1,10-Phenanthrolinium 4-chloro-2-hydroxy-benzoate-1,10-phenanthroline-4-chloro-2-hydroxy-benzoic acid (1/1/1).

The title compound, C(12)H(9)N(2) (+)·C(7)H(4)ClO(3) (-)·C(12)H(8)N(2)·C(7)H(5)ClO(3), contains one phenanthrolinium (Hphen) cation, one phenanthroline (phen) mol-ecule, one 4-chloro-2-hydroxy-benzoate anion (hcba) and one 4-chloro-2-hydroxy-benzoic acid (Hhcba) mol-ecule in the asymmetric unit. The phen mol-ecule is approximately parallel to Hphen, making a dihedral angle of 1.98 (6)°. The centroid-centroid distance between pyridine rings of adjacent phen and Hphen species is 3.7718 (15) Å, and that between the benzene and pyridine rings of adjacent phen and Hphen species is 3.7922 (16) Å, indicative of π-π stacking inter-actions. The crystal structure contains an extensive network of classical (O-H⋯O, N-H⋯N and O-H⋯Cl) and weak (C-H⋯O and C-H⋯N) hydrogen bonds. Finally, C-H⋯π inter-actions are seen between Hphen and hcba and between phen and Hhcba in the crystal structure. The hydroxy group of the anion is disordered over the two sites ortho to the carboxylate group in a 0.75:0.25 ratio.

Related literature

For general background, see: Su & Xu (2004 ▶); Pan et al. (2006 ▶). For a related structure, see: Fu et al. (2005 ▶).

Experimental

Crystal data

C12H9N2 +·C7H4ClO3 −·C12H8N2·C7H5ClO3

M = 705.53

Orthorhombic,

a = 8.0627 (6) Å

b = 19.6005 (15) Å

c = 20.7929 (17) Å

V = 3286.0 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.25 mm−1

T = 295 (2) K

0.43 × 0.37 × 0.32 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: none

37126 measured reflections

6394 independent reflections

4326 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.098

S = 0.98

6394 reflections

460 parameters

H-atom parameters constrained

Δρmax = 0.24 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Flack (1983 ▶), 2739 Friedel pairs

Flack parameter: −0.09 (5)

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808015110/hb2735sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015110/hb2735Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H9N2+·C7H4ClO3–·C12H8N2·C7H5ClO3	F000 = 1456
Mr = 705.53	Dx = 1.426 Mg m−3
Orthorhombic, P212121	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3820 reflections
a = 8.0627 (6) Å	θ = 2.0–25.0º
b = 19.6005 (15) Å	µ = 0.25 mm−1
c = 20.7929 (17) Å	T = 295 (2) K
V = 3286.0 (4) Å3	Chunk, red brown
Z = 4	0.43 × 0.37 × 0.32 mm

Rigaku R-AXIS RAPID IP diffractometer	6394 independent reflections
Radiation source: fine-focus sealed tube	4326 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.054
Detector resolution: 10.00 pixels mm-1	θmax = 26.0º
T = 295(2) K	θmin = 1.4º
ω scans	h = −9→9
Absorption correction: none	k = −24→24
37126 measured reflections	l = −23→24

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039	w = 1/[σ2(Fo2) + (0.051P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.098	(Δ/σ)max < 0.001
S = 0.98	Δρmax = 0.24 e Å−3
6394 reflections	Δρmin = −0.14 e Å−3
460 parameters	Extinction correction: none
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 2739 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.09 (5)

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cl1	−0.36861 (10)	0.67865 (4)	0.46601 (4)	0.0854 (2)
Cl2	1.02809 (9)	0.33001 (4)	0.13135 (4)	0.0900 (3)
N1	0.7137 (3)	0.28257 (9)	0.44997 (10)	0.0559 (5)
H1N	0.6923	0.2791	0.4897	0.084*
N2	0.5485 (3)	0.38638 (10)	0.51279 (11)	0.0633 (6)
N3	0.2373 (3)	0.26039 (11)	0.41612 (11)	0.0681 (6)
N4	0.0909 (3)	0.36501 (10)	0.48502 (10)	0.0666 (6)
O1	0.1928 (2)	0.60893 (10)	0.24138 (10)	0.0753 (5)
H1A	0.2861	0.5960	0.2236	0.113*
O2	0.3673 (3)	0.63537 (12)	0.32124 (11)	0.0952 (7)
O3	0.2480 (2)	0.66890 (12)	0.43318 (11)	0.0951 (6)
H3A	0.3418	0.6628	0.4062	0.143*
O4	0.2843 (2)	0.47959 (10)	0.15141 (10)	0.0746 (5)
O5	0.4445 (2)	0.56412 (9)	0.18697 (9)	0.0726 (5)
C1	0.0776 (3)	0.64335 (12)	0.33999 (13)	0.0547 (6)
C2	0.0958 (3)	0.66070 (12)	0.40499 (14)	0.0611 (7)
C3	−0.0418 (3)	0.67074 (13)	0.44405 (13)	0.0626 (7)
H3	−0.0291	0.6810	0.4874	0.075*
C4	−0.1972 (3)	0.66515 (12)	0.41731 (13)	0.0594 (7)
C5	−0.2199 (3)	0.64899 (13)	0.35319 (14)	0.0648 (7)
H5	−0.3261	0.6457	0.3360	0.078*
C6	−0.0819 (3)	0.63782 (13)	0.31511 (13)	0.0594 (7)
H6	−0.0961	0.6264	0.2720	0.071*
C7	0.2243 (4)	0.62942 (13)	0.30020 (16)	0.0648 (7)
C8	0.5737 (3)	0.46147 (12)	0.15467 (10)	0.0501 (6)
C9	0.5603 (3)	0.39317 (13)	0.13526 (12)	0.0595 (6)
H9	0.4564	0.3747	0.1267	0.071*	0.25
C10	0.7005 (3)	0.35299 (13)	0.12879 (13)	0.0656 (7)
H10	0.6912	0.3074	0.1168	0.079*
C11	0.8526 (3)	0.38097 (12)	0.14023 (13)	0.0589 (6)
C12	0.8724 (3)	0.44813 (13)	0.15866 (12)	0.0569 (6)
H12	0.9773	0.4663	0.1660	0.068*
C13	0.7316 (3)	0.48752 (13)	0.16586 (12)	0.0538 (6)
H13	0.7426	0.5328	0.1786	0.065*	0.75
C14	0.4216 (3)	0.50398 (14)	0.16457 (12)	0.0581 (7)
C21	0.7978 (4)	0.23170 (13)	0.42364 (13)	0.0662 (7)
H21	0.8293	0.1946	0.4487	0.079*
C22	0.8394 (3)	0.23341 (14)	0.35891 (15)	0.0700 (8)
H22	0.8981	0.1977	0.3403	0.084*
C23	0.7924 (4)	0.28875 (15)	0.32288 (13)	0.0673 (7)
H23	0.8182	0.2901	0.2793	0.081*
C24	0.7056 (3)	0.34341 (12)	0.35095 (12)	0.0560 (6)
C25	0.6560 (4)	0.40270 (15)	0.31662 (14)	0.0722 (8)
H25	0.6798	0.4059	0.2730	0.087*
C26	0.5762 (4)	0.45383 (15)	0.34530 (15)	0.0740 (8)
H26	0.5459	0.4920	0.3214	0.089*
C27	0.5366 (3)	0.45098 (12)	0.41213 (14)	0.0618 (7)
C28	0.4538 (4)	0.50332 (13)	0.44537 (19)	0.0791 (9)
H28	0.4206	0.5424	0.4236	0.095*
C29	0.4222 (4)	0.49694 (14)	0.50952 (18)	0.0839 (9)
H29	0.3688	0.5317	0.5318	0.101*
C30	0.4707 (4)	0.43793 (14)	0.54105 (15)	0.0779 (8)
H30	0.4472	0.4342	0.5847	0.093*
C31	0.5796 (3)	0.39333 (11)	0.44856 (12)	0.0520 (6)
C32	0.6662 (3)	0.33901 (11)	0.41681 (11)	0.0490 (6)
C33	0.3118 (4)	0.21255 (15)	0.38143 (17)	0.0835 (10)
H33	0.3379	0.1717	0.4019	0.100*
C34	0.3539 (4)	0.21872 (16)	0.31680 (16)	0.0803 (9)
H34	0.4077	0.1834	0.2954	0.096*
C35	0.3145 (4)	0.27756 (15)	0.28567 (15)	0.0737 (8)
H35	0.3409	0.2831	0.2424	0.088*
C36	0.2336 (3)	0.32990 (13)	0.31938 (12)	0.0565 (6)
C37	0.1823 (3)	0.39218 (13)	0.28871 (13)	0.0646 (7)
H37	0.2046	0.3987	0.2453	0.077*
C38	0.1031 (4)	0.44091 (13)	0.32165 (12)	0.0651 (7)
H38	0.0716	0.4807	0.3006	0.078*
C39	0.0659 (3)	0.43319 (11)	0.38807 (11)	0.0537 (6)
C40	−0.0182 (3)	0.48382 (13)	0.42393 (14)	0.0649 (7)
H40	−0.0584	0.5227	0.4036	0.078*
C41	−0.0399 (4)	0.47545 (13)	0.48783 (15)	0.0730 (8)
H41	−0.0913	0.5091	0.5122	0.088*
C42	0.0156 (4)	0.41596 (15)	0.51631 (14)	0.0760 (9)
H42	−0.0005	0.4110	0.5603	0.091*
C43	0.1165 (3)	0.37377 (11)	0.42085 (11)	0.0522 (6)
C44	0.1987 (3)	0.31975 (12)	0.38519 (11)	0.0532 (6)
O6A	0.4152 (3)	0.36325 (13)	0.12245 (13)	0.0825 (8)	0.75
H6A	0.3325	0.3958	0.1317	0.124*	0.75
O6B	0.7525 (8)	0.5525 (3)	0.1865 (4)	0.0664 (19)	0.25
H6B	0.6650	0.5674	0.2002	0.100*	0.25

	U11	U22	U33	U12	U13	U23
Cl1	0.0676 (4)	0.0996 (5)	0.0890 (6)	−0.0008 (4)	0.0144 (4)	−0.0178 (4)
Cl2	0.0706 (5)	0.0762 (5)	0.1232 (7)	0.0177 (4)	−0.0119 (4)	−0.0287 (5)
N1	0.0713 (13)	0.0502 (11)	0.0463 (12)	0.0009 (10)	0.0083 (11)	0.0075 (9)
N2	0.0744 (16)	0.0533 (12)	0.0623 (15)	−0.0072 (11)	0.0111 (12)	−0.0037 (11)
N3	0.0927 (18)	0.0526 (12)	0.0590 (14)	0.0024 (12)	−0.0153 (13)	0.0074 (11)
N4	0.0941 (18)	0.0588 (12)	0.0469 (14)	−0.0156 (12)	−0.0046 (12)	0.0017 (10)
O1	0.0561 (11)	0.0960 (13)	0.0736 (14)	0.0172 (10)	0.0067 (10)	0.0066 (11)
O2	0.0512 (12)	0.1293 (18)	0.1050 (17)	0.0025 (12)	0.0000 (12)	−0.0156 (14)
O3	0.0612 (13)	0.1030 (15)	0.1212 (18)	0.0034 (12)	−0.0074 (12)	−0.0249 (14)
O4	0.0514 (11)	0.0909 (14)	0.0816 (14)	−0.0026 (10)	−0.0025 (10)	0.0044 (10)
O5	0.0605 (12)	0.0680 (12)	0.0893 (14)	0.0038 (10)	0.0147 (10)	−0.0033 (10)
C1	0.0466 (14)	0.0511 (13)	0.0666 (18)	0.0076 (11)	−0.0001 (13)	0.0036 (12)
C2	0.0502 (16)	0.0534 (14)	0.0796 (19)	−0.0007 (12)	−0.0112 (14)	−0.0017 (13)
C3	0.0628 (18)	0.0589 (14)	0.0660 (17)	−0.0047 (13)	−0.0036 (14)	−0.0064 (13)
C4	0.0600 (16)	0.0477 (13)	0.0705 (19)	0.0023 (12)	0.0074 (14)	−0.0026 (13)
C5	0.0496 (15)	0.0712 (17)	0.074 (2)	0.0037 (13)	−0.0044 (14)	0.0064 (14)
C6	0.0514 (16)	0.0653 (15)	0.0615 (16)	0.0066 (12)	−0.0045 (13)	0.0048 (13)
C7	0.0534 (18)	0.0607 (16)	0.080 (2)	0.0092 (13)	−0.0016 (16)	0.0094 (14)
C8	0.0544 (15)	0.0584 (14)	0.0376 (13)	−0.0047 (12)	0.0013 (11)	0.0080 (10)
C9	0.0557 (16)	0.0701 (16)	0.0525 (16)	−0.0088 (14)	−0.0026 (13)	−0.0023 (13)
C10	0.0682 (18)	0.0590 (15)	0.0695 (18)	−0.0043 (14)	−0.0047 (15)	−0.0086 (13)
C11	0.0594 (16)	0.0622 (15)	0.0551 (16)	0.0072 (13)	−0.0017 (13)	−0.0042 (12)
C12	0.0500 (14)	0.0604 (15)	0.0602 (16)	−0.0021 (12)	−0.0011 (12)	0.0003 (12)
C13	0.0563 (16)	0.0549 (14)	0.0502 (16)	−0.0038 (12)	0.0023 (12)	0.0025 (11)
C14	0.0563 (17)	0.0699 (17)	0.0481 (16)	−0.0007 (14)	0.0084 (13)	0.0161 (13)
C21	0.0786 (19)	0.0538 (15)	0.066 (2)	0.0058 (14)	0.0056 (16)	0.0057 (13)
C22	0.0707 (19)	0.0711 (17)	0.068 (2)	0.0066 (14)	0.0054 (15)	−0.0076 (15)
C23	0.0681 (17)	0.087 (2)	0.0469 (16)	−0.0143 (16)	0.0028 (14)	−0.0019 (14)
C24	0.0586 (15)	0.0609 (15)	0.0486 (16)	−0.0076 (12)	−0.0043 (12)	0.0065 (12)
C25	0.080 (2)	0.084 (2)	0.0525 (17)	−0.0113 (17)	−0.0129 (15)	0.0186 (15)
C26	0.079 (2)	0.0660 (17)	0.077 (2)	−0.0018 (16)	−0.0179 (17)	0.0259 (16)
C27	0.0569 (16)	0.0526 (14)	0.076 (2)	−0.0056 (12)	−0.0137 (14)	0.0085 (14)
C28	0.073 (2)	0.0495 (15)	0.114 (3)	0.0013 (14)	−0.017 (2)	0.0003 (16)
C29	0.084 (2)	0.0571 (17)	0.111 (3)	−0.0002 (16)	0.008 (2)	−0.0194 (18)
C30	0.090 (2)	0.0618 (17)	0.082 (2)	−0.0074 (16)	0.0166 (17)	−0.0185 (16)
C31	0.0497 (14)	0.0463 (12)	0.0598 (17)	−0.0098 (11)	−0.0022 (13)	0.0012 (12)
C32	0.0507 (14)	0.0503 (13)	0.0461 (15)	−0.0090 (11)	−0.0019 (11)	0.0062 (11)
C33	0.107 (3)	0.0593 (17)	0.084 (2)	0.0125 (17)	−0.023 (2)	0.0040 (16)
C34	0.085 (2)	0.0715 (19)	0.084 (2)	0.0115 (16)	−0.0041 (18)	−0.0114 (17)
C35	0.076 (2)	0.0766 (19)	0.0690 (19)	−0.0025 (15)	0.0000 (16)	−0.0024 (16)
C36	0.0614 (15)	0.0573 (15)	0.0508 (16)	−0.0067 (13)	−0.0046 (12)	0.0011 (13)
C37	0.078 (2)	0.0686 (17)	0.0472 (16)	−0.0104 (15)	−0.0025 (14)	0.0102 (13)
C38	0.086 (2)	0.0558 (15)	0.0536 (17)	−0.0028 (14)	−0.0090 (15)	0.0106 (13)
C39	0.0597 (16)	0.0522 (14)	0.0492 (16)	−0.0082 (12)	−0.0088 (12)	0.0023 (12)
C40	0.0722 (18)	0.0515 (14)	0.071 (2)	−0.0046 (13)	−0.0034 (15)	−0.0009 (13)
C41	0.085 (2)	0.0613 (16)	0.072 (2)	−0.0110 (15)	0.0050 (16)	−0.0137 (15)
C42	0.107 (2)	0.0732 (18)	0.0478 (17)	−0.0254 (18)	0.0091 (16)	−0.0070 (15)
C43	0.0641 (16)	0.0487 (13)	0.0437 (15)	−0.0140 (11)	−0.0106 (12)	0.0043 (11)
C44	0.0599 (14)	0.0501 (13)	0.0495 (15)	−0.0065 (12)	−0.0114 (12)	−0.0003 (12)
O6A	0.0541 (15)	0.0888 (17)	0.105 (2)	−0.0090 (14)	−0.0027 (15)	−0.0180 (16)
O6B	0.058 (4)	0.048 (4)	0.093 (5)	−0.006 (3)	−0.001 (4)	−0.022 (4)

Cl1—C4	1.734 (3)	C21—H21	0.9300
Cl2—C11	1.742 (3)	C22—C23	1.372 (4)
N1—C21	1.324 (3)	C22—H22	0.9300
N1—C32	1.359 (3)	C23—C24	1.406 (4)
N1—H1N	0.8464	C23—H23	0.9300
N2—C30	1.327 (3)	C24—C32	1.408 (3)
N2—C31	1.366 (3)	C24—C25	1.421 (4)
N3—C33	1.327 (4)	C25—C26	1.332 (4)
N3—C44	1.365 (3)	C25—H25	0.9300
N4—C42	1.338 (4)	C26—C27	1.427 (4)
N4—C43	1.361 (3)	C26—H26	0.9300
C7—O1	1.312 (3)	C27—C31	1.404 (3)
C7—O2	1.239 (3)	C27—C28	1.405 (4)
O1—H1A	0.8758	C28—C29	1.364 (4)
O3—C2	1.370 (3)	C28—H28	0.9300
O3—H3A	0.9483	C29—C30	1.386 (4)
O4—C14	1.236 (3)	C29—H29	0.9300
O5—C14	1.281 (3)	C30—H30	0.9300
C1—C6	1.391 (3)	C31—C32	1.434 (3)
C1—C2	1.401 (4)	C33—C34	1.391 (4)
C1—C7	1.469 (4)	C33—H33	0.9300
C2—C3	1.389 (4)	C34—C35	1.360 (4)
C3—C4	1.375 (4)	C34—H34	0.9300
C3—H3	0.9300	C35—C36	1.403 (4)
C4—C5	1.382 (4)	C35—H35	0.9300
C5—C6	1.383 (4)	C36—C44	1.411 (3)
C5—H5	0.9300	C36—C37	1.438 (4)
C6—H6	0.9300	C37—C38	1.338 (4)
C8—C13	1.391 (3)	C37—H37	0.9300
C8—C9	1.402 (3)	C38—C39	1.421 (3)
C8—C14	1.496 (3)	C38—H38	0.9300
C9—O6A	1.336 (3)	C39—C43	1.410 (3)
C9—C10	1.384 (3)	C39—C40	1.415 (3)
C9—H9	0.9300	C40—C41	1.350 (4)
C10—C11	1.364 (3)	C40—H40	0.9300
C10—H10	0.9300	C41—C42	1.382 (4)
C11—C12	1.380 (3)	C41—H41	0.9300
C12—C13	1.381 (3)	C42—H42	0.9300
C12—H12	0.9300	C43—C44	1.453 (3)
C13—O6B	1.354 (6)	O6A—H6A	0.9422
C13—H13	0.9300	O6B—H6B	0.8159
C21—C22	1.388 (4)
C21—N1—C32	123.2 (2)	C23—C24—C25	123.7 (3)
C21—N1—H1N	116.6	C32—C24—C25	118.3 (2)
C32—N1—H1N	120.2	C26—C25—C24	121.8 (3)
C30—N2—C31	116.4 (2)	C26—C25—H25	119.1
C33—N3—C44	116.7 (2)	C24—C25—H25	119.1
C42—N4—C43	116.8 (2)	C25—C26—C27	121.0 (3)
C7—O1—H1A	108.4	C25—C26—H26	119.5
C2—O3—H3A	116.5	C27—C26—H26	119.5
C6—C1—C2	118.3 (2)	C31—C27—C28	116.1 (3)
C6—C1—C7	121.4 (3)	C31—C27—C26	120.1 (3)
C2—C1—C7	120.3 (2)	C28—C27—C26	123.8 (3)
O3—C2—C3	116.7 (2)	C29—C28—C27	120.2 (3)
O3—C2—C1	122.3 (3)	C29—C28—H28	119.9
C3—C2—C1	121.0 (2)	C27—C28—H28	119.9
C4—C3—C2	118.7 (3)	C28—C29—C30	119.1 (3)
C4—C3—H3	120.7	C28—C29—H29	120.4
C2—C3—H3	120.7	C30—C29—H29	120.4
C3—C4—C5	122.0 (3)	N2—C30—C29	124.0 (3)
C3—C4—Cl1	118.6 (2)	N2—C30—H30	118.0
C5—C4—Cl1	119.5 (2)	C29—C30—H30	118.0
C4—C5—C6	118.8 (3)	N2—C31—C27	124.2 (2)
C4—C5—H5	120.6	N2—C31—C32	117.7 (2)
C6—C5—H5	120.6	C27—C31—C32	118.0 (2)
C5—C6—C1	121.3 (3)	N1—C32—C24	118.7 (2)
C5—C6—H6	119.4	N1—C32—C31	120.5 (2)
C1—C6—H6	119.4	C24—C32—C31	120.8 (2)
O2—C7—O1	122.6 (3)	N3—C33—C34	125.0 (3)
O2—C7—C1	122.2 (3)	N3—C33—H33	117.5
O1—C7—C1	115.2 (3)	C34—C33—H33	117.5
C13—C8—C9	118.0 (2)	C35—C34—C33	118.4 (3)
C13—C8—C14	121.5 (2)	C35—C34—H34	120.8
C9—C8—C14	120.5 (2)	C33—C34—H34	120.8
O6A—C9—C10	116.5 (2)	C34—C35—C36	119.4 (3)
O6A—C9—C8	122.9 (3)	C34—C35—H35	120.3
C10—C9—C8	120.5 (2)	C36—C35—H35	120.3
C10—C9—H9	119.7	C35—C36—C44	118.3 (2)
C8—C9—H9	119.7	C35—C36—C37	122.2 (2)
C11—C10—C9	119.2 (2)	C44—C36—C37	119.5 (2)
C11—C10—H10	120.4	C38—C37—C36	121.1 (2)
C9—C10—H10	120.4	C38—C37—H37	119.5
C10—C11—C12	122.4 (2)	C36—C37—H37	119.5
C10—C11—Cl2	118.8 (2)	C37—C38—C39	121.5 (2)
C12—C11—Cl2	118.8 (2)	C37—C38—H38	119.3
C11—C12—C13	117.9 (2)	C39—C38—H38	119.3
C11—C12—H12	121.1	C43—C39—C40	117.6 (2)
C13—C12—H12	121.1	C43—C39—C38	119.8 (2)
O6B—C13—C12	117.2 (4)	C40—C39—C38	122.6 (2)
O6B—C13—C8	120.8 (4)	C41—C40—C39	119.7 (3)
C12—C13—C8	121.9 (2)	C41—C40—H40	120.1
C12—C13—H13	119.0	C39—C40—H40	120.1
C8—C13—H13	119.0	C40—C41—C42	118.8 (3)
O4—C14—O5	124.4 (3)	C40—C41—H41	120.6
O4—C14—C8	119.2 (2)	C42—C41—H41	120.6
O5—C14—C8	116.4 (2)	N4—C42—C41	124.6 (3)
N1—C21—C22	120.4 (2)	N4—C42—H42	117.7
N1—C21—H21	119.8	C41—C42—H42	117.7
C22—C21—H21	119.8	N4—C43—C39	122.3 (2)
C23—C22—C21	118.8 (3)	N4—C43—C44	118.5 (2)
C23—C22—H22	120.6	C39—C43—C44	119.2 (2)
C21—C22—H22	120.6	N3—C44—C36	122.1 (2)
C22—C23—C24	120.9 (3)	N3—C44—C43	119.0 (2)
C22—C23—H23	119.6	C36—C44—C43	118.9 (2)
C24—C23—H23	119.6	C9—O6A—H6A	106.4
C23—C24—C32	118.0 (2)	C13—O6B—H6B	109.9

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O5	0.88	1.61	2.484 (2)	173
N1—H1N···N3i	0.85	2.14	2.915 (3)	153
O3—H3A···Cl1ii	0.95	2.66	3.1714 (19)	114
O3—H3A···O2	0.95	1.86	2.603 (3)	133
O6A—H6A···O4	0.94	1.74	2.584 (3)	148
O6B—H6B···O5	0.82	1.80	2.494 (7)	142
C5—H5···O2iii	0.93	2.50	3.404 (3)	164
C12—H12···O4ii	0.93	2.51	3.381 (3)	157
C21—H21···N2i	0.93	2.51	3.345 (4)	150
C22—H22···O1iv	0.93	2.54	3.220 (4)	130
C37—H37···O4	0.93	2.60	3.430 (3)	150
C25—H25···Cg1	0.93	2.65	3.571 (3)	174
C40—H40···Cg2	0.93	2.63	3.489 (3)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O5	0.88	1.61	2.484 (2)	173
N1—H1N⋯N3i	0.85	2.14	2.915 (3)	153
O3—H3A⋯Cl1ii	0.95	2.66	3.1714 (19)	114
O3—H3A⋯O2	0.95	1.86	2.603 (3)	133
O6A—H6A⋯O4	0.94	1.74	2.584 (3)	148
O6B—H6B⋯O5	0.82	1.80	2.494 (7)	142
C5—H5⋯O2iii	0.93	2.50	3.404 (3)	164
C12—H12⋯O4ii	0.93	2.51	3.381 (3)	157
C21—H21⋯N2i	0.93	2.51	3.345 (4)	150
C22—H22⋯O1iv	0.93	2.54	3.220 (4)	130
C37—H37⋯O4	0.93	2.60	3.430 (3)	150
C25—H25⋯Cg1	0.93	2.65	3.571 (3)	174
C40—H40⋯Cg2	0.93	2.63	3.489 (3)	154

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . Cg1 is the centroid of the C8–C13 benzene ring and Cg2 is the centroid of the C1–C6 benzene ring.