Ethyl 5-carb­oxy-2,6-dimethyl-4-(4-nitro­phen­yl)-1,4-dihydro­pyridine-3-carboxyl­ate

The title compound, C₁₇H₁₈N₂O₆, is an important inter­mediate in the synthesis of nefidipine analogs. The crystal packing is stabilized by inter­molecular N—H...O hydrogen bonds and O—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.004 Å
• Disorder in main residue
• R factor = 0.051
• wR factor = 0.149
• Data-to-parameter ratio = 12.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.85 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.61 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT301_ALERT_3_C Main Residue  Disorder .........................       4.00 Perc.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      29.90 Deg.
              C10  -C9   -C10'    1.555   1.555   1.555

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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: SHELXTL.

Ethyl 3-carboxy-2,6-dimethyl-4-(4-nitrophenyl)-1,4-dihydropyridine-3-carboxylate

Crystal data

C17H18N2O6	Dx = 1.343 Mg m^−3
Mr = 346.33	Melting point = 446–447 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.323 (2) Å	Cell parameters from 2043 reflections
b = 15.590 (3) Å	θ = 2.3–23.4°
c = 11.202 (3) Å	µ = 0.10 mm^−1
β = 108.201 (4)°	T = 294 K
V = 1712.7 (7) Å^3	Block, yellow
Z = 4	0.40 × 0.28 × 0.10 mm
F(000) = 728

Data collection

Bruker SMART CCD area-detector diffractometer	3024 independent reflections
Radiation source: fine-focus sealed tube	1890 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→10
Tmin = 0.960, Tmax = 0.990	k = −15→18
8538 measured reflections	l = −13→13

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0635P)^2 + 0.8733P] where P = (Fo^2 + 2Fc^2)/3
3024 reflections	(Δ/σ)max = 0.003
239 parameters	Δρmax = 0.25 e Å^−3
20 restraints	Δρmin = −0.20 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	Occ. (<1)
O1	1.0062 (3)	0.39646 (17)	0.1318 (2)	0.0863 (9)
O2	1.0692 (2)	0.36792 (14)	0.33350 (19)	0.0691 (7)
O3	0.4342 (3)	0.41885 (17)	0.5179 (3)	0.0891 (9)
O4	0.6007 (3)	0.4136 (2)	0.6913 (3)	0.1034 (10)
O5	0.9897 (2)	0.10382 (12)	0.47880 (18)	0.0554 (6)
O6	0.8608 (2)	0.00384 (12)	0.35777 (19)	0.0644 (7)
H6	0.9094	−0.0271	0.4130	0.097*
N1	0.7219 (2)	0.19326 (14)	0.08153 (19)	0.0410 (6)
H1	0.6498	0.1892	0.0174	0.049*
N2	0.5510 (4)	0.40028 (19)	0.5787 (3)	0.0725 (8)
C1	0.8078 (3)	0.26264 (16)	0.0895 (2)	0.0376 (6)
C2	0.8931 (3)	0.28520 (16)	0.2031 (2)	0.0369 (6)
C3	0.8847 (3)	0.23861 (15)	0.3189 (2)	0.0361 (6)
H3	0.9774	0.2356	0.3781	0.043*
C4	0.8357 (3)	0.14722 (16)	0.2866 (2)	0.0367 (6)
C5	0.7471 (3)	0.13044 (16)	0.1722 (2)	0.0376 (6)
C6	0.6713 (3)	0.04851 (19)	0.1265 (3)	0.0539 (8)
H6A	0.7262	0.0117	0.0932	0.081*
H6B	0.5874	0.0612	0.0619	0.081*
H6C	0.6519	0.0203	0.1952	0.081*
C7	0.7948 (3)	0.3025 (2)	−0.0357 (3)	0.0545 (8)
H7A	0.7662	0.3611	−0.0358	0.082*
H7B	0.7284	0.2715	−0.1007	0.082*
H7C	0.8813	0.3005	−0.0507	0.082*
C8	0.9965 (3)	0.35184 (18)	0.2290 (3)	0.0441 (7)
C9	1.1164 (4)	0.4600 (3)	0.1573 (4)	0.0979 (15)
H9A	1.0872	0.5092	0.1026	0.118*
H9B	1.1398	0.4795	0.2437	0.118*
C10	1.2350 (11)	0.4200 (11)	0.135 (2)	0.103 (5)	0.54 (3)
H10A	1.2846	0.3876	0.2081	0.155*	0.54 (3)
H10B	1.2930	0.4637	0.1193	0.155*	0.54 (3)
H10C	1.2052	0.3825	0.0640	0.155*	0.54 (3)
C10'	1.200 (2)	0.4413 (9)	0.072 (2)	0.095 (5)	0.46 (3)
H10D	1.1607	0.4707	−0.0066	0.142*	0.46 (3)
H10E	1.1996	0.3807	0.0569	0.142*	0.46 (3)
H10F	1.2914	0.4607	0.1103	0.142*	0.46 (3)
C11	0.7962 (3)	0.28407 (15)	0.3858 (2)	0.0383 (6)
C12	0.6724 (3)	0.31877 (19)	0.3207 (3)	0.0534 (8)
H12	0.6428	0.3169	0.2333	0.064*
C13	0.5904 (3)	0.3567 (2)	0.3835 (3)	0.0617 (9)
H13	0.5057	0.3794	0.3390	0.074*
C14	0.6362 (3)	0.36014 (19)	0.5115 (3)	0.0535 (8)
C15	0.7605 (4)	0.3280 (2)	0.5786 (3)	0.0674 (9)
H15	0.7911	0.3320	0.6658	0.081*
C16	0.8396 (3)	0.2898 (2)	0.5157 (3)	0.0570 (8)
H16	0.9240	0.2672	0.5610	0.068*
C17	0.8992 (3)	0.08299 (17)	0.3805 (2)	0.0425 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0946 (18)	0.1036 (19)	0.0502 (13)	−0.0592 (16)	0.0071 (12)	0.0166 (13)
O2	0.0752 (15)	0.0648 (14)	0.0461 (13)	−0.0270 (12)	−0.0114 (11)	0.0100 (11)
O3	0.0821 (19)	0.0799 (19)	0.129 (2)	0.0025 (15)	0.0669 (19)	−0.0002 (16)
O4	0.124 (2)	0.120 (2)	0.088 (2)	−0.0030 (19)	0.064 (2)	−0.0296 (18)
O5	0.0688 (13)	0.0407 (11)	0.0413 (11)	0.0016 (10)	−0.0051 (10)	0.0087 (9)
O6	0.0848 (16)	0.0351 (12)	0.0550 (13)	0.0005 (11)	−0.0044 (11)	0.0100 (9)
N1	0.0357 (12)	0.0417 (13)	0.0361 (12)	−0.0007 (10)	−0.0026 (10)	0.0065 (10)
N2	0.083 (2)	0.0625 (19)	0.091 (2)	−0.0087 (17)	0.055 (2)	−0.0065 (17)
C1	0.0378 (14)	0.0371 (15)	0.0349 (14)	0.0044 (12)	0.0071 (12)	0.0065 (12)
C2	0.0370 (14)	0.0373 (15)	0.0334 (14)	0.0019 (12)	0.0065 (11)	0.0062 (11)
C3	0.0359 (14)	0.0351 (14)	0.0318 (14)	0.0021 (11)	0.0024 (11)	0.0048 (11)
C4	0.0402 (14)	0.0337 (14)	0.0341 (14)	0.0018 (12)	0.0086 (12)	0.0039 (11)
C5	0.0387 (14)	0.0331 (14)	0.0398 (15)	0.0030 (12)	0.0106 (12)	0.0021 (12)
C6	0.0552 (18)	0.0452 (17)	0.0519 (18)	−0.0075 (14)	0.0034 (14)	0.0003 (14)
C7	0.0597 (19)	0.0614 (19)	0.0361 (15)	−0.0060 (15)	0.0059 (14)	0.0108 (14)
C8	0.0449 (16)	0.0414 (16)	0.0404 (16)	−0.0014 (13)	0.0050 (13)	0.0094 (13)
C9	0.108 (3)	0.111 (3)	0.071 (3)	−0.059 (3)	0.022 (2)	0.013 (2)
C10	0.075 (6)	0.115 (8)	0.114 (8)	−0.023 (5)	0.022 (5)	−0.007 (6)
C10'	0.074 (7)	0.078 (7)	0.137 (9)	0.000 (5)	0.040 (7)	0.017 (6)
C11	0.0456 (16)	0.0282 (14)	0.0378 (14)	−0.0012 (12)	0.0085 (12)	0.0033 (11)
C12	0.0554 (19)	0.0581 (19)	0.0428 (16)	0.0115 (15)	0.0094 (15)	−0.0002 (14)
C13	0.0501 (18)	0.062 (2)	0.072 (2)	0.0096 (16)	0.0171 (17)	−0.0017 (17)
C14	0.067 (2)	0.0424 (17)	0.062 (2)	−0.0069 (15)	0.0359 (18)	−0.0064 (15)
C15	0.085 (3)	0.076 (2)	0.0440 (18)	0.010 (2)	0.0234 (18)	−0.0016 (17)
C16	0.0624 (19)	0.070 (2)	0.0360 (16)	0.0106 (17)	0.0116 (14)	0.0004 (15)
C17	0.0504 (17)	0.0356 (16)	0.0386 (16)	0.0013 (13)	0.0096 (14)	0.0022 (12)

Geometric parameters (Å, º)

O1—C8	1.322 (3)	C6—H6C	0.9600
O1—C9	1.468 (4)	C7—H7A	0.9600
O2—C8	1.203 (3)	C7—H7B	0.9600
O3—N2	1.220 (4)	C7—H7C	0.9600
O4—N2	1.221 (4)	C9—C10	1.462 (8)
O5—C17	1.244 (3)	C9—C10'	1.501 (9)
O6—C17	1.297 (3)	C9—H9A	0.9700
O6—H6	0.8200	C9—H9B	0.9700
N1—C5	1.376 (3)	C10—H10A	0.9600
N1—C1	1.384 (3)	C10—H10B	0.9600
N1—H1	0.8600	C10—H10C	0.9600
N2—C14	1.465 (4)	C10'—H10D	0.9600
C1—C2	1.349 (3)	C10'—H10E	0.9600
C1—C7	1.502 (4)	C10'—H10F	0.9600
C2—C8	1.452 (4)	C11—C12	1.370 (4)
C2—C3	1.512 (3)	C11—C16	1.385 (4)
C3—C4	1.517 (3)	C12—C13	1.391 (4)
C3—C11	1.525 (4)	C12—H12	0.9300
C3—H3	0.9800	C13—C14	1.363 (4)
C4—C5	1.347 (3)	C13—H13	0.9300
C4—C17	1.452 (4)	C14—C15	1.364 (4)
C5—C6	1.502 (4)	C15—C16	1.371 (4)
C6—H6A	0.9600	C15—H15	0.9300
C6—H6B	0.9600	C16—H16	0.9300
C8—O1—C9	116.7 (2)	C10—C9—C10'	29.9 (5)
C17—O6—H6	109.5	O1—C9—C10'	107.9 (6)
C5—N1—C1	122.6 (2)	C10—C9—H9A	110.0
C5—N1—H1	118.7	O1—C9—H9A	110.0
C1—N1—H1	118.7	C10'—C9—H9A	82.9
O3—N2—O4	124.0 (3)	C10—C9—H9B	110.0
O3—N2—C14	117.5 (3)	O1—C9—H9B	110.0
O4—N2—C14	118.5 (4)	C10'—C9—H9B	133.2
C2—C1—N1	118.7 (2)	H9A—C9—H9B	108.4
C2—C1—C7	128.0 (2)	C9—C10—H10A	109.5
N1—C1—C7	113.3 (2)	C9—C10—H10B	109.5
C1—C2—C8	126.7 (2)	H10A—C10—H10B	109.5
C1—C2—C3	119.3 (2)	C9—C10—H10C	109.5
C8—C2—C3	114.1 (2)	H10A—C10—H10C	109.5
C2—C3—C4	110.5 (2)	H10B—C10—H10C	109.5
C2—C3—C11	113.7 (2)	C9—C10'—H10D	109.5
C4—C3—C11	110.3 (2)	C9—C10'—H10E	109.5
C2—C3—H3	107.3	H10D—C10'—H10E	109.5
C4—C3—H3	107.3	C9—C10'—H10F	109.5
C11—C3—H3	107.3	H10D—C10'—H10F	109.5
C5—C4—C17	125.0 (2)	H10E—C10'—H10F	109.5
C5—C4—C3	119.1 (2)	C12—C11—C16	118.4 (3)
C17—C4—C3	115.7 (2)	C12—C11—C3	121.6 (2)
C4—C5—N1	118.7 (2)	C16—C11—C3	120.0 (2)
C4—C5—C6	128.0 (2)	C11—C12—C13	120.9 (3)
N1—C5—C6	113.3 (2)	C11—C12—H12	119.6
C5—C6—H6A	109.5	C13—C12—H12	119.6
C5—C6—H6B	109.5	C14—C13—C12	118.8 (3)
H6A—C6—H6B	109.5	C14—C13—H13	120.6
C5—C6—H6C	109.5	C12—C13—H13	120.6
H6A—C6—H6C	109.5	C13—C14—C15	121.6 (3)
H6B—C6—H6C	109.5	C13—C14—N2	119.3 (3)
C1—C7—H7A	109.5	C15—C14—N2	119.1 (3)
C1—C7—H7B	109.5	C14—C15—C16	119.0 (3)
H7A—C7—H7B	109.5	C14—C15—H15	120.5
C1—C7—H7C	109.5	C16—C15—H15	120.5
H7A—C7—H7C	109.5	C15—C16—C11	121.3 (3)
H7B—C7—H7C	109.5	C15—C16—H16	119.3
O2—C8—O1	120.4 (3)	C11—C16—H16	119.3
O2—C8—C2	122.6 (2)	O5—C17—O6	121.4 (2)
O1—C8—C2	116.9 (2)	O5—C17—C4	120.4 (2)
C10—C9—O1	108.5 (6)	O6—C17—C4	118.2 (2)
C5—N1—C1—C2	−21.4 (4)	C3—C2—C8—O1	−178.2 (3)
C5—N1—C1—C7	157.0 (2)	C8—O1—C9—C10	93.8 (11)
N1—C1—C2—C8	175.4 (2)	C8—O1—C9—C10'	125.3 (11)
C7—C1—C2—C8	−2.7 (5)	C2—C3—C11—C12	43.8 (3)
N1—C1—C2—C3	−4.6 (4)	C4—C3—C11—C12	−81.0 (3)
C7—C1—C2—C3	177.2 (3)	C2—C3—C11—C16	−137.3 (3)
C1—C2—C3—C4	29.4 (3)	C4—C3—C11—C16	97.9 (3)
C8—C2—C3—C4	−150.7 (2)	C16—C11—C12—C13	−1.8 (4)
C1—C2—C3—C11	−95.3 (3)	C3—C11—C12—C13	177.2 (3)
C8—C2—C3—C11	84.6 (3)	C11—C12—C13—C14	1.1 (5)
C2—C3—C4—C5	−32.7 (3)	C12—C13—C14—C15	0.6 (5)
C11—C3—C4—C5	93.9 (3)	C12—C13—C14—N2	179.7 (3)
C2—C3—C4—C17	142.2 (2)	O3—N2—C14—C13	9.6 (4)
C11—C3—C4—C17	−91.2 (3)	O4—N2—C14—C13	−170.0 (3)
C17—C4—C5—N1	−163.5 (2)	O3—N2—C14—C15	−171.2 (3)
C3—C4—C5—N1	10.9 (4)	O4—N2—C14—C15	9.2 (5)
C17—C4—C5—C6	14.7 (5)	C13—C14—C15—C16	−1.4 (5)
C3—C4—C5—C6	−170.9 (3)	N2—C14—C15—C16	179.4 (3)
C1—N1—C5—C4	18.1 (4)	C14—C15—C16—C11	0.7 (5)
C1—N1—C5—C6	−160.4 (2)	C12—C11—C16—C15	0.9 (5)
C9—O1—C8—O2	5.1 (5)	C3—C11—C16—C15	−178.0 (3)
C9—O1—C8—C2	−176.3 (3)	C5—C4—C17—O5	173.1 (3)
C1—C2—C8—O2	−179.7 (3)	C3—C4—C17—O5	−1.5 (4)
C3—C2—C8—O2	0.4 (4)	C5—C4—C17—O6	−5.6 (4)
C1—C2—C8—O1	1.7 (4)	C3—C4—C17—O6	179.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^i	0.86	2.16	2.894 (3)	143
O6—H6···O5^ii	0.82	1.79	2.605 (3)	174

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