4-Nitrophenanthrene

This study at 168 K shows that in the crystal structure of C₁₄H₉NO₂, the plane of the nitro group is inclined at 72.2 (7)° to the plane of the attached six-membered ring. The phenanthrene system is significantly non-planar.

Key indicators

• Single-crystal X-ray study
• T = 168 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.049
• wR factor = 0.110
• Data-to-parameter ratio = 10.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSMU_01  Alert C The ratio of given/expected absorption coefficient lies
          outside the range 0.99 <> 1.01
          Calculated value of mu =     0.096
          Value of mu given      =     0.100

ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.780     0.980
          Tmin' and Tmax expected:      0.929     0.974
          RR' =      0.834
          Please check that your absorption correction is appropriate.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

As part of a study directed towards relating NMR chemical shifts to the degree of conjugation of substituents in phenanthrene, the structure of 4-nitrophenanthrene, (I), has been determined. The angle between the NO₂ and phenanthrene planes indicates that there will be reduced conjugation. This angle of 72.2 (7)° can be compared with the value of 60.7° obtained by calculation using SPARTAN (Wavefunction, 1995).

S2. Experimental

A mixture of isomers was obtained by nitration of phenanthrene with nitric acid in benzene following the method of Heaney et al. (1965). After chromatography of the mixture, 4-nitrophenanthrene was obtained pure and was crystallized as yellow prisms from hexane.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT and Xtal3.4 ADDREF SORTRF (Hall et al., 1995); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: Xtal3.4 CRYLSQ; molecular graphics: Xtal3.4; software used to prepare material for publication: Xtal3.4 BONDLA CIFIO.

Figures

Fig. 1. The molecular structure of 4-nitrophenanthrene showing 50% probability displacement ellipsoids.

(I)

Crystal data

C14H9NO2	F(000) = 464
Mr = 223.23	Dx = 1.41 Mg m^−3
Monoclinic, P21/c	Melting point: 81.5-82.0 °C K
Hall symbol: -p 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.061 (2) Å	Cell parameters from 5719 reflections
b = 12.449 (3) Å	θ = 2.5–26.4°
c = 11.132 (3) Å	µ = 0.10 mm^−1
β = 109.73 (1)°	T = 168 K
V = 1051.5 (5) Å^3	Prism, pale yellow
Z = 4	0.72 × 0.46 × 0.26 mm

Data collection

Bruker SMART P4 diffractometer	1945 reflections with F^2 > 0
Detector resolution: 8.192 pixels mm^-1	Rint = 0.028
ω scans	θmax = 26.4°, θmin = 2.5°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = 0→10
Tmin = 0.78, Tmax = 0.98	k = 0→15
13110 measured reflections	l = −13→13
2135 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	0 constraints
R[F^2 > 2σ(F^2)] = 0.049	All H-atom parameters refined
wR(F^2) = 0.11	w = 1/[σ^2(Fo^2) + (0.06Fo^2)^2 + 0.5Fo^2]
S = 1.03	(Δ/σ)max < 0.001
1943 reflections	Δρmax = 0.29 e Å^−3
190 parameters	Δρmin = −0.22 e Å^−3

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections.

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

	x	y	z	Uiso*/Ueq
N	0.75013 (19)	0.30657 (11)	0.08041 (14)	0.0377 (7)
O1	0.85095 (16)	0.25134 (10)	0.04507 (13)	0.0487 (7)
O2	0.79833 (18)	0.38205 (11)	0.15553 (15)	0.0598 (8)
C1	0.2069 (2)	0.25122 (14)	−0.10627 (17)	0.0390 (8)
C2	0.2871 (3)	0.34201 (15)	−0.12965 (17)	0.0426 (9)
C3	0.4662 (2)	0.35883 (14)	−0.06233 (17)	0.0384 (8)
C4	0.5578 (2)	0.28431 (12)	0.02590 (15)	0.0319 (7)
C5	0.7442 (2)	0.12262 (14)	0.24429 (16)	0.0361 (8)
C6	0.8270 (2)	0.04098 (15)	0.32569 (17)	0.0417 (9)
C7	0.7421 (2)	−0.05733 (14)	0.32257 (16)	0.0396 (8)
C8	0.5714 (2)	−0.06978 (13)	0.24207 (16)	0.0347 (8)
C9	0.3012 (2)	−0.00034 (13)	0.07995 (16)	0.0345 (8)
C10	0.2131 (2)	0.07775 (14)	0.00120 (16)	0.0361 (8)
C4a	0.4819 (2)	0.19059 (11)	0.05832 (14)	0.0275 (7)
C4b	0.5727 (2)	0.11059 (12)	0.15396 (14)	0.0278 (7)
C8a	0.4823 (2)	0.01289 (12)	0.15837 (14)	0.0288 (7)
C10a	0.2999 (2)	0.17500 (12)	−0.01412 (15)	0.0316 (7)
H1	0.084 (3)	0.2316 (15)	−0.1558 (18)	0.043 (5)*
H2	0.223 (3)	0.3906 (17)	−0.1983 (19)	0.053 (6)*
H3	0.525 (2)	0.4204 (16)	−0.0779 (17)	0.045 (5)*
H5	0.803 (3)	0.1915 (16)	0.2473 (19)	0.053 (6)*
H6	0.949 (3)	0.0541 (15)	0.3881 (18)	0.048 (5)*
H7	0.800 (2)	−0.1151 (16)	0.3780 (18)	0.050 (5)*
H8	0.506 (2)	−0.1367 (15)	0.2402 (18)	0.041 (5)*
H9	0.248 (2)	−0.0656 (16)	0.0863 (18)	0.045 (5)*
H10	0.092 (3)	0.0680 (16)	−0.0524 (19)	0.053 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N	0.0414 (8)	0.0293 (7)	0.0454 (8)	−0.0073 (6)	0.0185 (7)	0.0006 (6)
O1	0.0415 (7)	0.0457 (7)	0.0650 (9)	−0.0015 (6)	0.0261 (6)	−0.0029 (6)
O2	0.0559 (9)	0.0433 (8)	0.0777 (10)	−0.0171 (6)	0.0194 (7)	−0.0218 (7)
C1	0.0337 (9)	0.0437 (10)	0.0396 (9)	0.0094 (8)	0.0122 (7)	0.0005 (8)
C2	0.0525 (11)	0.0386 (10)	0.0392 (9)	0.0151 (8)	0.0188 (8)	0.0088 (8)
C3	0.0509 (10)	0.0282 (8)	0.0429 (9)	0.0036 (7)	0.0250 (8)	0.0041 (7)
C4	0.0355 (9)	0.0275 (8)	0.0363 (9)	−0.0009 (6)	0.0169 (7)	−0.0028 (7)
C5	0.0341 (9)	0.0362 (9)	0.0371 (9)	−0.0065 (7)	0.0108 (7)	0.0026 (7)
C6	0.0343 (9)	0.0514 (11)	0.0370 (9)	0.0010 (8)	0.0090 (7)	0.0061 (8)
C7	0.0474 (10)	0.0380 (9)	0.0362 (9)	0.0109 (8)	0.0179 (8)	0.0074 (8)
C8	0.0462 (10)	0.0262 (8)	0.0384 (9)	−0.0002 (7)	0.0231 (8)	0.0007 (7)
C9	0.0354 (9)	0.0289 (8)	0.0439 (9)	−0.0083 (7)	0.0195 (7)	−0.0051 (7)
C10	0.0276 (8)	0.0385 (9)	0.0439 (9)	−0.0041 (7)	0.0142 (7)	−0.0063 (8)
C4a	0.0321 (8)	0.0234 (7)	0.0301 (8)	−0.0007 (6)	0.0146 (6)	−0.0042 (6)
C4b	0.0292 (8)	0.0275 (8)	0.0296 (7)	−0.0008 (6)	0.0137 (6)	−0.0026 (6)
C8a	0.0338 (8)	0.0261 (7)	0.0312 (8)	−0.0015 (6)	0.0170 (6)	−0.0030 (6)
C10a	0.0318 (8)	0.0315 (8)	0.0338 (8)	0.0034 (6)	0.0140 (7)	−0.0028 (7)

Geometric parameters (Å, º)

N—O1	1.226 (2)	C6—C7	1.397 (3)
N—O2	1.230 (2)	C6—H6	1.009 (18)
N—C4	1.488 (2)	C7—C8	1.374 (2)
C1—C2	1.370 (3)	C7—H7	0.96 (2)
C1—C10a	1.413 (2)	C8—C8a	1.411 (2)
C1—H1	0.990 (18)	C8—H8	0.98 (2)
C2—C3	1.400 (3)	C9—C10	1.341 (2)
C2—H2	0.976 (19)	C9—C8a	1.435 (2)
C3—C4	1.371 (2)	C9—H9	0.93 (2)
C3—H3	0.95 (2)	C10—C10a	1.437 (2)
C4—C4a	1.420 (2)	C10—H10	0.966 (18)
C5—C6	1.375 (2)	C4a—C4b	1.461 (2)
C5—C4b	1.417 (2)	C4a—C10a	1.428 (2)
C5—H5	0.98 (2)	C4b—C8a	1.427 (2)
O1—N—O2	123.69 (15)	C8—C7—H7	119.8 (11)
O1—N—C4	118.49 (13)	C7—C8—C8a	121.54 (15)
O2—N—C4	117.77 (15)	C7—C8—H8	121.5 (10)
C2—C1—C10a	121.55 (15)	C8a—C8—H8	117.0 (10)
C2—C1—H1	123.1 (11)	C10—C9—C8a	121.33 (15)
C10a—C1—H1	115.2 (11)	C10—C9—H9	121.6 (10)
C1—C2—C3	119.29 (16)	C8a—C9—H9	117.0 (10)
C1—C2—H2	120.0 (12)	C9—C10—C10a	121.10 (14)
C3—C2—H2	120.4 (12)	C9—C10—H10	121.0 (12)
C2—C3—C4	119.40 (17)	C10a—C10—H10	117.7 (12)
C2—C3—H3	120.9 (10)	C4—C4a—C4b	126.35 (13)
C4—C3—H3	119.7 (10)	C4—C4a—C10a	114.63 (12)
N—C4—C3	113.66 (15)	C4b—C4a—C10a	119.01 (14)
N—C4—C4a	121.92 (12)	C5—C4b—C4a	125.02 (14)
C3—C4—C4a	124.32 (14)	C5—C4b—C8a	116.94 (13)
C6—C5—C4b	122.00 (16)	C4a—C4b—C8a	118.04 (12)
C6—C5—H5	120.2 (10)	C8—C8a—C9	120.31 (15)
C4b—C5—H5	117.8 (10)	C8—C8a—C4b	119.47 (13)
C5—C6—C7	120.42 (15)	C9—C8a—C4b	120.21 (13)
C5—C6—H6	118.6 (11)	C1—C10a—C10	119.43 (13)
C7—C6—H6	121.0 (11)	C1—C10a—C4a	120.73 (15)
C6—C7—C8	119.30 (15)	C10—C10a—C4a	119.74 (13)
C6—C7—H7	120.8 (11)