tert-Butyl 4-cyano­phenyl carbonate

Abstract

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,

• a = 5.7347 (7) Å

• b = 14.3237 (16) Å

• c = 13.7727 (16) Å

• β = 101.110 (1)°

• V = 1110.1 (2) ų

• 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[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Structure solution and refinement were performed using the SHELX97 suite of programs (Sheldrick, 2008). The H atoms were placed in calculated positions, using and refined using a riding model, with C—H bond lengths fixed to 0.93 (aromatic CH) or 0.96 Å (methyl CH₃).

Figures

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.

Crystal data

C12H13NO3	F(000) = 464
Mr = 219.23	Dx = 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

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

Refinement

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(Fo2) + (0.0448P)2 + 0.3462P] where P = (Fo2 + 2Fc2)/3
2427 reflections	(Δ/σ)max < 0.001
148 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.23 e Å−3
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)