Dimethyl 3-(tert-butyl­amino)-5-oxo-7-phenyl-1H,5H-pyrazolo[1,2-a]pyrazole-1,2-dicarboxyl­ate

In the title compound, C₂₀H₂₃N₃O₅, the mol­ecule contains two pyrazole rings with an inter­planar angle of 34.1 (1)°. The phenyl and pyrazolone rings make a dihedral angle of 35.43 (13)° with one another. There is an intra­molecular hydrogen bond between the carbonyl O atom in one of the carboxyl­ate groups and the N atom of the tert-butyl­amine substituent of the pyrazole ring. This is the first structure reported of a polyfunctional pyrazolo[1,2-a]pyrazole derivative of potential synthetic and pharmaceutical inter­est.

Key indicators

• Single-crystal X-ray study
• T = 290 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.037
• wR factor = 0.105
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found





Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.73 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.44 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C5     -   C8      ..       5.07 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C12    -   C13     ..       5.48 su

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

   0 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
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Diamond (Brandenburg, 1999).

Dimethyl 3-(tert-butylamino)-7-phenyl-5-oxo-1H,5H-pyrazolo[1,2-a]pyrazole-1,2-dicarboxylate

Crystal data

C20H23N3O5	F(000) = 816
Mr = 385.41	Dx = 1.301 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 13972 reflections
a = 12.1826 (8) Å	θ = 3.9–32.1°
b = 9.4017 (6) Å	µ = 0.10 mm^−1
c = 17.1789 (12) Å	T = 290 K
β = 91.059 (6)°	Block, colourless
V = 1967.3 (2) Å^3	0.5 × 0.2 × 0.2 mm
Z = 4

Data collection

Oxford X-calibur 3 CCD diffractometer	4282 independent reflections
Radiation source: fine-focus sealed tube	2751 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 12 pixels mm^-1	θmax = 27.0°, θmin = 4.0°
ω–scans at different φ	h = −10→15
Absorption correction: numerical (X-RED; Stoe & Cie, 1997)	k = −12→12
Tmin = 0.976, Tmax = 0.995	l = −21→21
13972 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.037	H-atom parameters constrained
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.0609P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max < 0.001
4282 reflections	Δρmax = 0.28 e Å^−3
254 parameters	Δρmin = −0.20 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.026 (2)

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
O1	0.51544 (7)	0.38089 (9)	0.13910 (5)	0.0477 (3)
O2	0.50114 (7)	0.19775 (10)	0.05387 (5)	0.0496 (3)
O3	0.72430 (9)	0.62409 (11)	0.16902 (6)	0.0643 (3)
O4	0.82114 (9)	0.44505 (13)	0.11906 (7)	0.0730 (3)
O5	0.86023 (8)	0.34627 (12)	−0.14943 (6)	0.0616 (3)
N1	0.62403 (10)	0.22840 (11)	−0.08062 (6)	0.0492 (3)
H1	0.6083	0.1614	−0.0486	0.059*
N2	0.71815 (8)	0.57383 (11)	−0.02584 (6)	0.0395 (3)
N3	0.72357 (8)	0.45137 (11)	−0.07460 (6)	0.0401 (3)
C1	0.44002 (12)	0.30798 (16)	0.18939 (8)	0.0546 (4)
H1A	0.4288	0.3639	0.2353	0.082*
H1B	0.4700	0.2171	0.2039	0.082*
H1C	0.3711	0.2945	0.1624	0.082*
C2	0.53936 (10)	0.31444 (14)	0.07176 (7)	0.0384 (3)
C3	0.80293 (18)	0.6362 (3)	0.23332 (11)	0.1032 (7)
H3A	0.7795	0.7092	0.2684	0.155*
H3B	0.8737	0.6602	0.2135	0.155*
H3C	0.8075	0.5471	0.2605	0.155*
C4	0.74610 (11)	0.52679 (15)	0.11576 (8)	0.0449 (3)
C5	0.61418 (11)	0.18365 (14)	−0.16369 (8)	0.0455 (3)
C6	0.61698 (14)	0.30981 (16)	−0.21899 (9)	0.0617 (4)
H6A	0.5600	0.3757	−0.2060	0.093*
H6B	0.6057	0.2772	−0.2715	0.093*
H6C	0.6870	0.3562	−0.2144	0.093*
C7	0.50150 (13)	0.11272 (16)	−0.17103 (10)	0.0641 (4)
H7A	0.4988	0.0323	−0.1366	0.096*
H7B	0.4893	0.0816	−0.2237	0.096*
H7C	0.4456	0.1797	−0.1573	0.096*
C8	0.70317 (14)	0.07530 (17)	−0.18061 (10)	0.0670 (5)
H8A	0.6986	−0.0021	−0.1444	0.101*
H8B	0.7739	0.1197	−0.1755	0.101*
H8C	0.6933	0.0398	−0.2327	0.101*
C9	0.66330 (10)	0.53511 (13)	0.04784 (7)	0.0378 (3)
H9	0.6053	0.6037	0.0594	0.045*
C10	0.61441 (10)	0.39422 (13)	0.02618 (7)	0.0386 (3)
C11	0.65182 (10)	0.34926 (13)	−0.04497 (7)	0.0380 (3)
C12	0.83041 (11)	0.44252 (16)	−0.10672 (8)	0.0479 (4)
C13	0.88401 (11)	0.56962 (15)	−0.08064 (9)	0.0516 (4)
H13	0.9534	0.5989	−0.0957	0.062*
C14	0.81918 (10)	0.64132 (15)	−0.03081 (8)	0.0441 (3)
C15	0.83850 (11)	0.77380 (14)	0.01323 (8)	0.0465 (3)
C16	0.75579 (12)	0.87285 (15)	0.02347 (9)	0.0552 (4)
H16	0.6859	0.8557	0.0029	0.066*
C17	0.77661 (15)	0.99676 (19)	0.06409 (10)	0.0701 (5)
H17	0.7208	1.0631	0.0704	0.084*
C18	0.87924 (16)	1.0227 (2)	0.09518 (11)	0.0787 (5)
H18	0.8932	1.1067	0.1222	0.094*
C19	0.96089 (16)	0.9245 (2)	0.08633 (11)	0.0802 (6)
H19	1.0300	0.9413	0.1084	0.096*
C20	0.94181 (13)	0.80065 (18)	0.04503 (10)	0.0637 (4)
H20	0.9982	0.7353	0.0386	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0560 (6)	0.0484 (6)	0.0392 (5)	−0.0046 (4)	0.0163 (4)	−0.0026 (4)
O2	0.0579 (6)	0.0435 (6)	0.0477 (6)	−0.0087 (5)	0.0119 (4)	−0.0025 (4)
O3	0.0768 (7)	0.0721 (7)	0.0434 (6)	0.0026 (6)	−0.0130 (5)	−0.0089 (5)
O4	0.0620 (7)	0.0860 (9)	0.0705 (8)	0.0217 (6)	−0.0127 (6)	0.0054 (6)
O5	0.0551 (6)	0.0717 (7)	0.0586 (7)	0.0090 (5)	0.0199 (5)	−0.0079 (5)
N1	0.0704 (8)	0.0381 (6)	0.0396 (6)	−0.0036 (5)	0.0147 (5)	−0.0001 (5)
N2	0.0404 (6)	0.0410 (6)	0.0371 (6)	−0.0009 (5)	0.0053 (4)	0.0004 (5)
N3	0.0418 (6)	0.0423 (6)	0.0366 (6)	0.0027 (5)	0.0081 (5)	0.0009 (5)
C1	0.0635 (9)	0.0555 (9)	0.0456 (8)	−0.0008 (7)	0.0230 (7)	0.0063 (7)
C2	0.0383 (7)	0.0411 (7)	0.0360 (7)	0.0047 (6)	0.0052 (5)	0.0015 (6)
C3	0.1184 (17)	0.1293 (19)	0.0601 (12)	−0.0042 (14)	−0.0420 (12)	−0.0150 (12)
C4	0.0439 (8)	0.0491 (8)	0.0417 (8)	−0.0022 (7)	0.0017 (6)	0.0059 (6)
C5	0.0582 (8)	0.0394 (7)	0.0394 (7)	0.0005 (6)	0.0110 (6)	−0.0050 (6)
C6	0.0860 (11)	0.0550 (9)	0.0441 (9)	−0.0088 (8)	0.0005 (8)	0.0021 (7)
C7	0.0725 (11)	0.0526 (9)	0.0674 (11)	−0.0091 (8)	0.0092 (8)	−0.0083 (8)
C8	0.0812 (11)	0.0584 (10)	0.0620 (10)	0.0122 (8)	0.0193 (9)	−0.0088 (8)
C9	0.0360 (7)	0.0429 (7)	0.0347 (7)	0.0018 (5)	0.0055 (5)	0.0012 (6)
C10	0.0390 (7)	0.0412 (7)	0.0359 (7)	0.0013 (5)	0.0056 (5)	−0.0011 (5)
C11	0.0393 (7)	0.0380 (7)	0.0368 (7)	0.0040 (5)	0.0050 (5)	0.0043 (6)
C12	0.0445 (8)	0.0581 (9)	0.0416 (8)	0.0067 (7)	0.0104 (6)	0.0081 (7)
C13	0.0413 (7)	0.0604 (9)	0.0534 (9)	−0.0048 (7)	0.0087 (6)	0.0091 (7)
C14	0.0400 (7)	0.0502 (8)	0.0421 (7)	−0.0034 (6)	−0.0002 (6)	0.0107 (6)
C15	0.0466 (8)	0.0492 (8)	0.0438 (8)	−0.0089 (6)	−0.0005 (6)	0.0116 (6)
C16	0.0555 (9)	0.0535 (9)	0.0566 (9)	−0.0057 (7)	−0.0041 (7)	0.0024 (7)
C17	0.0776 (12)	0.0620 (10)	0.0708 (12)	−0.0020 (9)	−0.0002 (9)	−0.0076 (9)
C18	0.0898 (14)	0.0720 (12)	0.0742 (12)	−0.0227 (11)	−0.0024 (10)	−0.0141 (9)
C19	0.0683 (11)	0.0897 (14)	0.0819 (13)	−0.0240 (11)	−0.0179 (10)	−0.0008 (11)
C20	0.0516 (9)	0.0669 (11)	0.0722 (11)	−0.0094 (8)	−0.0087 (8)	0.0084 (9)

Geometric parameters (Å, º)

O1—C2	1.3512 (15)	C6—H6B	0.9600
O1—C1	1.4457 (15)	C6—H6C	0.9600
O2—C2	1.2286 (15)	C7—H7A	0.9600
O3—C4	1.3242 (17)	C7—H7B	0.9600
O3—C3	1.4531 (19)	C7—H7C	0.9600
O4—C4	1.1948 (16)	C8—H8A	0.9600
O5—C12	1.2244 (17)	C8—H8B	0.9600
N1—C11	1.3316 (16)	C8—H8C	0.9600
N1—C5	1.4906 (17)	C9—C10	1.4965 (17)
N1—H1	0.8600	C9—H9	0.9800
N2—C14	1.3888 (16)	C10—C11	1.3788 (17)
N2—N3	1.4260 (14)	C12—C13	1.430 (2)
N2—C9	1.4874 (16)	C13—C14	1.355 (2)
N3—C11	1.4004 (16)	C13—H13	0.9300
N3—C12	1.4255 (16)	C14—C15	1.474 (2)
C1—H1A	0.9600	C15—C20	1.3859 (19)
C1—H1B	0.9600	C15—C16	1.386 (2)
C1—H1C	0.9600	C16—C17	1.379 (2)
C2—C10	1.4277 (17)	C16—H16	0.9300
C3—H3A	0.9600	C17—C18	1.372 (2)
C3—H3B	0.9600	C17—H17	0.9300
C3—H3C	0.9600	C18—C19	1.368 (3)
C4—C9	1.5302 (18)	C18—H18	0.9300
C5—C8	1.520 (2)	C19—C20	1.381 (2)
C5—C6	1.520 (2)	C19—H19	0.9300
C5—C7	1.529 (2)	C20—H20	0.9300
C6—H6A	0.9600
C2—O1—C1	116.23 (10)	H7B—C7—H7C	109.5
C4—O3—C3	116.19 (13)	C5—C8—H8A	109.5
C11—N1—C5	134.14 (11)	C5—C8—H8B	109.5
C11—N1—H1	112.9	H8A—C8—H8B	109.5
C5—N1—H1	112.9	C5—C8—H8C	109.5
C14—N2—N3	106.38 (10)	H8A—C8—H8C	109.5
C14—N2—C9	125.21 (10)	H8B—C8—H8C	109.5
N3—N2—C9	109.18 (9)	N2—C9—C10	100.84 (9)
C11—N3—C12	132.93 (10)	N2—C9—C4	111.18 (9)
C11—N3—N2	107.70 (9)	C10—C9—C4	113.46 (10)
C12—N3—N2	109.09 (10)	N2—C9—H9	110.3
O1—C1—H1A	109.5	C10—C9—H9	110.3
O1—C1—H1B	109.5	C4—C9—H9	110.3
H1A—C1—H1B	109.5	C11—C10—C2	123.41 (12)
O1—C1—H1C	109.5	C11—C10—C9	110.80 (11)
H1A—C1—H1C	109.5	C2—C10—C9	125.78 (11)
H1B—C1—H1C	109.5	N1—C11—C10	125.73 (12)
O2—C2—O1	122.71 (11)	N1—C11—N3	124.96 (11)
O2—C2—C10	125.14 (12)	C10—C11—N3	109.32 (11)
O1—C2—C10	112.15 (11)	O5—C12—N3	123.94 (13)
O3—C3—H3A	109.5	O5—C12—C13	131.81 (13)
O3—C3—H3B	109.5	N3—C12—C13	104.18 (12)
H3A—C3—H3B	109.5	C14—C13—C12	110.22 (12)
O3—C3—H3C	109.5	C14—C13—H13	124.9
H3A—C3—H3C	109.5	C12—C13—H13	124.9
H3B—C3—H3C	109.5	C13—C14—N2	109.82 (12)
O4—C4—O3	125.07 (13)	C13—C14—C15	130.94 (12)
O4—C4—C9	124.19 (13)	N2—C14—C15	119.20 (12)
O3—C4—C9	110.72 (11)	C20—C15—C16	119.00 (14)
N1—C5—C8	109.11 (12)	C20—C15—C14	119.44 (13)
N1—C5—C6	112.07 (11)	C16—C15—C14	121.56 (12)
C8—C5—C6	112.28 (13)	C17—C16—C15	120.30 (14)
N1—C5—C7	104.97 (11)	C17—C16—H16	119.8
C8—C5—C7	109.54 (12)	C15—C16—H16	119.8
C6—C5—C7	108.61 (13)	C18—C17—C16	120.30 (17)
C5—C6—H6A	109.5	C18—C17—H17	119.8
C5—C6—H6B	109.5	C16—C17—H17	119.8
H6A—C6—H6B	109.5	C19—C18—C17	119.76 (17)
C5—C6—H6C	109.5	C19—C18—H18	120.1
H6A—C6—H6C	109.5	C17—C18—H18	120.1
H6B—C6—H6C	109.5	C18—C19—C20	120.68 (16)
C5—C7—H7A	109.5	C18—C19—H19	119.7
C5—C7—H7B	109.5	C20—C19—H19	119.7
H7A—C7—H7B	109.5	C19—C20—C15	119.95 (16)
C5—C7—H7C	109.5	C19—C20—H20	120.0
H7A—C7—H7C	109.5	C15—C20—H20	120.0
C14—N2—N3—C11	152.35 (10)	C2—C10—C11—N3	179.73 (11)
C9—N2—N3—C11	14.73 (12)	C9—C10—C11—N3	−0.44 (14)
C14—N2—N3—C12	2.23 (13)	C12—N3—C11—N1	−49.2 (2)
C9—N2—N3—C12	−135.39 (10)	N2—N3—C11—N1	170.80 (11)
C1—O1—C2—O2	−0.99 (17)	C12—N3—C11—C10	131.18 (14)
C1—O1—C2—C10	−179.89 (11)	N2—N3—C11—C10	−8.80 (13)
C3—O3—C4—O4	4.1 (2)	C11—N3—C12—O5	38.5 (2)
C3—O3—C4—C9	−174.56 (13)	N2—N3—C12—O5	178.14 (12)
C11—N1—C5—C8	112.17 (16)	C11—N3—C12—C13	−144.35 (13)
C11—N1—C5—C6	−12.8 (2)	N2—N3—C12—C13	−4.76 (13)
C11—N1—C5—C7	−130.52 (15)	O5—C12—C13—C14	−177.49 (15)
C14—N2—C9—C10	−141.71 (11)	N3—C12—C13—C14	5.73 (15)
N3—N2—C9—C10	−14.04 (11)	C12—C13—C14—N2	−4.60 (16)
C14—N2—C9—C4	−21.12 (16)	C12—C13—C14—C15	177.74 (13)
N3—N2—C9—C4	106.55 (11)	N3—N2—C14—C13	1.44 (14)
O4—C4—C9—N2	−62.13 (17)	C9—N2—C14—C13	130.25 (12)
O3—C4—C9—N2	116.57 (12)	N3—N2—C14—C15	179.41 (10)
O4—C4—C9—C10	50.70 (17)	C9—N2—C14—C15	−51.77 (17)
O3—C4—C9—C10	−130.60 (12)	C13—C14—C15—C20	−38.1 (2)
O2—C2—C10—C11	1.0 (2)	N2—C14—C15—C20	144.47 (13)
O1—C2—C10—C11	179.90 (11)	C13—C14—C15—C16	141.72 (16)
O2—C2—C10—C9	−178.78 (11)	N2—C14—C15—C16	−35.76 (18)
O1—C2—C10—C9	0.09 (17)	C20—C15—C16—C17	0.6 (2)
N2—C9—C10—C11	8.84 (13)	C14—C15—C16—C17	−179.15 (14)
C4—C9—C10—C11	−110.11 (12)	C15—C16—C17—C18	−0.4 (2)
N2—C9—C10—C2	−171.33 (11)	C16—C17—C18—C19	−0.5 (3)
C4—C9—C10—C2	69.72 (16)	C17—C18—C19—C20	1.3 (3)
C5—N1—C11—C10	150.41 (14)	C18—C19—C20—C15	−1.1 (3)
C5—N1—C11—N3	−29.1 (2)	C16—C15—C20—C19	0.2 (2)
C2—C10—C11—N1	0.1 (2)	C14—C15—C20—C19	179.93 (15)
C9—C10—C11—N1	179.97 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	2.24	2.7910 (14)	122
C6—H6C···O5	0.96	2.37	3.193 (2)	143
C6—H6C···O5	0.96	2.37	3.193 (2)	143
C7—H7A···O2^i	0.96	2.59	3.5461 (19)	175
C8—H8B···O5	0.96	2.41	3.225 (2)	142
C16—H16···O2^ii	0.93	2.51	3.4422 (18)	178

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