Crystal structure and Hirshfeld surface analysis of 3,4-dihydro-2-(2,4-dioxo-6-methylpyran-3-ylidene)-4-(4-pyridin-4-yl)-1,5-benzodiazepine

In the title compound, the pendant di­hydro­pyran ring is rotationally disordered in a 90.899 (3):0.101 (3) ratio with the orientation of each component largely determined by intra­molecular N—H...O hydrogen bonds. In the crystal, inversion-related mol­ecules form dimers through inter­molecular N—H...O hydrogen bonds with the dimers associated along the b-axis direction by slipped π-stacking inter­actions between the pyridyl and di­hydro­pyran rings.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• Disorder in main residue
• R factor = 0.048
• wR factor = 0.135
• Data-to-parameter ratio = 14.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.28 Report
PLAT411_ALERT_2_C Short Inter H...H Contact  H11      ..H17A     .       2.11 Ang.
                                            -x,-1/2+y,1/2-z  =      2_545 Check
PLAT413_ALERT_2_C Short Inter XH3 .. XHn     H4       ..H20F     .       2.12 Ang.
                                                 1+x,-1+y,z  =      1_645 Check
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ......      2.399 Check

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT171_ALERT_4_G The CIF-Embedded .res File Contains EADP Records          9 Report
PLAT176_ALERT_4_G The CIF-Embedded .res File Contains SADI Records          1 Report
PLAT301_ALERT_3_G Main Residue  Disorder ..............(Resd  1  )        35% Note
PLAT793_ALERT_4_G Model has Chirality at C7          (Centro SPGR)          S Verify
PLAT811_ALERT_5_G No ADDSYM Analysis: Too Many Excluded Atoms ....          ! Info
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          1 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         15 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.         16 Info

   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
   9 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 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
   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

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Computing details

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

3,4-Dihydro-2-(2,4-dioxo-6-methylpyran-3-ylidene)-4-(4-pyridin-4-yl)-1,5-benzodiazepine

Crystal data

C20H17N3O3	F(000) = 728
Mr = 347.36	Dx = 1.419 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.509 (9) Å	Cell parameters from 9961 reflections
b = 7.435 (6) Å	θ = 2.5–29.1°
c = 21.367 (16) Å	µ = 0.10 mm^−1
β = 103.041 (15)°	T = 100 K
V = 1626 (2) Å^3	Block, orange
Z = 4	0.31 × 0.23 × 0.21 mm

Data collection

Bruker SMART APEX CCD diffractometer	4368 independent reflections
Radiation source: fine-focus sealed tube	3541 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 8.3333 pixels mm^-1	θmax = 29.1°, θmin = 2.0°
φ and ω scans	h = −14→14
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −10→10
Tmin = 0.84, Tmax = 0.98	l = −29→29
30100 measured reflections

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)] = 0.048	Hydrogen site location: mixed
wR(F^2) = 0.135	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0814P)^2 + 0.2932P] where P = (Fo^2 + 2Fc^2)/3
4368 reflections	(Δ/σ)max < 0.001
294 parameters	Δρmax = 0.45 e Å^−3
1 restraint	Δρmin = −0.20 e Å^−3

Special details

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5 deg. in omega, colllected at phi = 0.00, 90.00 and 180.00 deg. and 2 sets of 800 frames, each of width 0.45 deg in phi, collected at omega = -30.00 and 210.00 deg. The scan time was 15 sec/frame.

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. Because of the slight disorder of the dihydropyranone ring, the hydrogen atoms on C17 and C20 and their disordered counterparts were placed in calculated positions and included as riding contributions. The alternate orientation of this ring was treated as a rigid group having the same geometry as the major component.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.50328 (10)	0.27877 (14)	0.42584 (5)	0.0216 (2)
H1	0.5339 (17)	0.167 (2)	0.4311 (8)	0.035 (4)*
N2	0.46375 (10)	0.66567 (14)	0.42864 (5)	0.0202 (2)
H2A	0.4561 (17)	0.766 (2)	0.4531 (8)	0.035 (4)*
N3	0.47709 (10)	0.02629 (13)	0.33122 (5)	0.0210 (2)
C1	0.58855 (12)	0.58808 (16)	0.43268 (6)	0.0195 (2)
C2	0.69547 (14)	0.70495 (18)	0.44401 (6)	0.0259 (3)
H2	0.6776 (16)	0.831 (2)	0.4477 (8)	0.030 (4)*
C3	0.82095 (14)	0.6385 (2)	0.45086 (7)	0.0303 (3)
H3	0.8932 (19)	0.721 (3)	0.4594 (9)	0.046 (5)*
C4	0.83965 (13)	0.4535 (2)	0.44650 (7)	0.0283 (3)
H4	0.9285 (17)	0.409 (2)	0.4496 (8)	0.034 (4)*
C5	0.73377 (13)	0.33768 (18)	0.43610 (6)	0.0231 (3)
H5	0.7506 (15)	0.206 (2)	0.4327 (7)	0.026 (4)*
C6	0.60577 (12)	0.40117 (16)	0.42916 (5)	0.0189 (2)
C7	0.38159 (12)	0.28441 (16)	0.37634 (6)	0.0210 (3)
H7	0.3049 (15)	0.268 (2)	0.3989 (7)	0.023 (4)*
C8	0.36516 (13)	0.46755 (16)	0.34292 (6)	0.0211 (3)
H8A	0.2883 (14)	0.4618 (19)	0.3074 (8)	0.018 (3)*
H8B	0.4473 (17)	0.490 (2)	0.3250 (8)	0.029 (4)*
C9	0.35388 (12)	0.61587 (16)	0.38909 (6)	0.0208 (3)
C10	0.37298 (12)	0.13296 (15)	0.32695 (6)	0.0195 (2)
C11	0.25688 (12)	0.10935 (17)	0.28020 (6)	0.0220 (3)
H11	0.1812 (15)	0.193 (2)	0.2789 (8)	0.028 (4)*
C12	0.24929 (13)	−0.02918 (17)	0.23603 (6)	0.0239 (3)
H12	0.1706 (16)	−0.050 (2)	0.2033 (8)	0.024 (4)*
C13	0.35724 (13)	−0.14053 (17)	0.24005 (6)	0.0228 (3)
H13	0.3539 (16)	−0.241 (2)	0.2093 (8)	0.033 (4)*
C14	0.46719 (13)	−0.10813 (16)	0.28802 (6)	0.0214 (3)
H14	0.5450 (16)	−0.187 (2)	0.2937 (8)	0.029 (4)*
O1	0.00669 (11)	0.75916 (18)	0.33696 (7)	0.0284 (3)	0.899 (3)
O2	0.33642 (11)	0.94052 (19)	0.46059 (7)	0.0210 (3)	0.899 (3)
O3	0.0900 (2)	0.4903 (3)	0.32931 (15)	0.0353 (6)	0.899 (3)
C15	0.23602 (14)	0.7124 (2)	0.38727 (7)	0.0179 (3)	0.899 (3)
C16	0.23681 (15)	0.8804 (2)	0.42163 (7)	0.0184 (3)	0.899 (3)
C17	0.11731 (18)	0.9845 (2)	0.40703 (8)	0.0223 (3)	0.899 (3)
H17	0.113329	1.095824	0.428316	0.027*	0.899 (3)
C18	0.01213 (16)	0.9261 (2)	0.36392 (8)	0.0243 (3)	0.899 (3)
C19	0.11368 (19)	0.6417 (3)	0.35030 (13)	0.0260 (3)	0.899 (3)
C20	−0.11056 (16)	1.0286 (2)	0.33797 (8)	0.0328 (4)	0.899 (3)
H20A	−0.105441	1.146502	0.358885	0.049*	0.899 (3)
H20B	−0.185256	0.961717	0.346453	0.049*	0.899 (3)
H20C	−0.121537	1.044791	0.291544	0.049*	0.899 (3)
C15A	0.2351 (8)	0.6865 (16)	0.4003 (7)	0.0179 (3)	0.101 (3)
C16A	0.1172 (11)	0.6489 (15)	0.3522 (8)	0.0184 (3)	0.101 (3)
C17A	0.0191 (9)	0.7874 (16)	0.3410 (7)	0.0223 (3)	0.101 (3)
H17A	−0.059812	0.768813	0.309749	0.027*	0.101 (3)
C18A	0.0373 (7)	0.9429 (13)	0.3741 (5)	0.0243 (3)	0.101 (3)
O1A	0.1528 (8)	0.9856 (13)	0.4151 (5)	0.0284 (3)	0.101 (3)
C19A	0.2584 (7)	0.8647 (17)	0.4267 (6)	0.0260 (3)	0.101 (3)
C20A	−0.0603 (10)	1.0911 (14)	0.3745 (7)	0.0328 (4)	0.101 (3)
H20D	−0.148892	1.041236	0.363612	0.049*	0.101 (3)
H20E	−0.051332	1.182826	0.342868	0.049*	0.101 (3)
H20F	−0.044162	1.145564	0.417348	0.049*	0.101 (3)
O2A	0.0956 (15)	0.5021 (19)	0.3224 (11)	0.0210 (3)	0.101 (3)
O3A	0.3599 (8)	0.926 (2)	0.4586 (9)	0.0353 (6)	0.101 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0252 (5)	0.0167 (5)	0.0189 (5)	−0.0021 (4)	−0.0032 (4)	0.0025 (4)
N2	0.0239 (5)	0.0173 (5)	0.0180 (5)	0.0024 (4)	0.0017 (4)	−0.0015 (4)
N3	0.0227 (5)	0.0182 (5)	0.0212 (5)	−0.0007 (4)	0.0032 (4)	−0.0006 (4)
C1	0.0216 (6)	0.0193 (5)	0.0159 (5)	0.0002 (4)	0.0006 (4)	−0.0011 (4)
C2	0.0303 (7)	0.0206 (6)	0.0238 (6)	−0.0047 (5)	−0.0004 (5)	−0.0012 (5)
C3	0.0253 (7)	0.0344 (7)	0.0280 (7)	−0.0087 (6)	−0.0007 (5)	0.0005 (6)
C4	0.0222 (7)	0.0373 (7)	0.0235 (6)	0.0011 (5)	0.0013 (5)	−0.0001 (5)
C5	0.0252 (6)	0.0251 (6)	0.0175 (5)	0.0040 (5)	0.0017 (5)	−0.0002 (5)
C6	0.0229 (6)	0.0198 (5)	0.0124 (5)	0.0000 (4)	0.0007 (4)	−0.0004 (4)
C7	0.0234 (6)	0.0179 (5)	0.0190 (5)	0.0003 (4)	−0.0004 (5)	−0.0007 (4)
C8	0.0253 (6)	0.0187 (5)	0.0175 (5)	0.0025 (4)	0.0010 (5)	−0.0015 (4)
C9	0.0258 (6)	0.0168 (5)	0.0188 (5)	0.0009 (4)	0.0027 (5)	−0.0003 (4)
C10	0.0225 (6)	0.0159 (5)	0.0194 (5)	−0.0023 (4)	0.0035 (4)	−0.0006 (4)
C11	0.0212 (6)	0.0194 (6)	0.0239 (6)	−0.0009 (4)	0.0019 (5)	−0.0014 (5)
C12	0.0251 (6)	0.0229 (6)	0.0211 (6)	−0.0012 (5)	0.0001 (5)	−0.0026 (5)
C13	0.0282 (6)	0.0199 (6)	0.0200 (6)	−0.0016 (5)	0.0050 (5)	−0.0032 (4)
C14	0.0236 (6)	0.0190 (5)	0.0219 (6)	0.0001 (5)	0.0058 (5)	−0.0003 (5)
O1	0.0218 (5)	0.0272 (7)	0.0338 (6)	0.0046 (4)	0.0013 (4)	−0.0068 (5)
O2	0.0261 (6)	0.0166 (5)	0.0190 (5)	0.0032 (4)	0.0021 (5)	−0.0011 (4)
O3	0.0278 (6)	0.0271 (7)	0.0482 (13)	−0.0006 (5)	0.0028 (6)	−0.0138 (8)
C15	0.0243 (6)	0.0143 (6)	0.0149 (8)	0.0022 (5)	0.0038 (5)	0.0020 (5)
C16	0.0250 (7)	0.0151 (6)	0.0150 (6)	0.0020 (5)	0.0042 (5)	0.0020 (5)
C17	0.0266 (8)	0.0180 (6)	0.0235 (7)	0.0045 (6)	0.0085 (7)	−0.0001 (5)
C18	0.0242 (7)	0.0244 (7)	0.0253 (7)	0.0058 (6)	0.0078 (6)	−0.0005 (5)
C19	0.0234 (7)	0.0254 (7)	0.0284 (7)	0.0046 (6)	0.0044 (6)	−0.0043 (6)
C20	0.0268 (8)	0.0368 (9)	0.0333 (8)	0.0117 (6)	0.0033 (6)	−0.0006 (7)
C15A	0.0243 (6)	0.0143 (6)	0.0149 (8)	0.0022 (5)	0.0038 (5)	0.0020 (5)
C16A	0.0250 (7)	0.0151 (6)	0.0150 (6)	0.0020 (5)	0.0042 (5)	0.0020 (5)
C17A	0.0266 (8)	0.0180 (6)	0.0235 (7)	0.0045 (6)	0.0085 (7)	−0.0001 (5)
C18A	0.0242 (7)	0.0244 (7)	0.0253 (7)	0.0058 (6)	0.0078 (6)	−0.0005 (5)
O1A	0.0218 (5)	0.0272 (7)	0.0338 (6)	0.0046 (4)	0.0013 (4)	−0.0068 (5)
C19A	0.0234 (7)	0.0254 (7)	0.0284 (7)	0.0046 (6)	0.0044 (6)	−0.0043 (6)
C20A	0.0268 (8)	0.0368 (9)	0.0333 (8)	0.0117 (6)	0.0033 (6)	−0.0006 (7)
O2A	0.0261 (6)	0.0166 (5)	0.0190 (5)	0.0032 (4)	0.0021 (5)	−0.0011 (4)
O3A	0.0278 (6)	0.0271 (7)	0.0482 (13)	−0.0006 (5)	0.0028 (6)	−0.0138 (8)

Geometric parameters (Å, º)

N1—C6	1.3996 (18)	C12—H12	0.967 (16)
N1—C7	1.4648 (18)	C13—C14	1.3818 (19)
N1—H1	0.889 (18)	C13—H13	0.987 (17)
N2—C9	1.3206 (18)	C14—H14	0.992 (16)
N2—C1	1.4175 (19)	O1—C18	1.364 (2)
N2—H2A	0.928 (18)	O1—C19	1.401 (2)
N3—C10	1.3377 (18)	O2—C16	1.2630 (18)
N3—C14	1.3485 (17)	O3—C19	1.217 (2)
C1—C2	1.3976 (19)	C15—C19	1.447 (2)
C1—C6	1.406 (2)	C15—C16	1.448 (2)
C2—C3	1.385 (2)	C16—C17	1.448 (2)
C2—H2	0.959 (17)	C17—C18	1.341 (2)
C3—C4	1.395 (2)	C17—H17	0.9500
C3—H3	0.96 (2)	C18—C20	1.493 (2)
C4—C5	1.385 (2)	C20—H20A	0.9800
C4—H4	0.980 (17)	C20—H20B	0.9800
C5—C6	1.402 (2)	C20—H20C	0.9800
C5—H5	0.997 (16)	C15A—C19A	1.4397
C7—C8	1.5291 (19)	C15A—C16A	1.4466
C7—C10	1.5319 (18)	C16A—O2A	1.2580
C7—H7	1.036 (16)	C16A—C17A	1.4385
C8—C9	1.5020 (18)	C17A—C18A	1.3459
C8—H8A	0.976 (15)	C17A—H17A	0.9500
C8—H8B	1.033 (17)	C18A—O1A	1.3649
C9—C15A	1.423 (3)	C18A—C20A	1.5066
C9—C15	1.4246 (19)	O1A—C19A	1.4057
C10—C11	1.4026 (19)	C19A—O3A	1.2185
C11—C12	1.3870 (19)	C20A—H20D	0.9800
C11—H11	1.006 (16)	C20A—H20E	0.9800
C12—C13	1.391 (2)	C20A—H20F	0.9799
O2···C7^i	3.22	N3···H1	2.330 (16)
O2···N1^i	3.25	N3···H13^vii	2.755 (17)
O2···N2	2.62	C5···C16^iii	3.40
O2···C2^ii	3.40	C7···C16^vi	3.60
O2···C10^i	3.29	C9···C14^i	3.38
O2···N1^iii	3.09	C10···C16^vi	3.31
O2···C5^iii	3.23	C11···C16^vi	3.52
O3···C8	2.85	C11···C17^vi	3.49
O3···C7	3.37	C1···H8B	2.547 (17)
O1···H11^iv	2.84	C4···H20A^viii	3.09
O2···H1^i	2.85	C5···H20A^viii	2.98
O2···H1^iii	2.54	C6···H8B	2.548 (17)
O2···H2A	1.84	C8···H11	2.930 (16)
O2···H5^iii	2.86	C11···H8A	2.688 (15)
O2···H7^i	2.75	C13···H8B^ix	2.895 (18)
O2···H2^ii	2.62	C14···H8B^ix	2.855 (17)
O3···H8A	2.25	C16···H2A	2.40
O3···H11	2.73	C17···H7^i	2.92
O3···H12^iv	2.69	C19···H8A	2.60
O3···H20C^v	2.71	H1···H5	2.29 (2)
N1···O2^vi	3.25	H1···H2A^iii	2.50 (2)
N1···N2	2.909 (3)	H2···H2A	2.41 (3)
N1···N3	2.727 (3)	H3···H4^x	2.57 (3)
N1···O2^iii	3.09	H5···H20A^viii	2.4596
N1···N2^iii	3.078 (3)	H7···H17^vi	2.58
N2···O2	2.62	H8A···H11	2.31 (2)
N2···C6^iii	3.319 (3)	H8A···H20C^v	2.50
N1···H2A^iii	2.547 (17)	H17···H20A	2.47
C6—N1—C7	123.68 (11)	C14—C13—C12	118.41 (12)
C6—N1—H1	110.4 (11)	C14—C13—H13	121.5 (10)
C7—N1—H1	110.5 (11)	C12—C13—H13	120.1 (10)
C9—N2—C1	126.03 (11)	N3—C14—C13	124.02 (12)
C9—N2—H2A	114.4 (11)	N3—C14—H14	114.9 (10)
C1—N2—H2A	119.4 (11)	C13—C14—H14	121.1 (10)
C10—N3—C14	117.20 (11)	C18—O1—C19	121.73 (12)
C2—C1—C6	121.05 (12)	C9—C15—C19	119.45 (14)
C2—C1—N2	117.01 (12)	C9—C15—C16	121.02 (13)
C6—C1—N2	121.85 (11)	C19—C15—C16	119.53 (12)
C3—C2—C1	120.38 (13)	O2—C16—C17	120.18 (13)
C3—C2—H2	122.5 (10)	O2—C16—C15	123.26 (12)
C1—C2—H2	117.1 (10)	C17—C16—C15	116.50 (12)
C2—C3—C4	119.32 (13)	C18—C17—C16	121.03 (13)
C2—C3—H3	118.9 (12)	C18—C17—H17	119.5
C4—C3—H3	121.8 (11)	C16—C17—H17	119.5
C5—C4—C3	120.23 (13)	C17—C18—O1	122.28 (13)
C5—C4—H4	121.3 (10)	C17—C18—C20	126.79 (15)
C3—C4—H4	118.5 (10)	O1—C18—C20	110.93 (14)
C4—C5—C6	121.66 (13)	O3—C19—O1	114.41 (14)
C4—C5—H5	118.1 (9)	O3—C19—C15	128.34 (14)
C6—C5—H5	120.3 (9)	O1—C19—C15	117.24 (14)
N1—C6—C5	119.71 (12)	C18—C20—H20A	109.5
N1—C6—C1	122.59 (12)	C18—C20—H20B	109.5
C5—C6—C1	117.35 (11)	H20A—C20—H20B	109.5
N1—C7—C8	110.54 (10)	C18—C20—H20C	109.5
N1—C7—C10	112.50 (10)	H20A—C20—H20C	109.5
C8—C7—C10	110.48 (11)	H20B—C20—H20C	109.5
N1—C7—H7	107.7 (9)	C9—C15A—C19A	109.1 (7)
C8—C7—H7	107.9 (8)	C9—C15A—C16A	116.9 (8)
C10—C7—H7	107.5 (8)	C19A—C15A—C16A	119.9
C9—C8—C7	111.37 (11)	O2A—C16A—C17A	119.7
C9—C8—H8A	111.6 (9)	O2A—C16A—C15A	123.7
C7—C8—H8A	108.1 (8)	C17A—C16A—C15A	116.5
C9—C8—H8B	108.8 (9)	C18A—C17A—C16A	121.0
C7—C8—H8B	107.4 (9)	C18A—C17A—H17A	119.5
H8A—C8—H8B	109.4 (13)	C16A—C17A—H17A	119.5
N2—C9—C15A	117.6 (6)	C17A—C18A—O1A	122.5
N2—C9—C15	120.36 (12)	C17A—C18A—C20A	128.0
N2—C9—C8	116.04 (11)	O1A—C18A—C20A	109.5
C15A—C9—C8	125.7 (6)	C18A—O1A—C19A	121.2
C15—C9—C8	123.30 (12)	O3A—C19A—O1A	114.5
N3—C10—C11	122.76 (12)	O3A—C19A—C15A	128.0
N3—C10—C7	117.94 (11)	O1A—C19A—C15A	117.4
C11—C10—C7	119.29 (11)	C18A—C20A—H20D	109.5
C12—C11—C10	118.99 (12)	C18A—C20A—H20E	109.5
C12—C11—H11	121.2 (9)	H20D—C20A—H20E	109.5
C10—C11—H11	119.8 (9)	C18A—C20A—H20F	109.5
C11—C12—C13	118.62 (12)	H20D—C20A—H20F	109.5
C11—C12—H12	121.3 (9)	H20E—C20A—H20F	109.5
C13—C12—H12	120.0 (9)
C9—N2—C1—C2	142.39 (13)	N2—C9—C15—C16	8.7 (2)
C9—N2—C1—C6	−41.15 (18)	C8—C9—C15—C16	−164.78 (12)
C6—C1—C2—C3	1.20 (19)	C9—C15—C16—O2	−8.5 (2)
N2—C1—C2—C3	177.69 (12)	C19—C15—C16—O2	171.68 (16)
C1—C2—C3—C4	−0.2 (2)	C9—C15—C16—C17	168.60 (13)
C2—C3—C4—C5	−0.7 (2)	C19—C15—C16—C17	−11.2 (2)
C3—C4—C5—C6	0.5 (2)	O2—C16—C17—C18	177.40 (14)
C7—N1—C6—C5	−130.76 (13)	C15—C16—C17—C18	0.2 (2)
C7—N1—C6—C1	56.17 (17)	C16—C17—C18—O1	7.3 (2)
C4—C5—C6—N1	−172.95 (11)	C16—C17—C18—C20	−171.50 (15)
C4—C5—C6—C1	0.47 (17)	C19—O1—C18—C17	−3.3 (2)
C2—C1—C6—N1	171.90 (11)	C19—O1—C18—C20	175.62 (14)
N2—C1—C6—N1	−4.42 (18)	C18—O1—C19—O3	171.40 (14)
C2—C1—C6—C5	−1.32 (17)	C18—O1—C19—C15	−7.8 (2)
N2—C1—C6—C5	−177.64 (11)	C9—C15—C19—O3	16.0 (3)
C6—N1—C7—C8	−16.96 (16)	C16—C15—C19—O3	−164.19 (17)
C6—N1—C7—C10	107.08 (14)	C9—C15—C19—O1	−164.88 (14)
N1—C7—C8—C9	−63.01 (14)	C16—C15—C19—O1	14.9 (3)
C10—C7—C8—C9	171.80 (10)	N2—C9—C15A—C19A	32.4 (8)
C1—N2—C9—C15A	168.4 (6)	C8—C9—C15A—C19A	−157.9 (5)
C1—N2—C9—C15	−176.24 (12)	N2—C9—C15A—C16A	172.6 (5)
C1—N2—C9—C8	−2.34 (18)	C8—C9—C15A—C16A	−17.7 (8)
C7—C8—C9—N2	76.22 (14)	C9—C15A—C16A—O2A	37.2 (8)
C7—C8—C9—C15A	−93.7 (6)	C19A—C15A—C16A—O2A	172.9
C7—C8—C9—C15	−110.09 (14)	C9—C15A—C16A—C17A	−145.4 (8)
C14—N3—C10—C11	0.16 (18)	C19A—C15A—C16A—C17A	−9.7
C14—N3—C10—C7	178.97 (11)	O2A—C16A—C17A—C18A	177.2
N1—C7—C10—N3	−5.14 (15)	C15A—C16A—C17A—C18A	−0.3
C8—C7—C10—N3	118.93 (12)	C16A—C17A—C18A—O1A	6.5
N1—C7—C10—C11	173.71 (11)	C16A—C17A—C18A—C20A	−171.8
C8—C7—C10—C11	−62.22 (15)	C17A—C18A—O1A—C19A	−2.4
N3—C10—C11—C12	−0.56 (19)	C20A—C18A—O1A—C19A	176.1
C7—C10—C11—C12	−179.35 (11)	C18A—O1A—C19A—O3A	172.4
C10—C11—C12—C13	0.40 (19)	C18A—O1A—C19A—C15A	−7.6
C11—C12—C13—C14	0.11 (19)	C9—C15A—C19A—O3A	−27.6 (8)
C10—N3—C14—C13	0.40 (18)	C16A—C15A—C19A—O3A	−166.4
C12—C13—C14—N3	−0.54 (19)	C9—C15A—C19A—O1A	152.3 (8)
N2—C9—C15—C19	−171.57 (17)	C16A—C15A—C19A—O1A	13.5
C8—C9—C15—C19	15.0 (2)

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, y+1/2, −z+1/2; (v) −x, y−1/2, −z+1/2; (vi) x, y−1, z; (vii) −x+1, y+1/2, −z+1/2; (viii) x+1, y−1, z; (ix) −x+1, y−1/2, −z+1/2; (x) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2^iii	0.889 (18)	2.536 (18)	3.089 (2)	121.0 (14)
N2—H2A···O2	0.928 (18)	1.836 (18)	2.616 (2)	140.1 (15)
N2—H2A···O3A	0.928 (18)	1.58 (2)	2.382 (15)	142.0 (17)

Symmetry code: (iii) −x+1, −y+1, −z+1.