4-Ammonio-1-hydroxy-2,2,6,6-tetra­methyl­piperidin-1-ium dichloride monohydrate

Hu, T.Q.; Patrick, B.O.; Osmond, D.A.; James, B.R.

doi:10.1107/S160053680302097X

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4-Ammonio-1-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium dichloride monohydrate

T. Q. Hu, B. O. Patrick, D. A. Osmond and B. R. James

The crystal structure of the title compound, C₉H₂₂N₂O²⁺·2Cl⁻·H₂O, has been determined at 173 (1) K. Attached to the piperidinyl ring, which adopts a chair conformation, the hydroxyl and the exocyclic ammonium groups are mutually trans, both occupying equatorial positions. The water molecule and the two chloride anions are involved in strong hydrogen bonding via O

H and H

Cl interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680302097X/lh6115sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680302097X/lh6115Isup2.hkl Contains datablock I

CCDC reference: 225865

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R factor = 0.033
wR factor = 0.081
Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low .......       0.93

Author Response: This problem of incomplete coverage is a common one for us, as our diffractometer has a large chi-circle and unreliable collision protection software, so achieving orientations that would allow us to collect all of the high-angle data is impossible. However, from the output below hopefully you can see that we have complete coverage out to 0.90 angstroms, near-complete data out to 0.86 angstroms, and that the only data missing is out beyond 0.86 angstroms.

 Redundancy vs Resolution
 

  Resolution      Calc  Percent of reflections measured N times, N =  %Comp %Comp
     range      unique    0     1     2     3     4   5-8  9-12   >12 shell cumul
 

   9.18 - 1.63     453  3.8   5.1   9.7  10.6   7.7  29.8  28.9   4.4  96.2  96.2
   1.63 - 1.30     420  0.7   2.1   5.0   9.0   5.7  28.1  45.0   4.3  99.3  97.7
   1.30 - 1.13     400  0.2   0.7   3.5   9.0   3.8  33.0  46.5   3.2  99.8  98.4
   1.13 - 1.03     397  0.0   0.3   2.8   5.5   6.5  32.2  49.9   2.8 100.0  98.7
   1.03 - 0.96     400  0.0   0.7   3.5   6.5   5.2  33.8  46.0   4.3 100.0  99.0
   0.96 - 0.90     386  0.0   2.6   2.6   6.5   6.0  36.0  42.0   4.4 100.0  99.1
   0.90 - 0.86     406  4.4   1.5   3.2   6.4   6.2  30.8  44.1   3.4  95.6  98.6
   0.86 - 0.82     381  8.9   6.6   9.2   8.7   5.8  28.6  30.2   2.1  91.1  97.7
   0.82 - 0.79     402 26.9   4.5   7.7  12.4   5.0  30.1  12.4   1.0  73.1  95.0
   0.79 - 0.76     380 41.8   8.4   3.4  12.1  11.1  20.8   2.4   0.0  58.2  91.6
 

   9.18 - 0.76    4025  8.4   3.2   5.1   8.7   6.3  30.3  34.9   3.0  91.6  91.6


PLAT707_ALERT_1_A D...A   Calc    3.833(6), Rep    3.531(5), Dev..      50.33 Sigma
              C7   -CL2B    1.555   1.555
PLAT726_ALERT_1_A H...A   Calc     3.05434, Rep     2.70000, Dev..       0.35 Ang.
              H(7A)-CL2B    1.555   1.555
PLAT728_ALERT_1_A D-H..A  Calc      137.32, Rep      142.00, Dev.        4.68 Deg.
              C7   -H(7A)-CL2B    1.555   1.555   1.555

Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H14    ..  H15      =       2.09 Ang.

Alert level C
CELLV02_ALERT_1_C  The supplied cell volume s.u. differs from that
            calculated from the cell parameter s.u.'s by > 2
            Calculated cell volume su =       2.44
            Cell volume su given      =       5.00
REFLT03_ALERT_3_C  Reflection count < 95% complete
           From the CIF: _diffrn_reflns_theta_max           27.87
           From the CIF: _diffrn_reflns_theta_full           0.00
           From the CIF: _reflns_number_total               3286
           TEST2: Reflns within _diffrn_reflns_theta_max
           Count of symmetry unique reflns         3552
           Completeness (_total/calc)             92.51%
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT213_ALERT_2_C Atom Cl2     has ADP max/min Ratio .............       3.10 prolat
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.38 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.39 Ratio
PLAT250_ALERT_2_C Large U3/U1 ratio for average U(i,j) tensor ....       2.44
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.
PLAT353_ALERT_3_C Long    N-H Bond (0.87A)   N2     -   H14      =       1.01 Ang.

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           27.87
           From the CIF: _reflns_number_total               3286
           From the CIF: _diffrn_reflns_limit_ max hkl   16.   10.   29.
           From the CIF: _diffrn_reflns_limit_ min hkl  -14.  -11.  -29.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   17.   12.   32.
           Calculated minimum hkl  -17.  -12.  -32.

   4 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
  10 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: D*TREK (Rigaku/MSC, 2001); cell refinement: D*TREK; data reduction: D*TREK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: TEXSAN (Molecular Structure Corporation, 1992–1997); software used to prepare material for publication: TEXSAN.

(I) top

Crystal data top

C₉H₂₂N₂O²⁺·2Cl⁻·H₂O	F(000) = 1136.00
M_r = 263.21	D_x = 1.173 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 13231 reflections
a = 13.2668 (6) Å	θ = 2.2–27.9°
b = 9.1840 (5) Å	µ = 0.42 mm⁻¹
c = 24.471 (1) Å	T = 173 K
V = 2981.6 (5) Å³	Platelet, colourless
Z = 8	0.50 × 0.30 × 0.10 mm

Data collection top

Rigaku/ADSC CCD diffractometer	3286 independent reflections
Radiation source: X-ray tube	2001 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 11.76 pixels mm^-1	θ_max = 27.9°, θ_min = 2.2°
area detector scans	h = −14→16
Absorption correction: multi-scan (Blessing, 1995)	k = −11→10
T_min = 0.767, T_max = 0.959	l = −29→29
27028 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	0 constraints
R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.081	Weighting scheme based on measured s.u.'s w = 1/[σ²(F_o²)
S = 1.10	(Δ/σ)_max = 0.001
3286 reflections	Δρ_max = 0.29 e Å⁻³
173 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

Experimental. Data were collected in 0.50° oscillations with 55.0 s exposures. A sweep of data was done using φ oscillations from 0.0 to 190.0° at χ = -90° and a second sweep was performed using ω oscillations between -17.0 and 23.0° at χ = 90.0°. The crystal-to-detector distance was 38.40 mm. The detector swing angle was -5.6°. The absorption correction is based on a three-dimensional analysis of symmetry-equivalent data and is performed along with batch scaling in a single step. The resulting transmission factors, therefore, include contributions from absorption, crystal decay, and detectable variations in beam intensity.

Geometry. C—C—C angles fall between 109.0 (2)–113.0 (2)°

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cl1	0.79754 (3)	−0.06817 (5)	0.74244 (2)	0.0477 (1)
Cl2	0.9734 (2)	−0.0956 (6)	0.5728 (2)	0.0724 (7)	0.608
Cl2B	0.9416 (3)	−0.0902 (8)	0.5687 (3)	0.0433 (7)	0.392
O1	1.0366 (1)	0.2944 (1)	0.52075 (5)	0.0441 (4)
O2	1.0384 (1)	0.2416 (2)	0.81589 (6)	0.0555 (5)
N1	0.9973 (1)	0.2420 (2)	0.57080 (5)	0.0268 (4)
N2	0.8914 (1)	0.2383 (2)	0.73479 (5)	0.0257 (4)
C1	1.0775 (1)	0.2635 (2)	0.61505 (7)	0.0387 (5)
C2	1.0312 (1)	0.2136 (2)	0.66898 (6)	0.0297 (4)
C3	0.9317 (1)	0.2875 (2)	0.68081 (6)	0.0235 (4)
C4	0.8569 (1)	0.2513 (2)	0.63584 (6)	0.0270 (4)
C5	0.8911 (1)	0.3038 (2)	0.57973 (6)	0.0291 (4)
C6	1.1142 (2)	0.4204 (3)	0.61668 (9)	0.0685 (7)
C7	1.1643 (1)	0.1623 (3)	0.59996 (9)	0.0791 (9)
C8	0.8260 (1)	0.2384 (3)	0.53490 (8)	0.0525 (6)
C9	0.8884 (2)	0.4690 (2)	0.57499 (8)	0.0556 (6)
H(2B)	1.0783	0.2358	0.6986	0.035*
H(2A)	1.0201	0.1082	0.6672	0.035*
H(3)	0.9421	0.3932	0.6819	0.028*
H(4B)	0.8482	0.1455	0.6345	0.032*
H(4A)	0.7923	0.2976	0.6445	0.032*
H(6A)	1.1341	0.4509	0.5799	0.082*
H(6B)	1.1723	0.4278	0.6413	0.082*
H(6C)	1.0599	0.4835	0.6299	0.082*
H(7C)	1.1926	0.1919	0.5647	0.095*
H(7A)	1.1393	0.0621	0.5974	0.095*
H(7B)	1.2166	0.1677	0.6281	0.095*
H(8B)	0.8449	0.2809	0.4996	0.063*
H(8C)	0.7549	0.2597	0.5424	0.063*
H(8A)	0.8360	0.1329	0.5338	0.063*
H(9A)	0.8183	0.5017	0.5720	0.067*
H(9B)	0.9258	0.4994	0.5424	0.067*
H(9C)	0.9193	0.5125	0.6075	0.067*
H(10)	0.991 (1)	0.147 (2)	0.5682 (7)	0.033 (5)*
H(11)	1.033 (2)	0.224 (2)	0.4962 (9)	0.078 (8)*
H(12)	0.872 (1)	0.135 (2)	0.7337 (8)	0.059 (6)*
H(13)	0.830 (2)	0.296 (2)	0.7433 (9)	0.079 (7)*
H(14)	0.947 (1)	0.247 (2)	0.7629 (8)	0.065 (6)*
H(15)	1.082 (2)	0.306 (3)	0.801 (1)	0.11 (1)*
H(16)	1.029 (2)	0.280 (3)	0.844 (1)	0.10 (1)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0525 (3)	0.0382 (3)	0.0523 (3)	−0.0165 (2)	−0.0191 (2)	0.0091 (2)
Cl2	0.172 (3)	0.0258 (7)	0.0190 (7)	0.009 (2)	0.014 (2)	0.0000 (6)
Cl2B	0.083 (1)	0.024 (1)	0.023 (2)	−0.009 (1)	0.016 (1)	−0.002 (1)
O1	0.0706 (9)	0.0430 (8)	0.0186 (6)	−0.0195 (7)	0.0179 (6)	−0.0042 (6)
O2	0.0615 (9)	0.074 (1)	0.0310 (8)	−0.0055 (9)	−0.0080 (7)	−0.0141 (8)
N1	0.0392 (7)	0.0249 (8)	0.0163 (7)	−0.0061 (6)	0.0083 (6)	−0.0016 (6)
N2	0.0298 (7)	0.0296 (8)	0.0178 (7)	−0.0007 (7)	0.0037 (6)	0.0005 (6)
C1	0.0302 (8)	0.060 (1)	0.026 (1)	−0.0090 (9)	0.0064 (7)	−0.0042 (9)
C2	0.0243 (8)	0.044 (1)	0.0211 (8)	−0.0005 (7)	0.0011 (6)	−0.0033 (8)
C3	0.0328 (8)	0.0217 (8)	0.0158 (8)	−0.0026 (6)	0.0060 (6)	−0.0003 (7)
C4	0.0281 (8)	0.0319 (9)	0.0212 (8)	0.0040 (7)	0.0027 (6)	0.0026 (7)
C5	0.0382 (9)	0.0285 (9)	0.0206 (9)	0.0040 (7)	0.0013 (7)	0.0036 (7)
C6	0.075 (1)	0.095 (2)	0.036 (1)	−0.058 (1)	0.010 (1)	−0.005 (1)
C7	0.037 (1)	0.154 (3)	0.046 (1)	0.025 (1)	0.017 (1)	0.003 (2)
C8	0.051 (1)	0.083 (2)	0.024 (1)	−0.004 (1)	−0.0096 (8)	0.009 (1)
C9	0.095 (2)	0.036 (1)	0.035 (1)	0.019 (1)	0.012 (1)	0.012 (1)

Geometric parameters (Å, º) top

Cl2—Cl2B	0.437 (8)	C3—H(3)	0.98
O1—N1	1.415 (2)	C4—C5	1.525 (2)
O1—H(11)	0.88 (2)	C4—H(4B)	0.98
O2—H(15)	0.91 (3)	C4—H(4A)	0.98
O2—H(16)	0.79 (2)	C5—C8	1.520 (2)
N1—C1	1.531 (2)	C5—C9	1.522 (2)
N1—C5	1.534 (2)	C6—H(6A)	0.98
N1—H(10)	0.88 (2)	C6—H(6B)	0.98
N2—C3	1.495 (2)	C6—H(6C)	0.98
N2—H(12)	0.98 (2)	C7—H(7C)	0.98
N2—H(13)	0.99 (2)	C7—H(7A)	0.98
N2—H(14)	1.01 (2)	C7—H(7B)	0.98
C1—C2	1.526 (2)	C8—H(8B)	0.98
C1—C6	1.522 (3)	C8—H(8C)	0.98
C1—C7	1.525 (3)	C8—H(8A)	0.98
C2—C3	1.513 (2)	C9—H(9A)	0.98
C2—H(2B)	0.98	C9—H(9B)	0.98
C2—H(2A)	0.98	C9—H(9C)	0.98
C3—C4	1.518 (2)

Cl1···N2ⁱ	3.079 (2)	Cl2B···O1ⁱⁱⁱ	2.897 (8)
Cl1···N2	3.083 (2)	Cl2B···N1	3.140 (7)
Cl1···O2ⁱⁱ	3.135 (2)	Cl2B···O2ⁱⁱ	3.230 (7)
Cl2···O1ⁱⁱⁱ	2.931 (5)	Cl2B···C8	3.485 (7)
Cl2···O2ⁱⁱ	3.112 (5)	O1···C9^iv	3.346 (2)
Cl2···N1	3.117 (5)	O2···N2	2.782 (2)
Cl2···C7	3.530 (5)

N1—O1—H(11)	109 (1)	C3—C4—H(4A)	108.7
H(15)—O2—H(16)	100 (3)	C5—C4—H(4B)	108.5
O1—N1—C1	108.2 (1)	C5—C4—H(4A)	108.6
O1—N1—C5	109.6 (1)	H(4B)—C4—H(4A)	109.5
O1—N1—H(10)	108 (1)	N1—C5—C4	106.5 (1)
C1—N1—C5	119.3 (1)	N1—C5—C8	105.8 (1)
C1—N1—H(10)	104 (1)	N1—C5—C9	112.3 (1)
C5—N1—H(10)	107 (1)	C4—C5—C8	110.8 (1)
C3—N2—H(12)	111 (1)	C4—C5—C9	112.1 (1)
C3—N2—H(13)	109 (1)	C8—C5—C9	109.0 (2)
C3—N2—H(14)	108 (1)	C1—C6—H(6A)	109.4
H(12)—N2—H(13)	108 (2)	C1—C6—H(6B)	109.5
H(12)—N2—H(14)	106 (2)	C1—C6—H(6C)	109.4
H(13)—N2—H(14)	114 (2)	H(6A)—C6—H(6B)	109.5
N1—C1—C2	107.0 (1)	H(6A)—C6—H(6C)	109.5
N1—C1—C6	111.3 (2)	H(6B)—C6—H(6C)	109.5
N1—C1—C7	105.9 (2)	C1—C7—H(7C)	109.4
C2—C1—C6	113.0 (2)	C1—C7—H(7A)	109.4
C2—C1—C7	109.3 (2)	C1—C7—H(7B)	109.5
C6—C1—C7	110.0 (2)	H(7C)—C7—H(7A)	109.5
C1—C2—C3	112.5 (1)	H(7C)—C7—H(7B)	109.5
C1—C2—H(2B)	108.7	H(7A)—C7—H(7B)	109.5
C1—C2—H(2A)	108.6	C5—C8—H(8B)	109.5
C3—C2—H(2B)	108.8	C5—C8—H(8C)	109.4
C3—C2—H(2A)	108.7	C5—C8—H(8A)	109.5
H(2B)—C2—H(2A)	109.5	H(8B)—C8—H(8C)	109.3
N2—C3—C2	110.2 (1)	H(8B)—C8—H(8A)	109.5
N2—C3—C4	109.9 (1)	H(8C)—C8—H(8A)	109.5
N2—C3—H(3)	109.1	C5—C9—H(9A)	109.5
C2—C3—C4	109.5 (1)	C5—C9—H(9B)	109.5
C2—C3—H(3)	109.1	C5—C9—H(9C)	109.5
C4—C3—H(3)	109.1	H(9A)—C9—H(9B)	109.4
C3—C4—C5	112.9 (1)	H(9A)—C9—H(9C)	109.5
C3—C4—H(4B)	108.6	H(9B)—C9—H(9C)	109.4

O1—N1—C1—C2	177.1 (1)	C1—N1—C5—C8	−168.8 (1)
O1—N1—C1—C6	53.2 (2)	C1—N1—C5—C9	72.4 (2)
O1—N1—C1—C7	−66.4 (2)	C1—C2—C3—C4	60.8 (2)
O1—N1—C5—C4	−176.2 (1)	C2—C1—N1—C5	51.0 (2)
O1—N1—C5—C8	65.7 (2)	C2—C3—C4—C5	−61.1 (2)
O1—N1—C5—C9	−53.1 (2)	C3—C2—C1—C6	69.4 (2)
N1—C1—C2—C3	−53.5 (2)	C3—C2—C1—C7	−167.8 (2)
N1—C5—C4—C3	53.4 (2)	C3—C4—C5—C8	168.1 (1)
N2—C3—C2—C1	−178.2 (1)	C3—C4—C5—C9	−69.9 (2)
N2—C3—C4—C5	177.8 (1)	C5—N1—C1—C6	−73.0 (2)
C1—N1—C5—C4	−50.8 (2)	C5—N1—C1—C7	167.5 (2)

Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) −x+2, y−1/2, −z+3/2; (iii) −x+2, −y, −z+1; (iv) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H(10)···Cl2	0.88 (2)	2.24 (2)	3.117 (6)	173 (2)
O1—H(11)···Cl2ⁱⁱⁱ	0.88 (2)	2.06 (2)	2.931 (5)	168 (2)
N2—H(12)···Cl1	0.98 (2)	2.12 (2)	3.084 (2)	165 (2)
N2—H(13)···Cl1^v	0.99 (2)	2.10 (2)	3.079 (2)	167 (2)
N2—H(14)···O2	1.01 (2)	1.78 (2)	2.783 (2)	173 (2)
O2—H(15)···Cl1^vi	0.90 (3)	2.24 (3)	3.135 (2)	170 (2)
O2—H(16)···Cl2^vi	0.78 (3)	2.33 (3)	3.111 (5)	171 (3)
C6—H(6A)···O1	0.98	2.42	2.812 (3)	104
C7—H(7A)···Cl2B	0.98	2.70	3.531 (5)	142
C9—H(9B)···O1	0.98	2.45	2.863 (3)	105
C9—H(9B)···O1^iv	0.98	2.49	3.347 (2)	145

Symmetry codes: (iii) −x+2, −y, −z+1; (iv) −x+2, −y+1, −z+1; (v) −x+3/2, y+1/2, z; (vi) −x+2, y+1/2, −z+3/2.

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