabcoH)Cl₃ (dabco is 1,4-bi­cyclo­[2.2.2]­octane), [ZnCl₃(C₆H₁₃N₂)], crystallizes as a neutral monomeric species with approximate C₃ symmetry. The tetrahedrally coordinated Zn^II ion has Zn-Cl distances ranging from 2.239 (2) to 2.250 (2) Å and a Zn-N distance of 2.094 (4) Å. The Cl-Zn-Cl angles are slightly larger than tetrahedral [112.44 (6)-114.38 (6)°]. The protonated aza group forms a weak interaction with a Cl atom of an adjacent mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.031
• wR factor = 0.077
• Data-to-parameter ratio = 9.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of Tmax/Tmin expected RT(exp) is > 1.10
          Absorption corrections should be applied.
          Tmin and Tmax expected:      0.417     0.469
          RT(exp) =      1.125

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.00
         From the CIF: _reflns_number_total               1038
         Count of symmetry unique reflns          972
         Completeness (_total/calc)            106.79%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured        66
         Fraction of Friedel pairs measured     0.068
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

The title compound, (I), was prepared in an attempt to make non-Jahn–Teller analogs to (dabcoH₂)₂Cl₃[CuCl₃(H₂O)₂]·H₂O (Wei & Willett, 1996) and to (dabcoH₂)CuCl₄ and (dabco₂)CuCl₄·H₂O (Wei & Willett, 2001).

S2. Experimental

A procedure similar to that employed in the synthesis of (dabcoH₂)₂Cl₃[CuCl₃(H₂O)₂]·H₂O (Wei & Willett, 1996) was followed. Equimolar mixtures of the dabco ligand and ZnCl₂ were dissolved in a dilute HCl solution. Colorless crystals separated out of the solution after several days of slow evaporation at room temperature. These were filtered off and air-dried.

Computing details

Data collection: XSCANS (Siemens, 1992); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS90 (Sheldrick, 1990); program(s) used to refine structure: SHELXL92 (Sheldrick, 1992); molecular graphics: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Zn(1-aza-4-azinium-bicyclo[2.2.2]octane)trichloride

Crystal data

[ZnCl3(C6H13N2)]	F(000) = 288
Mr = 284.94	Dx = 1.789 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
a = 6.7475 (10) Å	Cell parameters from 25 reflections
b = 12.5446 (16) Å	θ = 13.5–14°
c = 6.9788 (17) Å	µ = 3.03 mm^−1
β = 116.430 (14)°	T = 293 K
V = 528.98 (17) Å^3	Rhomboids, colorless
Z = 2	0.3 × 0.3 × 0.25 mm

Data collection

Bruker P4 diffractometer	Rint = 0.030
Radiation source: fine-focus sealed tube	θmax = 25.0°, θmin = 3.3°
Graphite monochromator	h = −1→7
ω scans	k = −1→14
1317 measured reflections	l = −8→7
1038 independent reflections	3 standard reflections every 97 reflections
1005 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0523P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
1038 reflections	Δρmax = 0.80 e Å^−3
110 parameters	Δρmin = −0.56 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.00 (2)

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
Zn	−0.43560 (8)	−0.88492 (5)	−0.29074 (8)	0.0255 (2)
Cl1	−0.7743 (2)	−0.83248 (13)	−0.5277 (2)	0.0355 (3)
Cl2	−0.2905 (2)	−1.01529 (12)	−0.4079 (2)	0.0353 (3)
Cl3	−0.4150 (3)	−0.92037 (13)	0.0336 (2)	0.0430 (4)
C8	−0.1499 (9)	−0.5639 (5)	−0.1314 (10)	0.0340 (13)
H8A	−0.2459	−0.5072	−0.2178	0.041*
H8B	−0.0740	−0.5396	0.0156	0.041*
C7	−0.2853 (10)	−0.6642 (5)	−0.1460 (9)	0.0303 (12)
H7A	−0.2591	−0.6855	−0.0031	0.036*
H7B	−0.4415	−0.6479	−0.2264	0.036*
C2	0.0077 (8)	−0.7823 (5)	−0.1193 (8)	0.0309 (12)
H2A	0.0496	−0.8376	−0.1914	0.037*
H2B	0.0278	−0.8101	0.0179	0.037*
C5	−0.2563 (9)	−0.7170 (5)	−0.4636 (8)	0.0295 (12)
H5A	−0.4088	−0.6955	−0.5492	0.035*
H5B	−0.2249	−0.7756	−0.5364	0.035*
C6	−0.1057 (10)	−0.6247 (5)	−0.4461 (10)	0.0382 (14)
H6A	−0.0007	−0.6453	−0.4993	0.046*
H6B	−0.1917	−0.5649	−0.5304	0.046*
N1	−0.2286 (7)	−0.7538 (4)	−0.2503 (6)	0.0227 (9)
C3	0.1564 (10)	−0.6847 (5)	−0.0838 (12)	0.0458 (17)
H3A	0.2277	−0.6660	0.0668	0.055*
H3B	0.2704	−0.7004	−0.1284	0.055*
N4	0.0151 (8)	−0.5936 (4)	−0.2132 (9)	0.0399 (12)
H4A	0.1032	−0.5365	−0.2000	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn	0.0272 (3)	0.0177 (3)	0.0334 (3)	−0.0013 (3)	0.0152 (2)	0.0005 (3)
Cl1	0.0289 (6)	0.0310 (7)	0.0419 (6)	0.0043 (6)	0.0115 (5)	−0.0035 (6)
Cl2	0.0381 (7)	0.0252 (7)	0.0433 (7)	0.0040 (6)	0.0186 (6)	−0.0059 (6)
Cl3	0.0510 (8)	0.0456 (9)	0.0426 (6)	0.0143 (7)	0.0301 (6)	0.0166 (6)
C8	0.033 (3)	0.020 (3)	0.052 (3)	0.001 (2)	0.022 (2)	−0.006 (3)
C7	0.037 (3)	0.023 (3)	0.040 (3)	0.000 (3)	0.026 (2)	−0.006 (2)
C2	0.023 (2)	0.027 (3)	0.035 (3)	0.000 (2)	0.005 (2)	0.003 (2)
C5	0.033 (3)	0.031 (3)	0.024 (2)	0.000 (3)	0.012 (2)	0.004 (2)
C6	0.052 (4)	0.025 (3)	0.052 (3)	−0.007 (3)	0.037 (3)	0.000 (3)
N1	0.024 (2)	0.018 (2)	0.028 (2)	0.0003 (19)	0.0136 (16)	−0.0012 (18)
C3	0.023 (3)	0.033 (4)	0.072 (4)	−0.003 (3)	0.013 (3)	−0.016 (3)
N4	0.033 (3)	0.020 (2)	0.072 (4)	−0.008 (2)	0.027 (2)	−0.007 (2)

Geometric parameters (Å, º)

Zn—N1	2.094 (4)	C2—N1	1.486 (6)
Zn—Cl2	2.2394 (15)	C2—C3	1.532 (9)
Zn—Cl1	2.2418 (14)	C5—N1	1.489 (6)
Zn—Cl3	2.2495 (15)	C5—C6	1.509 (8)
C8—N4	1.506 (7)	C6—N4	1.510 (8)
C8—C7	1.531 (8)	C3—N4	1.505 (9)
C7—N1	1.479 (7)
N1—Zn—Cl2	104.43 (12)	C7—N1—C2	108.8 (4)
N1—Zn—Cl1	105.59 (13)	C7—N1—C5	108.1 (4)
Cl2—Zn—Cl1	114.38 (6)	C2—N1—C5	108.2 (4)
N1—Zn—Cl3	106.31 (12)	C7—N1—Zn	111.1 (3)
Cl2—Zn—Cl3	112.44 (6)	C2—N1—Zn	111.2 (3)
Cl1—Zn—Cl3	112.73 (6)	C5—N1—Zn	109.2 (3)
N4—C8—C7	106.9 (5)	N4—C3—C2	108.4 (5)
N1—C7—C8	112.3 (4)	C3—N4—C8	109.8 (5)
N1—C2—C3	110.7 (5)	C3—N4—C6	110.2 (5)
N1—C5—C6	112.1 (4)	C8—N4—C6	109.6 (5)
N4—C6—C5	107.8 (5)
N4—C8—C7—N1	−5.0 (7)	Cl2—Zn—N1—C2	−51.2 (3)
N1—C5—C6—N4	−4.2 (6)	Cl1—Zn—N1—C2	−172.2 (3)
C8—C7—N1—C2	62.1 (6)	Cl3—Zn—N1—C2	67.9 (3)
C8—C7—N1—C5	−55.3 (6)	Cl2—Zn—N1—C5	68.2 (3)
C8—C7—N1—Zn	−175.1 (4)	Cl1—Zn—N1—C5	−52.8 (3)
C3—C2—N1—C7	−55.1 (6)	Cl3—Zn—N1—C5	−172.7 (3)
C3—C2—N1—C5	62.2 (6)	N1—C2—C3—N4	−5.7 (7)
C3—C2—N1—Zn	−177.8 (4)	C2—C3—N4—C8	64.2 (6)
C6—C5—N1—C7	60.9 (5)	C2—C3—N4—C6	−56.6 (7)
C6—C5—N1—C2	−56.8 (6)	C7—C8—N4—C3	−57.6 (6)
C6—C5—N1—Zn	−178.0 (4)	C7—C8—N4—C6	63.5 (6)
Cl2—Zn—N1—C7	−172.6 (3)	C5—C6—N4—C3	62.3 (6)
Cl1—Zn—N1—C7	66.5 (3)	C5—C6—N4—C8	−58.6 (6)
Cl3—Zn—N1—C7	−53.5 (3)