4-Nitro-1-[(trimethyl­sil­yl)ethyn­yl]benzene: low-temperature polymorph at 100 K

Millican, J.N.; Fronczek, F.R.; Watkins, S.F.

doi:10.1107/S1600536812034034

organic compounds

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Volume 68| Part 9| September 2012| Page o2652

doi:10.1107/S1600536812034034

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4-Nitro-1-[(trimethylsilyl)ethynyl]benzene: low-temperature polymorph at 100 K †

Jasmine N. Millican,^a Frank R. Fronczek ^a ^* and Steve F. Watkins ^a

^aDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 27 July 2012; accepted 30 July 2012; online 8 August 2012)

The title compound, C₁₁H₁₃NO₂Si, is a low-temperature form of the previously reported room-temperature structure [Garcia et al. (1998 ). Acta Cryst. C54, 489–491]. At 298 K, the material crystallizes in the space group Pnma and occupies a crystallographic mirror plane, but at 100 K the space group changes to P2₁2₁2₁, the volume decreases by 5% and the molecule distorts. The greatest molecular distortions from C_s symmetry are rotations of the trimethylsilyl and nitro groups by 10.56 (8) and 11.47 (9)°, respectively, to the benzene mean plane. At low temperature, the crystal also becomes an inversion twin, the refined ratio of the twin components being 0.35 (15):0.65 (15).

Related literature

For the synthesis of the title compound, see: Takahashi et al. (1980 ). For the crystal structure of the room temperature form of the title compound, see: Garcia et al. (1998). For a description of the Cambridge Structural Database, see: Allen (2002 ). For Hooft analysis of Bijvoet pairs, see: Hooft et al. (2008 ).

Experimental

Crystal data

C₁₁H₁₃NO₂Si
M_r = 219.31
Orthorhombic, P 2₁ 2₁ 2₁
a = 10.222 (2) Å
b = 7.128 (2) Å
c = 16.537 (4) Å
V = 1204.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.12 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.966, T_max = 0.979
17805 measured reflections
4690 independent reflections
3538 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.123
S = 1.02
4690 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 1953 Bijvoet pairs
Flack parameter: 0.35 (15)

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812034034/su2491sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034034/su2491Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812034034/su2491Isup3.cml

checkCIF report

Comment top

At 298 K title molecule has C_s symmetry (Garcia et al., 1998; CSD refcode NILWIO; Allen, 2002), with all but two methyl groups lying in the mirror plane. When the temperature is reduced to 100 K, the inversion center vanishes and the space group changes from Pnma to P2₁2₁2₁, the unit cell volume is reduced from 1261.8 (3) to 1204.9 (5) Å³, and the molecular symmetry is reduced to C₁. The mean plane of the six benzene C atoms, (mean deviation δ_r.m.s. = 0.004 Å), is normal to the b axis at 298 K but inclines +4.51 (8)° from normal at 100 K, while the C1—Si1—C9 plane is rotated off-normal by -6.05 (8)° and the NO₂ group is rotated off-normal by +15.78 (9)°.

Other geometrical parameters in the two polymorphs are similar, for example [those at 298 K are in parentheses] : C1≡C2 = 1.209 (2) [1.199 (4)] Å, Si1—C1 = 1.845 (2) [1.839 (3)] Å, Si1—C9 = 1.856 (2) [1.831 (4)] Å, Si1—C10 = 1.853 (2) [1.838 (3)] Å, Si1—C10B = 1.856 (2)[1.838 (3)] Å, N1—O1 = 1.219 (2) [1.201 (4)] Å, N1—O2 = 1.221 (2) [1.175 (4)] Å, Si1—C1≡C2 = 176.1 (2) [177.9 (3)]°, C1≡C2—C3 = 175.9 (2) [178.0 (3)]°, O1—N1—O2 = 123.5 (2) [122.9 (3)]°.

Related literature top

For the synthesis of the title compound, see: Takahashi et al. (1980). For the crystal structure of the room temperature form of the title compound, see: Garcia et al. (1998). For a description of the Cambridge Structural Database, see: Allen (2002). For Hooft analysis of Bijvoet pairs, see: Hooft et al. (2008).

Experimental top

The compound was prepared by palladium(II) coupling of trimethylsilylacetylene with 4-nitroiodobenzene as described by (Takahashi et al., 1980).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. View of the molecular structure of the title compound, with atom numbering. The displacement ellipsoids are drawn at the 50% probability level.

4-Nitro-1-[(trimethylsilyl)ethynyl]benzene top

Crystal data top

C₁₁H₁₃NO₂Si	F(000) = 464
M_r = 219.31	D_x = 1.209 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2709 reflections
a = 10.222 (2) Å	θ = 2.5–34.3°
b = 7.128 (2) Å	µ = 0.18 mm⁻¹
c = 16.537 (4) Å	T = 100 K
V = 1204.9 (5) Å³	Needle fragment, yellow
Z = 4	0.20 × 0.15 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	4690 independent reflections
Radiation source: sealed tube	3538 reflections with I > 2σ(I)
Horizonally mounted graphite crystal monochromator	R_int = 0.032
Detector resolution: 9 pixels mm^-1	θ_max = 33.8°, θ_min = 3.1°
ω and ϕ scans	h = −15→15
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −11→11
T_min = 0.966, T_max = 0.979	l = −25→25
17805 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.123	w = 1/[σ²(F_o²) + (0.046P)² + 0.4973P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
4690 reflections	Δρ_max = 0.36 e Å⁻³
139 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1953 Bijvoet pairs
0 constraints	Absolute structure parameter: 0.35 (15)
Primary atom site location: structure-invariant direct methods

Crystal data top

C₁₁H₁₃NO₂Si	V = 1204.9 (5) Å³
M_r = 219.31	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 10.222 (2) Å	µ = 0.18 mm⁻¹
b = 7.128 (2) Å	T = 100 K
c = 16.537 (4) Å	0.20 × 0.15 × 0.12 mm

Data collection top

Nonius KappaCCD diffractometer	4690 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	3538 reflections with I > 2σ(I)
T_min = 0.966, T_max = 0.979	R_int = 0.032
17805 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.123	Δρ_max = 0.36 e Å⁻³
S = 1.02	Δρ_min = −0.32 e Å⁻³
4690 reflections	Absolute structure: Flack (1983), 1953 Bijvoet pairs
139 parameters	Absolute structure parameter: 0.35 (15)
0 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
C1	0.67962 (16)	0.2773 (3)	0.66604 (9)	0.0270 (3)
C2	0.77829 (16)	0.2789 (3)	0.70632 (9)	0.0252 (3)
C3	0.89002 (14)	0.2769 (3)	0.75911 (9)	0.0218 (3)
C4	1.01780 (16)	0.2851 (3)	0.72849 (9)	0.0262 (3)
H4	1.0316	0.2956	0.6719	0.031*
C5	1.12430 (15)	0.2779 (3)	0.78050 (10)	0.0265 (3)
H5	1.2111	0.2842	0.7602	0.032*
C6	1.10107 (14)	0.2614 (3)	0.86239 (9)	0.0234 (3)
C7	0.97590 (14)	0.2541 (3)	0.89480 (9)	0.0242 (3)
H7	0.9629	0.2433	0.9515	0.029*
C8	0.87080 (14)	0.2629 (3)	0.84253 (9)	0.0225 (3)
H8	0.7843	0.2594	0.8635	0.027*
C9	0.5612 (2)	0.2384 (5)	0.50094 (10)	0.0415 (5)
H9A	0.6112	0.1226	0.4926	0.062*
H9B	0.6129	0.3459	0.4825	0.062*
H9C	0.4794	0.2322	0.4702	0.062*
C10	0.4263 (2)	0.0658 (3)	0.64911 (14)	0.0376 (5)
H10A	0.4097	0.0836	0.707	0.056*
H10B	0.475	−0.0512	0.6409	0.056*
H10C	0.3429	0.0593	0.6201	0.056*
C10B	0.4280 (2)	0.4829 (3)	0.62787 (15)	0.0394 (5)
H10D	0.477	0.5912	0.6075	0.059*
H10E	0.4124	0.4982	0.686	0.059*
H10F	0.3439	0.4742	0.5996	0.059*
N1	1.21298 (13)	0.2499 (3)	0.91772 (9)	0.0345 (3)
O1	1.32160 (13)	0.2830 (3)	0.89090 (11)	0.0531 (4)
O2	1.19270 (16)	0.2043 (4)	0.98780 (9)	0.0670 (7)
Si1	0.52365 (4)	0.26554 (7)	0.61012 (3)	0.02349 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0248 (7)	0.0341 (10)	0.0221 (7)	0.0007 (8)	−0.0007 (6)	−0.0014 (7)
C2	0.0248 (7)	0.0291 (9)	0.0219 (6)	0.0008 (7)	−0.0009 (5)	−0.0006 (7)
C3	0.0208 (6)	0.0240 (8)	0.0207 (6)	0.0008 (7)	−0.0020 (5)	0.0005 (6)
C4	0.0247 (7)	0.0345 (9)	0.0194 (6)	0.0007 (8)	0.0022 (6)	0.0026 (6)
C5	0.0189 (6)	0.0334 (10)	0.0270 (7)	−0.0001 (7)	0.0027 (5)	0.0008 (8)
C6	0.0183 (6)	0.0274 (9)	0.0245 (6)	0.0001 (8)	−0.0048 (5)	−0.0022 (8)
C7	0.0223 (6)	0.0311 (8)	0.0192 (5)	0.0013 (8)	−0.0001 (5)	−0.0013 (7)
C8	0.0177 (6)	0.0285 (9)	0.0212 (6)	−0.0005 (7)	0.0001 (5)	−0.0016 (7)
C9	0.0392 (9)	0.0626 (15)	0.0228 (7)	−0.0031 (12)	−0.0018 (7)	−0.0023 (10)
C10	0.0296 (10)	0.0364 (12)	0.0467 (12)	0.0002 (8)	0.0011 (9)	0.0090 (9)
C10B	0.0310 (10)	0.0343 (11)	0.0530 (13)	0.0074 (8)	−0.0112 (10)	−0.0091 (9)
N1	0.0235 (6)	0.0442 (10)	0.0357 (7)	0.0034 (8)	−0.0094 (6)	−0.0075 (9)
O1	0.0217 (6)	0.0733 (12)	0.0641 (10)	−0.0078 (7)	−0.0111 (7)	0.0065 (11)
O2	0.0388 (8)	0.136 (2)	0.0264 (7)	0.0166 (12)	−0.0122 (6)	−0.0023 (10)
Si1	0.02129 (18)	0.0293 (2)	0.01984 (18)	0.00030 (19)	−0.00383 (15)	−0.00043 (19)

Geometric parameters (Å, º) top

C1—C2	1.209 (2)	C9—Si1	1.8560 (18)
C1—Si1	1.8450 (17)	C9—H9A	0.98
C2—C3	1.438 (2)	C9—H9B	0.98
C3—C8	1.397 (2)	C9—H9C	0.98
C3—C4	1.402 (2)	C10—Si1	1.853 (2)
C4—C5	1.388 (2)	C10—H10A	0.98
C4—H4	0.95	C10—H10B	0.98
C5—C6	1.380 (2)	C10—H10C	0.98
C5—H5	0.95	C10B—Si1	1.856 (2)
C6—C7	1.388 (2)	C10B—H10D	0.98
C6—N1	1.4671 (19)	C10B—H10E	0.98
C7—C8	1.380 (2)	C10B—H10F	0.98
C7—H7	0.95	N1—O1	1.219 (2)
C8—H8	0.95	N1—O2	1.221 (2)

C2—C1—Si1	176.09 (16)	H9A—C9—H9C	109.5
C1—C2—C3	175.90 (18)	H9B—C9—H9C	109.5
C8—C3—C4	119.38 (13)	Si1—C10—H10A	109.5
C8—C3—C2	119.25 (14)	Si1—C10—H10B	109.5
C4—C3—C2	121.36 (14)	H10A—C10—H10B	109.5
C5—C4—C3	120.35 (14)	Si1—C10—H10C	109.5
C5—C4—H4	119.8	H10A—C10—H10C	109.5
C3—C4—H4	119.8	H10B—C10—H10C	109.5
C6—C5—C4	118.44 (14)	Si1—C10B—H10D	109.5
C6—C5—H5	120.8	Si1—C10B—H10E	109.5
C4—C5—H5	120.8	H10D—C10B—H10E	109.5
C5—C6—C7	122.73 (14)	Si1—C10B—H10F	109.5
C5—C6—N1	118.86 (13)	H10D—C10B—H10F	109.5
C7—C6—N1	118.42 (14)	H10E—C10B—H10F	109.5
C8—C7—C6	118.29 (13)	O1—N1—O2	123.47 (16)
C8—C7—H7	120.9	O1—N1—C6	118.21 (16)
C6—C7—H7	120.9	O2—N1—C6	118.31 (15)
C7—C8—C3	120.81 (13)	C1—Si1—C10	108.92 (10)
C7—C8—H8	119.6	C1—Si1—C10B	109.77 (10)
C3—C8—H8	119.6	C10—Si1—C10B	107.68 (10)
Si1—C9—H9A	109.5	C1—Si1—C9	108.27 (8)
Si1—C9—H9B	109.5	C10—Si1—C9	111.68 (12)
H9A—C9—H9B	109.5	C10B—Si1—C9	110.51 (12)
Si1—C9—H9C	109.5

C8—C3—C4—C5	0.5 (3)	C6—C7—C8—C3	0.6 (3)
C2—C3—C4—C5	−178.28 (19)	C4—C3—C8—C7	−1.0 (3)
C3—C4—C5—C6	0.4 (3)	C2—C3—C8—C7	177.76 (18)
C4—C5—C6—C7	−0.9 (3)	C5—C6—N1—O1	10.6 (3)
C4—C5—C6—N1	178.80 (18)	C7—C6—N1—O1	−169.7 (2)
C5—C6—C7—C8	0.3 (3)	C5—C6—N1—O2	−168.0 (2)
N1—C6—C7—C8	−179.33 (18)	C7—C6—N1—O2	11.7 (3)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃NO₂Si
M_r	219.31
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	10.222 (2), 7.128 (2), 16.537 (4)
V (Å³)	1204.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.18
Crystal size (mm)	0.20 × 0.15 × 0.12

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.966, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	17805, 4690, 3538
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.782

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.123, 1.02
No. of reflections	4690
No. of parameters	139
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.32
Absolute structure	Flack (1983), 1953 Bijvoet pairs
Absolute structure parameter	0.35 (15)

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Footnotes

†CAS 75867-38-8.

Acknowledgements

Purchase of the diffractometer was made possible by grant No. LEQSF(1999–2000)-ESH-TR-13, administered by the Louisiana Board of Regents.

References

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