The crystal structure of the title compound, C
9H
22N
2O
2+·2Cl
−·H
2O, 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.
Supporting information
CCDC reference: 225865
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
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.
Crystal data top
C9H22N2O2+·2Cl−·H2O | F(000) = 1136.00 |
Mr = 263.21 | Dx = 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 | Rint = 0.058 |
Detector resolution: 11.76 pixels mm-1 | θmax = 27.9°, θmin = 2.2° |
area detector scans | h = −14→16 |
Absorption correction: multi-scan (Blessing, 1995) | k = −11→10 |
Tmin = 0.767, Tmax = 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(Fo2) |
S = 1.10 | (Δ/σ)max = 0.001 |
3286 reflections | Δρmax = 0.29 e Å−3 |
173 parameters | Δρmin = −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 | Uiso*/Ueq | 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···C9iv | 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)···Cl1v | 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)···Cl1vi | 0.90 (3) | 2.24 (3) | 3.135 (2) | 170 (2) |
O2—H(16)···Cl2vi | 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)···O1iv | 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. |