Dimethyl 2-nitro­biphenyl-4,4′-di­carboxyl­ate

Vieira, V.C.M.; Golen, J.A.; Rheingold, A.L.; Manke, D.R.

doi:10.1107/S1600536814004218

organic compounds

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ISSN: 2056-9890

Volume 70| Part 3| March 2014| Page o371

doi:10.1107/S1600536814004218

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Dimethyl 2-nitrobiphenyl-4,4′-dicarboxylate

Vanessa C. M. Vieira,^a James A. Golen,^b Arnold L. Rheingold ^b and David R. Manke ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA, and ^bDepartment of Chemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
^*Correspondence e-mail: dmanke@umassd.edu

(Received 17 February 2014; accepted 23 February 2014; online 28 February 2014)

The title compound, C₁₆H₁₃NO₆, exhibits a biphenyl unit with a dihedral angle between the two aryl rings of 56.01 (5)°. The two ester groups vary slightly from planarity, with aryl–ester dihedral angles of 4.57 (5) and 16.73 (5)°. The nitro group is turned from the aromatic unit with an aryl–nitro dihedral angle of 48.66 (4)°. In the crystal, molecules are connected by weak C—H⋯O interactions, forming a three-dimensional network.

CCDC reference: 988449

Related literature

For the synthesis of the title compound, see: Olkhovik et al. (2008 ). For coordination polymers featuring the 2-nitrobiphenyl-4,4′-dicarboxylate linker, see: Jing et al. (2012 ).

Experimental

Crystal data

C₁₆H₁₃NO₆
M_r = 315.27
Monoclinic, C 2/c
a = 20.3958 (17) Å
b = 8.3334 (6) Å
c = 18.9386 (14) Å
β = 118.342 (7)°
V = 2833.1 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 90 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.972, T_max = 0.983
19059 measured reflections
2918 independent reflections
2360 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.04
2918 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O6ⁱ	0.95	2.50	3.3405 (16)	148
C13—H13A⋯O2ⁱⁱ	0.95	2.39	3.2435 (16)	150
C14—H14A⋯O4ⁱⁱⁱ	0.95	2.59	3.3954 (16)	143
Symmetry codes: (i) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) -x+1, -y+1, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 988449

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814004218/ff2127sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814004218/ff2127Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814004218/ff2127Isup3.cml

checkCIF report

Comment top

Biphenyl-4,4'-dicarboxylate and its derivatives have become prevalent linkers in the preparation of metal-organic frameworks (MOFs). The ability to incorporate different functional groups into the pores of MOFs is one advantage of this class of materials. As a part of our efforts in this arena, we prepared the previously reported dimethyl 2-nitrobiphenyl-4,4'-dicarboxylate (Olkhovik et al. 2008) and report its structure herein.

The structure of the title compound is shown in Figure 1. The structure has a torsion angle of 56.01 (5)° between the two aryl rings. The ester groups vary slightly from the planes of the aromatic rings, with aryl-ester dihedral angles of 4.57 (5)° and 16.73 (5)°. The nitro group shows an aryl-nitro torsion angle of 48.66 (4)°. No π-π interactions were noted between the aromatic rings. The packing for the title compound is shown in Figure 2.

Related literature top

For the synthesis of the title compound, see: Olkhovik et al. (2008). For coordination polymers featuring the 2-nitrobiphenyl-4,4'-dicarboxylate linker, see: Jing et al. (2012).

Experimental top

The compound was prepared by literature procedure (Olkhovik et al. 2008). Crystals suitable for single-crystal X-ray analysis were grown by slow evaporation of an ethanol solution.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as spheres of arbitrary radius.
	Fig. 2. Molecular packing of the title compound.

Dimethyl 2-nitrobiphenyl-4,4'-dicarboxylate top

Crystal data top

C₁₆H₁₃NO₆	F(000) = 1312
M_r = 315.27	D_x = 1.478 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7800 reflections
a = 20.3958 (17) Å	θ = 2.4–26.4°
b = 8.3334 (6) Å	µ = 0.12 mm⁻¹
c = 18.9386 (14) Å	T = 90 K
β = 118.342 (7)°	Block, colorless
V = 2833.1 (4) Å³	0.25 × 0.20 × 0.15 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	2918 independent reflections
Radiation source: fine-focus sealed tube	2360 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
φ and ω scans	θ_max = 26.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −25→25
T_min = 0.972, T_max = 0.983	k = −10→10
19059 measured reflections	l = −23→23

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) = 0.097	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0512P)² + 1.4779P] where P = (F_o² + 2F_c²)/3
2918 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₆H₁₃NO₆	V = 2833.1 (4) Å³
M_r = 315.27	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 20.3958 (17) Å	µ = 0.12 mm⁻¹
b = 8.3334 (6) Å	T = 90 K
c = 18.9386 (14) Å	0.25 × 0.20 × 0.15 mm
β = 118.342 (7)°

Data collection top

Bruker APEXII CCD diffractometer	2918 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2360 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.983	R_int = 0.029
19059 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.04	Δρ_max = 0.29 e Å⁻³
2918 reflections	Δρ_min = −0.22 e Å⁻³
210 parameters

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
O1	0.20578 (5)	0.35494 (11)	0.07049 (6)	0.0225 (2)
O2	0.19389 (5)	0.61983 (11)	0.04893 (6)	0.0241 (2)
O3	0.43918 (5)	0.91646 (12)	0.14067 (6)	0.0294 (3)
O4	0.48248 (5)	0.82157 (11)	0.06479 (5)	0.0231 (2)
O5	0.81617 (5)	0.57857 (12)	0.26263 (6)	0.0250 (2)
O6	0.78697 (5)	0.47958 (13)	0.14129 (6)	0.0304 (3)
N1	0.44911 (6)	0.80702 (13)	0.10372 (6)	0.0197 (3)
C1	0.12899 (7)	0.35323 (17)	0.05505 (9)	0.0239 (3)
H1A	0.1125	0.2420	0.0527	0.036*
H1B	0.0974	0.4064	0.0038	0.036*
H1C	0.1251	0.4101	0.0982	0.036*
C2	0.23120 (7)	0.49999 (15)	0.06615 (8)	0.0186 (3)
C3	0.31111 (7)	0.49867 (15)	0.08548 (7)	0.0182 (3)
C4	0.34421 (7)	0.64598 (16)	0.08921 (7)	0.0179 (3)
H4A	0.3169	0.7428	0.0807	0.022*
C5	0.41786 (7)	0.64881 (16)	0.10550 (7)	0.0178 (3)
C6	0.46139 (7)	0.51142 (16)	0.12059 (8)	0.0191 (3)
C7	0.42667 (7)	0.36580 (16)	0.11802 (8)	0.0210 (3)
H7A	0.4546	0.2693	0.1289	0.025*
C8	0.35235 (7)	0.35825 (16)	0.10001 (8)	0.0206 (3)
H8A	0.3297	0.2573	0.0976	0.025*
C9	0.54141 (7)	0.51468 (16)	0.14053 (8)	0.0188 (3)
C10	0.59328 (7)	0.60408 (16)	0.20508 (8)	0.0206 (3)
H10A	0.5775	0.6654	0.2366	0.025*
C11	0.66769 (7)	0.60418 (16)	0.22374 (8)	0.0201 (3)
H11A	0.7030	0.6635	0.2685	0.024*
C12	0.69054 (7)	0.51723 (15)	0.17669 (8)	0.0189 (3)
C13	0.63915 (7)	0.42696 (16)	0.11247 (8)	0.0204 (3)
H13A	0.6548	0.3671	0.0804	0.024*
C14	0.56517 (7)	0.42431 (16)	0.09521 (8)	0.0197 (3)
H14A	0.5304	0.3604	0.0521	0.024*
C15	0.76862 (7)	0.52180 (16)	0.19011 (8)	0.0206 (3)
C16	0.89312 (7)	0.58733 (19)	0.27969 (9)	0.0289 (3)
H16A	0.9252	0.6008	0.3375	0.043*
H16B	0.8997	0.6789	0.2512	0.043*
H16C	0.9066	0.4882	0.2619	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0154 (5)	0.0204 (5)	0.0315 (5)	−0.0001 (4)	0.0110 (4)	0.0023 (4)
O2	0.0175 (5)	0.0207 (5)	0.0339 (5)	0.0015 (4)	0.0119 (4)	−0.0003 (4)
O3	0.0263 (5)	0.0246 (5)	0.0434 (6)	−0.0047 (4)	0.0214 (5)	−0.0125 (5)
O4	0.0193 (5)	0.0267 (5)	0.0272 (5)	0.0007 (4)	0.0142 (4)	0.0032 (4)
O5	0.0147 (4)	0.0331 (6)	0.0258 (5)	−0.0010 (4)	0.0084 (4)	−0.0031 (4)
O6	0.0215 (5)	0.0371 (6)	0.0365 (6)	−0.0022 (4)	0.0170 (5)	−0.0112 (5)
N1	0.0128 (5)	0.0225 (6)	0.0228 (6)	0.0013 (4)	0.0075 (4)	−0.0013 (5)
C1	0.0149 (6)	0.0256 (7)	0.0309 (7)	−0.0014 (5)	0.0107 (6)	0.0017 (6)
C2	0.0181 (6)	0.0199 (7)	0.0176 (6)	−0.0011 (5)	0.0082 (5)	−0.0019 (5)
C3	0.0160 (6)	0.0225 (7)	0.0158 (6)	0.0004 (5)	0.0073 (5)	−0.0002 (5)
C4	0.0176 (6)	0.0199 (7)	0.0163 (6)	0.0025 (5)	0.0080 (5)	0.0000 (5)
C5	0.0181 (6)	0.0205 (7)	0.0158 (6)	−0.0007 (5)	0.0089 (5)	−0.0010 (5)
C6	0.0173 (6)	0.0248 (7)	0.0152 (6)	0.0022 (5)	0.0076 (5)	−0.0008 (5)
C7	0.0192 (6)	0.0205 (7)	0.0230 (7)	0.0035 (5)	0.0096 (5)	0.0011 (5)
C8	0.0202 (6)	0.0203 (7)	0.0213 (7)	−0.0008 (5)	0.0099 (5)	0.0005 (5)
C9	0.0158 (6)	0.0204 (7)	0.0198 (7)	0.0026 (5)	0.0081 (5)	0.0036 (5)
C10	0.0201 (6)	0.0245 (7)	0.0184 (6)	0.0038 (5)	0.0100 (5)	0.0004 (5)
C11	0.0178 (6)	0.0228 (7)	0.0172 (6)	0.0009 (5)	0.0064 (5)	0.0007 (5)
C12	0.0160 (6)	0.0188 (7)	0.0214 (7)	0.0026 (5)	0.0086 (5)	0.0034 (5)
C13	0.0205 (6)	0.0189 (7)	0.0235 (7)	0.0036 (5)	0.0119 (5)	−0.0001 (5)
C14	0.0182 (6)	0.0193 (7)	0.0199 (6)	0.0006 (5)	0.0077 (5)	−0.0002 (5)
C15	0.0187 (6)	0.0164 (7)	0.0258 (7)	0.0006 (5)	0.0099 (6)	−0.0001 (5)
C16	0.0155 (6)	0.0345 (8)	0.0337 (8)	−0.0018 (6)	0.0094 (6)	−0.0025 (7)

Geometric parameters (Å, º) top

O1—C2	1.3331 (16)	C6—C9	1.4906 (17)
O1—C1	1.4504 (14)	C7—C8	1.3883 (18)
O2—C2	1.2030 (16)	C7—H7A	0.9500
O3—N1	1.2235 (14)	C8—H8A	0.9500
O4—N1	1.2240 (14)	C9—C14	1.3905 (19)
O5—C15	1.3364 (16)	C9—C10	1.3932 (18)
O5—C16	1.4461 (15)	C10—C11	1.3853 (17)
O6—C15	1.2030 (17)	C10—H10A	0.9500
N1—C5	1.4716 (17)	C11—C12	1.3894 (18)
C1—H1A	0.9800	C11—H11A	0.9500
C1—H1B	0.9800	C12—C13	1.3905 (18)
C1—H1C	0.9800	C12—C15	1.4891 (18)
C2—C3	1.4913 (17)	C13—C14	1.3841 (17)
C3—C4	1.3866 (18)	C13—H13A	0.9500
C3—C8	1.3902 (18)	C14—H14A	0.9500
C4—C5	1.3828 (17)	C16—H16A	0.9800
C4—H4A	0.9500	C16—H16B	0.9800
C5—C6	1.3928 (18)	C16—H16C	0.9800
C6—C7	1.3942 (19)

C2—O1—C1	114.26 (10)	C7—C8—H8A	120.1
C15—O5—C16	115.38 (11)	C3—C8—H8A	120.1
O3—N1—O4	124.13 (11)	C14—C9—C10	119.29 (12)
O3—N1—C5	117.62 (10)	C14—C9—C6	119.63 (11)
O4—N1—C5	118.25 (10)	C10—C9—C6	121.06 (12)
O1—C1—H1A	109.5	C11—C10—C9	120.51 (12)
O1—C1—H1B	109.5	C11—C10—H10A	119.7
H1A—C1—H1B	109.5	C9—C10—H10A	119.7
O1—C1—H1C	109.5	C10—C11—C12	119.77 (12)
H1A—C1—H1C	109.5	C10—C11—H11A	120.1
H1B—C1—H1C	109.5	C12—C11—H11A	120.1
O2—C2—O1	123.70 (11)	C11—C12—C13	120.00 (12)
O2—C2—C3	123.34 (12)	C11—C12—C15	122.29 (12)
O1—C2—C3	112.95 (11)	C13—C12—C15	117.66 (12)
C4—C3—C8	120.06 (12)	C14—C13—C12	119.98 (12)
C4—C3—C2	117.06 (11)	C14—C13—H13A	120.0
C8—C3—C2	122.87 (11)	C12—C13—H13A	120.0
C5—C4—C3	118.53 (11)	C13—C14—C9	120.40 (12)
C5—C4—H4A	120.7	C13—C14—H14A	119.8
C3—C4—H4A	120.7	C9—C14—H14A	119.8
C4—C5—C6	123.42 (12)	O6—C15—O5	123.68 (12)
C4—C5—N1	116.52 (11)	O6—C15—C12	123.98 (12)
C6—C5—N1	120.03 (11)	O5—C15—C12	112.34 (12)
C5—C6—C7	116.40 (12)	O5—C16—H16A	109.5
C5—C6—C9	123.47 (12)	O5—C16—H16B	109.5
C7—C6—C9	120.11 (11)	H16A—C16—H16B	109.5
C8—C7—C6	121.69 (12)	O5—C16—H16C	109.5
C8—C7—H7A	119.2	H16A—C16—H16C	109.5
C6—C7—H7A	119.2	H16B—C16—H16C	109.5
C7—C8—C3	119.86 (12)

C1—O1—C2—O2	−1.86 (18)	C2—C3—C8—C7	−179.73 (11)
C1—O1—C2—C3	177.73 (10)	C5—C6—C9—C14	−125.48 (14)
O2—C2—C3—C4	4.93 (19)	C7—C6—C9—C14	55.96 (17)
O1—C2—C3—C4	−174.66 (11)	C5—C6—C9—C10	56.00 (18)
O2—C2—C3—C8	−175.54 (13)	C7—C6—C9—C10	−122.56 (14)
O1—C2—C3—C8	4.87 (18)	C14—C9—C10—C11	0.48 (19)
C8—C3—C4—C5	1.65 (19)	C6—C9—C10—C11	179.01 (12)
C2—C3—C4—C5	−178.80 (11)	C9—C10—C11—C12	1.38 (19)
C3—C4—C5—C6	−1.81 (19)	C10—C11—C12—C13	−1.77 (19)
C3—C4—C5—N1	176.20 (11)	C10—C11—C12—C15	175.57 (12)
O3—N1—C5—C4	48.64 (15)	C11—C12—C13—C14	0.28 (19)
O4—N1—C5—C4	−130.48 (12)	C15—C12—C13—C14	−177.17 (12)
O3—N1—C5—C6	−133.27 (12)	C12—C13—C14—C9	1.60 (19)
O4—N1—C5—C6	47.60 (16)	C10—C9—C14—C13	−1.98 (19)
C4—C5—C6—C7	0.46 (19)	C6—C9—C14—C13	179.47 (12)
N1—C5—C6—C7	−177.48 (11)	C16—O5—C15—O6	0.21 (19)
C4—C5—C6—C9	−178.14 (12)	C16—O5—C15—C12	−179.65 (11)
N1—C5—C6—C9	3.91 (19)	C11—C12—C15—O6	−162.42 (13)
C5—C6—C7—C8	1.06 (19)	C13—C12—C15—O6	15.0 (2)
C9—C6—C7—C8	179.72 (12)	C11—C12—C15—O5	17.44 (18)
C6—C7—C8—C3	−1.2 (2)	C13—C12—C15—O5	−165.16 (12)
C4—C3—C8—C7	−0.20 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O6ⁱ	0.95	2.50	3.3405 (16)	148
C13—H13A···O2ⁱⁱ	0.95	2.39	3.2435 (16)	150
C14—H14A···O4ⁱⁱⁱ	0.95	2.59	3.3954 (16)	143

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O6ⁱ	0.95	2.50	3.3405 (16)	147.6
C13—H13A···O2ⁱⁱ	0.95	2.39	3.2435 (16)	150.1
C14—H14A···O4ⁱⁱⁱ	0.95	2.59	3.3954 (16)	142.5

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

Acknowledgements

VCMV thanks the the UMass Dartmouth Office of Undergraduate Research Award and the Urban Massachusetts Louis Stokes Alliance for Minority Participation (UMLSAMP) for funding. DRM gratefully acknowledges support from the National Science Foundation (CHE-1229339).

References

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