Bis(1,10-phenanthrolin-1-ium) tetra­chlorido­zincate monohydrate

Govindan, E.; Thirumurugan, S.; Ganeshraja, A.S.; Anbalagan, K.; SubbiahPandi, A.

doi:10.1107/S1600536814000208

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Page m53

doi:10.1107/S1600536814000208

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Bis(1,10-phenanthrolin-1-ium) tetrachloridozincate monohydrate

E. Govindan,^a Subramani Thirumurugan,^b Ayyakannu Sundaram Ganeshraja,^b Krishnamoorthy Anbalagan ^b and A. SubbiahPandi ^a ^*

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^bDepartment of Chemistry, Pondicherry University, Pondicherry 605 014, India
^*Correspondence e-mail: a_sp59@yahoo.in

(Received 29 December 2013; accepted 4 January 2014; online 18 January 2014)

In the crystal structure of the title compound, (C₁₂H₉N₂)₂[ZnCl₄]·H₂O, the two independent 1,10-phenanthrolinium cations are bridged by the water molecule and the tetrahedral tetrachloridozincate anion via N—H⋯O, O—H⋯Cl and N—H⋯Cl hydrogen bonds, forming chains along [100]. The chains are linked via C—H⋯Cl hydrogen bonds and a number of π–π interactions [centroid–centroid distances vary from 3.5594 (14) to 3.7057 (13) Å], forming a three-dimensional network. In each 1,10-phenanthrolinium cation, there is a short N—H⋯N interaction.

CCDC reference: 979772

Related literature

For an example of the crystal structure of a hybrid compound combining an organic cation and the tetrachloridozincate anion, see: Dong & Liu (2012 ). For details of the Cambridge Structural Database, see: Allen (2002 ).

Experimental

Crystal data

(C₁₂H₉N₂)₂[ZnCl₄]·H₂O
M_r = 587.61
Monoclinic, P 2₁ /a
a = 14.6046 (5) Å
b = 10.8008 (3) Å
c = 16.3151 (6) Å
β = 107.390 (4)°
V = 2455.93 (14) Å³
Z = 4
Mo Kα radiation
μ = 1.46 mm⁻¹
T = 293 K
0.21 × 0.18 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with Eos detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.743, T_max = 0.803
10373 measured reflections
4293 independent reflections
3414 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.068
S = 1.05
4293 reflections
324 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.74 (3)	2.01 (3)	2.711 (4)	158 (2)
O1—H1A⋯Cl1	0.80 (4)	2.44 (4)	3.231 (3)	172 (3)
O1—H1B⋯Cl2ⁱⁱ	0.73 (3)	2.82 (4)	3.317 (3)	128 (4)
N15—H15⋯Cl3	0.83 (3)	2.50 (2)	3.225 (2)	146 (2)
C3—H3⋯Cl2ⁱⁱⁱ	0.93	2.80	3.728 (3)	172
C24—H24⋯Cl2^iv	0.93	2.74	3.629 (3)	160
N1—H1⋯N12	0.74 (3)	2.42 (2)	2.737 (3)	107 (2)
N15—H15⋯N26	0.83 (3)	2.41 (2)	2.731 (3)	104 (2)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (iii) -x, -y+2, -z+1; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+2]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis CCD, CrysAlis RED and CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 979772

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814000208/su2681sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814000208/su2681Isup2.hkl

checkCIF report

Comment top

As part of an ongoing investigation of the structures of and non-covalent interactions present in self-assembling organic and inorganic hybrid materials prepared by the combination of an organic cation and the tetrachloridozincate anion we synthesized the title compound. There are only a small number of structures of materials containing bis(1,10-phenanthrolinium) cations and perhalometallate anions in the Cambridge Structural Database (CSD; V5.35, last update Nov. 2013; Allen, 2002), and none of them involve the tetrachloridozincate anion.

The molecule structure of the title compound is shown in Fig. 1. The asymmetric unit contains one inorganic tetrachloridozincate anion and two 1,10-phenanthrolinium organic cations. The compound crystallized as a monohydrate. The tetrachlorozincate anion has a perfect tetrahedral coordination environment. The bond lengths Zn—Cl [2.556 (7) - 2.3085 (7) Å] and C—N [1.320 (3) - 1.362 (3) Å] are comparable with the values reported for Bis(10-methoxybenzo[h]quinolinium) tetrachloridozinc [Dong & Liu, 2012]. The sum of the bond angles around atoms N1 and N15 (360°) in the 1,10-phenanthrolinium cations indicates sp² hybridization states. The two 1,10-phenanthrolinium ring systems (N1/N12/C2-C11/C13/C14) and (N15/N26/C16-C25/C27/C28) are planar with r.m.s values of 0.029 (3) and 0.022 (2) Å, respectively. In each 1,10-phenanthrolinium cation there is a short N-H···N interaction (Table 1).

In the crystal, the two independent 1,10-phenanthrolinium cations are bridged by the water molecule and the tetrachloridozinc anion via N-H···O, O-H···Cl and N-H···Cl hydrogen bonds (Table 1 and Fig. 2) forming chains along [100]. The chains are linked via C-H···Cl hydrogen bonds (Table 1) and a number of π-π interactions forming a three-dimensional network.

The centroid-centroid distances are 3.5594 (14) Å for Cg1···Cg2ⁱ [Cg1 and Cg2 and the centroids of rings N1/C2-C5/C14 and N12/C8-C11/C13, respectively; symmetry code: (i) = -x, -y+2, -z+1 ], 3.6501 (15) Å for Cg1···Cg3ⁱ [Cg3 is the centroid of ring C5-C8/C13/C14] and 3.7057 (13) Å for Cg8···Cg9ⁱⁱ [Cg8 and Cg9 are the centroids of rings N26/C22-C25/C27 and C19-C22/C27/C28, respectively; symmetry code: (ii) -x, -y, -z+2].

Related literature top

For an example of the crystal structure of an inorganic hybrid compound combining an organic cation and the tetrachloridozincate anion, see: Dong & Liu (2012). For details of the Cambridge Structural Database, see: Allen (2002).

Experimental top

Zinc chloride (136 mg, 1 mmol) was dissolved in 10 mL of water. To this 1,10-phenanthroline (396 mg, 2 mmol) in 20 ml of an EtOH/HCl mixture (1:9 v/v) was added drop wise. The mixture was heated to 323 K for 2–3 hrs and then allowed to stand. On slow evaporation colourless crystals separated out. They were filtered off and recrystallized using acidified water.

Structure description top

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis CCD (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A view along the b-axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

Bis(1,10-phenanthrolin-1-ium) tetrachloridozincate monohydrate top

Crystal data top

(C₁₂H₉N₂)₂[ZnCl₄]·H₂O	F(000) = 1192
M_r = 587.61	D_x = 1.589 Mg m⁻³
Monoclinic, P2₁/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 3414 reflections
a = 14.6046 (5) Å	θ = 3.8–25.0°
b = 10.8008 (3) Å	µ = 1.46 mm⁻¹
c = 16.3151 (6) Å	T = 293 K
β = 107.390 (4)°	Block, colourless
V = 2455.93 (14) Å³	0.21 × 0.18 × 0.15 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur diffractometer with Eos detector	4293 independent reflections
Radiation source: fine-focus sealed tube	3414 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω and φ scans	θ_max = 25.0°, θ_min = 3.8°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −17→17
T_min = 0.743, T_max = 0.803	k = −11→12
10373 measured reflections	l = −19→19

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0278P)² + 0.2557P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
4293 reflections	Δρ_max = 0.38 e Å⁻³
324 parameters	Δρ_min = −0.29 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0165 (5)

Crystal data top

(C₁₂H₉N₂)₂[ZnCl₄]·H₂O	V = 2455.93 (14) Å³
M_r = 587.61	Z = 4
Monoclinic, P2₁/a	Mo Kα radiation
a = 14.6046 (5) Å	µ = 1.46 mm⁻¹
b = 10.8008 (3) Å	T = 293 K
c = 16.3151 (6) Å	0.21 × 0.18 × 0.15 mm
β = 107.390 (4)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with Eos detector	4293 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	3414 reflections with I > 2σ(I)
T_min = 0.743, T_max = 0.803	R_int = 0.028
10373 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.068	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.38 e Å⁻³
4293 reflections	Δρ_min = −0.29 e Å⁻³
324 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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.

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

	x	y	z	U_iso*/U_eq
N1	0.05391 (18)	1.17583 (19)	0.56437 (14)	0.0382 (8)
N12	0.13002 (14)	0.97933 (17)	0.66837 (13)	0.0364 (7)
C2	0.0227 (2)	1.2729 (2)	0.51338 (17)	0.0498 (10)
C3	−0.0746 (2)	1.2890 (3)	0.47489 (18)	0.0574 (10)
C4	−0.1379 (2)	1.2056 (3)	0.49016 (18)	0.0533 (11)
C5	−0.10528 (18)	1.1038 (2)	0.54406 (16)	0.0401 (9)
C6	−0.16693 (19)	1.0148 (3)	0.56456 (18)	0.0497 (10)
C7	−0.13202 (18)	0.9219 (3)	0.61895 (18)	0.0475 (10)
C8	−0.03095 (17)	0.9048 (2)	0.65657 (15)	0.0354 (8)
C9	0.0097 (2)	0.8067 (2)	0.71173 (17)	0.0437 (9)
C10	0.1068 (2)	0.7959 (2)	0.74208 (18)	0.0469 (10)
C11	0.16361 (19)	0.8837 (2)	0.71874 (16)	0.0427 (9)
C13	0.03328 (16)	0.9889 (2)	0.63748 (14)	0.0293 (7)
C14	−0.00593 (17)	1.0909 (2)	0.58142 (14)	0.0306 (8)
N15	−0.07856 (15)	0.34171 (18)	0.92218 (13)	0.0339 (7)
N26	0.08664 (14)	0.25794 (18)	1.03725 (13)	0.0378 (7)
C16	−0.15449 (18)	0.3854 (2)	0.86201 (17)	0.0424 (9)
C17	−0.24346 (18)	0.3314 (3)	0.84870 (17)	0.0460 (9)
C18	−0.25201 (17)	0.2333 (2)	0.89907 (17)	0.0428 (9)
C19	−0.17174 (16)	0.1862 (2)	0.96188 (15)	0.0339 (8)
C20	−0.17495 (18)	0.0817 (2)	1.01531 (17)	0.0411 (9)
C21	−0.09527 (18)	0.0398 (2)	1.07310 (16)	0.0407 (9)
C22	−0.00318 (17)	0.0967 (2)	1.08369 (15)	0.0327 (8)
C23	0.08261 (19)	0.0549 (2)	1.14257 (16)	0.0417 (9)
C24	0.16602 (19)	0.1130 (2)	1.14723 (17)	0.0473 (9)
C25	0.16456 (18)	0.2136 (3)	1.09347 (18)	0.0470 (9)
C27	0.00304 (16)	0.1986 (2)	1.03291 (15)	0.0291 (7)
C28	−0.08273 (16)	0.2437 (2)	0.97183 (15)	0.0287 (7)
Zn1	0.02573 (2)	0.43561 (2)	0.73719 (2)	0.0324 (1)
Cl1	−0.11018 (5)	0.52315 (6)	0.64898 (5)	0.0584 (3)
Cl2	0.15128 (4)	0.45542 (6)	0.68453 (4)	0.0445 (2)
Cl3	0.06504 (5)	0.53130 (5)	0.86969 (4)	0.0429 (2)
Cl4	−0.00552 (5)	0.23479 (5)	0.76075 (4)	0.0433 (2)
O1	−0.25358 (17)	0.2883 (3)	0.61679 (19)	0.0609 (9)
H1	0.1064 (18)	1.169 (2)	0.5852 (17)	0.033 (8)*
H2	0.06620	1.32970	0.50370	0.0600*
H3	−0.09690	1.35620	0.43880	0.0690*
H4	−0.20340	1.21660	0.46450	0.0640*
H6	−0.23290	1.02140	0.53950	0.0600*
H7	−0.17430	0.86710	0.63270	0.0570*
H9	−0.02950	0.74930	0.72740	0.0530*
H10	0.13470	0.73060	0.77800	0.0560*
H11	0.22980	0.87460	0.74000	0.0510*
H15	−0.0270 (18)	0.379 (2)	0.9296 (16)	0.040 (8)*
H16	−0.14770	0.45270	0.82870	0.0510*
H17	−0.29670	0.36120	0.80630	0.0550*
H18	−0.31190	0.19750	0.89150	0.0510*
H20	−0.23320	0.04250	1.00970	0.0490*
H21	−0.09940	−0.02770	1.10720	0.0490*
H23	0.08200	−0.01220	1.17810	0.0500*
H24	0.22340	0.08620	1.18570	0.0570*
H25	0.22260	0.25230	1.09750	0.0560*
H1A	−0.217 (3)	0.344 (3)	0.620 (2)	0.083 (15)*
H1B	−0.239 (3)	0.241 (3)	0.650 (2)	0.079 (16)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0427 (15)	0.0374 (13)	0.0337 (13)	0.0058 (11)	0.0103 (11)	0.0005 (10)
N12	0.0342 (11)	0.0336 (11)	0.0368 (12)	0.0014 (9)	0.0034 (9)	−0.0013 (9)
C2	0.081 (2)	0.0349 (15)	0.0369 (17)	0.0056 (14)	0.0228 (15)	0.0018 (12)
C3	0.087 (2)	0.0461 (17)	0.0368 (17)	0.0339 (17)	0.0149 (16)	0.0047 (13)
C4	0.0546 (18)	0.066 (2)	0.0358 (17)	0.0293 (16)	0.0081 (14)	−0.0022 (14)
C5	0.0395 (15)	0.0489 (15)	0.0312 (15)	0.0145 (12)	0.0096 (12)	−0.0083 (12)
C6	0.0301 (14)	0.0680 (19)	0.0472 (18)	0.0052 (14)	0.0058 (13)	−0.0136 (15)
C7	0.0374 (15)	0.0549 (17)	0.0524 (18)	−0.0112 (13)	0.0168 (13)	−0.0128 (14)
C8	0.0396 (14)	0.0367 (13)	0.0299 (14)	−0.0049 (11)	0.0105 (11)	−0.0108 (11)
C9	0.0582 (18)	0.0342 (14)	0.0405 (16)	−0.0133 (13)	0.0173 (14)	−0.0057 (12)
C10	0.0600 (19)	0.0330 (14)	0.0402 (16)	0.0000 (13)	0.0036 (14)	0.0023 (12)
C11	0.0407 (15)	0.0394 (14)	0.0388 (16)	0.0024 (12)	−0.0019 (12)	−0.0012 (12)
C13	0.0325 (13)	0.0291 (12)	0.0248 (13)	0.0011 (10)	0.0062 (10)	−0.0079 (10)
C14	0.0365 (13)	0.0317 (13)	0.0241 (13)	0.0034 (11)	0.0099 (11)	−0.0065 (10)
N15	0.0305 (12)	0.0374 (12)	0.0362 (13)	0.0010 (10)	0.0138 (10)	0.0036 (10)
N26	0.0319 (11)	0.0453 (12)	0.0355 (13)	−0.0040 (9)	0.0090 (9)	0.0053 (10)
C16	0.0423 (15)	0.0481 (15)	0.0396 (16)	0.0136 (13)	0.0164 (12)	0.0134 (12)
C17	0.0326 (15)	0.0642 (18)	0.0382 (16)	0.0129 (13)	0.0059 (12)	0.0039 (14)
C18	0.0282 (13)	0.0558 (17)	0.0437 (17)	−0.0009 (12)	0.0098 (12)	−0.0058 (13)
C19	0.0320 (13)	0.0379 (13)	0.0340 (15)	−0.0021 (11)	0.0131 (11)	−0.0053 (11)
C20	0.0382 (15)	0.0454 (15)	0.0435 (16)	−0.0125 (12)	0.0180 (13)	−0.0040 (13)
C21	0.0482 (16)	0.0377 (14)	0.0404 (16)	−0.0082 (12)	0.0195 (13)	0.0033 (12)
C22	0.0389 (14)	0.0338 (13)	0.0277 (13)	0.0002 (11)	0.0137 (11)	−0.0008 (11)
C23	0.0520 (17)	0.0420 (15)	0.0316 (15)	0.0045 (13)	0.0133 (12)	0.0067 (12)
C24	0.0388 (15)	0.0594 (17)	0.0373 (16)	0.0056 (13)	0.0015 (12)	0.0101 (14)
C25	0.0305 (14)	0.0625 (18)	0.0444 (17)	−0.0057 (13)	0.0057 (12)	0.0052 (14)
C27	0.0302 (12)	0.0321 (13)	0.0264 (13)	−0.0010 (10)	0.0106 (10)	−0.0030 (10)
C28	0.0336 (13)	0.0285 (12)	0.0267 (13)	−0.0002 (10)	0.0132 (10)	−0.0025 (10)
Zn1	0.0315 (2)	0.0318 (2)	0.0336 (2)	−0.0033 (1)	0.0091 (1)	−0.0023 (1)
Cl1	0.0373 (4)	0.0486 (4)	0.0735 (5)	−0.0010 (3)	−0.0074 (3)	0.0052 (4)
Cl2	0.0409 (4)	0.0505 (4)	0.0470 (4)	−0.0073 (3)	0.0208 (3)	−0.0059 (3)
Cl3	0.0575 (4)	0.0369 (3)	0.0369 (4)	−0.0085 (3)	0.0182 (3)	−0.0086 (3)
Cl4	0.0575 (4)	0.0299 (3)	0.0460 (4)	−0.0072 (3)	0.0210 (3)	−0.0050 (3)
O1	0.0530 (14)	0.0493 (14)	0.083 (2)	0.0033 (13)	0.0242 (13)	0.0021 (14)

Geometric parameters (Å, º) top

Zn1—Cl4	2.2728 (6)	C2—H2	0.9300
Zn1—Cl1	2.2798 (8)	C3—H3	0.9300
Zn1—Cl2	2.2556 (7)	C4—H4	0.9300
Zn1—Cl3	2.3085 (7)	C6—H6	0.9300
O1—H1A	0.80 (4)	C7—H7	0.9300
O1—H1B	0.73 (3)	C9—H9	0.9300
N1—C2	1.331 (3)	C10—H10	0.9300
N1—C14	1.352 (3)	C11—H11	0.9300
N12—C13	1.355 (3)	C16—C17	1.381 (4)
N12—C11	1.320 (3)	C17—C18	1.369 (4)
N1—H1	0.74 (3)	C18—C19	1.402 (3)
N15—C28	1.345 (3)	C19—C20	1.435 (3)
N15—C16	1.329 (3)	C19—C28	1.406 (3)
N26—C25	1.320 (4)	C20—C21	1.339 (4)
N26—C27	1.362 (3)	C21—C22	1.441 (4)
N15—H15	0.83 (3)	C22—C27	1.397 (3)
C2—C3	1.382 (4)	C22—C23	1.406 (4)
C3—C4	1.366 (4)	C23—C24	1.352 (4)
C4—C5	1.400 (4)	C24—C25	1.393 (4)
C5—C6	1.424 (4)	C27—C28	1.433 (3)
C5—C14	1.403 (4)	C16—H16	0.9300
C6—C7	1.336 (4)	C17—H17	0.9300
C7—C8	1.431 (4)	C18—H18	0.9300
C8—C13	1.406 (3)	C20—H20	0.9300
C8—C9	1.402 (3)	C21—H21	0.9300
C9—C10	1.360 (4)	C23—H23	0.9300
C10—C11	1.386 (4)	C24—H24	0.9300
C13—C14	1.437 (3)	C25—H25	0.9300

Cl3—Zn1—Cl4	105.98 (2)	C8—C7—H7	119.00
Cl1—Zn1—Cl4	108.76 (3)	C8—C9—H9	120.00
Cl1—Zn1—Cl2	111.95 (3)	C10—C9—H9	120.00
Cl1—Zn1—Cl3	109.35 (3)	C9—C10—H10	120.00
Cl2—Zn1—Cl3	108.14 (3)	C11—C10—H10	120.00
Cl2—Zn1—Cl4	112.47 (3)	N12—C11—H11	118.00
H1A—O1—H1B	116 (4)	C10—C11—H11	118.00
C2—N1—C14	122.8 (3)	N15—C16—C17	120.3 (2)
C11—N12—C13	116.3 (2)	C16—C17—C18	118.9 (2)
C14—N1—H1	118.7 (18)	C17—C18—C19	120.9 (2)
C2—N1—H1	118.5 (18)	C18—C19—C28	117.8 (2)
C16—N15—C28	123.1 (2)	C18—C19—C20	123.9 (2)
C25—N26—C27	116.0 (2)	C20—C19—C28	118.3 (2)
C28—N15—H15	119.8 (16)	C19—C20—C21	121.0 (2)
C16—N15—H15	117.1 (16)	C20—C21—C22	121.6 (2)
N1—C2—C3	119.8 (3)	C21—C22—C27	119.3 (2)
C2—C3—C4	119.6 (3)	C23—C22—C27	117.1 (2)
C3—C4—C5	120.7 (3)	C21—C22—C23	123.6 (2)
C4—C5—C14	117.7 (2)	C22—C23—C24	119.6 (2)
C4—C5—C6	123.9 (3)	C23—C24—C25	118.9 (2)
C6—C5—C14	118.4 (2)	N26—C25—C24	124.7 (3)
C5—C6—C7	121.4 (3)	C22—C27—C28	118.8 (2)
C6—C7—C8	121.5 (3)	N26—C27—C28	117.4 (2)
C9—C8—C13	116.6 (2)	N26—C27—C22	123.8 (2)
C7—C8—C13	119.5 (2)	C19—C28—C27	121.1 (2)
C7—C8—C9	123.9 (2)	N15—C28—C19	119.0 (2)
C8—C9—C10	119.6 (2)	N15—C28—C27	119.9 (2)
C9—C10—C11	119.1 (2)	N15—C16—H16	120.00
N12—C11—C10	124.4 (3)	C17—C16—H16	120.00
C8—C13—C14	118.1 (2)	C18—C17—H17	121.00
N12—C13—C14	117.9 (2)	C16—C17—H17	121.00
N12—C13—C8	124.0 (2)	C17—C18—H18	120.00
N1—C14—C5	119.4 (2)	C19—C18—H18	120.00
N1—C14—C13	119.5 (2)	C21—C20—H20	120.00
C5—C14—C13	121.1 (2)	C19—C20—H20	120.00
N1—C2—H2	120.00	C20—C21—H21	119.00
C3—C2—H2	120.00	C22—C21—H21	119.00
C4—C3—H3	120.00	C22—C23—H23	120.00
C2—C3—H3	120.00	C24—C23—H23	120.00
C3—C4—H4	120.00	C23—C24—H24	121.00
C5—C4—H4	120.00	C25—C24—H24	121.00
C5—C6—H6	119.00	N26—C25—H25	118.00
C7—C6—H6	119.00	C24—C25—H25	118.00
C6—C7—H7	119.00

C14—N1—C2—C3	−0.6 (4)	C8—C9—C10—C11	1.0 (4)
C2—N1—C14—C13	−179.7 (2)	C9—C10—C11—N12	0.2 (4)
C2—N1—C14—C5	0.3 (4)	C8—C13—C14—C5	−2.4 (3)
C11—N12—C13—C14	−179.1 (2)	N12—C13—C14—C5	177.2 (2)
C11—N12—C13—C8	0.5 (3)	C8—C13—C14—N1	177.6 (2)
C13—N12—C11—C10	−0.9 (4)	N12—C13—C14—N1	−2.7 (3)
C16—N15—C28—C27	177.3 (2)	N15—C16—C17—C18	0.7 (4)
C28—N15—C16—C17	1.0 (4)	C16—C17—C18—C19	−1.4 (4)
C16—N15—C28—C19	−1.9 (3)	C17—C18—C19—C28	0.6 (4)
C25—N26—C27—C28	−179.4 (2)	C17—C18—C19—C20	−178.3 (2)
C25—N26—C27—C22	0.0 (3)	C20—C19—C28—C27	0.8 (3)
C27—N26—C25—C24	−0.3 (4)	C18—C19—C20—C21	178.7 (2)
N1—C2—C3—C4	0.6 (4)	C28—C19—C20—C21	−0.1 (4)
C2—C3—C4—C5	−0.3 (4)	C18—C19—C28—C27	−178.2 (2)
C3—C4—C5—C14	0.0 (4)	C20—C19—C28—N15	180.0 (2)
C3—C4—C5—C6	178.5 (3)	C18—C19—C28—N15	1.1 (3)
C4—C5—C14—N1	0.0 (4)	C19—C20—C21—C22	−0.5 (4)
C4—C5—C6—C7	−177.5 (3)	C20—C21—C22—C23	−179.0 (2)
C14—C5—C6—C7	1.0 (4)	C20—C21—C22—C27	0.5 (4)
C4—C5—C14—C13	−180.0 (2)	C23—C22—C27—N26	0.3 (3)
C6—C5—C14—C13	1.5 (3)	C21—C22—C27—N26	−179.2 (2)
C6—C5—C14—N1	−178.6 (2)	C21—C22—C27—C28	0.2 (3)
C5—C6—C7—C8	−2.4 (4)	C23—C22—C27—C28	179.7 (2)
C6—C7—C8—C9	−177.8 (3)	C21—C22—C23—C24	179.1 (2)
C6—C7—C8—C13	1.4 (4)	C27—C22—C23—C24	−0.5 (3)
C7—C8—C9—C10	177.8 (3)	C22—C23—C24—C25	0.3 (4)
C9—C8—C13—N12	0.6 (3)	C23—C24—C25—N26	0.2 (4)
C7—C8—C13—N12	−178.6 (2)	N26—C27—C28—N15	−0.6 (3)
C9—C8—C13—C14	−179.7 (2)	C22—C27—C28—C19	−0.8 (3)
C7—C8—C13—C14	1.0 (3)	N26—C27—C28—C19	178.6 (2)
C13—C8—C9—C10	−1.4 (4)	C22—C27—C28—N15	−180.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.74 (3)	2.01 (3)	2.711 (4)	158 (2)
O1—H1A···Cl1	0.80 (4)	2.44 (4)	3.231 (3)	172 (3)
O1—H1B···Cl2ⁱⁱ	0.73 (3)	2.82 (4)	3.317 (3)	128 (4)
N15—H15···Cl3	0.83 (3)	2.50 (2)	3.225 (2)	146 (2)
C3—H3···Cl2ⁱⁱⁱ	0.93	2.80	3.728 (3)	172
C24—H24···Cl2^iv	0.93	2.74	3.629 (3)	160
N1—H1···N12	0.74 (3)	2.42 (2)	2.737 (3)	107 (2)
N15—H15···N26	0.83 (3)	2.41 (2)	2.731 (3)	104 (2)

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+1/2, z; (iii) −x, −y+2, −z+1; (iv) −x+1/2, y−1/2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.74 (3)	2.01 (3)	2.711 (4)	158 (2)
O1—H1A···Cl1	0.80 (4)	2.44 (4)	3.231 (3)	172 (3)
O1—H1B···Cl2ⁱⁱ	0.73 (3)	2.82 (4)	3.317 (3)	128 (4)
N15—H15···Cl3	0.83 (3)	2.50 (2)	3.225 (2)	146 (2)
C3—H3···Cl2ⁱⁱⁱ	0.93	2.80	3.728 (3)	172
C24—H24···Cl2^iv	0.93	2.74	3.629 (3)	160
N1—H1···N12	0.74 (3)	2.42 (2)	2.737 (3)	107 (2)
N15—H15···N26	0.83 (3)	2.41 (2)	2.731 (3)	104 (2)

Symmetry codes: (i) x+1/2, −y+3/2, z; (ii) x−1/2, −y+1/2, z; (iii) −x, −y+2, −z+1; (iv) −x+1/2, y−1/2, −z+2.

Acknowledgements

EG and KA thank the CSIR, New Delhi (Lr: No. 01 (2570)/12/EMR-II/3.4.2012) for financial support through a major research project. The authors also thank the Department of Chemistry, Pondicherry University, for the single-crystal XRD instrumentation facility.

References

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