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The title compound {systematic name: (S,E)-3-[4-(furan-2-yl)-2,3,4,5-tetra­hydro-1H-benzo[b][1,4]diazepin-2-yl­idene]-6-methyl-2H-pyran-2,4(3H)-dione}, C19H16N2O4, is constructed from a benzodiazepine ring system linked to furan and pendant di­hydro­pyran rings, where the benzene and furan rings are oriented at a dihedral angle of 48.7 (2)°. The pyran ring is modestly non-planar [largest deviation of 0.029 (4) Å from the least-squares plane] while the tetra­hydro­diazepine ring adopts a boat conformation. The rotational orientation of the pendant di­hydro­pyran ring is partially determined by an intra­molecular N—HDiazp...ODhydp (Diazp = diazepine and Dhydp = di­hydro­pyran) hydrogen bond. In the crystal, layers of mol­ecules parallel to the bc plane are formed by N—HDiazp...ODhydp hydrogen bonds and slipped π–π stacking inter­actions. The layers are connected by additional slipped π–π stacking inter­actions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H...H (46.8%), H...O/O...H (23.5%) and H...C/C...H (15.8%) inter­actions, indicating that van der Waals inter­actions are the dominant forces in the crystal packing. Computational chemistry indicates that in the crystal the N—H...O hydrogen-bond energy is 57.5 kJ mol−1.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989021007441/wm5612sup1.cif
Contains datablocks I, global

cdx

Chemdraw file https://doi.org/10.1107/S2056989021007441/wm5612Isup3.cdx
Supplementary material

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S2056989021007441/wm5612Isup4.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989021007441/wm5612Isup4.cml
Supplementary material

CCDC reference: 2097593

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.079
  • wR factor = 0.214
  • Data-to-parameter ratio = 22.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full value Low . 0.973 Why? PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.00567 Ang. PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ...... 3.275 Check PLAT911_ALERT_3_C Missing FCF Refl Between Thmin & STh/L= 0.600 71 Report
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 4 Note PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check PLAT172_ALERT_4_G The CIF-Embedded .res File Contains DFIX Records 1 Report PLAT398_ALERT_2_G Deviating C-O-C Angle From 120 for O4 106.0 Degree PLAT793_ALERT_4_G Model has Chirality at C9 (Centro SPGR) S Verify PLAT860_ALERT_3_G Number of Least-Squares Restraints ............. 2 Note PLAT870_ALERT_4_G ALERTS Related to Twinning Effects Suppressed .. ! Info PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 2 Note PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 109 Note PLAT931_ALERT_5_G CIFcalcFCF Twin Law [ 1 0 3] Est.d BASF 0.24 Check PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ... 5 Note
0 ALERT level A = Most likely a serious problem - resolve or explain 0 ALERT level B = A potentially serious problem, consider carefully 4 ALERT level C = Check. Ensure it is not caused by an omission or oversight 11 ALERT level G = General information/check it is not something unexpected 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 6 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
checkCIF publication errors
Alert level A PUBL024_ALERT_1_A The number of authors is greater than 5. Please specify the role of each of the co-authors for your paper.
1 ALERT level A = Data missing that is essential or data in wrong format 0 ALERT level G = General alerts. Data that may be required is missing

Computing details top

Data collection: APEX3 (Bruker, 2020); cell refinement: SAINT (Bruker, 2020); data reduction: SAINT (Bruker, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/1 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

(S,E)-3-[4-(Furan-2-yl)-2,3,4,5-tetrahydro-1H-benzo[b][1,4]diazepin-2-ylidene]-6-methyl-2H-pyran-2,4(3H)-dione top
Crystal data top
C19H16N2O4F(000) = 704
Mr = 336.34Dx = 1.420 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.0111 (8) ÅCell parameters from 9980 reflections
b = 11.0123 (13) Åθ = 2.7–28.4°
c = 20.493 (2) ŵ = 0.10 mm1
β = 96.202 (5)°T = 150 K
V = 1573.0 (3) Å3Block, colourless
Z = 40.34 × 0.22 × 0.11 mm
Data collection top
Bruker D8 QUEST PHOTON 3
diffractometer
5201 independent reflections
Radiation source: fine-focus sealed tube4007 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.081
Detector resolution: 7.3910 pixels mm-1θmax = 28.5°, θmin = 2.7°
φ and ω scansh = 99
Absorption correction: multi-scan
(TWINABS; Sheldrick, 2009)
k = 014
Tmin = 0.97, Tmax = 0.99l = 027
5201 measured reflections
Refinement top
Refinement on F2Primary atom site location: dual
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.079Hydrogen site location: mixed
wR(F2) = 0.214H atoms treated by a mixture of independent and constrained refinement
S = 1.14 w = 1/[σ2(Fo2) + (0.0648P)2 + 2.9838P]
where P = (Fo2 + 2Fc2)/3
5201 reflections(Δ/σ)max < 0.001
236 parametersΔρmax = 0.54 e Å3
2 restraintsΔρmin = 0.30 e Å3
Special details top

Experimental. The diffraction data were obtained from 9 sets of frames, each of width 0.5° in ω or φ, collected with scan parameters determined by the "strategy" routine in APEX3. The scan time was 20 sec/frame. Analysis of 2110 reflections having I/σ(I) > 15 and chosen from the full data set with CELL_NOW (Sheldrick, 2008) showed the crystal to belong to the monoclinic system and to be twinned by a 180° rotation about the a axis. The raw data were processed using the multi-component version of SAINT under control of the two-component orientation file generated by CELL_NOW.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å) and were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms. Those attached to nitrogen were placed in locations derived from a difference map and refined with a DFIX 0.91 0.01 instruction. Refined as a 2-component twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.8749 (4)0.5209 (2)0.31078 (12)0.0307 (6)
O20.7779 (4)0.3547 (3)0.48140 (13)0.0386 (7)
O30.8042 (4)0.3592 (3)0.25076 (12)0.0348 (7)
O40.6845 (5)0.1158 (3)0.23160 (17)0.0516 (9)
N10.7413 (5)0.1528 (3)0.42168 (15)0.0309 (7)
H10.750 (7)0.206 (3)0.4557 (16)0.052 (14)*
N20.4861 (5)0.0341 (3)0.32311 (16)0.0325 (8)
H2A0.381 (5)0.006 (4)0.305 (2)0.066 (17)*
C10.5648 (5)0.0283 (3)0.37991 (18)0.0293 (8)
C20.5022 (6)0.1448 (4)0.3935 (2)0.0346 (9)
H20.4173570.1859840.3616390.042*
C30.5608 (7)0.2015 (4)0.4524 (2)0.0410 (11)
H30.5155970.2808020.4605480.049*
C40.6847 (7)0.1440 (4)0.4995 (2)0.0422 (11)
H40.7260160.1835960.5397290.051*
C50.7479 (6)0.0280 (4)0.48747 (19)0.0350 (9)
H50.8317450.0126670.5198690.042*
C60.6895 (6)0.0296 (3)0.42827 (18)0.0278 (8)
C70.7802 (5)0.2070 (3)0.36688 (18)0.0270 (8)
C80.8001 (6)0.1246 (4)0.30983 (19)0.0342 (9)
H8A0.8737000.0515970.3254640.041*
H8B0.8733510.1670010.2779630.041*
C90.6076 (6)0.0860 (4)0.27573 (19)0.0322 (9)
H90.5417950.1607450.2569970.039*
C100.8108 (5)0.3343 (3)0.36710 (17)0.0261 (8)
C110.8122 (5)0.4025 (3)0.42765 (18)0.0288 (8)
C120.8580 (5)0.5294 (3)0.42500 (18)0.0292 (8)
H120.8646320.5762540.4641030.035*
C130.8913 (6)0.5830 (3)0.36913 (19)0.0290 (8)
C140.8277 (5)0.3984 (3)0.30673 (18)0.0264 (8)
C150.9490 (7)0.7108 (4)0.3614 (2)0.0390 (10)
H15A0.9670500.7500570.4045070.058*
H15B0.8486670.7535210.3332460.058*
H15C1.0694200.7135700.3411960.058*
C160.6325 (6)0.0022 (3)0.21928 (19)0.0305 (8)
C170.6236 (6)0.0268 (4)0.15511 (18)0.0382 (10)
H170.5941680.1024850.1341010.046*
C180.6687 (7)0.0869 (5)0.1245 (2)0.0530 (14)
H180.6718560.1005530.0788680.064*
C190.7044 (7)0.1673 (5)0.1713 (3)0.0563 (14)
H190.7390390.2493970.1647140.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0372 (16)0.0320 (14)0.0233 (13)0.0023 (12)0.0052 (11)0.0010 (11)
O20.0556 (18)0.0400 (16)0.0201 (13)0.0164 (14)0.0036 (12)0.0005 (12)
O30.0434 (17)0.0393 (16)0.0213 (13)0.0028 (13)0.0017 (12)0.0026 (11)
O40.063 (2)0.0425 (18)0.052 (2)0.0052 (16)0.0182 (17)0.0024 (16)
N10.0393 (19)0.0303 (17)0.0230 (16)0.0078 (15)0.0023 (14)0.0018 (13)
N20.0335 (19)0.0390 (19)0.0253 (16)0.0079 (15)0.0038 (14)0.0006 (14)
C10.032 (2)0.032 (2)0.0263 (19)0.0001 (17)0.0106 (16)0.0033 (16)
C20.040 (2)0.031 (2)0.034 (2)0.0042 (18)0.0112 (18)0.0050 (17)
C30.057 (3)0.028 (2)0.042 (2)0.005 (2)0.022 (2)0.0029 (18)
C40.055 (3)0.043 (2)0.031 (2)0.007 (2)0.013 (2)0.0119 (19)
C50.039 (2)0.042 (2)0.0250 (19)0.0008 (19)0.0062 (17)0.0020 (17)
C60.034 (2)0.0257 (18)0.0252 (18)0.0027 (16)0.0093 (15)0.0001 (15)
C70.0247 (19)0.0323 (19)0.0238 (18)0.0049 (16)0.0020 (15)0.0009 (15)
C80.041 (2)0.034 (2)0.030 (2)0.0044 (18)0.0093 (17)0.0025 (17)
C90.038 (2)0.034 (2)0.0251 (19)0.0018 (18)0.0073 (16)0.0003 (16)
C100.029 (2)0.0281 (18)0.0213 (17)0.0044 (15)0.0037 (15)0.0008 (14)
C110.030 (2)0.034 (2)0.0218 (18)0.0079 (16)0.0009 (15)0.0001 (15)
C120.036 (2)0.0288 (19)0.0227 (18)0.0055 (16)0.0021 (15)0.0031 (15)
C130.030 (2)0.0299 (19)0.0277 (19)0.0011 (16)0.0040 (16)0.0011 (15)
C140.0254 (19)0.0285 (19)0.0253 (18)0.0006 (15)0.0027 (15)0.0005 (15)
C150.049 (3)0.034 (2)0.035 (2)0.004 (2)0.014 (2)0.0023 (18)
C160.034 (2)0.0289 (19)0.0282 (19)0.0054 (17)0.0044 (16)0.0004 (16)
C170.036 (2)0.056 (3)0.0219 (19)0.008 (2)0.0042 (17)0.0102 (18)
C180.033 (3)0.090 (4)0.035 (2)0.003 (3)0.003 (2)0.026 (3)
C190.048 (3)0.047 (3)0.078 (4)0.003 (2)0.025 (3)0.023 (3)
Geometric parameters (Å, º) top
O1—C131.372 (4)C7—C101.419 (5)
O1—C141.389 (4)C7—C81.498 (5)
O2—C111.267 (4)C8—C91.513 (6)
O3—C141.220 (4)C8—H8A0.9900
O4—C161.366 (5)C8—H8B0.9900
O4—C191.380 (6)C9—C161.504 (5)
N1—C71.326 (5)C9—H91.0000
N1—C61.415 (5)C10—C141.440 (5)
N1—H10.912 (12)C10—C111.449 (5)
N2—C11.412 (5)C11—C121.436 (5)
N2—C91.474 (5)C12—C131.331 (5)
N2—H2A0.906 (12)C12—H120.9500
C1—C21.393 (5)C13—C151.477 (5)
C1—C61.402 (5)C15—H15A0.9800
C2—C31.382 (6)C15—H15B0.9800
C2—H20.9500C15—H15C0.9800
C3—C41.381 (6)C16—C171.338 (5)
C3—H30.9500C17—C181.451 (7)
C4—C51.383 (6)C17—H170.9500
C4—H40.9500C18—C191.309 (7)
C5—C61.391 (5)C18—H180.9500
C5—H50.9500C19—H190.9500
O2···C3i3.322 (5)C3···C15v3.591 (6)
O2···N12.537 (4)C4···C6i3.387 (5)
O2···C12ii3.282 (4)C10···C18iii3.497 (6)
O3···C93.372 (4)C11···C17iii3.600 (5)
O3···C82.856 (4)C11···C18iii3.428 (5)
O3···N2iii3.079 (4)C12···C12ii3.541 (5)
O4···N22.955 (5)C12···C17iii3.589 (5)
O4···C13.376 (5)C14···C16iii3.407 (5)
O1···H2Aiii2.84 (4)C1···H8A2.68
O2···H12ii2.74C2···H17vi2.91
O2···H3i2.62C3···H17vi2.93
O2···H11.72 (3)C6···H8A2.59
O3···H92.87C11···H12.28 (3)
O3···H2Aiii2.20 (4)C14···H2Aiii2.79 (4)
H15C···O3iv2.70C14···H8B2.64
O3···H2iii2.68H2···H2A2.29
O3···H8B2.23H2···H17vi2.33
O4···H8A2.88H3···H17vi2.38
O4···H15Bv2.70H5···H12.55
N1···N22.865 (4)H12···H15A2.42
N2···H19iii2.89
C13—O1—C14122.3 (3)C16—C9—C8110.8 (3)
C16—O4—C19106.0 (4)N2—C9—H9107.3
C7—N1—C6126.2 (3)C16—C9—H9107.3
C7—N1—H1111 (3)C8—C9—H9107.3
C6—N1—H1123 (3)C7—C10—C14120.5 (3)
C1—N2—C9122.0 (3)C7—C10—C11120.1 (3)
C1—N2—H2A109 (3)C14—C10—C11119.2 (3)
C9—N2—H2A115 (3)O2—C11—C12120.1 (3)
C2—C1—C6117.6 (4)O2—C11—C10123.0 (3)
C2—C1—N2120.6 (4)C12—C11—C10116.9 (3)
C6—C1—N2121.3 (3)C13—C12—C11121.7 (3)
C3—C2—C1121.4 (4)C13—C12—H12119.2
C3—C2—H2119.3C11—C12—H12119.2
C1—C2—H2119.3C12—C13—O1121.5 (3)
C4—C3—C2120.6 (4)C12—C13—C15126.2 (4)
C4—C3—H3119.7O1—C13—C15112.3 (3)
C2—C3—H3119.7O3—C14—O1114.0 (3)
C3—C4—C5119.3 (4)O3—C14—C10128.3 (3)
C3—C4—H4120.4O1—C14—C10117.7 (3)
C5—C4—H4120.4C13—C15—H15A109.5
C4—C5—C6120.5 (4)C13—C15—H15B109.5
C4—C5—H5119.8H15A—C15—H15B109.5
C6—C5—H5119.8C13—C15—H15C109.5
C5—C6—C1120.8 (4)H15A—C15—H15C109.5
C5—C6—N1117.8 (3)H15B—C15—H15C109.5
C1—C6—N1121.1 (3)C17—C16—O4111.0 (4)
N1—C7—C10119.1 (3)C17—C16—C9129.4 (4)
N1—C7—C8115.7 (3)O4—C16—C9119.5 (3)
C10—C7—C8125.0 (3)C16—C17—C18105.1 (4)
C7—C8—C9112.2 (3)C16—C17—H17127.4
C7—C8—H8A109.2C18—C17—H17127.4
C9—C8—H8A109.2C19—C18—C17107.5 (4)
C7—C8—H8B109.2C19—C18—H18126.3
C9—C8—H8B109.2C17—C18—H18126.3
H8A—C8—H8B107.9C18—C19—O4110.4 (4)
N2—C9—C16113.1 (3)C18—C19—H19124.8
N2—C9—C8110.8 (3)O4—C19—H19124.8
C9—N2—C1—C2126.6 (4)C7—C10—C11—O23.5 (6)
C9—N2—C1—C661.5 (5)C14—C10—C11—O2172.3 (4)
C6—C1—C2—C30.2 (6)C7—C10—C11—C12175.6 (3)
N2—C1—C2—C3172.4 (4)C14—C10—C11—C128.6 (5)
C1—C2—C3—C40.3 (6)O2—C11—C12—C13178.7 (4)
C2—C3—C4—C50.8 (7)C10—C11—C12—C132.2 (6)
C3—C4—C5—C60.8 (6)C11—C12—C13—O13.1 (6)
C4—C5—C6—C10.4 (6)C11—C12—C13—C15176.7 (4)
C4—C5—C6—N1173.1 (4)C14—O1—C13—C121.7 (6)
C2—C1—C6—C50.1 (5)C14—O1—C13—C15178.1 (3)
N2—C1—C6—C5172.2 (4)C13—O1—C14—O3174.5 (3)
C2—C1—C6—N1172.3 (3)C13—O1—C14—C104.9 (5)
N2—C1—C6—N10.2 (5)C7—C10—C14—O36.4 (6)
C7—N1—C6—C5147.3 (4)C11—C10—C14—O3169.4 (4)
C7—N1—C6—C140.0 (6)C7—C10—C14—O1174.3 (3)
C6—N1—C7—C10173.6 (4)C11—C10—C14—O19.9 (5)
C6—N1—C7—C810.1 (6)C19—O4—C16—C171.4 (5)
N1—C7—C8—C979.4 (4)C19—O4—C16—C9177.3 (4)
C10—C7—C8—C9104.5 (4)N2—C9—C16—C17135.7 (4)
C1—N2—C9—C1694.4 (4)C8—C9—C16—C1799.2 (5)
C1—N2—C9—C830.7 (5)N2—C9—C16—O449.3 (5)
C7—C8—C9—N252.9 (4)C8—C9—C16—O475.8 (5)
C7—C8—C9—C16179.3 (3)O4—C16—C17—C181.8 (5)
N1—C7—C10—C14171.6 (4)C9—C16—C17—C18177.1 (4)
C8—C7—C10—C1412.4 (6)C16—C17—C18—C191.4 (5)
N1—C7—C10—C114.1 (6)C17—C18—C19—O40.6 (6)
C8—C7—C10—C11171.9 (4)C16—O4—C19—C180.5 (5)
Symmetry codes: (i) x+1, y, z+1; (ii) x+2, y+1, z+1; (iii) x+1, y+1/2, z+1/2; (iv) x+2, y+1/2, z+1/2; (v) x, y1, z; (vi) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O20.91 (1)1.72 (3)2.538 (4)148 (4)
N2—H2A···O3vi0.91 (1)2.20 (2)3.079 (4)162 (5)
Symmetry code: (vi) x+1, y1/2, z+1/2.
 

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