2,9-Dimethyl-1,10-phenanthrolin-1-ium (6-carb-oxy-4-hy-droxy-pyridine-2-carboxyl-ato-κO,N,O)(4-hy-droxy-pyridine-2,6-dicarboxyl-ato-κO,N,O)zincate(II) 2.35-hydrate: a proton-transfer compound.

In the title compound, (C(14)H(13)N(2))[Zn(C(7)H(3)NO(5))(C(7)H(4)NO(5))]·2.35H(2)O, the Zn(II) atom is coordinated by two N atoms and four O atoms from the carboxyl-ate groups of the 4-hy-droxy-pyridine-2,6-dicarboxyl-ate and 6-carb-oxy-4-hy-droxy-pyridine-2-carboxyl-ate ligands, forming a distored octa-hedral geometry. In the anion, the two pyridine rings are inclined to one another by 87.75 (13)°. Two types of robust O-H⋯O hydrogen bond synthons, viz. R(2) (2)(16) and R(6) (6)(42), link the anions to form a two-dimensional network parallel to the bc plane. Furthermore, O-H⋯O, N-H⋯O, N-H⋯N and weak C-H⋯O hydrogen bonds connect the two dimensional networks, forming a three-dimensional structure. In the crystal, there are also C-H⋯π and π-π inter-actions [centroid-centroid distances of 3.5554 (18) and 3.7681 (18) Å], and C=O⋯π inter-actions [O⋯centroid distance = 3.117 (2) Å] present. One of the three crystal water molecules shows an occupancy of 0.35.

Related literature

For related structures, see: Aghabozorg et al. (2007a ▶,b ▶,c ▶, 2008a ▶,b ▶,c ▶); Derakhshandeh et al. (2010 ▶); Moghimi et al. (2005a ▶,b ▶).

Experimental

Crystal data

(C14H13N2)[Zn(C7H3NO5)(C7H4NO5)]·2.35H2O

M = 680.19

Monoclinic,

a = 11.0687 (18) Å

b = 9.7888 (14) Å

c = 25.776 (4) Å

β = 94.160 (19)°

V = 2785.4 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.96 mm−1

T = 223 K

0.38 × 0.15 × 0.15 mm

Data collection

Stoe IPDS diffractometer

Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009 ▶) T min = 0.972, T max = 1.000

20517 measured reflections

5464 independent reflections

3242 reflections with I > 2σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.081

S = 0.82

5464 reflections

437 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.82 e Å−3

Data collection: EXPOSE in IPDS-I (Stoe & Cie, 2000 ▶); cell refinement: CELL in IPDS-I; data reduction: INTEGRATE in IPDS-I; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, PLATON and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052445/lh5386sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052445/lh5386Isup2.hkl

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

(C14H13N2)[Zn(C7H3NO5)(C7H4NO5)]·2.35H2O	F(000) = 1398
Mr = 680.19	Dx = 1.622 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8000 reflections
a = 11.0687 (18) Å	θ = 2.2–26.0°
b = 9.7888 (14) Å	µ = 0.96 mm−1
c = 25.776 (4) Å	T = 223 K
β = 94.160 (19)°	Rod, colourless
V = 2785.4 (7) Å3	0.38 × 0.15 × 0.15 mm
Z = 4

Stoe IPDS diffractometer	5464 independent reflections
Radiation source: fine-focus sealed tube	3242 reflections with I > 2σ(I)
graphite	Rint = 0.079
phi rotation scans	θmax = 26.1°, θmin = 2.2°
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)	h = −13→13
Tmin = 0.972, Tmax = 1.000	k = −12→12
20517 measured reflections	l = −31→31

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081	w = 1/[σ2(Fo2) + (0.0381P)2] where P = (Fo2 + 2Fc2)/3
S = 0.82	(Δ/σ)max = 0.002
5464 reflections	Δρmax = 0.39 e Å−3
437 parameters	Δρmin = −0.82 e Å−3
12 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: 0.00093 (19)

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 e.s.d.'s 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zn1	0.14673 (3)	0.98758 (4)	0.15309 (1)	0.0276 (1)
O1	0.15029 (16)	1.0865 (2)	0.22605 (8)	0.0289 (7)
O2	0.25273 (17)	1.0801 (2)	0.30401 (8)	0.0274 (6)
O3	0.21577 (18)	0.8234 (2)	0.09690 (8)	0.0314 (7)
O4	0.3476 (2)	0.6508 (3)	0.09550 (10)	0.0689 (10)
O5	0.5868 (2)	0.7374 (2)	0.27002 (9)	0.0447 (8)
O6	−0.00735 (17)	0.8304 (2)	0.17669 (8)	0.0297 (7)
O7	−0.19803 (19)	0.7776 (2)	0.14763 (9)	0.0401 (8)
O8	0.20512 (17)	1.1572 (2)	0.11038 (8)	0.0322 (7)
O9	0.1454 (2)	1.2917 (2)	0.04327 (9)	0.0413 (8)
O10	−0.26324 (18)	1.0555 (2)	−0.01266 (8)	0.0389 (8)
N1	0.28365 (19)	0.8892 (2)	0.19133 (9)	0.0215 (7)
N2	0.00293 (18)	1.0208 (2)	0.10403 (9)	0.0213 (7)
C1	0.3153 (2)	0.9352 (3)	0.23913 (11)	0.0201 (8)
C2	0.4150 (2)	0.8856 (3)	0.26789 (11)	0.0228 (8)
C3	0.4854 (2)	0.7857 (3)	0.24588 (12)	0.0278 (10)
C4	0.4493 (3)	0.7357 (3)	0.19700 (12)	0.0281 (9)
C5	0.3486 (2)	0.7895 (3)	0.17071 (11)	0.0230 (9)
C6	0.2327 (2)	1.0437 (3)	0.25746 (11)	0.0220 (8)
C7	0.3012 (3)	0.7494 (3)	0.11652 (12)	0.0317 (10)
C8	−0.0969 (2)	0.9428 (3)	0.10265 (11)	0.0222 (8)
C9	−0.1869 (2)	0.9531 (3)	0.06417 (11)	0.0270 (9)
C10	−0.1751 (2)	1.0492 (3)	0.02501 (11)	0.0260 (9)
C11	−0.0730 (2)	1.1329 (3)	0.02694 (11)	0.0237 (9)
C12	0.0138 (2)	1.1140 (3)	0.06687 (11)	0.0218 (9)
C13	−0.0976 (2)	0.8425 (3)	0.14675 (11)	0.0255 (9)
C14	0.1313 (3)	1.1960 (3)	0.07331 (12)	0.0279 (10)
N3	0.8557 (2)	0.4051 (2)	0.10378 (9)	0.0258 (8)
N4	0.6479 (2)	0.2623 (3)	0.08062 (10)	0.0367 (9)
C15	0.9555 (2)	0.4806 (3)	0.11164 (11)	0.0291 (9)
C16	1.0300 (3)	0.4557 (3)	0.15657 (12)	0.0356 (11)
C17	1.0020 (3)	0.3569 (3)	0.19104 (13)	0.0336 (10)
C18	0.8955 (3)	0.2793 (3)	0.18217 (12)	0.0280 (9)
C19	0.8607 (3)	0.1741 (3)	0.21645 (13)	0.0350 (11)
C20	0.7593 (3)	0.1014 (3)	0.20556 (13)	0.0383 (11)
C21	0.6825 (3)	0.1273 (3)	0.15952 (12)	0.0333 (10)
C22	0.5761 (3)	0.0541 (4)	0.14581 (16)	0.0508 (12)
C23	0.5108 (3)	0.0864 (4)	0.10097 (16)	0.0546 (16)
C24	0.5479 (3)	0.1905 (4)	0.06875 (14)	0.0463 (13)
C25	0.7131 (3)	0.2303 (3)	0.12519 (12)	0.0301 (10)
C26	0.8223 (3)	0.3064 (3)	0.13721 (12)	0.0267 (9)
C27	0.9843 (3)	0.5828 (3)	0.07228 (13)	0.0380 (11)
C28	0.4762 (3)	0.2261 (5)	0.01921 (16)	0.0668 (18)
O1W	0.7545 (3)	0.4750 (3)	0.00253 (10)	0.0581 (10)
O2W	0.6528 (3)	0.8705 (3)	0.35323 (11)	0.0646 (11)
O3W	0.5323 (7)	0.4978 (8)	0.0999 (3)	0.067 (3)	0.350
H2	0.43540	0.91820	0.30170	0.0270*
H4	0.49330	0.66560	0.18210	0.0340*
H5	0.59810	0.77430	0.29900	0.0670*
H7	−0.19040	0.71470	0.16920	0.0600*
H9	−0.25570	0.89670	0.06400	0.0320*
H10	−0.24150	1.10420	−0.03660	0.0580*
H11	−0.06410	1.20040	0.00160	0.0280*
H3	0.80910	0.41970	0.07570	0.0310*
H16	1.10080	0.50780	0.16320	0.0430*
H17	1.05410	0.34060	0.22090	0.0400*
H19	0.90950	0.15550	0.24700	0.0420*
H20	0.73840	0.03220	0.22850	0.0460*
H22	0.55050	−0.01610	0.16730	0.0610*
H23	0.43930	0.03780	0.09140	0.0660*
H27A	0.91050	0.62890	0.05940	0.0570*
H27B	1.02020	0.53750	0.04370	0.0570*
H27C	1.04090	0.64920	0.08790	0.0570*
H28A	0.44320	0.31740	0.02190	0.1000*
H28B	0.52840	0.22280	−0.00940	0.1000*
H28C	0.41050	0.16120	0.01300	0.1000*
H1WA	0.774 (4)	0.546 (3)	−0.0123 (16)	0.0870*
H1WB	0.713 (4)	0.427 (3)	−0.0189 (14)	0.0870*
H2WA	0.687 (4)	0.814 (3)	0.3724 (16)	0.0970*
H2WB	0.657 (3)	0.948 (2)	0.3640 (17)	0.0970*
H3WA	0.483 (6)	0.559 (4)	0.105 (5)	0.1010*	0.350
H3WB	0.523 (3)	0.430 (3)	0.1179 (8)	0.1010*	0.350

	U11	U22	U33	U12	U13	U23
Zn1	0.0267 (2)	0.0298 (2)	0.0248 (2)	0.0004 (2)	−0.0081 (1)	0.0028 (2)
O1	0.0257 (10)	0.0283 (12)	0.0313 (12)	0.0070 (9)	−0.0067 (9)	−0.0021 (10)
O2	0.0335 (11)	0.0264 (11)	0.0219 (11)	0.0065 (9)	−0.0003 (9)	−0.0041 (9)
O3	0.0339 (12)	0.0381 (13)	0.0211 (11)	−0.0020 (10)	−0.0047 (9)	−0.0005 (10)
O4	0.0615 (17)	0.091 (2)	0.0508 (17)	0.0338 (16)	−0.0196 (13)	−0.0456 (16)
O5	0.0410 (13)	0.0526 (16)	0.0375 (14)	0.0277 (11)	−0.0168 (11)	−0.0113 (12)
O6	0.0293 (11)	0.0335 (12)	0.0253 (11)	−0.0030 (9)	−0.0039 (9)	0.0067 (10)
O7	0.0355 (12)	0.0417 (14)	0.0419 (14)	−0.0137 (11)	−0.0056 (10)	0.0226 (12)
O8	0.0279 (11)	0.0344 (12)	0.0324 (13)	−0.0099 (9)	−0.0108 (9)	0.0035 (10)
O9	0.0481 (14)	0.0333 (13)	0.0408 (14)	−0.0172 (11)	−0.0079 (11)	0.0170 (12)
O10	0.0306 (11)	0.0603 (16)	0.0238 (12)	−0.0119 (10)	−0.0114 (9)	0.0133 (11)
N1	0.0228 (12)	0.0219 (12)	0.0195 (12)	−0.0016 (10)	−0.0009 (9)	−0.0034 (10)
N2	0.0232 (11)	0.0196 (12)	0.0208 (11)	−0.0016 (10)	−0.0006 (9)	−0.0015 (11)
C1	0.0240 (14)	0.0176 (14)	0.0187 (14)	−0.0021 (11)	0.0015 (11)	0.0000 (12)
C2	0.0258 (14)	0.0244 (15)	0.0172 (14)	0.0016 (12)	−0.0045 (11)	0.0009 (13)
C3	0.0268 (16)	0.0275 (17)	0.0281 (17)	0.0076 (13)	−0.0052 (13)	0.0011 (14)
C4	0.0331 (16)	0.0248 (16)	0.0260 (16)	0.0078 (13)	0.0005 (13)	−0.0041 (14)
C5	0.0272 (15)	0.0217 (15)	0.0197 (15)	0.0014 (12)	−0.0002 (12)	−0.0040 (13)
C6	0.0210 (13)	0.0236 (16)	0.0211 (15)	−0.0017 (11)	−0.0007 (11)	0.0020 (12)
C7	0.0308 (17)	0.039 (2)	0.0250 (17)	−0.0003 (14)	0.0009 (13)	−0.0107 (15)
C8	0.0198 (14)	0.0242 (15)	0.0224 (15)	−0.0023 (11)	0.0009 (11)	0.0015 (12)
C9	0.0218 (14)	0.0349 (18)	0.0238 (16)	−0.0066 (12)	−0.0008 (12)	0.0015 (13)
C10	0.0224 (14)	0.0356 (17)	0.0192 (15)	0.0027 (12)	−0.0047 (12)	−0.0002 (13)
C11	0.0285 (15)	0.0241 (16)	0.0179 (14)	0.0016 (12)	−0.0018 (12)	0.0036 (13)
C12	0.0263 (15)	0.0193 (15)	0.0196 (15)	−0.0010 (12)	0.0011 (11)	0.0001 (13)
C13	0.0256 (15)	0.0264 (16)	0.0242 (16)	−0.0045 (13)	−0.0004 (12)	0.0017 (14)
C14	0.0305 (16)	0.0258 (17)	0.0266 (17)	−0.0064 (13)	−0.0025 (13)	0.0003 (14)
N3	0.0271 (13)	0.0261 (14)	0.0240 (13)	−0.0001 (11)	−0.0002 (10)	−0.0024 (11)
N4	0.0306 (14)	0.0492 (18)	0.0300 (15)	−0.0070 (12)	0.0001 (12)	0.0005 (13)
C15	0.0306 (15)	0.0296 (17)	0.0273 (15)	−0.0015 (13)	0.0036 (12)	−0.0037 (15)
C16	0.0342 (17)	0.038 (2)	0.0338 (18)	−0.0056 (14)	−0.0037 (14)	−0.0048 (15)
C17	0.0322 (17)	0.0376 (19)	0.0295 (18)	0.0059 (14)	−0.0083 (13)	−0.0032 (16)
C18	0.0340 (16)	0.0254 (16)	0.0244 (16)	0.0064 (13)	0.0010 (13)	−0.0027 (14)
C19	0.0419 (19)	0.0329 (18)	0.0302 (18)	0.0104 (15)	0.0027 (14)	−0.0008 (15)
C20	0.051 (2)	0.0303 (19)	0.0353 (19)	0.0047 (16)	0.0148 (16)	0.0063 (16)
C21	0.0373 (17)	0.0335 (18)	0.0302 (18)	−0.0054 (14)	0.0091 (14)	0.0008 (15)
C22	0.048 (2)	0.052 (2)	0.054 (2)	−0.0172 (17)	0.0154 (19)	0.0017 (19)
C23	0.040 (2)	0.069 (3)	0.055 (3)	−0.0253 (19)	0.0050 (18)	0.001 (2)
C24	0.0295 (17)	0.065 (3)	0.044 (2)	−0.0114 (17)	0.0000 (15)	−0.0022 (19)
C25	0.0307 (16)	0.0339 (18)	0.0257 (16)	0.0009 (13)	0.0017 (13)	−0.0038 (14)
C26	0.0301 (16)	0.0248 (16)	0.0253 (16)	0.0024 (13)	0.0030 (13)	−0.0027 (14)
C27	0.0466 (19)	0.0337 (19)	0.0338 (19)	−0.0114 (15)	0.0041 (15)	−0.0014 (16)
C28	0.035 (2)	0.106 (4)	0.057 (3)	−0.020 (2)	−0.0126 (18)	0.006 (3)
O1W	0.0858 (19)	0.0464 (17)	0.0386 (14)	−0.0232 (14)	−0.0184 (13)	0.0125 (13)
O2W	0.081 (2)	0.0485 (17)	0.0573 (18)	0.0233 (15)	−0.0433 (15)	−0.0106 (15)
O3W	0.065 (5)	0.047 (5)	0.087 (6)	0.020 (4)	−0.011 (4)	−0.001 (5)

Zn1—O1	2.113 (2)	C4—C5	1.367 (4)
Zn1—O3	2.329 (2)	C5—C7	1.508 (4)
Zn1—O6	2.408 (2)	C8—C13	1.503 (4)
Zn1—O8	2.119 (2)	C8—C9	1.358 (4)
Zn1—N1	1.995 (2)	C9—C10	1.393 (4)
Zn1—N2	1.987 (2)	C10—C11	1.394 (4)
O1—C6	1.247 (3)	C11—C12	1.369 (4)
O2—C6	1.256 (3)	C12—C14	1.527 (4)
O3—C7	1.267 (4)	C2—H2	0.9400
O4—C7	1.237 (4)	C4—H4	0.9400
O5—C3	1.330 (3)	C9—H9	0.9400
O6—C13	1.223 (3)	C11—H11	0.9400
O7—C13	1.282 (3)	C15—C27	1.476 (4)
O8—C14	1.270 (4)	C15—C16	1.394 (4)
O9—C14	1.233 (4)	C16—C17	1.364 (4)
O10—C10	1.327 (3)	C17—C18	1.407 (5)
O5—H5	0.8300	C18—C19	1.428 (4)
O7—H7	0.8300	C18—C26	1.391 (4)
O10—H10	0.8300	C19—C20	1.341 (5)
O1W—H1WB	0.84 (4)	C20—C21	1.431 (5)
O1W—H1WA	0.83 (3)	C21—C25	1.399 (4)
O2W—H2WB	0.81 (2)	C21—C22	1.402 (5)
O2W—H2WA	0.82 (4)	C22—C23	1.355 (6)
O3W—H3WB	0.82 (3)	C23—C24	1.395 (5)
O3W—H3WA	0.83 (6)	C24—C28	1.495 (5)
N1—C1	1.335 (4)	C25—C26	1.434 (5)
N1—C5	1.344 (3)	C16—H16	0.9400
N2—C12	1.335 (4)	C17—H17	0.9400
N2—C8	1.342 (3)	C19—H19	0.9400
N3—C26	1.363 (4)	C20—H20	0.9400
N3—C15	1.332 (3)	C22—H22	0.9400
N4—C25	1.349 (4)	C23—H23	0.9400
N4—C24	1.328 (4)	C27—H27B	0.9700
N3—H3	0.8700	C27—H27A	0.9700
C1—C6	1.500 (4)	C27—H27C	0.9700
C1—C2	1.373 (4)	C28—H28C	0.9700
C2—C3	1.396 (4)	C28—H28A	0.9700
C3—C4	1.383 (4)	C28—H28B	0.9700
O1—Zn1—O3	152.10 (8)	O6—C13—C8	119.5 (2)
O1—Zn1—O6	92.05 (7)	O7—C13—C8	112.9 (2)
O1—Zn1—O8	96.70 (8)	O6—C13—O7	127.6 (3)
O1—Zn1—N1	79.45 (8)	O9—C14—C12	118.5 (3)
O1—Zn1—N2	116.99 (8)	O8—C14—O9	126.6 (3)
O3—Zn1—O6	89.23 (7)	O8—C14—C12	114.9 (3)
O3—Zn1—O8	95.25 (8)	C1—C2—H2	121.00
O3—Zn1—N1	72.69 (8)	C3—C2—H2	121.00
O3—Zn1—N2	90.06 (8)	C5—C4—H4	120.00
O6—Zn1—O8	151.69 (7)	C3—C4—H4	120.00
O6—Zn1—N1	95.35 (8)	C8—C9—H9	121.00
O6—Zn1—N2	73.50 (8)	C10—C9—H9	121.00
O8—Zn1—N1	112.68 (8)	C12—C11—H11	121.00
O8—Zn1—N2	78.55 (8)	C10—C11—H11	121.00
N1—Zn1—N2	159.81 (9)	N3—C15—C27	119.3 (2)
Zn1—O1—C6	112.91 (18)	N3—C15—C16	117.6 (3)
Zn1—O3—C7	114.54 (19)	C16—C15—C27	123.1 (3)
Zn1—O6—C13	109.86 (18)	C15—C16—C17	121.1 (3)
Zn1—O8—C14	114.93 (18)	C16—C17—C18	120.3 (3)
C3—O5—H5	109.00	C17—C18—C26	117.6 (3)
C13—O7—H7	109.00	C19—C18—C26	119.1 (3)
C10—O10—H10	109.00	C17—C18—C19	123.3 (3)
H1WA—O1W—H1WB	108 (4)	C18—C19—C20	120.8 (3)
H2WA—O2W—H2WB	115 (4)	C19—C20—C21	121.1 (3)
H3WA—O3W—H3WB	113 (7)	C20—C21—C22	123.8 (3)
Zn1—N1—C5	124.33 (19)	C22—C21—C25	116.5 (3)
Zn1—N1—C1	115.63 (17)	C20—C21—C25	119.7 (3)
C1—N1—C5	119.9 (2)	C21—C22—C23	118.8 (3)
Zn1—N2—C8	122.97 (18)	C22—C23—C24	121.1 (3)
Zn1—N2—C12	117.32 (16)	N4—C24—C28	117.1 (3)
C8—N2—C12	119.2 (2)	N4—C24—C23	121.7 (3)
C15—N3—C26	123.8 (3)	C23—C24—C28	121.2 (3)
C24—N4—C25	117.3 (3)	C21—C25—C26	118.5 (3)
C26—N3—H3	118.00	N4—C25—C21	124.5 (3)
C15—N3—H3	118.00	N4—C25—C26	117.0 (3)
C2—C1—C6	124.4 (3)	C18—C26—C25	120.8 (3)
N1—C1—C6	113.9 (2)	N3—C26—C25	119.6 (3)
N1—C1—C2	121.8 (2)	N3—C26—C18	119.6 (3)
C1—C2—C3	118.6 (3)	C15—C16—H16	119.00
O5—C3—C4	118.6 (3)	C17—C16—H16	119.00
O5—C3—C2	122.4 (3)	C16—C17—H17	120.00
C2—C3—C4	119.0 (2)	C18—C17—H17	120.00
C3—C4—C5	119.1 (3)	C20—C19—H19	120.00
N1—C5—C7	113.3 (2)	C18—C19—H19	120.00
C4—C5—C7	125.1 (3)	C19—C20—H20	119.00
N1—C5—C4	121.6 (3)	C21—C20—H20	119.00
O2—C6—C1	115.6 (2)	C21—C22—H22	121.00
O1—C6—C1	117.9 (2)	C23—C22—H22	121.00
O1—C6—O2	126.5 (3)	C24—C23—H23	119.00
O3—C7—O4	126.4 (3)	C22—C23—H23	119.00
O3—C7—C5	114.9 (3)	C15—C27—H27B	109.00
O4—C7—C5	118.8 (3)	H27A—C27—H27C	109.00
N2—C8—C13	113.7 (2)	C15—C27—H27C	110.00
N2—C8—C9	122.4 (3)	H27A—C27—H27B	110.00
C9—C8—C13	123.9 (2)	C15—C27—H27A	109.00
C8—C9—C10	118.5 (2)	H27B—C27—H27C	110.00
O10—C10—C11	123.4 (3)	C24—C28—H28C	109.00
O10—C10—C9	117.3 (2)	H28A—C28—H28C	109.00
C9—C10—C11	119.3 (2)	H28B—C28—H28C	109.00
C10—C11—C12	118.1 (3)	H28A—C28—H28B	109.00
N2—C12—C11	122.5 (2)	C24—C28—H28A	109.00
C11—C12—C14	123.8 (3)	C24—C28—H28B	109.00
N2—C12—C14	113.7 (2)
O3—Zn1—O1—C6	4.4 (3)	C26—N3—C15—C27	178.7 (3)
O6—Zn1—O1—C6	96.58 (18)	C15—N3—C26—C25	−179.9 (3)
O8—Zn1—O1—C6	−110.39 (18)	C24—N4—C25—C21	−0.1 (5)
N1—Zn1—O1—C6	1.51 (18)	C25—N4—C24—C23	0.3 (5)
N2—Zn1—O1—C6	169.07 (17)	C25—N4—C24—C28	−179.8 (3)
O1—Zn1—O3—C7	−0.9 (3)	C24—N4—C25—C26	178.8 (3)
O6—Zn1—O3—C7	−93.9 (2)	N1—C1—C2—C3	0.9 (4)
O8—Zn1—O3—C7	114.1 (2)	N1—C1—C6—O2	173.5 (2)
N1—Zn1—O3—C7	2.0 (2)	C6—C1—C2—C3	−179.1 (3)
N2—Zn1—O3—C7	−167.4 (2)	N1—C1—C6—O1	−5.0 (4)
O1—Zn1—O6—C13	119.77 (19)	C2—C1—C6—O1	175.0 (3)
O3—Zn1—O6—C13	−88.10 (19)	C2—C1—C6—O2	−6.6 (4)
O8—Zn1—O6—C13	11.6 (3)	C1—C2—C3—C4	−3.0 (4)
N1—Zn1—O6—C13	−160.63 (19)	C1—C2—C3—O5	176.4 (3)
N2—Zn1—O6—C13	2.19 (19)	C2—C3—C4—C5	2.7 (4)
O1—Zn1—O8—C14	−120.2 (2)	O5—C3—C4—C5	−176.7 (3)
O3—Zn1—O8—C14	85.1 (2)	C3—C4—C5—C7	177.5 (3)
O6—Zn1—O8—C14	−13.1 (3)	C3—C4—C5—N1	−0.3 (4)
N1—Zn1—O8—C14	158.5 (2)	N1—C5—C7—O3	6.4 (4)
N2—Zn1—O8—C14	−3.9 (2)	N1—C5—C7—O4	−173.9 (3)
O1—Zn1—N1—C1	−4.36 (18)	C4—C5—C7—O4	8.1 (5)
O1—Zn1—N1—C5	−179.5 (2)	C4—C5—C7—O3	−171.6 (3)
O3—Zn1—N1—C1	177.0 (2)	N2—C8—C9—C10	−0.6 (4)
O3—Zn1—N1—C5	2.0 (2)	C13—C8—C9—C10	−179.2 (3)
O6—Zn1—N1—C1	−95.45 (19)	N2—C8—C13—O6	−6.4 (4)
O6—Zn1—N1—C5	89.5 (2)	N2—C8—C13—O7	174.0 (2)
O8—Zn1—N1—C1	88.55 (19)	C9—C8—C13—O6	172.4 (3)
O8—Zn1—N1—C5	−86.5 (2)	C9—C8—C13—O7	−7.3 (4)
N2—Zn1—N1—C1	−150.6 (2)	C8—C9—C10—O10	178.8 (2)
N2—Zn1—N1—C5	34.3 (4)	C8—C9—C10—C11	−1.1 (4)
O1—Zn1—N2—C8	−90.0 (2)	C9—C10—C11—C12	1.9 (4)
O1—Zn1—N2—C12	98.8 (2)	O10—C10—C11—C12	−178.0 (3)
O3—Zn1—N2—C8	83.0 (2)	C10—C11—C12—C14	178.7 (3)
O3—Zn1—N2—C12	−88.3 (2)	C10—C11—C12—N2	−1.2 (4)
O6—Zn1—N2—C8	−6.2 (2)	N2—C12—C14—O8	5.1 (4)
O6—Zn1—N2—C12	−177.5 (2)	C11—C12—C14—O8	−174.8 (3)
O8—Zn1—N2—C8	178.3 (2)	C11—C12—C14—O9	5.7 (4)
O8—Zn1—N2—C12	7.01 (19)	N2—C12—C14—O9	−174.4 (3)
N1—Zn1—N2—C8	52.2 (4)	N3—C15—C16—C17	0.4 (4)
N1—Zn1—N2—C12	−119.1 (3)	C27—C15—C16—C17	−177.7 (3)
Zn1—O1—C6—O2	−176.9 (2)	C15—C16—C17—C18	−1.1 (5)
Zn1—O1—C6—C1	1.3 (3)	C16—C17—C18—C19	179.8 (3)
Zn1—O3—C7—O4	175.4 (3)	C16—C17—C18—C26	0.7 (5)
Zn1—O3—C7—C5	−4.9 (3)	C17—C18—C19—C20	−178.7 (3)
Zn1—O6—C13—O7	−178.8 (2)	C26—C18—C19—C20	0.4 (5)
Zn1—O6—C13—C8	1.5 (3)	C17—C18—C26—N3	0.2 (4)
Zn1—O8—C14—O9	−180.0 (3)	C17—C18—C26—C25	179.2 (3)
Zn1—O8—C14—C12	0.6 (3)	C19—C18—C26—N3	−178.9 (3)
Zn1—N1—C1—C2	−173.8 (2)	C19—C18—C26—C25	0.1 (5)
Zn1—N1—C1—C6	6.2 (3)	C18—C19—C20—C21	−0.4 (5)
C5—N1—C1—C2	1.5 (4)	C19—C20—C21—C22	179.4 (3)
C5—N1—C1—C6	−178.5 (2)	C19—C20—C21—C25	−0.2 (5)
Zn1—N1—C5—C4	173.1 (2)	C20—C21—C22—C23	−179.3 (3)
Zn1—N1—C5—C7	−5.0 (3)	C25—C21—C22—C23	0.2 (5)
C1—N1—C5—C4	−1.8 (4)	C20—C21—C25—N4	179.4 (3)
C1—N1—C5—C7	−179.9 (2)	C20—C21—C25—C26	0.6 (4)
Zn1—N2—C8—C9	−169.8 (2)	C22—C21—C25—N4	−0.2 (5)
Zn1—N2—C8—C13	9.0 (3)	C22—C21—C25—C26	−179.0 (3)
C12—N2—C8—C9	1.3 (4)	C21—C22—C23—C24	0.0 (6)
C12—N2—C8—C13	−179.9 (2)	C22—C23—C24—N4	−0.2 (6)
Zn1—N2—C12—C11	171.2 (2)	C22—C23—C24—C28	179.9 (4)
Zn1—N2—C12—C14	−8.7 (3)	N4—C25—C26—N3	−0.5 (4)
C8—N2—C12—C11	−0.4 (4)	N4—C25—C26—C18	−179.5 (3)
C8—N2—C12—C14	179.7 (2)	C21—C25—C26—N3	178.4 (3)
C15—N3—C26—C18	−0.8 (4)	C21—C25—C26—C18	−0.6 (5)
C26—N3—C15—C16	0.5 (4)

Cg1 is the centroid of the N1,C1–C5 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N4	0.87	2.37	2.721 (3)	105
N3—H3···O1W	0.87	2.01	2.848 (4)	161
O5—H5···O2W	0.83	1.76	2.570 (4)	166
O7—H7···O2i	0.83	1.66	2.402 (3)	147
O10—H10···O3ii	0.83	1.75	2.562 (3)	166
O1W—H1WA···O9iii	0.83 (3)	2.02 (4)	2.833 (4)	169 (4)
O1W—H1WB···O4iv	0.84 (4)	2.18 (4)	2.960 (4)	156 (3)
O2W—H2WA···O8v	0.82 (4)	1.98 (4)	2.738 (4)	155 (4)
O2W—H2WB···O4vi	0.81 (2)	2.25 (3)	3.046 (4)	171 (4)
O3W—H3WA···O4	0.83 (2)	1.75 (5)	2.530 (7)	157 (13)
O3W—H3WB···O2Wv	0.82 (2)	2.21 (4)	2.750 (9)	123 (3)
C27—H27C···O3vii	0.97	2.58	3.504 (4)	160
C22—H22···Cg1viii	0.94	2.76	3.634 (4)	155

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1,C1–C5 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N4	0.87	2.37	2.721 (3)	105
N3—H3⋯O1W	0.87	2.01	2.848 (4)	161
O5—H5⋯O2W	0.83	1.76	2.570 (4)	166
O7—H7⋯O2i	0.83	1.66	2.402 (3)	147
O10—H10⋯O3ii	0.83	1.75	2.562 (3)	166
O1W—H1WA⋯O9iii	0.83 (3)	2.02 (4)	2.833 (4)	169 (4)
O1W—H1WB⋯O4iv	0.84 (4)	2.18 (4)	2.960 (4)	156 (3)
O2W—H2WA⋯O8v	0.82 (4)	1.98 (4)	2.738 (4)	155 (4)
O2W—H2WB⋯O4vi	0.81 (2)	2.25 (3)	3.046 (4)	171 (4)
O3W—H3WA⋯O4	0.83 (2)	1.75 (5)	2.530 (7)	157 (13)
O3W—H3WB⋯O2Wv	0.82 (2)	2.21 (4)	2.750 (9)	123 (3)
C27—H27C⋯O3vii	0.97	2.58	3.504 (4)	160
C22—H22⋯Cg1viii	0.94	2.76	3.634 (4)	155

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .