tert-Butyl 4-cyano­phenyl carbonate

Applewhite, M.J.

doi:10.1107/S1600536810038602

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2681

doi:10.1107/S1600536810038602

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tert-Butyl 4-cyanophenyl carbonate

Malcolm J. Applewhite ^a ^*

^aDepartment of Chemistry and Polymer Science, Stellenbosch University, Private Bag X1, Matieland 7602, South Africa
^*Correspondence e-mail: malcolma@sun.ac.za

(Received 15 September 2010; accepted 27 September 2010; online 30 September 2010)

The title compound, C₁₂H₁₃NO₃, was prepared by reacting one equivalent of di-tert-butyl dicarbonate with 4-cyanophenol. Herringbone crystal packing is observed and there are no significant intermolecular interactions.

Related literature

For a similar packing arrangement in related structures, see: Girard et al. (2005 ); Nagata et al. (2008 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₂H₁₃NO₃
M_r = 219.23
Monoclinic, P 2₁ /c
a = 5.7347 (7) Å
b = 14.3237 (16) Å
c = 13.7727 (16) Å
β = 101.110 (1)°
V = 1110.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.45 × 0.25 × 0.12 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.959, T_max = 0.989
6536 measured reflections
2427 independent reflections
2100 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.091
S = 1.05
2427 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ; Atwood & Barbour, 2003 ); software used to prepare material for publication: X-SEED (Barbour, 2001; Atwood & Barbour, 2003).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810038602/bh2315sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810038602/bh2315Isup2.hkl

checkCIF report

Comment top

In the title molecule, all bond lengths after refinement are within the normal values as previously collected by Allen et al. (1987).

The two-dimensional herring-bone type packing along the b and c axis observed has two molecules oriented in opposite directions in each turn. Such an arrangement is similar to that described by Girard et al. (2005) and Nagata et al. (2008) for related organics.

Related literature top

For a similar packing arrangement in related structures, see: Girard et al. (2005); Nagata et al. (2008). For reference structural data, see: Allen et al. (1987).

Experimental top

Di-tert-butyl dicarbonate (279 mg, 1.28 mmol) was added to 4-cyano phenol in 5 ml of dichloromethane. 4-Dimethylamino pyridine (5.20 mg, 0.043 mmol) as a catalyst and triethylamine (0.263 ml, 1.87 mmol) as a base were also added. The solution was stirred at room temperature for six hours.

The reaction was then worked-up using 20 ml of H₂O and 10 ml of 2M HCl which was repeated. The solution was then dried over MgSO₄ after which the solvent was reduced. The resultant white solid was then dried thoroughly under vacuum.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001; Atwood & Barbour, 2003); software used to prepare material for publication: X-SEED (Barbour, 2001; Atwood & Barbour, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound showing the 50% probability ellipsoids for non-H atoms.
	Fig. 2. The crystal packing viewed down the a axis which shows the herring-bone type packing and the two oppositely oriented molecules in each turn.

tert-Butyl 4-cyanophenyl carbonate top

Crystal data top

C₁₂H₁₃NO₃	F(000) = 464
M_r = 219.23	D_x = 1.312 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3143 reflections
a = 5.7347 (7) Å	θ = 2.8–27.5°
b = 14.3237 (16) Å	µ = 0.10 mm⁻¹
c = 13.7727 (16) Å	T = 296 K
β = 101.110 (1)°	Plate, colourless
V = 1110.1 (2) Å³	0.45 × 0.25 × 0.12 mm
Z = 4

Data collection top

Bruker APEX CCD area-detector diffractometer	2427 independent reflections
Radiation source: fine-focus sealed tube	2100 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.9°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→7
T_min = 0.959, T_max = 0.989	k = −18→14
6536 measured reflections	l = −17→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0448P)² + 0.3462P] where P = (F_o² + 2F_c²)/3
2427 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³
0 constraints

Crystal data top

C₁₂H₁₃NO₃	V = 1110.1 (2) Å³
M_r = 219.23	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 5.7347 (7) Å	µ = 0.10 mm⁻¹
b = 14.3237 (16) Å	T = 296 K
c = 13.7727 (16) Å	0.45 × 0.25 × 0.12 mm
β = 101.110 (1)°

Data collection top

Bruker APEX CCD area-detector diffractometer	2427 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2100 reflections with I > 2σ(I)
T_min = 0.959, T_max = 0.989	R_int = 0.017
6536 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.091	H-atom parameters constrained
S = 1.05	Δρ_max = 0.31 e Å⁻³
2427 reflections	Δρ_min = −0.23 e Å⁻³
148 parameters

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

	x	y	z	U_iso*/U_eq
N1	0.33241 (18)	0.70351 (7)	0.16270 (7)	0.0241 (2)
C2	0.4174 (2)	0.69212 (8)	0.24446 (8)	0.0182 (2)
C3	0.52163 (19)	0.67936 (8)	0.34783 (8)	0.0163 (2)
C4	0.74719 (19)	0.71664 (8)	0.38553 (8)	0.0180 (2)
H4	0.8322	0.7469	0.3438	0.022*
C5	0.84213 (19)	0.70792 (8)	0.48552 (8)	0.0187 (2)
H5	0.9911	0.7325	0.5117	0.022*
C6	0.7118 (2)	0.66212 (8)	0.54586 (8)	0.0170 (2)
C7	0.4902 (2)	0.62391 (8)	0.50998 (8)	0.0187 (2)
H7	0.4072	0.5931	0.5521	0.022*
C8	0.3944 (2)	0.63258 (8)	0.40994 (8)	0.0182 (2)
H8	0.2459	0.6073	0.3843	0.022*
O9	0.79952 (14)	0.65945 (6)	0.64836 (6)	0.0199 (2)
C10	0.97513 (19)	0.59643 (8)	0.68019 (8)	0.0159 (2)
O11	1.04663 (14)	0.53999 (6)	0.62887 (6)	0.0211 (2)
O12	1.04148 (14)	0.61088 (6)	0.77662 (5)	0.01731 (19)
C13	1.22277 (19)	0.54939 (8)	0.83729 (8)	0.0161 (2)
C14	1.2463 (2)	0.59433 (9)	0.93865 (8)	0.0210 (3)
H14A	1.3021	0.6573	0.9359	0.032*
H14B	1.3575	0.5594	0.9860	0.032*
H14C	1.0943	0.5947	0.9581	0.032*
C15	1.1255 (2)	0.45053 (8)	0.83660 (9)	0.0203 (2)
H15A	0.9751	0.4516	0.8574	0.030*
H15B	1.2350	0.4123	0.8811	0.030*
H15C	1.1050	0.4254	0.7709	0.030*
C16	1.45548 (19)	0.55369 (8)	0.79966 (8)	0.0189 (2)
H16A	1.4385	0.5204	0.7382	0.028*
H16B	1.5798	0.5257	0.8475	0.028*
H16C	1.4948	0.6177	0.7896	0.028*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0254 (5)	0.0257 (6)	0.0193 (5)	−0.0037 (4)	−0.0003 (4)	0.0010 (4)
C2	0.0180 (5)	0.0158 (5)	0.0206 (6)	−0.0013 (4)	0.0029 (4)	−0.0008 (4)
C3	0.0179 (5)	0.0151 (5)	0.0150 (5)	0.0023 (4)	0.0012 (4)	−0.0004 (4)
C4	0.0181 (5)	0.0186 (5)	0.0176 (5)	−0.0002 (4)	0.0039 (4)	0.0022 (4)
C5	0.0150 (5)	0.0210 (6)	0.0189 (6)	−0.0004 (4)	0.0007 (4)	0.0001 (4)
C6	0.0187 (5)	0.0184 (5)	0.0135 (5)	0.0058 (4)	0.0019 (4)	0.0013 (4)
C7	0.0201 (5)	0.0181 (6)	0.0191 (6)	0.0015 (4)	0.0070 (4)	0.0025 (4)
C8	0.0158 (5)	0.0175 (5)	0.0207 (6)	−0.0009 (4)	0.0022 (4)	−0.0012 (4)
O9	0.0201 (4)	0.0259 (4)	0.0133 (4)	0.0071 (3)	0.0020 (3)	0.0025 (3)
C10	0.0144 (5)	0.0171 (5)	0.0160 (5)	−0.0008 (4)	0.0029 (4)	0.0025 (4)
O11	0.0240 (4)	0.0221 (4)	0.0167 (4)	0.0043 (3)	0.0026 (3)	−0.0016 (3)
O12	0.0181 (4)	0.0204 (4)	0.0130 (4)	0.0056 (3)	0.0018 (3)	0.0013 (3)
C13	0.0153 (5)	0.0179 (5)	0.0144 (5)	0.0036 (4)	0.0008 (4)	0.0032 (4)
C14	0.0238 (6)	0.0241 (6)	0.0144 (5)	0.0055 (5)	0.0016 (4)	0.0012 (4)
C15	0.0192 (5)	0.0197 (6)	0.0221 (6)	0.0001 (4)	0.0040 (4)	0.0035 (4)
C16	0.0168 (5)	0.0191 (6)	0.0208 (6)	0.0010 (4)	0.0037 (4)	0.0014 (4)

Geometric parameters (Å, º) top

N1—C2	1.1493 (15)	C10—O12	1.3254 (13)
C2—C3	1.4455 (15)	O12—C13	1.4899 (13)
C3—C8	1.3979 (16)	C13—C14	1.5194 (15)
C3—C4	1.4032 (15)	C13—C15	1.5214 (16)
C4—C5	1.3855 (15)	C13—C16	1.5231 (15)
C4—H4	0.9300	C14—H14A	0.9600
C5—C6	1.3850 (16)	C14—H14B	0.9600
C5—H5	0.9300	C14—H14C	0.9600
C6—C7	1.3846 (16)	C15—H15A	0.9600
C6—O9	1.4049 (13)	C15—H15B	0.9600
C7—C8	1.3871 (16)	C15—H15C	0.9600
C7—H7	0.9300	C16—H16A	0.9600
C8—H8	0.9300	C16—H16B	0.9600
O9—C10	1.3605 (13)	C16—H16C	0.9600
C10—O11	1.1971 (14)

N1—C2—C3	178.86 (13)	O12—C13—C14	101.18 (8)
C8—C3—C4	120.57 (10)	O12—C13—C15	109.34 (9)
C8—C3—C2	119.85 (10)	C14—C13—C15	111.57 (9)
C4—C3—C2	119.55 (10)	O12—C13—C16	110.35 (9)
C5—C4—C3	119.42 (10)	C14—C13—C16	111.52 (9)
C5—C4—H4	120.3	C15—C13—C16	112.32 (9)
C3—C4—H4	120.3	C13—C14—H14A	109.5
C6—C5—C4	119.01 (10)	C13—C14—H14B	109.5
C6—C5—H5	120.5	H14A—C14—H14B	109.5
C4—C5—H5	120.5	C13—C14—H14C	109.5
C7—C6—C5	122.50 (10)	H14A—C14—H14C	109.5
C7—C6—O9	118.29 (10)	H14B—C14—H14C	109.5
C5—C6—O9	119.07 (10)	C13—C15—H15A	109.5
C6—C7—C8	118.67 (10)	C13—C15—H15B	109.5
C6—C7—H7	120.7	H15A—C15—H15B	109.5
C8—C7—H7	120.7	C13—C15—H15C	109.5
C7—C8—C3	119.82 (10)	H15A—C15—H15C	109.5
C7—C8—H8	120.1	H15B—C15—H15C	109.5
C3—C8—H8	120.1	C13—C16—H16A	109.5
C10—O9—C6	116.18 (9)	C13—C16—H16B	109.5
O11—C10—O12	129.21 (10)	H16A—C16—H16B	109.5
O11—C10—O9	125.05 (10)	C13—C16—H16C	109.5
O12—C10—O9	105.73 (9)	H16A—C16—H16C	109.5
C10—O12—C13	120.28 (8)	H16B—C16—H16C	109.5

C8—C3—C4—C5	−0.93 (17)	C7—C6—O9—C10	105.80 (12)
C2—C3—C4—C5	177.14 (10)	C5—C6—O9—C10	−78.37 (13)
C3—C4—C5—C6	0.27 (17)	C6—O9—C10—O11	−5.43 (16)
C4—C5—C6—C7	0.48 (17)	C6—O9—C10—O12	175.49 (9)
C4—C5—C6—O9	−175.16 (10)	O11—C10—O12—C13	−2.85 (17)
C5—C6—C7—C8	−0.55 (17)	O9—C10—O12—C13	176.18 (8)
O9—C6—C7—C8	175.12 (10)	C10—O12—C13—C14	177.84 (9)
C6—C7—C8—C3	−0.12 (17)	C10—O12—C13—C15	−64.35 (12)
C4—C3—C8—C7	0.86 (17)	C10—O12—C13—C16	59.67 (12)
C2—C3—C8—C7	−177.20 (10)

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₃
M_r	219.23
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	5.7347 (7), 14.3237 (16), 13.7727 (16)
β (°)	101.110 (1)
V (Å³)	1110.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.45 × 0.25 × 0.12

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.959, 0.989
No. of measured, independent and observed [I > 2σ(I)] reflections	6536, 2427, 2100
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.05
No. of reflections	2427
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.23

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001; Atwood & Barbour, 2003).

Acknowledgements

The author would like to thank the Central Analytical Facility (CAF) at the University of Stellenbosch (US) for the use of their diffractometer as well as the US and the NRF for funding.

References

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