Dimethyl 2,6-dimethyl-4-(3-phenyl-1H-pyrazol-4-yl)-1,4-dihydro-pyridine-3,5-dicarboxyl-ate.

In the title compound, C(20)H(21)N(3)O(4), the 1,4-dihydro-pyridine ring adopts a boat conformation. An intra-molecular C-H⋯O hydrogen bond generates an S(6) ring motif. The pyrazole ring makes dihedral angles of 87.81 (7) and 45.09 (7)° with the mean plane of the 1,4-dihydro-pyridine ring and the phenyl ring, respectively. In the crystal, mol-ecules are linked by N-H⋯N, N-H⋯O and C-H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For a related structure and background references, see: Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C20H21N3O4

M = 367.40

Orthorhombic,

a = 13.9632 (6) Å

b = 10.9908 (5) Å

c = 11.8465 (5) Å

V = 1818.04 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.38 × 0.22 × 0.14 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.965, T max = 0.987

17004 measured reflections

2788 independent reflections

2687 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.080

S = 1.03

2788 reflections

256 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812008306/hb6648sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008306/hb6648Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812008306/hb6648Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C20H21N3O4	F(000) = 776
Mr = 367.40	Dx = 1.342 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 8800 reflections
a = 13.9632 (6) Å	θ = 2.4–30.1°
b = 10.9908 (5) Å	µ = 0.10 mm−1
c = 11.8465 (5) Å	T = 100 K
V = 1818.04 (14) Å3	Block, yellow
Z = 4	0.38 × 0.22 × 0.14 mm

Bruker SMART APEXII DUO CCD diffractometer	2788 independent reflections
Radiation source: fine-focus sealed tube	2687 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
φ and ω scans	θmax = 30.1°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −19→19
Tmin = 0.965, Tmax = 0.987	k = −14→15
17004 measured reflections	l = −16→15

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0556P)2 + 0.1941P] where P = (Fo2 + 2Fc2)/3
2788 reflections	(Δ/σ)max = 0.001
256 parameters	Δρmax = 0.30 e Å−3
1 restraint	Δρmin = −0.24 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
O1	0.46234 (8)	0.61784 (10)	0.30293 (11)	0.0235 (2)
O2	0.32205 (8)	0.59619 (9)	0.39414 (10)	0.0205 (2)
O3	0.15716 (8)	1.09597 (9)	0.48010 (9)	0.0191 (2)
O4	0.14156 (7)	0.90479 (9)	0.54372 (10)	0.0178 (2)
N1	0.37507 (9)	0.72586 (11)	0.77599 (10)	0.0156 (2)
N2	0.42080 (9)	0.83459 (11)	0.77451 (10)	0.0175 (2)
N3	0.44724 (8)	0.99042 (10)	0.40046 (10)	0.0142 (2)
C1	0.18445 (9)	0.58580 (12)	0.61291 (12)	0.0156 (2)
H1A	0.1551	0.6602	0.5914	0.019*
C2	0.13659 (10)	0.47622 (13)	0.59534 (13)	0.0181 (3)
H2A	0.0751	0.4764	0.5611	0.022*
C3	0.17821 (10)	0.36647 (13)	0.62751 (13)	0.0186 (3)
H3A	0.1454	0.2919	0.6152	0.022*
C4	0.26818 (10)	0.36682 (12)	0.67776 (12)	0.0184 (3)
H4A	0.2966	0.2922	0.7004	0.022*
C5	0.31710 (10)	0.47597 (12)	0.69520 (12)	0.0154 (2)
H5A	0.3786	0.4753	0.7295	0.018*
C6	0.27552 (9)	0.58674 (11)	0.66210 (11)	0.0130 (2)
C7	0.32755 (9)	0.70190 (11)	0.67790 (11)	0.0123 (2)
C8	0.40266 (10)	0.87859 (12)	0.67155 (12)	0.0155 (2)
H8A	0.4266	0.9542	0.6448	0.019*
C9	0.34428 (9)	0.80077 (11)	0.60694 (11)	0.0120 (2)
C10	0.31482 (9)	0.82217 (11)	0.48536 (11)	0.0114 (2)
H10A	0.2572	0.7714	0.4684	0.014*
C11	0.39518 (9)	0.78588 (11)	0.40562 (11)	0.0122 (2)
C12	0.46244 (9)	0.86881 (12)	0.37489 (11)	0.0136 (2)
C13	0.35839 (9)	1.03464 (11)	0.43207 (11)	0.0128 (2)
C14	0.28952 (9)	0.95537 (11)	0.46742 (11)	0.0126 (2)
C15	0.39982 (10)	0.66120 (12)	0.36172 (12)	0.0147 (2)
C16	0.31848 (13)	0.47237 (13)	0.35474 (17)	0.0275 (3)
H16A	0.2655	0.4297	0.3918	0.041*
H16B	0.3790	0.4315	0.3727	0.041*
H16C	0.3085	0.4717	0.2729	0.041*
C17	0.55479 (10)	0.84310 (13)	0.31417 (14)	0.0191 (3)
H17A	0.5858	0.7719	0.3480	0.029*
H17B	0.5973	0.9137	0.3205	0.029*
H17C	0.5415	0.8269	0.2344	0.029*
C18	0.35149 (10)	1.17080 (12)	0.42430 (12)	0.0173 (2)
H18A	0.2991	1.1995	0.4724	0.026*
H18B	0.3390	1.1944	0.3459	0.026*
H18C	0.4119	1.2072	0.4495	0.026*
C19	0.19231 (9)	0.99557 (12)	0.49572 (11)	0.0134 (2)
C20	0.04439 (10)	0.93544 (15)	0.57625 (14)	0.0215 (3)
H20A	0.0114	0.8621	0.6027	0.032*
H20B	0.0102	0.9690	0.5110	0.032*
H20C	0.0458	0.9960	0.6370	0.032*
H1N3	0.4908 (15)	1.047 (2)	0.373 (2)	0.025 (5)*
H1N1	0.3705 (16)	0.689 (2)	0.838 (2)	0.032 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0253 (5)	0.0200 (5)	0.0252 (5)	0.0015 (4)	0.0071 (4)	−0.0072 (4)
O2	0.0264 (5)	0.0108 (4)	0.0242 (5)	−0.0030 (4)	0.0078 (4)	−0.0029 (4)
O3	0.0224 (5)	0.0171 (5)	0.0176 (5)	0.0067 (4)	0.0022 (4)	0.0028 (4)
O4	0.0129 (4)	0.0163 (4)	0.0243 (5)	−0.0002 (3)	0.0041 (4)	−0.0003 (4)
N1	0.0178 (5)	0.0164 (5)	0.0126 (5)	−0.0043 (4)	−0.0023 (4)	0.0031 (4)
N2	0.0193 (5)	0.0176 (5)	0.0156 (5)	−0.0068 (4)	−0.0020 (4)	0.0010 (4)
N3	0.0147 (5)	0.0125 (5)	0.0153 (5)	−0.0017 (4)	0.0018 (4)	0.0008 (4)
C1	0.0145 (6)	0.0155 (6)	0.0168 (6)	0.0001 (4)	−0.0005 (5)	0.0018 (5)
C2	0.0140 (6)	0.0207 (6)	0.0197 (6)	−0.0030 (5)	−0.0012 (5)	−0.0009 (5)
C3	0.0208 (7)	0.0160 (6)	0.0190 (6)	−0.0044 (5)	0.0025 (5)	−0.0021 (5)
C4	0.0225 (7)	0.0125 (5)	0.0201 (6)	−0.0004 (5)	0.0003 (5)	0.0019 (5)
C5	0.0153 (6)	0.0150 (5)	0.0157 (6)	0.0000 (4)	−0.0008 (4)	0.0022 (5)
C6	0.0139 (5)	0.0129 (5)	0.0122 (5)	−0.0014 (4)	0.0005 (4)	0.0009 (4)
C7	0.0112 (5)	0.0128 (5)	0.0129 (5)	−0.0004 (4)	−0.0005 (4)	0.0011 (4)
C8	0.0169 (6)	0.0150 (5)	0.0146 (6)	−0.0045 (4)	−0.0009 (5)	0.0006 (5)
C9	0.0127 (5)	0.0109 (5)	0.0124 (5)	−0.0008 (4)	0.0007 (4)	0.0004 (4)
C10	0.0127 (5)	0.0104 (5)	0.0111 (5)	0.0011 (4)	0.0007 (4)	0.0002 (4)
C11	0.0144 (5)	0.0115 (5)	0.0107 (5)	0.0016 (4)	0.0006 (4)	−0.0003 (4)
C12	0.0150 (5)	0.0140 (5)	0.0120 (5)	0.0022 (4)	0.0001 (4)	0.0008 (4)
C13	0.0159 (6)	0.0118 (5)	0.0109 (5)	0.0001 (4)	−0.0002 (4)	0.0005 (4)
C14	0.0144 (5)	0.0114 (5)	0.0120 (5)	0.0009 (4)	0.0003 (4)	0.0013 (4)
C15	0.0182 (6)	0.0130 (5)	0.0130 (5)	0.0010 (4)	−0.0002 (5)	0.0010 (4)
C16	0.0344 (9)	0.0131 (6)	0.0350 (9)	−0.0061 (6)	0.0101 (7)	−0.0078 (6)
C17	0.0171 (6)	0.0190 (6)	0.0211 (6)	0.0014 (5)	0.0059 (5)	0.0008 (5)
C18	0.0214 (6)	0.0107 (5)	0.0199 (6)	−0.0008 (4)	0.0021 (5)	0.0017 (5)
C19	0.0149 (5)	0.0149 (5)	0.0103 (5)	0.0004 (4)	−0.0001 (4)	−0.0009 (4)
C20	0.0124 (6)	0.0252 (7)	0.0270 (7)	−0.0012 (5)	0.0041 (5)	−0.0059 (6)

O1—C15	1.2142 (17)	C7—C9	1.3936 (18)
O2—C15	1.3555 (17)	C8—C9	1.4078 (18)
O2—C16	1.4396 (17)	C8—H8A	0.9500
O3—C19	1.2219 (16)	C9—C10	1.5163 (18)
O4—C19	1.3494 (16)	C10—C11	1.5200 (17)
O4—C20	1.4501 (16)	C10—C14	1.5209 (17)
N1—N2	1.3551 (16)	C10—H10A	1.0000
N1—C7	1.3638 (16)	C11—C12	1.3584 (17)
N1—H1N1	0.84 (3)	C11—C15	1.4671 (17)
N2—C8	1.3363 (18)	C12—C17	1.5034 (18)
N3—C13	1.3840 (17)	C13—C14	1.3635 (17)
N3—C12	1.3868 (16)	C13—C18	1.5024 (17)
N3—H1N3	0.93 (2)	C14—C19	1.4663 (18)
C1—C2	1.3929 (19)	C16—H16A	0.9800
C1—C6	1.3989 (18)	C16—H16B	0.9800
C1—H1A	0.9500	C16—H16C	0.9800
C2—C3	1.392 (2)	C17—H17A	0.9800
C2—H2A	0.9500	C17—H17B	0.9800
C3—C4	1.390 (2)	C17—H17C	0.9800
C3—H3A	0.9500	C18—H18A	0.9800
C4—C5	1.3958 (18)	C18—H18B	0.9800
C4—H4A	0.9500	C18—H18C	0.9800
C5—C6	1.4045 (17)	C20—H20A	0.9800
C5—H5A	0.9500	C20—H20B	0.9800
C6—C7	1.4713 (17)	C20—H20C	0.9800
C15—O2—C16	115.74 (12)	C12—C11—C15	120.08 (11)
C19—O4—C20	115.57 (11)	C12—C11—C10	120.06 (11)
N2—N1—C7	112.86 (11)	C15—C11—C10	119.87 (11)
N2—N1—H1N1	117.8 (16)	C11—C12—N3	118.84 (11)
C7—N1—H1N1	128.1 (16)	C11—C12—C17	126.52 (12)
C8—N2—N1	103.98 (11)	N3—C12—C17	114.64 (11)
C13—N3—C12	122.32 (11)	C14—C13—N3	119.40 (11)
C13—N3—H1N3	116.5 (13)	C14—C13—C18	127.59 (12)
C12—N3—H1N3	117.8 (13)	N3—C13—C18	112.99 (11)
C2—C1—C6	120.31 (12)	C13—C14—C19	122.05 (11)
C2—C1—H1A	119.8	C13—C14—C10	119.61 (11)
C6—C1—H1A	119.8	C19—C14—C10	118.23 (11)
C3—C2—C1	120.53 (13)	O1—C15—O2	122.11 (12)
C3—C2—H2A	119.7	O1—C15—C11	126.99 (13)
C1—C2—H2A	119.7	O2—C15—C11	110.89 (11)
C4—C3—C2	119.47 (13)	O2—C16—H16A	109.5
C4—C3—H3A	120.3	O2—C16—H16B	109.5
C2—C3—H3A	120.3	H16A—C16—H16B	109.5
C3—C4—C5	120.53 (13)	O2—C16—H16C	109.5
C3—C4—H4A	119.7	H16A—C16—H16C	109.5
C5—C4—H4A	119.7	H16B—C16—H16C	109.5
C4—C5—C6	120.09 (13)	C12—C17—H17A	109.5
C4—C5—H5A	120.0	C12—C17—H17B	109.5
C6—C5—H5A	120.0	H17A—C17—H17B	109.5
C1—C6—C5	119.05 (11)	C12—C17—H17C	109.5
C1—C6—C7	120.54 (11)	H17A—C17—H17C	109.5
C5—C6—C7	120.40 (12)	H17B—C17—H17C	109.5
N1—C7—C9	106.37 (11)	C13—C18—H18A	109.5
N1—C7—C6	120.98 (11)	C13—C18—H18B	109.5
C9—C7—C6	132.60 (12)	H18A—C18—H18B	109.5
N2—C8—C9	112.72 (12)	C13—C18—H18C	109.5
N2—C8—H8A	123.6	H18A—C18—H18C	109.5
C9—C8—H8A	123.6	H18B—C18—H18C	109.5
C7—C9—C8	104.06 (12)	O3—C19—O4	121.37 (12)
C7—C9—C10	130.43 (12)	O3—C19—C14	127.54 (12)
C8—C9—C10	125.40 (12)	O4—C19—C14	111.09 (11)
C9—C10—C11	110.45 (10)	O4—C20—H20A	109.5
C9—C10—C14	110.18 (10)	O4—C20—H20B	109.5
C11—C10—C14	109.71 (10)	H20A—C20—H20B	109.5
C9—C10—H10A	108.8	O4—C20—H20C	109.5
C11—C10—H10A	108.8	H20A—C20—H20C	109.5
C14—C10—H10A	108.8	H20B—C20—H20C	109.5
C7—N1—N2—C8	−1.15 (16)	C14—C10—C11—C15	−147.94 (11)
C6—C1—C2—C3	0.7 (2)	C15—C11—C12—N3	168.44 (12)
C1—C2—C3—C4	0.1 (2)	C10—C11—C12—N3	−11.42 (18)
C2—C3—C4—C5	−0.5 (2)	C15—C11—C12—C17	−11.6 (2)
C3—C4—C5—C6	0.1 (2)	C10—C11—C12—C17	168.57 (13)
C2—C1—C6—C5	−1.1 (2)	C13—N3—C12—C11	−15.16 (19)
C2—C1—C6—C7	178.25 (13)	C13—N3—C12—C17	164.85 (12)
C4—C5—C6—C1	0.7 (2)	C12—N3—C13—C14	17.20 (19)
C4—C5—C6—C7	−178.63 (13)	C12—N3—C13—C18	−163.94 (12)
N2—N1—C7—C9	0.79 (15)	N3—C13—C14—C19	−176.37 (12)
N2—N1—C7—C6	178.43 (12)	C18—C13—C14—C19	5.0 (2)
C1—C6—C7—N1	136.67 (13)	N3—C13—C14—C10	7.47 (18)
C5—C6—C7—N1	−43.99 (18)	C18—C13—C14—C10	−171.21 (13)
C1—C6—C7—C9	−46.4 (2)	C9—C10—C14—C13	92.04 (14)
C5—C6—C7—C9	132.93 (16)	C11—C10—C14—C13	−29.76 (16)
N1—N2—C8—C9	1.08 (16)	C9—C10—C14—C19	−84.27 (14)
N1—C7—C9—C8	−0.10 (14)	C11—C10—C14—C19	153.92 (11)
C6—C7—C9—C8	−177.35 (13)	C16—O2—C15—O1	0.2 (2)
N1—C7—C9—C10	176.07 (12)	C16—O2—C15—C11	179.37 (13)
C6—C7—C9—C10	−1.2 (2)	C12—C11—C15—O1	4.6 (2)
N2—C8—C9—C7	−0.63 (16)	C10—C11—C15—O1	−175.57 (14)
N2—C8—C9—C10	−177.05 (12)	C12—C11—C15—O2	−174.55 (12)
C7—C9—C10—C11	−95.43 (16)	C10—C11—C15—O2	5.31 (17)
C8—C9—C10—C11	80.01 (15)	C20—O4—C19—O3	−0.85 (19)
C7—C9—C10—C14	143.21 (14)	C20—O4—C19—C14	179.34 (11)
C8—C9—C10—C14	−41.35 (16)	C13—C14—C19—O3	9.1 (2)
C9—C10—C11—C12	−89.73 (14)	C10—C14—C19—O3	−174.67 (13)
C14—C10—C11—C12	31.92 (16)	C13—C14—C19—O4	−171.09 (12)
C9—C10—C11—C15	90.41 (14)	C10—C14—C19—O4	5.13 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18A···O3	0.98	2.29	2.9114 (18)	121
N3—H1N3···N2i	0.93 (2)	2.14 (2)	3.0529 (17)	167 (2)
N1—H1N1···O3ii	0.84 (3)	2.01 (3)	2.8438 (16)	173 (2)
C5—H5A···O1iii	0.95	2.60	3.4895 (18)	157
C20—H20C···O1iv	0.98	2.38	3.3524 (19)	170

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18A⋯O3	0.98	2.29	2.9114 (18)	121
N3—H1N3⋯N2i	0.93 (2)	2.14 (2)	3.0529 (17)	167 (2)
N1—H1N1⋯O3ii	0.84 (3)	2.01 (3)	2.8438 (16)	173 (2)
C5—H5A⋯O1iii	0.95	2.60	3.4895 (18)	157
C20—H20C⋯O1iv	0.98	2.38	3.3524 (19)	170

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .