3-Benzotriazol-1-yl 5-methyl 2,6-dimethyl-4-(3-nitro­phen­yl)-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

The title compound, C₂₂H₁₉N₅O₆, is an important inter­mediate in the synthesis of nefidipine-type pharmaceuticals. The dihydro­pyridine ring has a flattened boat conformation. Mol­ecules are linked by N—H...N 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 = 0.052
• wR factor = 0.146
• Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.56 Ratio
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        O6'

Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT215_ALERT_3_C Disordered O6      has ADP max/min Ratio .......       3.50
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.18 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         O6
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N5
PLAT301_ALERT_3_C Main Residue  Disorder .........................       6.00 Perc.

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   6 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
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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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.

3-Benzotriazol-1-yl 5-methyl-2,6-dimethyl -4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-dicarboxylate

Crystal data

C22H19N5O6	F(000) = 936
Mr = 449.42	Dx = 1.407 Mg m^−3
Monoclinic, P21/c	Melting point = 429–430 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.113 (3) Å	Cell parameters from 2365 reflections
b = 17.934 (5) Å	θ = 2.5–22.6°
c = 14.723 (4) Å	µ = 0.11 mm^−1
β = 98.008 (6)°	T = 294 K
V = 2121.2 (11) Å^3	Block, colourless
Z = 4	0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART CCD area detector diffractometer	4343 independent reflections
Radiation source: fine-focus sealed tube	2397 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
φ and ω scans	θmax = 26.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
Tmin = 0.973, Tmax = 0.979	k = −20→22
11847 measured reflections	l = −14→18

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.063P)^2 + 0.4855P] where P = (Fo^2 + 2Fc^2)/3
4343 reflections	(Δ/σ)max < 0.001
324 parameters	Δρmax = 0.46 e Å^−3
31 restraints	Δρmin = −0.33 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. Nitro groups are found to be disorderde·The site occupancy of the nitro group is fixed to 0.5:0.5 at final refinement.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.3789 (2)	0.22224 (9)	0.40187 (12)	0.0416 (5)
O2	0.3818 (3)	0.21413 (10)	0.24759 (14)	0.0582 (6)
O3	0.2770 (3)	0.44245 (10)	0.56114 (13)	0.0520 (5)
O4	0.2114 (4)	0.55108 (13)	0.49432 (18)	0.1088 (12)
O5	−0.2573 (8)	0.2440 (4)	0.6048 (8)	0.074 (2)	0.50
O6	0.0012 (11)	0.2270 (4)	0.6493 (7)	0.131 (4)	0.50
O5'	−0.2363 (9)	0.2170 (4)	0.5990 (9)	0.078 (3)	0.50
O6'	−0.0010 (11)	0.2639 (5)	0.6560 (7)	0.148 (4)	0.50
N1	0.4895 (3)	0.03816 (12)	0.39329 (16)	0.0453 (6)
N2	0.5261 (3)	0.10948 (12)	0.39813 (16)	0.0446 (6)
N3	0.3822 (3)	0.14608 (11)	0.39955 (15)	0.0395 (6)
N4	0.3449 (3)	0.45249 (12)	0.25111 (16)	0.0406 (6)
N5	−0.1117 (4)	0.24950 (13)	0.5918 (2)	0.0743 (9)
C1	0.3200 (4)	0.03033 (14)	0.39134 (17)	0.0397 (7)
C2	0.2185 (4)	−0.03337 (16)	0.3865 (2)	0.0529 (8)
H2	0.2631	−0.0810	0.3847	0.064*
C3	0.0520 (4)	−0.02240 (17)	0.3844 (2)	0.0620 (9)
H3	−0.0182	−0.0636	0.3805	0.074*
C4	−0.0175 (4)	0.04936 (18)	0.3879 (2)	0.0605 (9)
H4	−0.1318	0.0540	0.3875	0.073*
C5	0.0783 (4)	0.11232 (16)	0.3919 (2)	0.0508 (8)
H5	0.0330	0.1599	0.3934	0.061*
C6	0.2485 (3)	0.10037 (14)	0.39373 (17)	0.0370 (6)
C7	0.3686 (3)	0.25395 (14)	0.31099 (19)	0.0383 (6)
C8	0.3450 (3)	0.33366 (13)	0.31817 (17)	0.0335 (6)
C9	0.3621 (3)	0.37702 (13)	0.24479 (18)	0.0340 (6)
C10	0.3963 (4)	0.35060 (15)	0.15251 (18)	0.0473 (7)
H10A	0.4958	0.3210	0.1597	0.071*
H10B	0.4105	0.3929	0.1143	0.071*
H10C	0.3044	0.3211	0.1244	0.071*
C11	0.3176 (4)	0.57312 (14)	0.3214 (2)	0.0565 (9)
H11A	0.2054	0.5912	0.3081	0.085*
H11B	0.3785	0.5868	0.2725	0.085*
H11C	0.3699	0.5947	0.3778	0.085*
C12	0.3158 (3)	0.48959 (14)	0.33047 (19)	0.0386 (6)
C13	0.2913 (3)	0.44995 (13)	0.40437 (18)	0.0361 (6)
C14	0.2900 (3)	0.36479 (13)	0.40546 (17)	0.0330 (6)
H14	0.3687	0.3477	0.4579	0.040*
C15	0.2566 (4)	0.48777 (16)	0.4887 (2)	0.0507 (8)
C16	0.2292 (5)	0.4709 (2)	0.6448 (2)	0.0721 (10)
H16A	0.2935	0.5146	0.6634	0.108*
H16B	0.2491	0.4336	0.6919	0.108*
H16C	0.1131	0.4835	0.6352	0.108*
C17	0.1167 (3)	0.33541 (13)	0.41654 (17)	0.0335 (6)
C18	0.0838 (3)	0.30599 (13)	0.49878 (19)	0.0391 (6)
H18	0.1671	0.3034	0.5489	0.047*
C19	−0.0742 (4)	0.28055 (14)	0.5054 (2)	0.0435 (7)
C20	−0.2008 (4)	0.28213 (16)	0.4336 (2)	0.0565 (9)
H20	−0.3063	0.2645	0.4403	0.068*
C21	−0.1673 (4)	0.31053 (19)	0.3515 (2)	0.0618 (9)
H21	−0.2503	0.3115	0.3011	0.074*
C22	−0.0107 (4)	0.33762 (16)	0.3437 (2)	0.0475 (7)
H22	0.0096	0.3578	0.2881	0.057*
H4A	0.368 (3)	0.4783 (13)	0.2079 (17)	0.034 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0513 (12)	0.0246 (9)	0.0504 (12)	0.0025 (8)	0.0126 (9)	−0.0016 (8)
O2	0.0861 (17)	0.0388 (11)	0.0535 (13)	0.0071 (10)	0.0232 (12)	−0.0095 (10)
O3	0.0690 (15)	0.0476 (11)	0.0399 (12)	0.0011 (10)	0.0094 (10)	−0.0063 (10)
O4	0.216 (4)	0.0485 (15)	0.0711 (18)	0.0382 (18)	0.053 (2)	−0.0047 (12)
O5	0.071 (4)	0.049 (5)	0.114 (5)	−0.014 (3)	0.054 (3)	−0.005 (4)
O6	0.084 (5)	0.185 (7)	0.125 (6)	−0.001 (5)	0.022 (4)	0.124 (5)
O5'	0.092 (5)	0.036 (4)	0.123 (5)	−0.016 (3)	0.073 (4)	0.000 (4)
O6'	0.098 (6)	0.220 (9)	0.127 (6)	−0.018 (6)	0.025 (5)	0.119 (6)
N1	0.0466 (15)	0.0324 (13)	0.0582 (15)	0.0064 (11)	0.0119 (12)	0.0010 (11)
N2	0.0401 (14)	0.0376 (13)	0.0576 (16)	0.0077 (11)	0.0121 (11)	0.0004 (11)
N3	0.0411 (14)	0.0261 (11)	0.0528 (15)	0.0029 (10)	0.0122 (11)	−0.0001 (10)
N4	0.0507 (15)	0.0315 (13)	0.0419 (15)	−0.0023 (10)	0.0144 (11)	0.0056 (11)
N5	0.061 (2)	0.080 (2)	0.088 (2)	−0.0022 (19)	0.0323 (18)	0.0279 (19)
C1	0.0516 (19)	0.0332 (14)	0.0347 (15)	0.0034 (13)	0.0067 (12)	0.0012 (12)
C2	0.064 (2)	0.0361 (16)	0.059 (2)	−0.0019 (15)	0.0089 (16)	−0.0009 (14)
C3	0.063 (2)	0.0509 (19)	0.072 (2)	−0.0179 (17)	0.0085 (17)	−0.0043 (17)
C4	0.0435 (19)	0.067 (2)	0.072 (2)	−0.0065 (16)	0.0093 (16)	−0.0075 (18)
C5	0.049 (2)	0.0466 (17)	0.057 (2)	0.0035 (14)	0.0081 (15)	−0.0054 (15)
C6	0.0433 (17)	0.0335 (14)	0.0353 (16)	0.0023 (12)	0.0092 (12)	0.0005 (12)
C7	0.0337 (15)	0.0357 (14)	0.0474 (17)	0.0006 (12)	0.0125 (12)	−0.0015 (13)
C8	0.0278 (14)	0.0313 (13)	0.0427 (16)	−0.0007 (11)	0.0100 (11)	−0.0027 (12)
C9	0.0280 (14)	0.0330 (14)	0.0420 (16)	−0.0024 (11)	0.0086 (11)	−0.0033 (12)
C10	0.0526 (19)	0.0448 (16)	0.0475 (18)	−0.0038 (14)	0.0179 (14)	−0.0041 (14)
C11	0.077 (2)	0.0338 (16)	0.061 (2)	−0.0026 (15)	0.0171 (17)	0.0005 (14)
C12	0.0368 (16)	0.0320 (14)	0.0475 (17)	−0.0008 (12)	0.0079 (13)	−0.0035 (13)
C13	0.0366 (15)	0.0296 (13)	0.0426 (16)	−0.0002 (11)	0.0075 (12)	−0.0040 (12)
C14	0.0333 (14)	0.0294 (13)	0.0367 (15)	0.0002 (11)	0.0065 (11)	−0.0007 (11)
C15	0.066 (2)	0.0365 (16)	0.051 (2)	−0.0015 (14)	0.0135 (16)	−0.0072 (14)
C16	0.099 (3)	0.078 (2)	0.0417 (19)	0.003 (2)	0.0176 (18)	−0.0147 (18)
C17	0.0308 (15)	0.0299 (13)	0.0411 (16)	0.0028 (11)	0.0095 (12)	−0.0041 (12)
C18	0.0384 (16)	0.0332 (14)	0.0466 (17)	0.0028 (12)	0.0094 (13)	0.0034 (12)
C19	0.0428 (17)	0.0326 (14)	0.0589 (19)	0.0020 (13)	0.0208 (15)	0.0033 (13)
C20	0.0351 (18)	0.0567 (19)	0.081 (2)	−0.0086 (14)	0.0198 (17)	−0.0145 (17)
C21	0.0330 (18)	0.089 (2)	0.062 (2)	−0.0071 (16)	0.0021 (15)	−0.0170 (19)
C22	0.0387 (17)	0.0614 (19)	0.0427 (17)	−0.0025 (14)	0.0065 (13)	−0.0038 (14)

Geometric parameters (Å, º)

O1—N3	1.367 (2)	C8—C9	1.354 (3)
O1—C7	1.445 (3)	C8—C14	1.524 (3)
O2—C7	1.192 (3)	C9—C10	1.501 (3)
O3—C15	1.333 (3)	C10—H10A	0.960
O3—C16	1.436 (3)	C10—H10B	0.960
O4—C15	1.199 (3)	C10—H10C	0.960
O5—N5	1.226 (7)	C11—C12	1.504 (3)
O6—N5	1.227 (7)	C11—H11A	0.960
O5'—N5	1.184 (7)	C11—H11B	0.960
O6'—N5	1.238 (8)	C11—H11C	0.960
N1—N2	1.313 (3)	C12—C13	1.338 (3)
N1—C1	1.379 (3)	C13—C15	1.475 (4)
N2—N3	1.342 (3)	C13—C14	1.527 (3)
N3—C6	1.353 (3)	C14—C17	1.532 (3)
N4—C9	1.365 (3)	C14—H14	0.980
N4—C12	1.393 (3)	C16—H16A	0.960
N4—H4A	0.83 (2)	C16—H16B	0.960
N5—C19	1.459 (4)	C16—H16C	0.960
C1—C6	1.386 (4)	C17—C18	1.380 (3)
C1—C2	1.404 (4)	C17—C22	1.382 (4)
C2—C3	1.361 (4)	C18—C19	1.377 (4)
C2—H2	0.930	C18—H18	0.930
C3—C4	1.409 (4)	C19—C20	1.367 (4)
C3—H3	0.930	C20—C21	1.374 (4)
C4—C5	1.367 (4)	C20—H20	0.930
C4—H4	0.930	C21—C22	1.380 (4)
C5—C6	1.394 (4)	C21—H21	0.930
C5—H5	0.930	C22—H22	0.930
C7—C8	1.448 (4)
N3—O1—C7	111.65 (18)	H10A—C10—H10C	109.5
C15—O3—C16	116.9 (2)	H10B—C10—H10C	109.5
N2—N1—C1	108.5 (2)	C12—C11—H11A	109.5
N1—N2—N3	106.6 (2)	C12—C11—H11B	109.5
N2—N3—C6	113.2 (2)	H11A—C11—H11B	109.5
N2—N3—O1	120.6 (2)	C12—C11—H11C	109.5
C6—N3—O1	126.1 (2)	H11A—C11—H11C	109.5
C9—N4—C12	124.2 (2)	H11B—C11—H11C	109.5
C9—N4—H4A	117.7 (17)	C13—C12—N4	119.4 (2)
C12—N4—H4A	117.4 (17)	C13—C12—C11	127.3 (3)
O5—N5—O6	120.6 (7)	N4—C12—C11	113.3 (2)
O5'—N5—O6'	124.9 (7)	C12—C13—C15	120.5 (2)
O5'—N5—C19	123.4 (7)	C12—C13—C14	122.8 (2)
O5—N5—C19	119.3 (6)	C15—C13—C14	116.7 (2)
O6—N5—C19	120.1 (6)	C8—C14—C13	110.8 (2)
O6'—N5—C19	111.7 (6)	C8—C14—C17	110.2 (2)
N1—C1—C6	109.1 (2)	C13—C14—C17	110.65 (19)
N1—C1—C2	131.3 (2)	C8—C14—H14	108.4
C6—C1—C2	119.6 (3)	C13—C14—H14	108.4
C3—C2—C1	117.2 (3)	C17—C14—H14	108.4
C3—C2—H2	121.4	O4—C15—O3	121.8 (3)
C1—C2—H2	121.4	O4—C15—C13	126.1 (3)
C2—C3—C4	122.2 (3)	O3—C15—C13	112.1 (2)
C2—C3—H3	118.9	O3—C16—H16A	109.5
C4—C3—H3	118.9	O3—C16—H16B	109.5
C5—C4—C3	121.9 (3)	H16A—C16—H16B	109.5
C5—C4—H4	119.1	O3—C16—H16C	109.5
C3—C4—H4	119.1	H16A—C16—H16C	109.5
C4—C5—C6	115.4 (3)	H16B—C16—H16C	109.5
C4—C5—H5	122.3	C18—C17—C22	118.5 (2)
C6—C5—H5	122.3	C18—C17—C14	121.1 (2)
N3—C6—C1	102.5 (2)	C22—C17—C14	120.4 (2)
N3—C6—C5	133.8 (2)	C19—C18—C17	118.9 (3)
C1—C6—C5	123.8 (3)	C19—C18—H18	120.5
O2—C7—O1	119.3 (2)	C17—C18—H18	120.5
O2—C7—C8	132.5 (3)	C20—C19—C18	123.1 (3)
O1—C7—C8	108.2 (2)	C20—C19—N5	117.1 (3)
C9—C8—C7	118.7 (2)	C18—C19—N5	119.8 (3)
C9—C8—C14	122.5 (2)	C19—C20—C21	117.9 (3)
C7—C8—C14	118.7 (2)	C19—C20—H20	121.0
C8—C9—N4	119.5 (2)	C21—C20—H20	121.0
C8—C9—C10	126.4 (2)	C20—C21—C22	120.1 (3)
N4—C9—C10	114.1 (2)	C20—C21—H21	120.0
C9—C10—H10A	109.5	C22—C21—H21	120.0
C9—C10—H10B	109.5	C21—C22—C17	121.5 (3)
H10A—C10—H10B	109.5	C21—C22—H22	119.2
C9—C10—H10C	109.5	C17—C22—H22	119.2
C1—N1—N2—N3	0.2 (3)	N4—C12—C13—C14	−1.3 (4)
N1—N2—N3—C6	−1.3 (3)	C11—C12—C13—C14	179.2 (3)
N1—N2—N3—O1	−178.2 (2)	C9—C8—C14—C13	−10.9 (3)
C7—O1—N3—N2	84.9 (3)	C7—C8—C14—C13	173.6 (2)
C7—O1—N3—C6	−91.5 (3)	C9—C8—C14—C17	111.9 (3)
N2—N1—C1—C6	0.9 (3)	C7—C8—C14—C17	−63.7 (3)
N2—N1—C1—C2	−180.0 (3)	C12—C13—C14—C8	8.4 (4)
N1—C1—C2—C3	−179.1 (3)	C15—C13—C14—C8	−174.2 (2)
C6—C1—C2—C3	0.0 (4)	C12—C13—C14—C17	−114.1 (3)
C1—C2—C3—C4	−0.7 (5)	C15—C13—C14—C17	63.4 (3)
C2—C3—C4—C5	1.3 (5)	C16—O3—C15—O4	5.0 (5)
C3—C4—C5—C6	−1.0 (5)	C16—O3—C15—C13	−173.4 (3)
N2—N3—C6—C1	1.8 (3)	C12—C13—C15—O4	17.4 (5)
O1—N3—C6—C1	178.5 (2)	C14—C13—C15—O4	−160.1 (3)
N2—N3—C6—C5	−179.4 (3)	C12—C13—C15—O3	−164.2 (2)
O1—N3—C6—C5	−2.8 (5)	C14—C13—C15—O3	18.3 (4)
N1—C1—C6—N3	−1.6 (3)	C8—C14—C17—C18	131.9 (2)
C2—C1—C6—N3	179.2 (2)	C13—C14—C17—C18	−105.3 (3)
N1—C1—C6—C5	179.5 (2)	C8—C14—C17—C22	−47.9 (3)
C2—C1—C6—C5	0.3 (4)	C13—C14—C17—C22	74.9 (3)
C4—C5—C6—N3	−178.3 (3)	C22—C17—C18—C19	−0.5 (4)
C4—C5—C6—C1	0.2 (4)	C14—C17—C18—C19	179.8 (2)
N3—O1—C7—O2	−7.8 (3)	C17—C18—C19—C20	0.8 (4)
N3—O1—C7—C8	173.0 (2)	C17—C18—C19—N5	−179.8 (2)
O2—C7—C8—C9	−10.9 (4)	O5'—N5—C19—C20	10.8 (5)
O1—C7—C8—C9	168.1 (2)	O5—N5—C19—C20	−18.4 (4)
O2—C7—C8—C14	164.9 (3)	O6—N5—C19—C20	159.4 (5)
O1—C7—C8—C14	−16.1 (3)	O6'—N5—C19—C20	−166.7 (5)
C7—C8—C9—N4	−178.2 (2)	O5'—N5—C19—C18	−168.7 (4)
C14—C8—C9—N4	6.3 (4)	O5—N5—C19—C18	162.2 (4)
C7—C8—C9—C10	3.0 (4)	O6—N5—C19—C18	−20.1 (5)
C14—C8—C9—C10	−172.5 (2)	O6'—N5—C19—C18	13.8 (5)
C12—N4—C9—C8	2.3 (4)	C18—C19—C20—C21	0.0 (4)
C12—N4—C9—C10	−178.8 (2)	N5—C19—C20—C21	−179.4 (3)
C9—N4—C12—C13	−4.8 (4)	C19—C20—C21—C22	−1.2 (5)
C9—N4—C12—C11	174.7 (3)	C20—C21—C22—C17	1.6 (5)
N4—C12—C13—C15	−178.7 (2)	C18—C17—C22—C21	−0.7 (4)
C11—C12—C13—C15	1.9 (4)	C14—C17—C22—C21	179.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1^i	0.83 (2)	2.28 (3)	3.079 (3)	163 (2)

Symmetry code: (i) −x+1, y+1/2, −z+1/2.