Crystal structure of 4-(prop-2-yn­yloxy)-2,2,6,6-tetra­methyl­piperidin-1-ox­yl

Goswami, S.K.; Hanton, L.R.; McAdam, C.J.; Moratti, S.C.; Simpson, J.

doi:10.1107/S1600536814017991

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ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages 130-133

doi:10.1107/S1600536814017991

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Crystal structure of 4-(prop-2-ynyloxy)-2,2,6,6-tetramethylpiperidin-1-oxyl

Shailesh K. Goswami,^a Lyall R. Hanton,^a C. John McAdam,^a Stephen C. Moratti ^a and Jim Simpson ^a ^*

^aDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
^*Correspondence e-mail: jsimpson@alkali.otago.ac.nz

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 4 August 2014; accepted 5 August 2014; online 9 August 2014)

The title compound, C₁₂H₂₀NO₂, was synthesized from 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (hydroxy-TEMPO) and propargyl bromide. The six-membered ring adopts a flattened chair conformation and carries a propynyloxy substituent in an equatorial orientation at the 4-position. The N—O bond length of the piperidin-1-oxyl unit is 1.289 (3) Å. In the crystal, C—H⋯O hydrogen bonds combine with unusual C—H⋯π interactions involving the alkyne unit as acceptor to generate a three-dimensional network.

Keywords: crystal structure; TEMPO derivative; C—H⋯alkyne contact.

CCDC reference: 1017949

1. Chemical context

TEMPO, 2,2,6,6-tetramethylpiperidin-1-oxyl, and its derivatives have attracted significant interest in recent years as functional organic radicals with considerable chemical stability (Soegiarto et al., 2011 ). They are known to exhibit both ferromagnetism and antiferromagnetism at low temperatures (Togashi et al., 1996 ; Ishida et al., 1995 ), and the effect of intermolecular contacts on their magnetic properties has been examined (Iwasaki et al., 1999a ,b ). TEMPO and its derivatives have been utilized in applications as diverse as catalysis in organic synthesis (Zhao et al., 2005 ), pulsed electron–electron double-resonance (PELDOR) spectroscopy (Bode et al., 2007 ), and use as qubits (quantum bits) in quantum computing (Nakazawa et al., 2012 ).

Our interest in TEMPO derivatives is as reversible redox-active subunits in polymer-gel actuators (Goswami et al., 2013 ). In particular, the alkyne group present in the title compound, (1), allows us to utilize the versatile CuAAC `click' cycloaddition with organic azides (Hein & Fokin, 2010 ; Lewis et al., 2013 ) as a means to attach the TEMPO unit to the gel skeleton.

2. Structural commentary

The structure of (1) and its atom numbering are shown in Fig. 1. The molecule comprises a standard TEMPO unit with a propynyloxy substituent at the 4-position. The N1/C2–C6 ring adopts a flattened chair conformation with the C4 atom 0.706 (4) Å from the best fit plane through the remaining four C atoms, while N1 lies only 0.384 (4) Å from the plane in the opposite direction. The propynyl C7–C9 unit points away from this plane in the same direction as C4, with C7—C8—C9 = 178.6 (3)°. The N—O bond is 1.289 (3) Å long, which compares favorably with the average value of 1.285 (18) Å for other TEMPO structures (Macrae et al., 2008 ).

Figure 1
The structure of (1), showing the atom numbering and with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

In the crystal structure of (1), C9—H9⋯O1 hydrogen bonds link molecules into C(9) chains along b (Table 1). Additional C61—H61A⋯O1 contacts form R₃²(16) rings, resulting in double chains of molecules along b (Fig. 2). In an almost orthogonal direction, C7—H7B⋯O2 hydrogen bonds form C(3) chains along a. An interesting feature of these latter contacts is the support provided by C5—H5B⋯Cg interactions (Cg is the mid-point of the C8—C9 bond) involving the alkyne unit (Fig. 3). Such contacts are often overlooked, but they have been reported previously for both terminal and non-terminal alkyne systems (Banerjee et al., 2006 ; Thakur et al., 2010 ; McAdam et al., 2012 ). Overall, these contacts generate a three-dimensional network with molecules stacked in interconnected columns along the b axis (Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the mid-point of the C8–C9 bond.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1ⁱ	0.95	2.28	3.205 (4)	163
C7—H7B⋯O2ⁱⁱ	0.99	2.52	3.298 (4)	135
C61—H61A⋯O1ⁱⁱⁱ	0.98	2.56	3.481 (4)	157
C5—H5B⋯Cg^iv	0.99	2.93	3.885 (4)	156
Symmetry codes: (i) x, y+1, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{5\over 2}}, -z+1]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) $[-x-1, y+{\script{5\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
Double chains formed from molecules of (1) along b. In this and subsequent Figures, C—H⋯O hydrogen bonds are drawn as dashed lines and H atoms bound to atoms not involved in hydrogen bonding are not shown.

Figure 3
Zigzag chains formed along a from C—H⋯O and C—H⋯π (green dotted lines) contacts. The mid-point of the C8=C9 triple bond is shown as a red sphere.

Figure 4
The overall packing for (1), viewed along the b axis.

4. Database survey

The Cambridge Structural Database (CSD; Version 5.35, November 2013 with 2 updates; Allen, 2002 ) reveals a total of 175 structures of TEMPO and its derivatives. However, structures of alkoxy-TEMPO derivatives are rare with only a single example, albeit in two separate papers in which Polovyanenko et al. (2008 ) and Soegiarto et al. (2011) report the structure of 4-(methoxy)-TEMPO, 4-(methoxy)-2,2,6,6-tetramethylpiperidin-1-oxyl. The first paper examines the TEMPO derivative as an inclusion complex of p-hexanoyl calix[4]arene (C₆OH), and investigates the magnetism and orientation dependent motion of the encapsulated radical. In the second, the molecule is included in the cavities of two porous frameworks derived from guanidinium cations and two organodisulfonate anions; the magnetic behaviour of the radical guest is investigated. Aryloyloxy-TEMPO derivatives are more abundant with 19 entries in the CSD (see, for example, Pang et al., 2013 ; Nakazawa et al., 2012; Akutsu et al., 2005 ). Again, the focus is very much on the magnetic properties of the materials.

5. Synthesis and crystallization

Synthesis and characterization (IR and mass spectroscopy) are as previously described (Gheorghe et al., 2006 ; Kulis et al., 2009 ). Colourless blocks were obtained from diethyl ether solution at room temperature. Analysis calculated for C₁₂H₂₀NO₂: C 68.54, H 9.59, N 6.66%; found: C 68.57, H 9.66, N 6.68%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. With no heavy atom in the non-centrosymmetric structure, the absolute structure could not be reliably determined. Friedel opposites were not, however, merged. All H atoms were refined using a riding model, with C—H = 0.99 Å and U_iso(H) = 1.2U_eq(C) for methylene H atoms, C—H = 1.00 Å and U_iso(H) = 1.2U_eq(C) for methine H atoms, C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms, and C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C) for the terminal alkyne H atom. Anisiotropic refinement of the non-H atoms was constrained using the ISOR command in SHELXL to prevent atoms becoming non-positive definite. 10 reflections with F_o >> F_c were omitted from the final refinement cycles.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₂₀NO₂
M_r	210.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.94506 (13), 10.17919 (16), 14.8052 (3)
V (Å³)	1197.36 (4)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.63
Crystal size (mm)	0.18 × 0.15 × 0.08

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas)
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013 )
T_min, T_max	0.522, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6622, 2307, 2203
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.15
No. of reflections	2307
No. of parameters	140
No. of restraints	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28
Absolute structure	Flack x determined using 858 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons & Flack, 2004 )
Absolute structure parameter	0.0 (3)
Computer programs: CrysAlis PRO (Agilent, 2013), SIR2011 (Burla et al., 2012 ), SHELXL2013 (Sheldrick, 2008 ), TITAN2000 (Hunter & Simpson, 1999 ), Mercury (Macrae et al., 2008), enCIFer (Allen et al., 2004 ), PLATON (Spek, 2009 ) and publCIF (Westrip 2010 ).

Supporting information

CCDC reference: 1017949

Crystal structure: contains datablocks global, 1. DOI: 10.1107/S1600536814017991/hb7267sup1.cif

Structure factors: contains datablock 1. DOI: 10.1107/S1600536814017991/hb72671sup2.hkl

checkCIF report

Chemical context top

TEMPO, 2,2,6,6-tetramethylpiperidin-1-oxyl, and its derivatives have attracted significant interest in recent years as functional organic radicals with considerable chemical stability (Soegiarto et al., 2011). They are known to exhibit both ferromagnetism and antiferromagnetism at low temperatures (Togashi et al., 1996; Ishida et al., 1995), and the effect of intermolecular contacts on their magnetic properties has been examined (Iwasaki et al., 1999a,b). TEMPO and its derivatives have been utilized in applications as diverse as catalysis in organic synthesis (Zhao et al., 2005), pulsed electron–electron double-resonance (PELDOR) spectroscopy (Bode et al., 2007), and use as qubits (quantum bits) in quantum computing (Nakazawa et al., 2012).

Our interest in TEMPO derivatives is as reversible redox-active subunits in polymer-gel actuators (Goswami et al., 2013). In particular, the alkyne group present in the title compound, (1), allows us to utilize the versatile CuAAC `click' cycloaddition with organic azides (Hein & Fokin, 2010; Lewis et al., 2013) as a means to attach the TEMPO unit to the gel skeleton.

Structural commentary top

Supramolecular features top

In the crystal structure of (1), C9—H9···O1 hydrogen bonds link molecules into C(9) chains along b (Table 1). Additional C61—H61A···O1 contacts form R₃²(16) rings, resulting in double chains of molecules along b (Fig. 2). In an almost orthogonal direction, C7—H7B···O2 hydrogen bonds form C(3) chains along a. An interesting feature of these latter contacts is the support provided by C5—H5B···Cg interactions (Cg is the mid-point of the C8—C9 bond) involving the alkyne unit (Fig. 3). Such contacts are often overlooked, but they have been reported previously for both terminal and non-terminal alkyne systems (Banerjee et al., 2006; Thakur et al., 2010; McAdam et al., 2012). Overall, these contacts generate a three-dimensional network with molecules stacked in interconnected columns along the b axis (Fig. 4).

Database survey top

The Cambridge Structural Database (CSD; Version 5.35, November 2013 with 2 updates; Allen, 2002) reveals a total of 175 structures of TEMPO and its derivatives. However, structures of alkoxy-TEMPO derivatives are rare with only a single example, albeit in two separate papers in which Polovyanenko et al. (2008) and Soegiarto et al. (2011) report the structure of 4-(methoxy)-TEMPO, 4-(methoxy)-2,2,6,6-tetramethylpiperidin-1-oxyl. The first paper examines the TEMPO derivative as an inclusion complex of p-hexanoyl calix[4]arene (C₆OH), and investigates the magnetism and orientation dependent motion of the encapsulated radical. In the second, the molecule is included in the cavities of two porous frameworks derived from guanidinium cations and two organodisulfonate anions; the magnetic behaviour of the radical guest is investigated. Aryloyloxy-TEMPO derivatives are more abundant with 19 entries in the CSD (see, for example, Pang et al., 2013; Nakazawa et al., 2012; Akutsu et al., 2005). Again, the focus is very much on the magnetic properties of the materials.

Synthesis and crystallization top

Synthesis and characterisation (IR and mass spectroscopy) are as previously described (Gheorghe et al., 2006; Kulis et al., 2009). Colourless blocks were obtained from diethyl ether solution at room temperature. Analysis calculated for C₁₂H₂₀NO₂: C 68.54, H 9.59, N 6.66%; found: C 68.57, H 9.66, N 6.68%.

Refinement top

Related literature top

For related literature, see: Akutsu et al. (2005); Allen (2002); Banerjee et al. (2006); Bode et al. (2007); Gheorghe et al. (2006); Goswami et al. (2013); Hein & Fokin (2010); Ishida et al. (1995); Iwasaki et al. (1999a, 1999b); Kulis et al. (2009); Lewis et al. (2013); Macrae et al. (2008); McAdam et al. (2012); Nakazawa et al. (2012); Pang et al. (2013); Polovyanenko et al. (2008); Soegiarto et al. (2011); Thakur et al. (2010); Togashi et al. (1996); Zhao et al. (2005).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2013); cell refinement: CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SIR2011 (Burla et al., 2012); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip 2010).

Figures top

	Fig. 1. The structure of (1), showing the atom numbering and with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Double chains formed from molecules of (1) along b. In this and subsequent Figures, C—H···O hydrogen bonds are drawn as dashed lines and H atoms bound to atoms not involved in hydrogen bonding are not shown.
	Fig. 3. Zigzag chains formed along a from C—H···O and C—H···π (green dotted lines) contacts. The mid-point of the C8═C9 triple bond is shown as a red sphere.
	Fig. 4. The overall packing for (1), viewed along the b axis.

4-(Prop-2-ynyloxy)-2,2,6,6-tetramethylpiperidin-1-oxyl top

Crystal data top

C₁₂H₂₀NO₂	D_x = 1.167 Mg m⁻³
M_r = 210.29	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 4862 reflections
a = 7.94506 (13) Å	θ = 5.3–74.2°
b = 10.17919 (16) Å	µ = 0.63 mm⁻¹
c = 14.8052 (3) Å	T = 100 K
V = 1197.36 (4) Å³	Block, colourless
Z = 4	0.18 × 0.15 × 0.08 mm
F(000) = 460

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2307 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	2203 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.046
Detector resolution: 5.1725 pixels mm^-1	θ_max = 74.3°, θ_min = 5.3°
ω scans	h = −9→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −12→12
T_min = 0.522, T_max = 1.000	l = −18→13
6622 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.043	w = 1/[σ²(F_o²) + (0.0376P)² + 1.029P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.123	(Δ/σ)_max < 0.001
S = 1.15	Δρ_max = 0.22 e Å⁻³
2307 reflections	Δρ_min = −0.28 e Å⁻³
140 parameters	Absolute structure: Flack x determined using 858 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
90 restraints	Absolute structure parameter: 0.0 (3)

Crystal data top

C₁₂H₂₀NO₂	V = 1197.36 (4) Å³
M_r = 210.29	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 7.94506 (13) Å	µ = 0.63 mm⁻¹
b = 10.17919 (16) Å	T = 100 K
c = 14.8052 (3) Å	0.18 × 0.15 × 0.08 mm

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	2307 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	2203 reflections with I > 2σ(I)
T_min = 0.522, T_max = 1.000	R_int = 0.046
6622 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.123	Δρ_max = 0.22 e Å⁻³
S = 1.15	Δρ_min = −0.28 e Å⁻³
2307 reflections	Absolute structure: Flack x determined using 858 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
140 parameters	Absolute structure parameter: 0.0 (3)
90 restraints

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.3936 (3)	0.73046 (19)	0.71556 (15)	0.0174 (5)
N1	0.3444 (3)	0.8315 (2)	0.67027 (16)	0.0107 (5)
C2	0.2036 (4)	0.9093 (3)	0.71116 (19)	0.0116 (6)
C21	0.2698 (4)	0.9827 (3)	0.7945 (2)	0.0169 (6)
H21A	0.3310	0.9214	0.8335	0.025*
H21B	0.1750	1.0205	0.8280	0.025*
H21C	0.3457	1.0533	0.7753	0.025*
C22	0.0670 (4)	0.8118 (3)	0.7398 (2)	0.0179 (7)
H22A	0.0301	0.7611	0.6872	0.027*
H22B	−0.0289	0.8599	0.7651	0.027*
H22C	0.1125	0.7520	0.7856	0.027*
C3	0.1325 (3)	1.0046 (3)	0.6408 (2)	0.0119 (6)
H3A	0.0654	0.9543	0.5964	0.014*
H3B	0.0558	1.0671	0.6714	0.014*
C4	0.2663 (4)	1.0812 (3)	0.59126 (19)	0.0099 (6)
H4	0.3331	1.1364	0.6341	0.012*
C5	0.3796 (4)	0.9843 (3)	0.54137 (19)	0.0112 (6)
H5A	0.4664	1.0342	0.5078	0.013*
H5B	0.3110	0.9357	0.4966	0.013*
C6	0.4674 (4)	0.8850 (3)	0.6036 (2)	0.0114 (6)
C61	0.6167 (4)	0.9461 (3)	0.6539 (2)	0.0152 (6)
H61A	0.5803	1.0270	0.6840	0.023*
H61B	0.7065	0.9665	0.6108	0.023*
H61C	0.6587	0.8839	0.6991	0.023*
C62	0.5300 (4)	0.7698 (3)	0.5464 (2)	0.0168 (6)
H62A	0.5934	0.7087	0.5846	0.025*
H62B	0.6031	0.8028	0.4982	0.025*
H62C	0.4335	0.7240	0.5197	0.025*
O2	0.1772 (3)	1.16202 (19)	0.52724 (14)	0.0140 (5)
C7	0.2733 (4)	1.2682 (3)	0.4916 (2)	0.0149 (6)
H7A	0.2201	1.2992	0.4350	0.018*
H7B	0.3877	1.2362	0.4765	0.018*
C8	0.2872 (4)	1.3793 (3)	0.5551 (2)	0.0160 (6)
C9	0.2975 (4)	1.4705 (3)	0.6048 (2)	0.0198 (7)
H9	0.3058	1.5435	0.6445	0.024*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0281 (11)	0.0083 (9)	0.0159 (11)	0.0025 (9)	0.0015 (10)	0.0060 (8)
N1	0.0172 (11)	0.0066 (10)	0.0085 (10)	0.0001 (9)	0.0007 (10)	0.0011 (8)
C2	0.0163 (13)	0.0110 (12)	0.0075 (12)	−0.0005 (11)	0.0037 (12)	0.0002 (10)
C21	0.0245 (15)	0.0169 (14)	0.0092 (14)	−0.0002 (12)	−0.0002 (13)	−0.0026 (11)
C22	0.0208 (15)	0.0190 (15)	0.0140 (15)	−0.0056 (12)	0.0028 (13)	0.0044 (12)
C3	0.0145 (12)	0.0110 (12)	0.0101 (13)	0.0020 (10)	0.0011 (11)	−0.0008 (10)
C4	0.0148 (13)	0.0087 (12)	0.0061 (12)	0.0005 (10)	0.0000 (11)	0.0012 (9)
C5	0.0160 (12)	0.0092 (12)	0.0084 (13)	−0.0001 (10)	0.0009 (11)	0.0009 (10)
C6	0.0161 (12)	0.0090 (12)	0.0090 (13)	0.0008 (10)	−0.0008 (11)	0.0015 (10)
C61	0.0165 (13)	0.0132 (13)	0.0160 (15)	−0.0004 (11)	−0.0003 (13)	0.0025 (11)
C62	0.0229 (14)	0.0122 (13)	0.0153 (16)	0.0036 (11)	0.0048 (13)	−0.0019 (11)
O2	0.0178 (10)	0.0102 (9)	0.0140 (10)	0.0000 (8)	−0.0032 (9)	0.0041 (7)
C7	0.0209 (14)	0.0105 (12)	0.0133 (14)	0.0004 (11)	−0.0017 (12)	0.0040 (10)
C8	0.0178 (13)	0.0139 (13)	0.0161 (14)	−0.0007 (11)	−0.0008 (12)	0.0057 (11)
C9	0.0275 (15)	0.0155 (15)	0.0164 (15)	−0.0025 (12)	−0.0026 (14)	0.0022 (12)

Geometric parameters (Å, º) top

O1—N1	1.289 (3)	C5—C6	1.535 (4)
N1—C6	1.492 (4)	C5—H5A	0.9900
N1—C2	1.498 (4)	C5—H5B	0.9900
C2—C3	1.531 (4)	C6—C62	1.530 (4)
C2—C22	1.531 (4)	C6—C61	1.532 (4)
C2—C21	1.536 (4)	C61—H61A	0.9800
C21—H21A	0.9800	C61—H61B	0.9800
C21—H21B	0.9800	C61—H61C	0.9800
C21—H21C	0.9800	C62—H62A	0.9800
C22—H22A	0.9800	C62—H62B	0.9800
C22—H22B	0.9800	C62—H62C	0.9800
C22—H22C	0.9800	O2—C7	1.424 (3)
C3—C4	1.509 (4)	C7—C8	1.475 (4)
C3—H3A	0.9900	C7—H7A	0.9900
C3—H3B	0.9900	C7—H7B	0.9900
C4—O2	1.441 (3)	C8—C9	1.187 (5)
C4—C5	1.526 (4)	C9—H9	0.9500
C4—H4	1.0000

O1—N1—C6	115.9 (2)	C4—C5—C6	113.8 (2)
O1—N1—C2	116.0 (2)	C4—C5—H5A	108.8
C6—N1—C2	124.3 (2)	C6—C5—H5A	108.8
N1—C2—C3	109.6 (2)	C4—C5—H5B	108.8
N1—C2—C22	107.3 (2)	C6—C5—H5B	108.8
C3—C2—C22	109.7 (2)	H5A—C5—H5B	107.7
N1—C2—C21	109.1 (2)	N1—C6—C62	107.4 (2)
C3—C2—C21	111.4 (2)	N1—C6—C61	109.5 (2)
C22—C2—C21	109.6 (2)	C62—C6—C61	109.2 (2)
C2—C21—H21A	109.5	N1—C6—C5	109.9 (2)
C2—C21—H21B	109.5	C62—C6—C5	108.7 (2)
H21A—C21—H21B	109.5	C61—C6—C5	112.1 (2)
C2—C21—H21C	109.5	C6—C61—H61A	109.5
H21A—C21—H21C	109.5	C6—C61—H61B	109.5
H21B—C21—H21C	109.5	H61A—C61—H61B	109.5
C2—C22—H22A	109.5	C6—C61—H61C	109.5
C2—C22—H22B	109.5	H61A—C61—H61C	109.5
H22A—C22—H22B	109.5	H61B—C61—H61C	109.5
C2—C22—H22C	109.5	C6—C62—H62A	109.5
H22A—C22—H22C	109.5	C6—C62—H62B	109.5
H22B—C22—H22C	109.5	H62A—C62—H62B	109.5
C4—C3—C2	113.5 (2)	C6—C62—H62C	109.5
C4—C3—H3A	108.9	H62A—C62—H62C	109.5
C2—C3—H3A	108.9	H62B—C62—H62C	109.5
C4—C3—H3B	108.9	C7—O2—C4	114.4 (2)
C2—C3—H3B	108.9	O2—C7—C8	112.7 (2)
H3A—C3—H3B	107.7	O2—C7—H7A	109.1
O2—C4—C3	105.6 (2)	C8—C7—H7A	109.1
O2—C4—C5	109.9 (2)	O2—C7—H7B	109.1
C3—C4—C5	108.5 (2)	C8—C7—H7B	109.1
O2—C4—H4	110.9	H7A—C7—H7B	107.8
C3—C4—H4	110.9	C9—C8—C7	178.6 (3)
C5—C4—H4	110.9	C8—C9—H9	180.0

O1—N1—C2—C3	−166.8 (2)	O1—N1—C6—C62	49.9 (3)
C6—N1—C2—C3	36.2 (4)	C2—N1—C6—C62	−153.1 (3)
O1—N1—C2—C22	−47.7 (3)	O1—N1—C6—C61	−68.6 (3)
C6—N1—C2—C22	155.3 (3)	C2—N1—C6—C61	88.4 (3)
O1—N1—C2—C21	71.0 (3)	O1—N1—C6—C5	167.9 (2)
C6—N1—C2—C21	−86.0 (3)	C2—N1—C6—C5	−35.1 (4)
N1—C2—C3—C4	−47.6 (3)	C4—C5—C6—N1	45.1 (3)
C22—C2—C3—C4	−165.2 (2)	C4—C5—C6—C62	162.3 (2)
C21—C2—C3—C4	73.2 (3)	C4—C5—C6—C61	−76.9 (3)
C2—C3—C4—O2	178.6 (2)	C3—C4—O2—C7	163.0 (2)
C2—C3—C4—C5	60.8 (3)	C5—C4—O2—C7	−80.2 (3)
O2—C4—C5—C6	−174.6 (2)	C4—O2—C7—C8	−77.8 (3)
C3—C4—C5—C6	−59.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg is the mid-point of the C8–C9 bond.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.95	2.28	3.205 (4)	163
C7—H7B···O2ⁱⁱ	0.99	2.52	3.298 (4)	135
C61—H61A···O1ⁱⁱⁱ	0.98	2.56	3.481 (4)	157
C5—H5B···Cg^iv	0.99	2.93	3.885 (4)	156

Symmetry codes: (i) x, y+1, z; (ii) x+1/2, −y+5/2, −z+1; (iii) −x+1, y+1/2, −z+3/2; (iv) −x−1, y+5/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

Cg is the mid-point of the C8–C9 bond.

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.95	2.28	3.205 (4)	163
C7—H7B···O2ⁱⁱ	0.99	2.52	3.298 (4)	135
C61—H61A···O1ⁱⁱⁱ	0.98	2.56	3.481 (4)	157
C5—H5B···Cg^iv	0.99	2.93	3.885 (4)	156

Symmetry codes: (i) x, y+1, z; (ii) x+1/2, −y+5/2, −z+1; (iii) −x+1, y+1/2, −z+3/2; (iv) −x−1, y+5/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₂₀NO₂
M_r	210.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.94506 (13), 10.17919 (16), 14.8052 (3)
V (Å³)	1197.36 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.63
Crystal size (mm)	0.18 × 0.15 × 0.08

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2013)
T_min, T_max	0.522, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6622, 2307, 2203
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.624

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.123, 1.15
No. of reflections	2307
No. of parameters	140
No. of restraints	90
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.28
Absolute structure	Flack x determined using 858 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons & Flack, 2004)
Absolute structure parameter	0.0 (3)

Computer programs: CrysAlis PRO (Agilent, 2013), SIR2011 (Burla et al., 2012), SHELXL2013 (Sheldrick, 2008) and TITAN2000 (Hunter & Simpson, 1999), Mercury (Macrae et al., 2008), SHELXL2013 (Sheldrick, 2008), enCIFer (Allen et al., 2004), PLATON (Spek, 2009) and publCIF (Westrip 2010).

Acknowledgements

We thank the University of Otago for the purchase of the diffractometer.

References

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Volume 70| Part 9| September 2014| Pages 130-133

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of 4-(prop-2-yn­yl­oxy)-2,2,6,6-tetra­methyl­piperidin-1-ox­yl

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Crystal structure of 4-(prop-2-ynyloxy)-2,2,6,6-tetramethylpiperidin-1-oxyl

3. Supramolecular features