Diethyl 4-(4-tert-butyl­phen­yl)pyridine-2,6-dicarboxyl­ate

The title crystal structure, C₂₁H₂₅NO₄, is stabilized by π-stacking inter­actions between inversion-related pyridyl groups with a ring centroid-to-centroid distance of 3.450 (14) Å. In addition, non-polar tert-butyl groups face each other, forming alternating polar and non-polar layers.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.059
• wR factor = 0.176
• Data-to-parameter ratio = 14.4

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Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: UdMX (local program).

Diethyl 4-(4-tert-butylphenyl)pyridine-2,6-dicarboxylate

Crystal data

C21H25NO4	F(000) = 760
Mr = 355.42	Dx = 1.233 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -P 2ybc	Cell parameters from 5127 reflections
a = 13.857 (2) Å	θ = 3.3–67.3°
b = 12.0094 (17) Å	µ = 0.69 mm^−1
c = 12.0553 (17) Å	T = 100 K
β = 107.368 (7)°	Block, colorless
V = 1914.7 (5) Å^3	0.40 × 0.24 × 0.20 mm
Z = 4

Data collection

Bruker SMART 6000 diffractometer	3456 independent reflections
Radiation source: Rotating Anode	2627 reflections with I > 2σ(I)
Montel 200 optics monochromator	Rint = 0.088
Detector resolution: 5.5 pixels mm^-1	θmax = 67.9°, θmin = 3.3°
ω scans	h = −16→15
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→14
Tmin = 0.750, Tmax = 0.875	l = −14→14
23628 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.176	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.1014P)^2 + 0.7898P] where P = (Fo^2 + 2Fc^2)/3
3456 reflections	(Δ/σ)max = 0.002
240 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	1.11228 (14)	0.09805 (16)	0.56437 (16)	0.0202 (4)
O1	0.99506 (12)	0.03157 (15)	0.78030 (14)	0.0280 (4)
O2	1.15467 (12)	0.00956 (14)	0.77502 (13)	0.0234 (4)
O3	1.23999 (13)	0.07048 (15)	0.42732 (15)	0.0288 (4)
O4	1.16207 (12)	0.21675 (14)	0.32084 (14)	0.0244 (4)
C2	1.03836 (17)	0.09696 (19)	0.61445 (18)	0.0199 (5)
C3	0.94201 (17)	0.13790 (19)	0.56180 (19)	0.0207 (5)
H3	0.8918	0.1337	0.6008	0.025*
C4	0.91918 (17)	0.18521 (19)	0.45137 (19)	0.0202 (5)
C5	0.99749 (17)	0.19105 (18)	0.40106 (19)	0.0202 (5)
H5	0.9871	0.2259	0.3277	0.024*
C6	1.09049 (17)	0.14541 (18)	0.45931 (19)	0.0197 (5)
C7	0.81571 (17)	0.22261 (19)	0.38787 (19)	0.0207 (5)
C8	0.73172 (18)	0.1663 (2)	0.40198 (19)	0.0237 (5)
H8	0.7408	0.1046	0.4533	0.028*
C9	0.63523 (17)	0.2012 (2)	0.3406 (2)	0.0231 (5)
H9	0.5788	0.1629	0.3514	0.028*
C10	0.61819 (17)	0.2907 (2)	0.26352 (19)	0.0206 (5)
C11	0.70250 (18)	0.3456 (2)	0.24986 (19)	0.0220 (5)
H11	0.6934	0.4069	0.1980	0.026*
C12	0.79982 (18)	0.3118 (2)	0.31121 (19)	0.0221 (5)
H12	0.8563	0.3504	0.3005	0.027*
C13	0.51007 (18)	0.3275 (2)	0.1992 (2)	0.0254 (5)
C14	0.4617 (2)	0.3753 (2)	0.2882 (2)	0.0326 (6)
H14A	0.5012	0.4394	0.3274	0.049*
H14B	0.4608	0.3181	0.3458	0.049*
H14C	0.3924	0.3990	0.2482	0.049*
C15	0.44875 (19)	0.2272 (2)	0.1370 (2)	0.0302 (6)
H15A	0.3804	0.2515	0.0934	0.045*
H15B	0.4447	0.1712	0.1945	0.045*
H15C	0.4820	0.1948	0.0833	0.045*
C16	0.5073 (2)	0.4163 (2)	0.1087 (2)	0.0343 (6)
H16A	0.5418	0.4835	0.1471	0.051*
H16B	0.4369	0.4343	0.0666	0.051*
H16C	0.5415	0.3886	0.0538	0.051*
C17	1.05944 (17)	0.04349 (19)	0.73194 (19)	0.0210 (5)
C18	1.17855 (19)	−0.0487 (2)	0.8857 (2)	0.0275 (6)
H18A	1.1462	−0.1230	0.8752	0.033*
H18B	1.1536	−0.0059	0.9418	0.033*
C19	1.2910 (2)	−0.0601 (3)	0.9293 (2)	0.0344 (6)
H19A	1.3148	−0.1014	0.8724	0.052*
H19B	1.3099	−0.1004	1.0034	0.052*
H19C	1.3220	0.0140	0.9408	0.052*
C20	1.17338 (17)	0.13881 (19)	0.40280 (18)	0.0200 (5)
C21	1.23030 (18)	0.2097 (2)	0.2494 (2)	0.0255 (5)
H21A	1.2970	0.1816	0.2968	0.031*
H21B	1.2400	0.2847	0.2203	0.031*
C22	1.1867 (2)	0.1326 (2)	0.1482 (2)	0.0308 (6)
H22A	1.1821	0.0571	0.1772	0.046*
H22B	1.2306	0.1320	0.0978	0.046*
H22C	1.1191	0.1584	0.1039	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0194 (10)	0.0199 (10)	0.0200 (10)	−0.0004 (8)	0.0037 (7)	−0.0014 (8)
O1	0.0211 (9)	0.0398 (11)	0.0237 (9)	0.0036 (7)	0.0077 (7)	0.0041 (7)
O2	0.0200 (9)	0.0292 (9)	0.0187 (8)	0.0034 (7)	0.0023 (6)	0.0030 (7)
O3	0.0224 (9)	0.0343 (10)	0.0299 (9)	0.0069 (8)	0.0083 (7)	0.0089 (7)
O4	0.0199 (9)	0.0285 (9)	0.0259 (9)	0.0034 (7)	0.0085 (6)	0.0073 (7)
C2	0.0209 (12)	0.0194 (11)	0.0181 (11)	−0.0012 (9)	0.0037 (9)	−0.0020 (9)
C3	0.0179 (12)	0.0229 (12)	0.0199 (12)	−0.0004 (9)	0.0037 (9)	−0.0023 (9)
C4	0.0192 (12)	0.0178 (11)	0.0216 (12)	0.0002 (9)	0.0032 (9)	−0.0025 (9)
C5	0.0216 (12)	0.0192 (11)	0.0181 (11)	−0.0012 (9)	0.0033 (9)	0.0003 (9)
C6	0.0200 (12)	0.0195 (11)	0.0182 (11)	0.0000 (9)	0.0036 (9)	−0.0015 (9)
C7	0.0195 (12)	0.0218 (12)	0.0188 (11)	−0.0007 (9)	0.0025 (9)	−0.0015 (9)
C8	0.0229 (13)	0.0253 (12)	0.0209 (12)	0.0006 (10)	0.0036 (9)	0.0036 (9)
C9	0.0163 (12)	0.0289 (13)	0.0234 (12)	−0.0016 (10)	0.0051 (9)	0.0015 (10)
C10	0.0182 (12)	0.0237 (12)	0.0180 (11)	0.0007 (9)	0.0029 (8)	−0.0024 (9)
C11	0.0220 (12)	0.0224 (12)	0.0205 (12)	0.0007 (9)	0.0045 (9)	0.0036 (9)
C12	0.0197 (12)	0.0246 (12)	0.0214 (12)	−0.0016 (9)	0.0051 (9)	0.0008 (9)
C13	0.0167 (12)	0.0308 (14)	0.0260 (13)	0.0005 (10)	0.0023 (9)	0.0029 (10)
C14	0.0206 (13)	0.0400 (16)	0.0355 (15)	0.0032 (11)	0.0057 (10)	−0.0009 (12)
C15	0.0200 (13)	0.0371 (15)	0.0287 (13)	−0.0008 (11)	−0.0002 (10)	−0.0014 (11)
C16	0.0213 (13)	0.0429 (16)	0.0342 (14)	0.0038 (11)	0.0015 (10)	0.0119 (12)
C17	0.0180 (12)	0.0219 (12)	0.0201 (12)	0.0013 (9)	0.0013 (9)	−0.0020 (9)
C18	0.0270 (13)	0.0346 (14)	0.0181 (12)	0.0016 (11)	0.0024 (9)	0.0045 (10)
C19	0.0272 (14)	0.0473 (17)	0.0252 (13)	0.0071 (12)	0.0027 (10)	0.0096 (12)
C20	0.0162 (12)	0.0226 (12)	0.0190 (12)	−0.0001 (9)	0.0018 (8)	−0.0007 (9)
C21	0.0179 (12)	0.0329 (13)	0.0278 (13)	0.0026 (10)	0.0101 (9)	0.0067 (10)
C22	0.0324 (15)	0.0294 (14)	0.0328 (14)	−0.0002 (11)	0.0129 (11)	0.0049 (11)

Geometric parameters (Å, º)

N1—C2	1.335 (3)	C11—H11	0.95
N1—C6	1.338 (3)	C12—H12	0.95
O1—C17	1.211 (3)	C13—C16	1.519 (3)
O2—C17	1.330 (3)	C13—C15	1.535 (3)
O2—C18	1.454 (3)	C13—C14	1.535 (3)
O3—C20	1.204 (3)	C14—H14a	0.98
O4—C20	1.336 (3)	C14—H14b	0.98
O4—C21	1.459 (3)	C14—H14c	0.98
C2—C3	1.386 (3)	C15—H15a	0.98
C2—C17	1.502 (3)	C15—H15b	0.98
C3—C4	1.394 (3)	C15—H15c	0.98
C3—H3	0.95	C16—H16a	0.98
C4—C5	1.394 (3)	C16—H16b	0.98
C4—C7	1.479 (3)	C16—H16c	0.98
C5—C6	1.383 (3)	C18—C19	1.495 (4)
C5—H5	0.95	C18—H18a	0.99
C6—C20	1.502 (3)	C18—H18b	0.99
C7—C12	1.389 (3)	C19—H19a	0.98
C7—C8	1.399 (3)	C19—H19b	0.98
C8—C9	1.386 (3)	C19—H19c	0.98
C8—H8	0.95	C21—C22	1.507 (4)
C9—C10	1.393 (3)	C21—H21a	0.99
C9—H9	0.95	C21—H21b	0.99
C10—C11	1.394 (3)	C22—H22a	0.98
C10—C13	1.532 (3)	C22—H22b	0.98
C11—C12	1.391 (3)	C22—H22c	0.98
C2—N1—C6	116.44 (19)	C13—C14—H14C	109.5
C17—O2—C18	115.68 (18)	H14A—C14—H14C	109.5
C20—O4—C21	116.26 (17)	H14B—C14—H14C	109.5
N1—C2—C3	123.6 (2)	C13—C15—H15A	109.5
N1—C2—C17	118.1 (2)	C13—C15—H15B	109.5
C3—C2—C17	118.2 (2)	H15A—C15—H15B	109.5
C2—C3—C4	119.7 (2)	C13—C15—H15C	109.5
C2—C3—H3	120.2	H15A—C15—H15C	109.5
C4—C3—H3	120.2	H15B—C15—H15C	109.5
C5—C4—C3	116.8 (2)	C13—C16—H16A	109.5
C5—C4—C7	121.3 (2)	C13—C16—H16B	109.5
C3—C4—C7	121.8 (2)	H16A—C16—H16B	109.5
C6—C5—C4	119.2 (2)	C13—C16—H16C	109.5
C6—C5—H5	120.4	H16A—C16—H16C	109.5
C4—C5—H5	120.4	H16B—C16—H16C	109.5
N1—C6—C5	124.2 (2)	O1—C17—O2	124.3 (2)
N1—C6—C20	114.82 (19)	O1—C17—C2	122.7 (2)
C5—C6—C20	120.87 (19)	O2—C17—C2	112.97 (19)
C12—C7—C8	118.8 (2)	O2—C18—C19	107.2 (2)
C12—C7—C4	121.0 (2)	O2—C18—H18A	110.3
C8—C7—C4	120.2 (2)	C19—C18—H18A	110.3
C9—C8—C7	119.6 (2)	O2—C18—H18B	110.3
C9—C8—H8	120.2	C19—C18—H18B	110.3
C7—C8—H8	120.2	H18A—C18—H18B	108.5
C8—C9—C10	122.3 (2)	C18—C19—H19A	109.5
C8—C9—H9	118.9	C18—C19—H19B	109.5
C10—C9—H9	118.9	H19A—C19—H19B	109.5
C11—C10—C9	117.5 (2)	C18—C19—H19C	109.5
C11—C10—C13	122.1 (2)	H19A—C19—H19C	109.5
C9—C10—C13	120.4 (2)	H19B—C19—H19C	109.5
C12—C11—C10	120.9 (2)	O3—C20—O4	124.8 (2)
C12—C11—H11	119.6	O3—C20—C6	123.9 (2)
C10—C11—H11	119.6	O4—C20—C6	111.20 (18)
C7—C12—C11	121.0 (2)	O4—C21—C22	109.86 (19)
C7—C12—H12	119.5	O4—C21—H21A	109.7
C11—C12—H12	119.5	C22—C21—H21A	109.7
C16—C13—C10	112.2 (2)	O4—C21—H21B	109.7
C16—C13—C15	108.0 (2)	C22—C21—H21B	109.7
C10—C13—C15	109.6 (2)	H21A—C21—H21B	108.2
C16—C13—C14	108.5 (2)	C21—C22—H22A	109.5
C10—C13—C14	108.62 (19)	C21—C22—H22B	109.5
C15—C13—C14	110.0 (2)	H22A—C22—H22B	109.5
C13—C14—H14A	109.5	C21—C22—H22C	109.5
C13—C14—H14B	109.5	H22A—C22—H22C	109.5
H14A—C14—H14B	109.5	H22B—C22—H22C	109.5
C6—N1—C2—C3	2.4 (3)	C8—C7—C12—C11	0.4 (3)
C6—N1—C2—C17	179.38 (19)	C4—C7—C12—C11	178.8 (2)
N1—C2—C3—C4	−1.2 (3)	C10—C11—C12—C7	−0.1 (3)
C17—C2—C3—C4	−178.2 (2)	C11—C10—C13—C16	8.6 (3)
C2—C3—C4—C5	−1.7 (3)	C9—C10—C13—C16	−172.9 (2)
C2—C3—C4—C7	175.5 (2)	C11—C10—C13—C15	128.5 (2)
C3—C4—C5—C6	3.3 (3)	C9—C10—C13—C15	−53.0 (3)
C7—C4—C5—C6	−173.9 (2)	C11—C10—C13—C14	−111.3 (2)
C2—N1—C6—C5	−0.7 (3)	C9—C10—C13—C14	67.2 (3)
C2—N1—C6—C20	−176.45 (19)	C18—O2—C17—O1	2.2 (3)
C4—C5—C6—N1	−2.2 (3)	C18—O2—C17—C2	−176.63 (19)
C4—C5—C6—C20	173.3 (2)	N1—C2—C17—O1	−174.6 (2)
C5—C4—C7—C12	−34.0 (3)	C3—C2—C17—O1	2.5 (3)
C3—C4—C7—C12	148.9 (2)	N1—C2—C17—O2	4.2 (3)
C5—C4—C7—C8	144.3 (2)	C3—C2—C17—O2	−178.62 (19)
C3—C4—C7—C8	−32.7 (3)	C17—O2—C18—C19	−169.4 (2)
C12—C7—C8—C9	−0.7 (3)	C21—O4—C20—O3	6.4 (3)
C4—C7—C8—C9	−179.0 (2)	C21—O4—C20—C6	−172.30 (18)
C7—C8—C9—C10	0.6 (4)	N1—C6—C20—O3	22.4 (3)
C8—C9—C10—C11	−0.3 (3)	C5—C6—C20—O3	−153.6 (2)
C8—C9—C10—C13	−178.9 (2)	N1—C6—C20—O4	−158.93 (19)
C9—C10—C11—C12	0.0 (3)	C5—C6—C20—O4	25.1 (3)
C13—C10—C11—C12	178.6 (2)	C20—O4—C21—C22	86.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O3^i	0.95	2.52	3.463 (3)	175
C12—H12···O1^ii	0.95	2.46	3.406 (3)	174
C21—H21B···N1^ii	0.99	2.58	3.287 (3)	128

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