On the Hirshfeld surface for copper(II) atoms in different coordination environments

Copper(II) chemistry has always attracted interest owing to its rich coordination geometry. On the one hand, the variety of geometries that the copper(II) atom can adopt makes it a versatile metal with high applicability. On the other hand, the difficulties in controlling the copper(II) geometry may hinder its use in the design of molecules. To evaluate the use of Hirshfeld surfaces for obtaining information related to coordination geometry in copper(II) compounds, the behaviour of the surfaces generated for the copper(II) centres in different coordination environments is analysed. Structural details of four compounds were retrieved from the Cambridge Structural Database and analysed along with the crystal structure of a new compound, namely chloro-bis­(1,10-phenanthroline)copper(II) 2-carb­oxy-4-nitro­benzoate 4-nitro­phthalic acid dihydrate {[CuCl(C₁₂H₈N₂)₂]⁺(C₈H₄NO₆)⁻·C₈H₅NO₆·2H₂O}, here described. The obtained Hirshfeld surfaces behave differently according to the coordination environment, presenting different shapes and shape-related parameters. Furthermore, the curvature properties and fingerprint plots can be useful for evaluating the differences that might occur in the coordination environment.

Computing details

Data collection: CrysAlis PRO (Agilent Technologies, ); cell refinement: CrysAlis PRO (Agilent Technologies, ); data reduction: CrysAlis PRO (Agilent Technologies, ); program(s) used to refine structure: SHELXL2016/6 (Sheldrick, 2016).

(I)

Crystal data

C24H16ClCuN4·C8H4NO6·C8H5NO6·2(H2O)	Z = 2
Mr = 916.68	F(000) = 938
Triclinic, P1	Dx = 1.628 Mg m^−3
a = 10.6656 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.4599 (4) Å	Cell parameters from 9267 reflections
c = 14.7567 (5) Å	θ = 2.7–29.1°
α = 98.635 (3)°	µ = 0.74 mm^−1
β = 101.650 (3)°	T = 150 K
γ = 97.962 (3)°	Prism, green
V = 1869.79 (11) Å^3	0.16 × 0.14 × 0.04 mm

Data collection

Xcalibur, Atlas, Gemini ultra diffractometer	7652 independent reflections
Radiation source: fine-focus sealed X-ray tube	6228 reflections with I > 2σ(I)
Detector resolution: 10.4186 pixels mm^-1	Rint = 0.047
ω scans	θmax = 26.4°, θmin = 2.4°
Absorption correction: multi-scan CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.	h = −13→13
Tmin = 0.872, Tmax = 1.000	k = −15→15
30117 measured reflections	l = −18→18

Refinement

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.062	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.146	w = 1/[σ^2(Fo^2) + (0.0465P)^2 + 5.4285P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
7652 reflections	Δρmax = 2.66 e Å^−3
574 parameters	Δρmin = −0.96 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Cu1	0.80693 (5)	0.59291 (4)	0.72850 (3)	0.02945 (14)
Cl1	0.65710 (11)	0.44407 (8)	0.64770 (9)	0.0453 (3)
N1	0.9206 (3)	0.6624 (2)	0.6371 (2)	0.0235 (6)
N2	0.9477 (3)	0.5012 (2)	0.7378 (2)	0.0315 (7)
N3	0.6759 (3)	0.6933 (2)	0.7280 (2)	0.0272 (7)
N4	0.8866 (3)	0.6936 (2)	0.8594 (2)	0.0268 (7)
N5	0.7191 (3)	0.4503 (3)	0.9373 (2)	0.0292 (7)
N6	0.4294 (3)	0.2271 (3)	0.6050 (3)	0.0375 (8)
O1	0.6939 (3)	0.7840 (2)	1.14046 (19)	0.0417 (7)
O2	0.5215 (3)	0.8558 (2)	1.09077 (19)	0.0366 (7)
O3	0.3435 (3)	0.8260 (3)	0.9576 (2)	0.0537 (9)
H3A	0.401765	0.830720	1.004492	0.081*
O4	0.2514 (3)	0.7049 (2)	0.8308 (2)	0.0413 (7)
O5	0.6863 (3)	0.3581 (2)	0.8892 (2)	0.0443 (7)
O6	0.8243 (3)	0.4833 (3)	0.9911 (2)	0.0456 (8)
O7	0.7003 (3)	0.0488 (3)	0.40834 (19)	0.0391 (7)
H7A	0.730298	0.017343	0.366822	0.059*
O8	0.8236 (3)	−0.0403 (3)	0.4995 (2)	0.0481 (8)
O9	0.9796 (3)	0.0931 (2)	0.6693 (2)	0.0418 (7)
H9	1.045233	0.065765	0.681651	0.063*
O10	0.8888 (3)	−0.0446 (2)	0.7309 (2)	0.0442 (7)
O11	0.3919 (3)	0.2415 (3)	0.5241 (2)	0.0539 (9)
O12	0.3815 (3)	0.2596 (3)	0.6703 (2)	0.0537 (9)
O13	0.7923 (3)	−0.0385 (2)	0.27223 (18)	0.0332 (6)
O14	0.1201 (3)	0.8826 (2)	0.8133 (2)	0.0438 (7)
C1	0.9062 (4)	0.7415 (3)	0.5861 (3)	0.0272 (8)
H1	0.840075	0.781763	0.591692	0.033*
C2	0.9854 (4)	0.7669 (3)	0.5246 (3)	0.0306 (8)
H2	0.972249	0.823296	0.490860	0.037*
C3	1.0823 (4)	0.7078 (3)	0.5146 (3)	0.0308 (8)
H3	1.134876	0.722901	0.473330	0.037*
C4	1.1017 (3)	0.6236 (3)	0.5676 (2)	0.0247 (7)
C5	1.0187 (3)	0.6049 (3)	0.6277 (2)	0.0231 (7)
C6	1.1991 (4)	0.5561 (3)	0.5604 (3)	0.0296 (8)
H6	1.253783	0.567891	0.519724	0.036*
C7	1.2126 (4)	0.4756 (3)	0.6119 (3)	0.0299 (8)
H7	1.276958	0.433285	0.606425	0.036*
C8	1.0326 (4)	0.5189 (3)	0.6822 (2)	0.0247 (7)
C9	1.1300 (4)	0.4543 (3)	0.6743 (2)	0.0267 (8)
C10	1.1389 (4)	0.3714 (3)	0.7288 (3)	0.0343 (9)
H10	1.202422	0.327489	0.726363	0.041*
C11	1.0543 (4)	0.3554 (3)	0.7853 (3)	0.0383 (10)
H11	1.060338	0.301082	0.822125	0.046*
C12	0.9582 (5)	0.4210 (3)	0.7879 (3)	0.0398 (10)
H12	0.899845	0.408177	0.825710	0.048*
C13	0.5683 (4)	0.6883 (3)	0.6631 (3)	0.0378 (9)
H13	0.548730	0.633157	0.609805	0.045*
C14	0.4837 (4)	0.7627 (4)	0.6720 (3)	0.0407 (10)
H14	0.408685	0.756449	0.625332	0.049*
C15	0.5104 (4)	0.8445 (3)	0.7486 (3)	0.0374 (10)
H15	0.454336	0.894763	0.754218	0.045*
C16	0.6235 (4)	0.8530 (3)	0.8194 (3)	0.0289 (8)
C17	0.7030 (3)	0.7741 (3)	0.8055 (3)	0.0245 (7)
C18	0.6595 (4)	0.9340 (3)	0.9035 (3)	0.0343 (9)
H18	0.607032	0.986510	0.912796	0.041*
C19	0.7677 (4)	0.9364 (3)	0.9698 (3)	0.0358 (9)
H19	0.788762	0.990534	1.023782	0.043*
C20	0.8171 (3)	0.7755 (3)	0.8762 (2)	0.0243 (7)
C21	0.8508 (4)	0.8565 (3)	0.9582 (3)	0.0286 (8)
C22	0.9629 (4)	0.8503 (4)	1.0250 (3)	0.0380 (9)
H22	0.989033	0.901191	1.081122	0.046*
C23	1.0330 (4)	0.7692 (4)	1.0069 (3)	0.0388 (10)
H23	1.108437	0.765864	1.050111	0.047*
C24	0.9921 (4)	0.6915 (3)	0.9241 (3)	0.0347 (9)
H24	1.040345	0.636014	0.913708	0.042*
C25	0.5934 (4)	0.7833 (3)	1.0821 (3)	0.0274 (8)
C26	0.5566 (3)	0.6900 (3)	0.9963 (2)	0.0232 (7)
C27	0.6442 (3)	0.6169 (3)	0.9987 (2)	0.0238 (7)
H27	0.716872	0.629574	1.048410	0.029*
C28	0.6247 (3)	0.5264 (3)	0.9289 (2)	0.0240 (7)
C29	0.5211 (4)	0.5043 (3)	0.8522 (3)	0.0269 (8)
H29	0.509741	0.442906	0.805014	0.032*
C30	0.4346 (3)	0.5774 (3)	0.8483 (3)	0.0264 (8)
H30	0.364398	0.564802	0.796818	0.032*
C31	0.4485 (3)	0.6697 (3)	0.9189 (2)	0.0230 (7)
C32	0.3396 (4)	0.7378 (3)	0.9003 (3)	0.0292 (8)
C33	0.7497 (3)	0.0223 (3)	0.4886 (3)	0.0259 (8)
C34	0.6994 (4)	0.0778 (3)	0.5686 (3)	0.0265 (8)
C35	0.5912 (3)	0.1274 (3)	0.5499 (3)	0.0266 (8)
H35	0.552602	0.131786	0.488412	0.032*
C36	0.5413 (4)	0.1707 (3)	0.6248 (3)	0.0314 (8)
C37	0.5912 (4)	0.1631 (3)	0.7158 (3)	0.0361 (9)
H37	0.552887	0.189550	0.764013	0.043*
C38	0.7008 (4)	0.1147 (3)	0.7341 (3)	0.0349 (9)
H38	0.737174	0.109215	0.795699	0.042*
C39	0.7574 (4)	0.0741 (3)	0.6620 (3)	0.0279 (8)
C40	0.8824 (4)	0.0323 (3)	0.6893 (3)	0.0316 (9)
H13A	0.809 (4)	0.012 (2)	0.242 (2)	0.050*
H13B	0.752 (4)	−0.094 (2)	0.2307 (19)	0.050*
H14A	0.0435 (18)	0.868 (3)	0.779 (3)	0.050*
H14B	0.147 (3)	0.8214 (16)	0.812 (3)	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0365 (3)	0.0218 (2)	0.0344 (3)	0.01380 (19)	0.0124 (2)	0.00493 (18)
Cl1	0.0456 (6)	0.0267 (5)	0.0617 (7)	−0.0020 (4)	0.0200 (5)	−0.0012 (5)
N1	0.0255 (15)	0.0179 (14)	0.0250 (15)	0.0060 (12)	0.0020 (12)	0.0005 (11)
N2	0.047 (2)	0.0222 (16)	0.0346 (18)	0.0181 (14)	0.0190 (16)	0.0084 (13)
N3	0.0306 (17)	0.0239 (16)	0.0284 (16)	0.0085 (13)	0.0064 (13)	0.0060 (12)
N4	0.0276 (16)	0.0281 (16)	0.0307 (16)	0.0150 (13)	0.0107 (13)	0.0090 (13)
N5	0.0344 (18)	0.0272 (17)	0.0332 (17)	0.0146 (14)	0.0149 (15)	0.0103 (14)
N6	0.0267 (17)	0.0346 (19)	0.052 (2)	0.0063 (14)	0.0120 (17)	0.0044 (16)
O1	0.0488 (18)	0.0384 (16)	0.0301 (15)	0.0198 (14)	−0.0084 (13)	−0.0056 (12)
O2	0.0417 (16)	0.0337 (15)	0.0333 (15)	0.0218 (13)	0.0037 (13)	−0.0049 (12)
O3	0.048 (2)	0.054 (2)	0.050 (2)	0.0371 (16)	−0.0129 (15)	−0.0102 (16)
O4	0.0310 (15)	0.0471 (18)	0.0409 (17)	0.0171 (13)	−0.0064 (13)	0.0033 (13)
O5	0.0484 (18)	0.0277 (15)	0.059 (2)	0.0181 (13)	0.0160 (15)	−0.0022 (14)
O6	0.0360 (17)	0.0437 (18)	0.0537 (19)	0.0233 (14)	−0.0035 (15)	0.0016 (14)
O7	0.0406 (16)	0.0513 (18)	0.0278 (14)	0.0229 (14)	0.0068 (13)	0.0025 (13)
O8	0.068 (2)	0.0463 (18)	0.0363 (16)	0.0354 (17)	0.0102 (15)	0.0045 (14)
O9	0.0322 (16)	0.0346 (16)	0.063 (2)	0.0118 (13)	0.0118 (15)	0.0147 (14)
O10	0.0450 (18)	0.0430 (18)	0.0487 (18)	0.0165 (14)	0.0037 (14)	0.0228 (15)
O11	0.0344 (17)	0.074 (2)	0.052 (2)	0.0242 (16)	0.0008 (15)	0.0077 (17)
O12	0.0471 (19)	0.059 (2)	0.066 (2)	0.0268 (16)	0.0304 (17)	0.0074 (17)
O13	0.0327 (15)	0.0352 (15)	0.0276 (14)	0.0095 (12)	0.0002 (12)	−0.0018 (11)
O14	0.0399 (17)	0.0450 (18)	0.0449 (18)	0.0177 (14)	−0.0043 (14)	0.0129 (14)
C1	0.0289 (19)	0.0209 (18)	0.0291 (19)	0.0088 (15)	−0.0010 (15)	0.0025 (14)
C2	0.035 (2)	0.0217 (18)	0.033 (2)	0.0042 (16)	−0.0002 (17)	0.0080 (15)
C3	0.032 (2)	0.028 (2)	0.030 (2)	0.0009 (16)	0.0056 (16)	0.0041 (15)
C4	0.0234 (18)	0.0216 (17)	0.0245 (18)	0.0036 (14)	−0.0014 (14)	−0.0011 (14)
C5	0.0253 (18)	0.0181 (16)	0.0222 (17)	0.0063 (14)	0.0001 (14)	−0.0026 (13)
C6	0.0260 (19)	0.030 (2)	0.0280 (19)	0.0029 (15)	0.0032 (15)	−0.0031 (15)
C7	0.0275 (19)	0.029 (2)	0.031 (2)	0.0132 (16)	0.0017 (16)	−0.0038 (15)
C8	0.0307 (19)	0.0176 (17)	0.0245 (18)	0.0084 (14)	0.0039 (15)	−0.0011 (13)
C9	0.033 (2)	0.0214 (18)	0.0241 (18)	0.0123 (15)	0.0014 (15)	−0.0018 (14)
C10	0.044 (2)	0.028 (2)	0.034 (2)	0.0212 (18)	0.0066 (18)	0.0021 (16)
C11	0.057 (3)	0.029 (2)	0.038 (2)	0.0239 (19)	0.016 (2)	0.0125 (17)
C12	0.056 (3)	0.032 (2)	0.046 (2)	0.025 (2)	0.029 (2)	0.0156 (19)
C13	0.041 (2)	0.032 (2)	0.037 (2)	0.0049 (18)	0.0011 (19)	0.0077 (17)
C14	0.028 (2)	0.042 (2)	0.051 (3)	0.0063 (18)	−0.0032 (19)	0.020 (2)
C15	0.029 (2)	0.036 (2)	0.056 (3)	0.0160 (17)	0.0131 (19)	0.023 (2)
C16	0.0290 (19)	0.0255 (19)	0.041 (2)	0.0129 (15)	0.0155 (17)	0.0149 (16)
C17	0.0282 (19)	0.0201 (17)	0.0289 (19)	0.0091 (14)	0.0096 (15)	0.0072 (14)
C18	0.042 (2)	0.0239 (19)	0.046 (2)	0.0180 (17)	0.022 (2)	0.0069 (17)
C19	0.054 (3)	0.0224 (19)	0.035 (2)	0.0140 (18)	0.016 (2)	0.0017 (16)
C20	0.0294 (19)	0.0229 (18)	0.0256 (18)	0.0110 (15)	0.0111 (15)	0.0072 (14)
C21	0.033 (2)	0.0286 (19)	0.0268 (19)	0.0075 (16)	0.0102 (16)	0.0070 (15)
C22	0.045 (2)	0.038 (2)	0.028 (2)	0.0023 (19)	0.0048 (18)	0.0067 (17)
C23	0.030 (2)	0.052 (3)	0.037 (2)	0.0120 (19)	0.0030 (18)	0.017 (2)
C24	0.031 (2)	0.042 (2)	0.040 (2)	0.0185 (18)	0.0131 (18)	0.0165 (18)
C25	0.0291 (19)	0.0273 (19)	0.0260 (19)	0.0086 (15)	0.0061 (16)	0.0024 (15)
C26	0.0259 (18)	0.0240 (18)	0.0222 (17)	0.0107 (14)	0.0061 (14)	0.0050 (14)
C27	0.0240 (18)	0.0269 (18)	0.0215 (17)	0.0089 (15)	0.0027 (14)	0.0067 (14)
C28	0.0269 (18)	0.0219 (17)	0.0284 (18)	0.0095 (14)	0.0111 (15)	0.0093 (14)
C29	0.032 (2)	0.0233 (18)	0.0253 (18)	0.0031 (15)	0.0102 (16)	0.0010 (14)
C30	0.0247 (18)	0.0288 (19)	0.0240 (18)	0.0050 (15)	0.0023 (15)	0.0038 (15)
C31	0.0235 (18)	0.0241 (18)	0.0239 (18)	0.0084 (14)	0.0061 (14)	0.0073 (14)
C32	0.0272 (19)	0.032 (2)	0.033 (2)	0.0124 (16)	0.0078 (17)	0.0107 (16)
C33	0.0252 (18)	0.0201 (17)	0.0287 (19)	0.0046 (14)	−0.0008 (15)	0.0013 (14)
C34	0.0268 (18)	0.0207 (18)	0.0304 (19)	0.0029 (14)	0.0052 (15)	0.0024 (14)
C35	0.0243 (18)	0.0217 (18)	0.0297 (19)	0.0021 (14)	0.0019 (15)	0.0001 (14)
C36	0.029 (2)	0.0249 (19)	0.042 (2)	0.0056 (16)	0.0119 (17)	0.0050 (16)
C37	0.045 (2)	0.029 (2)	0.038 (2)	0.0077 (18)	0.0189 (19)	0.0024 (17)
C38	0.040 (2)	0.034 (2)	0.030 (2)	0.0073 (18)	0.0057 (18)	0.0057 (17)
C39	0.032 (2)	0.0191 (17)	0.031 (2)	0.0055 (15)	0.0027 (16)	0.0039 (14)
C40	0.038 (2)	0.029 (2)	0.0249 (19)	0.0094 (17)	0.0005 (16)	0.0009 (15)

Geometric parameters (Å, º)

Cu1—N3	1.999 (3)	C7—C9	1.425 (6)
Cu1—N2	2.004 (3)	C8—C9	1.413 (5)
Cu1—N4	2.083 (3)	C9—C10	1.404 (5)
Cu1—N1	2.181 (3)	C10—C11	1.362 (6)
Cu1—Cl1	2.2716 (12)	C11—C12	1.399 (5)
N1—C1	1.333 (4)	C13—C14	1.391 (6)
N1—C5	1.365 (4)	C14—C15	1.357 (6)
N2—C12	1.333 (5)	C15—C16	1.407 (6)
N2—C8	1.356 (5)	C16—C17	1.403 (5)
N3—C13	1.326 (5)	C16—C18	1.425 (6)
N3—C17	1.358 (5)	C17—C20	1.430 (5)
N4—C24	1.327 (5)	C18—C19	1.348 (6)
N4—C20	1.364 (4)	C19—C21	1.435 (5)
N5—O6	1.214 (4)	C20—C21	1.404 (5)
N5—O5	1.221 (4)	C21—C22	1.407 (6)
N5—C28	1.475 (4)	C22—C23	1.364 (6)
N6—O12	1.222 (4)	C23—C24	1.391 (6)
N6—O11	1.228 (5)	C25—C26	1.530 (5)
N6—C36	1.469 (5)	C26—C27	1.392 (5)
O1—C25	1.230 (5)	C26—C31	1.413 (5)
O2—C25	1.272 (4)	C27—C28	1.370 (5)
O3—C32	1.272 (5)	C28—C29	1.377 (5)
O4—C32	1.217 (5)	C29—C30	1.382 (5)
O7—C33	1.305 (4)	C30—C31	1.400 (5)
O8—C33	1.188 (4)	C31—C32	1.536 (5)
O9—C40	1.307 (5)	C33—C34	1.508 (5)
O10—C40	1.214 (5)	C34—C35	1.382 (5)
C1—C2	1.400 (6)	C34—C39	1.401 (5)
C2—C3	1.368 (5)	C35—C36	1.391 (5)
C3—C4	1.413 (5)	C36—C37	1.364 (6)
C4—C5	1.394 (5)	C37—C38	1.386 (6)
C4—C6	1.435 (5)	C38—C39	1.391 (5)
C5—C8	1.440 (5)	C39—C40	1.501 (5)
C6—C7	1.353 (5)
N3—Cu1—N2	175.33 (14)	C17—C16—C18	119.0 (3)
N3—Cu1—N4	81.03 (12)	C15—C16—C18	124.3 (3)
N2—Cu1—N4	94.45 (12)	N3—C17—C16	123.2 (3)
N3—Cu1—N1	100.14 (12)	N3—C17—C20	117.2 (3)
N2—Cu1—N1	79.70 (12)	C16—C17—C20	119.6 (3)
N4—Cu1—N1	103.22 (11)	C19—C18—C16	121.6 (3)
N3—Cu1—Cl1	93.50 (10)	C18—C19—C21	120.9 (4)
N2—Cu1—Cl1	90.89 (10)	N4—C20—C21	123.5 (3)
N4—Cu1—Cl1	145.50 (9)	N4—C20—C17	116.2 (3)
N1—Cu1—Cl1	111.26 (8)	C21—C20—C17	120.3 (3)
C1—N1—C5	116.9 (3)	C20—C21—C22	116.6 (3)
C1—N1—Cu1	132.8 (2)	C20—C21—C19	118.6 (3)
C5—N1—Cu1	110.1 (2)	C22—C21—C19	124.8 (4)
C12—N2—C8	118.6 (3)	C23—C22—C21	119.5 (4)
C12—N2—Cu1	125.7 (3)	C22—C23—C24	120.2 (4)
C8—N2—Cu1	115.5 (2)	N4—C24—C23	122.4 (4)
C13—N3—C17	118.2 (3)	O1—C25—O2	122.8 (3)
C13—N3—Cu1	127.9 (3)	O1—C25—C26	117.0 (3)
C17—N3—Cu1	114.0 (2)	O2—C25—C26	120.1 (3)
C24—N4—C20	117.8 (3)	C27—C26—C31	118.3 (3)
C24—N4—Cu1	130.6 (3)	C27—C26—C25	112.7 (3)
C20—N4—Cu1	111.5 (2)	C31—C26—C25	129.0 (3)
O6—N5—O5	124.1 (3)	C28—C27—C26	120.8 (3)
O6—N5—C28	118.1 (3)	C27—C28—C29	122.5 (3)
O5—N5—C28	117.7 (3)	C27—C28—N5	118.1 (3)
O12—N6—O11	124.0 (4)	C29—C28—N5	119.4 (3)
O12—N6—C36	118.1 (4)	C28—C29—C30	117.1 (3)
O11—N6—C36	117.9 (3)	C29—C30—C31	122.6 (3)
N1—C1—C2	123.4 (3)	C30—C31—C26	118.7 (3)
C3—C2—C1	119.2 (3)	C30—C31—C32	113.3 (3)
C2—C3—C4	119.4 (4)	C26—C31—C32	128.0 (3)
C5—C4—C3	117.2 (3)	O4—C32—O3	122.0 (3)
C5—C4—C6	119.6 (3)	O4—C32—C31	118.5 (3)
C3—C4—C6	123.2 (4)	O3—C32—C31	119.5 (3)
N1—C5—C4	123.8 (3)	O8—C33—O7	125.4 (4)
N1—C5—C8	116.6 (3)	O8—C33—C34	122.2 (3)
C4—C5—C8	119.6 (3)	O7—C33—C34	112.4 (3)
C7—C6—C4	120.9 (4)	C35—C34—C39	119.6 (3)
C6—C7—C9	121.3 (3)	C35—C34—C33	119.9 (3)
N2—C8—C9	122.4 (3)	C39—C34—C33	120.4 (3)
N2—C8—C5	117.9 (3)	C34—C35—C36	118.6 (3)
C9—C8—C5	119.7 (3)	C37—C36—C35	123.1 (4)
C10—C9—C8	117.2 (3)	C37—C36—N6	118.4 (4)
C10—C9—C7	123.7 (3)	C35—C36—N6	118.5 (4)
C8—C9—C7	119.1 (3)	C36—C37—C38	117.8 (4)
C11—C10—C9	119.8 (3)	C37—C38—C39	121.2 (4)
C10—C11—C12	119.8 (4)	C38—C39—C34	119.5 (3)
N2—C12—C11	122.2 (4)	C38—C39—C40	117.4 (3)
N3—C13—C14	122.2 (4)	C34—C39—C40	123.0 (3)
C15—C14—C13	120.2 (4)	O10—C40—O9	126.4 (4)
C14—C15—C16	119.6 (4)	O10—C40—C39	121.6 (4)
C17—C16—C15	116.6 (4)	O9—C40—C39	111.8 (3)