Crystal structure of 9-(t-butyl)-3,11-dihydro-6H-pyrazolo [1,5-a]pyrrolo[3′,2′:5,6]pyrido[4,3-d]pyrimidin-6-one hemihydrate, C30H32N10O3

Zhi-Qiang Song; Ying-Jie Hou; Hai-Yang Sun; Qi-Di Zhong

doi:10.1515/ncrs-2022-0265

Open Access Published by De Gruyter (O) July 6, 2022

Crystal structure of 9-(t-butyl)-3,11-dihydro-6H-pyrazolo [1,5-a]pyrrolo[3′,2′:5,6]pyrido[4,3-d]pyrimidin-6-one hemihydrate, C₃₀H₃₂N₁₀O₃

Zhi-Qiang Song , Ying-Jie Hou , Hai-Yang Sun and Qi-Di Zhong

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2022-0265

Abstract

C₃₀H₃₂N₁₀O₃, monoclinic, P2₁/c (no. 14), a = 10.447(2) Å, b = 20.130(4) Å, c = 14.772(3) Å, β = 113.001(3)°, V = 2859.7(10) Å³, Z = 4, R _gt(F) = 0.0556, wR _ref(F ²) = 0.1663, T = 296 K.

CCDC no.: 2171359

The title crystal structure is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:	Colourless block
Size:	0.18 × 0.15 × 0.13 mm
Wavelength:	MoKα radiation (0.71073 Å)
μ:	0.09 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II, φ and ω
θ _max, completeness:	26.5°, >99%
N(hkl)_measured, N(hkl)_unique, R _int:	16503, 5904, 0.050
Criterion for I _obs, N(hkl)_gt:	I _obs > 2 σ(I _obs), 3552
N(param)_refined:	441
Programs:	Bruker [1], SHELX [2, 3], Olex2 [4]

Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²).

Atom	x	y	z	U _iso*/U _eq
C1	0.9093 (2)	0.93311 (11)	0.76724 (16)	0.0447 (6)
H1A	0.995356	0.946982	0.812694	0.054*
C2	0.8244 (2)	0.88836 (10)	0.78561 (16)	0.0405 (5)
H2	0.841525	0.866556	0.844711	0.049*
C3	0.7055 (2)	0.88157 (10)	0.69735 (15)	0.0357 (5)
C4	0.7251 (2)	0.92348 (10)	0.62811 (15)	0.0406 (5)
C5	0.5273 (3)	0.89385 (12)	0.50471 (17)	0.0565 (7)
H5	0.465090	0.897077	0.439506	0.068*
C6	0.4929 (2)	0.84959 (10)	0.56547 (15)	0.0405 (6)
C7	0.5830 (2)	0.84369 (10)	0.66482 (14)	0.0338 (5)
C8	0.3703 (3)	0.80853 (11)	0.52296 (16)	0.0468 (6)
C9	0.4391 (2)	0.76006 (10)	0.68822 (14)	0.0348 (5)
C10	0.3928 (2)	0.70872 (10)	0.72622 (16)	0.0422 (6)
H10	0.428050	0.694095	0.791093	0.051*
C11	0.2796 (2)	0.68216 (10)	0.64636 (15)	0.0390 (5)
C12	0.2007 (2)	0.61909 (11)	0.64614 (16)	0.0448 (6)
C13	0.1291 (3)	0.62573 (12)	0.71787 (18)	0.0533 (7)
H13A	0.074538	0.586705	0.714379	0.080*
H13B	0.069629	0.664042	0.700969	0.080*
H13C	0.197930	0.630640	0.783479	0.080*
C14	0.0935 (3)	0.60425 (16)	0.5439 (2)	0.0836 (11)
H14A	0.045125	0.563985	0.545449	0.125*
H14B	0.139195	0.599134	0.499210	0.125*
H14C	0.028223	0.640261	0.522415	0.125*
C15	0.3070 (3)	0.56253 (12)	0.6819 (2)	0.0743 (9)
H15A	0.374862	0.572998	0.746091	0.111*
H15B	0.352344	0.557101	0.637020	0.111*
H15C	0.260189	0.522052	0.684914	0.111*
C16	1.3056 (3)	0.96265 (13)	0.68488 (18)	0.0594 (7)
H16	1.381316	0.981722	0.735126	0.071*
C17	1.2237 (3)	0.91382 (13)	0.69746 (19)	0.0529 (7)
H17	1.231 (2)	0.8944 (11)	0.7545 (18)	0.053 (7)*
C18	1.1228 (2)	0.89875 (10)	0.60212 (15)	0.0375 (5)
C19	1.1494 (2)	0.94113 (10)	0.53594 (16)	0.0400 (5)
C20	0.9793 (3)	0.90075 (12)	0.40211 (17)	0.0459 (6)
H20	0.930 (2)	0.9003 (11)	0.3294 (18)	0.062 (7)*
C21	0.9410 (2)	0.85458 (10)	0.45924 (15)	0.0385 (5)
C22	1.0123 (2)	0.85388 (10)	0.56187 (15)	0.0346 (5)
C23	0.8327 (2)	0.80734 (11)	0.40892 (15)	0.0431 (6)
C24	0.8681 (2)	0.76590 (10)	0.57415 (14)	0.0324 (5)
C25	0.8088 (2)	0.71718 (10)	0.60892 (16)	0.0375 (5)
H25	0.830 (2)	0.7079 (10)	0.6788 (16)	0.046 (6)*
C26	0.7142 (2)	0.68506 (10)	0.52384 (15)	0.0353 (5)
C27	0.6283 (2)	0.62407 (11)	0.51898 (15)	0.0425 (6)
C28A^a	0.6427 (11)	0.6027 (5)	0.6188 (5)	0.106 (4)
H28A^a	0.736789	0.589035	0.655868	0.159*
H28B^a	0.580903	0.566256	0.613326	0.159*
H28C^a	0.619710	0.639123	0.651696	0.159*
C28B^b	0.5671 (12)	0.6251 (7)	0.5902 (9)	0.103 (4)
H28D^b	0.637203	0.635369	0.653724	0.154*
H28E^b	0.527536	0.582439	0.592389	0.154*
H28F^b	0.495559	0.658365	0.572422	0.154*
C29A^a	0.4703 (6)	0.6440 (4)	0.4625 (7)	0.099 (3)
H29A^a	0.413349	0.604934	0.449854	0.148*
H29B^a	0.458266	0.664983	0.401348	0.148*
H29C^a	0.443401	0.674335	0.502149	0.148*
C29B^b	0.5347 (11)	0.6070 (5)	0.4179 (6)	0.104 (4)
H29D^b	0.496844	0.563419	0.417048	0.156*
H29E^b	0.460594	0.638889	0.395778	0.156*
H29F^b	0.584224	0.607859	0.375188	0.156*
C30A^a	0.6579 (9)	0.5726 (3)	0.4614 (7)	0.090 (2)
H30A^a	0.631377	0.587693	0.394892	0.135*
H30B^a	0.606333	0.533314	0.462167	0.135*
H30C^a	0.755562	0.562831	0.489030	0.135*
C30B^b	0.7386 (8)	0.5631 (3)	0.5540 (9)	0.096 (3)
H30D^b	0.792391	0.562046	0.514128	0.144*
H30E^b	0.689240	0.521905	0.546947	0.144*
H30F^b	0.799484	0.569198	0.621662	0.144*
N1	0.8491 (2)	0.95452 (9)	0.67206 (13)	0.0452 (5)
H1	0.884081	0.982923	0.644678	0.054*
N2	0.6398 (2)	0.93116 (10)	0.53200 (14)	0.0545 (6)
N3	0.55128 (18)	0.80141 (8)	0.72508 (12)	0.0371 (4)
H3	0.602441	0.800761	0.786961	0.044*
N4	0.35224 (19)	0.76509 (8)	0.59052 (12)	0.0403 (5)
N5	0.2520 (2)	0.71599 (9)	0.56403 (13)	0.0450 (5)
N6	1.2604 (2)	0.97955 (10)	0.58755 (14)	0.0526 (6)
H6	1.296418	1.009522	0.563289	0.063*
N7	1.0797 (2)	0.94471 (9)	0.43773 (13)	0.0464 (5)
N8	0.97254 (19)	0.81096 (8)	0.61764 (13)	0.0377 (5)
H8	1.017 (2)	0.8088 (10)	0.6828 (16)	0.046 (7)*
N9	0.80704 (19)	0.76369 (8)	0.47332 (12)	0.0372 (5)
N10	0.71097 (19)	0.71314 (8)	0.44169 (12)	0.0395 (5)
O1	0.2909 (2)	0.80857 (9)	0.43710 (12)	0.0740 (6)
O2	0.7678 (2)	0.80251 (9)	0.32083 (11)	0.0683 (6)
O3	0.1075 (2)	0.70990 (10)	0.32388 (12)	0.0819 (7)
H3A	0.134034	0.687827	0.380827	0.123*
H3B	0.165584	0.744077	0.334967	0.123*

^aOccupancy: 0.552 (6), ^bOccupancy: 0.448 (6).

Source of material

An oven-dried round bottom flask was charged with a stirring bar, 4-chloro-1H-pyrrolo[2,3-b]pyridine-5-carboxamide (100 mg, 0.5 mmol), 5-(tert-butyl)-1H-pyrazol-3-amine (70 mg, 0.5 mmol), cesium carbonate (500 mg, 1.5 mmol), and DMF (5 mL), and then the reaction mixture was stirred at 120 °C under nitrogen atmosphere for 8 h [5]. The product was obtained by column chromatography eluting with dichloromethane and methanol 15:1. The resulting solution was evaporated to get some colorless crystals.

Experimental details

All hydrogen atoms were placed in the calculated positions and all the non-hydrogen atoms were refined anisotropically.

Comment

Derivatives similar to the title compound have been reported to have antitumor activity, anti pulmonary fibrosis activity and janus kinase protein inhibitory activity [6], [7], [8], [9], [10]. Exactly the same skeleton as the title compound has not been reported in the literature, which may arouse the interest of researchers.

The asymmetric unit of the title structure contains two molecules 9-(tert-butyl)-3,11-dihydro-6H-pyrazolo [1,5-a]pyrrolo[3′,2′:5,6]pyrido[4,3-d]pyrimidin-6-one molecules and a water molecule. There is a disorder of the t-butyl group and the ratio is 0.552:0.448. All other values of the geometric parameters are normal. The bond lengths and angles are in the expected ranges.

Corresponding author: Qi-Di Zhong, School of Pharmacy, North China University of Science and Technology, 063200, Caofeidian District, Tangshan, P. R. China, E-mail: qidizhong@hotmail.com

Funding source: Science and Technology Innovation Ability Cultivation Special Project for College and High School Students the Foundation Programs http://dx.doi.org/10.13039/501100003482

Award Identifier / Grant number: 2021H020904

Funding source: Hebei Biomedical Joint Fund http://dx.doi.org/10.13039/501100015285

Award Identifier / Grant number: C2020209081

Funding source: Basic Scientific Research Business Expenses of Hebei Provincial Colleges and Universities http://dx.doi.org/10.13039/501100017680

Award Identifier / Grant number: JQN2020016

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This work was supported by Science and Technology Innovation Ability Cultivation Special Project for College and High School Students the Foundation Programs (2021H020904), Hebei Biomedical Joint Fund (C2020209081) and Basic Scientific Research Business Expenses of Hebei Provincial Colleges and Universities (JQN2020016).
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2022-05-23

Accepted: 2022-06-20

Published Online: 2022-07-06

Published in Print: 2022-10-26

This work is licensed under the Creative Commons Attribution 4.0 International License.