Bis{N,N,N-trimethyl-2-oxo-2-[2-(2,3,4- trihydroxy­benzyl­idene)hydrazin­yl]ethanaminium} tetra­chlorido­zincate(II) methanol solvate

Novaković, S.B.; Drašković, B.M.; Vojinović-Ješić, L.S.; Češljević, V.I.; Leovac, V.M.

doi:10.1107/S160053681000615X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m328-m329

doi:10.1107/S160053681000615X

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Bis{N,N,N-trimethyl-2-oxo-2-[2-(2,3,4- trihydroxybenzylidene)hydrazinyl]ethanaminium} tetrachloridozincate(II) methanol solvate †

Sladjana B. Novaković,^a ^* Bojana M. Drašković,^a Ljiljana S. Vojinović-Ješić,^b Valerija I. Češljević ^b and Vukadin M. Leovac ^b

^a'Vinča' Institute of Nuclear Sciences, Laboratory of Theoretical Physics and Condensed Matter Physics, PO Box 522, 11001 Belgrade, Serbia, and ^bDepartment of Chemistry, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3, 21000 Novi Sad, Serbia
^*Correspondence e-mail: snovak@vinca.rs

(Received 1 February 2010; accepted 16 February 2010; online 24 February 2010)

The asymmetric unit of the title compound, (C₁₂H₁₈N₃O₄)₂[ZnCl₄]·CH₃OH, consists of two Girard reagent-based cations, a tetrachloridozincate anion and a molecule of methanol as solvate. These components are interconnected in the crystal structure by an extensive network of O—H⋯O, N—H⋯O, C—H⋯O, O—H⋯N, O—H⋯Cl, N—H⋯Cl and C—H⋯Cl hydrogen bonds. The shortest intermolecular interaction is realized between the cation and anion [H⋯Cl = 2.29 (5) Å; O—H⋯Cl = 167 (3)°]. C—H⋯O interactions also play a important role in the interconnection of the cations.

Related literature

For the crystal structures of the related Girard reagent-based ligands and coordination compounds, see: Leovac et al. (2006 , 2007 ); Vojinović et al. (2004 ) and references therein; Vojinović-Ješić et al. (2008 , 2010 ); Revenko et al. (2009 ). For the crystal structures containing the tetrachloridozincate ion, see: Jin et al. (2005 ); Valkonen et al. (2006 ).

Experimental

Crystal data

(C₁₂H₁₈N₃O₄)₂[ZnCl₄]·CH₄O
M_r = 775.82
Triclinic, $[P \overline 1]$
a = 9.471 (3) Å
b = 13.389 (4) Å
c = 14.986 (5) Å
α = 110.90 (4)°
β = 94.91 (4)°
γ = 103.94 (5)°
V = 1691.9 (12) Å³
Z = 2
Mo Kα radiation
μ = 1.10 mm⁻¹
T = 295 K
0.33 × 0.21 × 0.18 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
7056 measured reflections
6632 independent reflections
5226 reflections with I > 2σ(I)
R_int = 0.017
3 standard reflections every 60 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.128
S = 1.05
6632 reflections
440 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4A—H4A⋯N1A	0.84 (5)	1.82 (5)	2.592 (4)	153 (5)
O5A—H5A⋯Cl2ⁱ	0.83 (5)	2.29 (5)	3.094 (4)	167 (3)
O6A—H6A⋯O5A	0.82 (7)	2.30 (6)	2.693 (4)	110 (5)
O6A—H6A⋯Cl4ⁱ	0.82 (7)	2.64 (6)	3.317 (3)	141 (5)
O4B—H4B⋯N1B	0.80 (4)	1.86 (4)	2.599 (4)	155 (4)
O5B—H5B⋯O4B	0.77 (6)	2.28 (6)	2.721 (4)	118 (5)
O5B—H5B⋯Cl1ⁱⁱ	0.77 (6)	2.60 (5)	3.217 (3)	139 (5)
O6B—H6B⋯O5B	0.85 (5)	2.32 (5)	2.728 (4)	110 (4)
O6B—H6B⋯Cl4ⁱⁱⁱ	0.85 (5)	2.59 (5)	3.193 (3)	129 (4)
C10A—H10A⋯O1A	0.96	2.34	2.992 (5)	124
C10B—H10F⋯O1B	0.96	2.33	2.978 (4)	124
C10B—H10E⋯O4A	0.96	2.50	3.404 (5)	157
C10B—H10F⋯O1B	0.96	2.33	2.978 (4)	124
C12A—H12A⋯O6Aⁱ	0.96	2.60	3.307 (6)	131
C12A—H12B⋯O1A	0.96	2.41	3.043 (7)	123
C12B—H12E⋯O1B	0.96	2.40	3.028 (5)	123
C12A—H12C⋯Cl1ⁱⁱ	0.96	2.83	3.715 (5)	154
O7—H7O⋯Cl3^iv	0.82	2.44	3.251 (4)	169
N2A—H2NA⋯Cl1	0.77 (4)	2.59 (4)	3.287 (3)	154 (4)
N2B—H2NB⋯O7	0.78 (4)	2.05 (4)	2.826 (5)	175 (4)
Symmetry codes: (i) -x, -y+1, -z; (ii) x+1, y, z; (iii) -x+2, -y+2, -z+1; (iv) x+1, y-1, z.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ), PLATON (Spek, 2009 ) and PARST (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681000615X/rk2191sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000615X/rk2191Isup2.hkl

checkCIF report

Comment top

The Schiff base derivatives of Girard reagent are recently investigated as ligands in coordination chemistry (Vojinović et al., 2004 and references therein; Leovac et al., 2006, 2007; Revenko et al., 2009; Vojinović-Ješić et al., 2008, 2010). Considering the specific distribution of charge and simultaneous presence of several donor and acceptor atoms these compounds are able to build extensive hydrogen bonding networks consisting of various types of interactions.

The asymmetric unit of the title compound is given in Fig. 1. Two crystallographically independent cations (A and B) display very similar geometry. The bond lengths and angles within the aliphatic parts of the cations are consistent with those of two previously reported Girard-T based hydrazones (Leovac et al., 2007; Revenko et al., 2009).

Excluding the quaternary ammonium groups, non-hydrogen atoms of two cations (A and B) lie in plane, i.e. the root-mean-square deviations of fitted atoms 0.1Å or less. These approximately planar forms of the molecules are stabilized by number of intramolecular hydrogen bonds with the shortest being O4—H4···N1 (see Table 1). The C9—N3 bonds are single and allow for free rotation of the N(CH₃)₃) moiety (as was observed in complexes (Leovac et al., 2007), yet in each of the cations the deviation of the quaternary ammonium groups is restrained due to intramolecular C—H···O interactions.

Anion (ZnCl₄)^2- exhibits regular tetrahedral geometry with Zn—Cl distances comparable to similar anions (Jin et al., 2005; Valkonen et al., 2006). Through O—H···Cl, N—H···Cl and C—H···Cl hydrogen bonds the anion intermediates between five different cations. The strongest among these interactions is rather short and directional O5A—H5A···Cl2ⁱ (symmetry code: (i) -x, -y+1, -z) (see Table 1). It is worth noticing that the hydroxyl hydrogen involved in this interaction is the only one (from the six in totals) which significantly deviates from the trihydroxybenzyl moiety.

In the crystal packing, centrosymmetrically related cationic molecules, by C—H···O interactions, with H···O distances all shorter than 2.7Å, associate into corresponding AA and BB dimers. The distances between the parallel planes (passing trough all atoms except N(CH₃)₃) are 3.386 (8) and 3.194 (7)Å for AA and BB dimers respectively. The pairs of AA and BB dimers further arrange in approximately parallel fashion (angle between planes of A and B molecule is 0.92 (8)°) along the c axis with the closest distance between non-H atoms of 3.407 (5)Å (Fig. 2.). The C—H···O hydrogen interactions relating the dimers mainly include the methyl groups from the quaternary ammonium fragment and oxygen O6 which is in para-position concerning the aliphatic fragment.

Related literature top

For the crystal structures of the related Girard reagent-based ligands and coordination compounds, see: Leovac et al. (2006, 2007); Vojinović et al. (2004) and references therein; Vojinović-Ješić et al. (2008, 2010); Revenko et al. (2009). For the crystal structures containing the tetrachloridozincate ion, see: Jin et al. (2005); Valkonen et al. (2006).

Experimental top

To a warm solution of L (L = [(CH₃)₃NCH₂C(O)NHNCHC₆H₂(OH)₃]⁺ Cl^-) (0.15 g, 0.5 mmol) in MeOH (5 ml) was added a solution ZnCl₂ (anhydrous) (0.07 g, 0.5 mmol) in MeOH (3 ml). The reaction mixture was refluxed for 45 min. After two days the resulting light-green crystals have been filtered and washed with methanol and ether (yield 37%).

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (cheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Figures top

	Fig. 1. The molecular structure of title compound with atom labels. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius. The intramolecular H-bonds are indicated as dashed lines.
	Fig. 2. The packing diagram of title compound shows the intermolecular H-bonds (dashed lines). H atoms not involved in intermolecular H-bonds are omitted for clarity.

Bis{N,N,N-trimethyl-2-oxo-2-[2-(2,3,4- trihydroxybenzylidene)hydrazinyl]ethanaminium} tetrachloridozincate(II) methanol solvate top

Crystal data top

(C₁₂H₁₈N₃O₄)₂[ZnCl₄]·CH₄O	Z = 2
M_r = 775.82	F(000) = 804
Triclinic, P1	D_x = 1.523 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.471 (3) Å	Cell parameters from 25 reflections
b = 13.389 (4) Å	θ = 11.5–19.4°
c = 14.986 (5) Å	µ = 1.10 mm⁻¹
α = 110.90 (4)°	T = 295 K
β = 94.91 (4)°	Prism, light-green
γ = 103.94 (5)°	0.33 × 0.21 × 0.18 mm
V = 1691.9 (12) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.017
Radiation source: fine-focus sealed tube	θ_max = 26.0°, θ_min = 1.5°
Graphite monochromator	h = 0→11
ω/2θ–scans	k = −16→16
7056 measured reflections	l = −18→18
6632 independent reflections	3 standard reflections every 60 min
5226 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0754P)² + 0.7588P] where P = (F_o² + 2F_c²)/3
6632 reflections	(Δ/σ)_max = 0.001
440 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

(C₁₂H₁₈N₃O₄)₂[ZnCl₄]·CH₄O	γ = 103.94 (5)°
M_r = 775.82	V = 1691.9 (12) Å³
Triclinic, P1	Z = 2
a = 9.471 (3) Å	Mo Kα radiation
b = 13.389 (4) Å	µ = 1.10 mm⁻¹
c = 14.986 (5) Å	T = 295 K
α = 110.90 (4)°	0.33 × 0.21 × 0.18 mm
β = 94.91 (4)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.017
7056 measured reflections	3 standard reflections every 60 min
6632 independent reflections	intensity decay: none
5226 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.81 e Å⁻³
6632 reflections	Δρ_min = −0.58 e Å⁻³
440 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.12662 (4)	0.97209 (3)	0.27361 (2)	0.03615 (12)
Cl1	0.08234 (9)	0.87169 (6)	0.36739 (6)	0.0457 (2)
Cl2	−0.02229 (10)	0.86775 (8)	0.12557 (6)	0.0582 (2)
Cl3	0.07728 (10)	1.13575 (7)	0.34252 (7)	0.0550 (2)
Cl4	0.36959 (9)	0.99260 (7)	0.25977 (7)	0.0542 (2)
O1A	0.3976 (3)	0.5823 (2)	0.2618 (2)	0.0630 (7)
O4A	0.0152 (3)	0.3662 (2)	0.11211 (17)	0.0436 (5)
O5A	−0.2207 (3)	0.1888 (2)	−0.00766 (19)	0.0516 (6)
O6A	−0.4465 (3)	0.2247 (2)	−0.10178 (19)	0.0547 (6)
O1B	0.6208 (3)	0.44499 (19)	0.23238 (19)	0.0510 (6)
O4B	0.9987 (2)	0.63770 (19)	0.40319 (17)	0.0425 (5)
O5B	1.2379 (3)	0.80292 (19)	0.52686 (19)	0.0508 (6)
O6B	1.4654 (3)	0.7511 (2)	0.60703 (17)	0.0484 (6)
N1A	0.1257 (3)	0.5816 (2)	0.19456 (18)	0.0365 (5)
N2A	0.2344 (3)	0.6776 (2)	0.25321 (19)	0.0382 (6)
N3A	0.6305 (3)	0.7890 (2)	0.36455 (18)	0.0427 (6)
N1B	0.8729 (2)	0.4242 (2)	0.31181 (16)	0.0327 (5)
N2B	0.7550 (3)	0.3346 (2)	0.25584 (18)	0.0336 (5)
N3B	0.3590 (3)	0.2561 (2)	0.14515 (17)	0.0354 (5)
C1A	0.3662 (3)	0.6692 (3)	0.2858 (2)	0.0390 (6)
C2A	0.0097 (3)	0.5939 (3)	0.1539 (2)	0.0365 (6)
H2A	0.0015	0.6651	0.1655	0.044*
C3A	−0.1076 (3)	0.4967 (2)	0.0901 (2)	0.0340 (6)
C4A	−0.1013 (3)	0.3874 (3)	0.0709 (2)	0.0338 (6)
C5A	−0.2159 (3)	0.2969 (3)	0.0080 (2)	0.0373 (6)
C6A	−0.3357 (3)	0.3144 (3)	−0.0383 (2)	0.0402 (7)
C7A	−0.3442 (3)	0.4209 (3)	−0.0204 (2)	0.0424 (7)
H7A	−0.4253	0.4316	−0.0513	0.051*
C8A	−0.2319 (3)	0.5109 (3)	0.0430 (2)	0.0395 (7)
H9A	−0.2381	0.5827	0.0553	0.047*
C9A	0.4695 (3)	0.7812 (3)	0.3546 (3)	0.0446 (7)
H9A1	0.4536	0.8381	0.3324	0.054*
H9A2	0.4432	0.7981	0.4184	0.054*
C10A	0.6698 (4)	0.7172 (4)	0.4147 (3)	0.0652 (11)
H10B	0.7738	0.7245	0.4196	0.098*
H10A	0.6142	0.6405	0.3777	0.098*
H10C	0.6465	0.7408	0.4786	0.098*
C11A	0.7131 (5)	0.9079 (3)	0.4276 (4)	0.0787 (14)
H11A	0.6905	0.9560	0.3975	0.118*
H11C	0.8177	0.9167	0.4358	0.118*
H11B	0.6841	0.9272	0.4900	0.118*
C12A	0.6778 (5)	0.7560 (5)	0.2689 (3)	0.0796 (14)
H12C	0.7816	0.7622	0.2784	0.119*
H12A	0.6598	0.8042	0.2377	0.119*
H12B	0.6226	0.6801	0.2288	0.119*
C1B	0.6326 (3)	0.3538 (2)	0.2203 (2)	0.0338 (6)
C2B	0.9820 (3)	0.4038 (2)	0.3508 (2)	0.0329 (6)
H2B	0.9809	0.3303	0.3378	0.039*
C3B	1.1081 (3)	0.4953 (2)	0.41539 (19)	0.0307 (6)
C4B	1.1095 (3)	0.6063 (2)	0.4389 (2)	0.0319 (6)
C5B	1.2296 (3)	0.6925 (2)	0.5024 (2)	0.0346 (6)
C6B	1.3468 (3)	0.6685 (2)	0.54445 (19)	0.0347 (6)
C7B	1.3446 (3)	0.5582 (3)	0.5228 (2)	0.0377 (6)
H7B	1.4223	0.5420	0.5516	0.045*
C8B	1.2270 (3)	0.4731 (2)	0.4586 (2)	0.0356 (6)
H8B	1.2266	0.3994	0.4437	0.043*
C9B	0.5121 (3)	0.2445 (2)	0.1623 (2)	0.0368 (6)
H9B2	0.5382	0.2095	0.0997	0.044*
H9B1	0.5101	0.1948	0.1963	0.044*
C10B	0.3479 (4)	0.3179 (3)	0.0803 (2)	0.0470 (8)
H10D	0.3735	0.2794	0.0193	0.071*
H10F	0.4148	0.3921	0.1108	0.071*
H10E	0.2484	0.3218	0.0693	0.071*
C11B	0.2541 (4)	0.1409 (3)	0.0978 (3)	0.0578 (9)
H11D	0.2795	0.1022	0.0368	0.087*
H11E	0.1549	0.1453	0.0868	0.087*
H11F	0.2607	0.1012	0.1394	0.087*
C12B	0.3156 (4)	0.3150 (3)	0.2399 (2)	0.0504 (8)
H12D	0.2158	0.3178	0.2276	0.076*
H12E	0.3813	0.3896	0.2711	0.076*
H12F	0.3221	0.2751	0.2813	0.076*
H4B	0.940 (4)	0.579 (3)	0.370 (3)	0.051 (11)*
H5B	1.166 (6)	0.804 (4)	0.500 (4)	0.085 (17)*
H6B	1.454 (5)	0.816 (4)	0.621 (3)	0.075 (15)*
H4A	0.075 (5)	0.430 (4)	0.143 (3)	0.070 (14)*
H5A	−0.147 (5)	0.177 (4)	−0.030 (3)	0.067 (14)*
H6A	−0.427 (6)	0.165 (5)	−0.114 (4)	0.10 (2)*
H2NB	0.758 (4)	0.276 (3)	0.254 (2)	0.038 (9)*
H2NA	0.212 (4)	0.731 (3)	0.267 (3)	0.044 (11)*
C13	0.7289 (7)	0.0438 (5)	0.1584 (4)	0.1002 (18)
H13A	0.8041	0.0717	0.1271	0.150*
H13B	0.6329	0.0310	0.1224	0.150*
H13C	0.7380	−0.0251	0.1608	0.150*
O7	0.7452 (4)	0.1197 (3)	0.2501 (3)	0.0843 (10)
H7O	0.8265	0.1296	0.2811	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.03453 (19)	0.03438 (19)	0.0375 (2)	0.00982 (14)	−0.00078 (14)	0.01356 (14)
Cl1	0.0518 (4)	0.0427 (4)	0.0458 (4)	0.0134 (3)	0.0046 (3)	0.0223 (3)
Cl2	0.0511 (5)	0.0706 (6)	0.0384 (4)	0.0232 (4)	−0.0089 (4)	0.0048 (4)
Cl3	0.0607 (5)	0.0396 (4)	0.0602 (5)	0.0222 (4)	−0.0016 (4)	0.0122 (4)
Cl4	0.0351 (4)	0.0513 (5)	0.0666 (5)	0.0088 (3)	0.0055 (4)	0.0155 (4)
O1A	0.0412 (13)	0.0405 (13)	0.0897 (19)	0.0182 (11)	−0.0098 (13)	0.0062 (13)
O4A	0.0375 (11)	0.0466 (13)	0.0444 (12)	0.0177 (10)	−0.0002 (10)	0.0134 (10)
O5A	0.0532 (15)	0.0411 (13)	0.0540 (14)	0.0108 (11)	0.0069 (12)	0.0139 (11)
O6A	0.0368 (12)	0.0543 (16)	0.0525 (14)	0.0054 (11)	−0.0063 (10)	0.0058 (12)
O1B	0.0411 (12)	0.0402 (12)	0.0673 (15)	0.0134 (10)	−0.0047 (11)	0.0181 (11)
O4B	0.0375 (12)	0.0382 (12)	0.0512 (13)	0.0121 (10)	−0.0059 (10)	0.0194 (11)
O5B	0.0522 (14)	0.0348 (12)	0.0558 (15)	0.0079 (10)	−0.0105 (12)	0.0146 (10)
O6B	0.0395 (12)	0.0476 (14)	0.0423 (12)	0.0020 (10)	−0.0094 (10)	0.0104 (11)
O7	0.076 (2)	0.0651 (19)	0.097 (2)	0.0241 (16)	−0.0165 (17)	0.0207 (17)
N1A	0.0286 (12)	0.0391 (13)	0.0355 (13)	0.0067 (10)	0.0029 (10)	0.0103 (10)
N2A	0.0276 (12)	0.0362 (14)	0.0430 (14)	0.0110 (11)	−0.0006 (10)	0.0071 (11)
N3A	0.0303 (13)	0.0478 (15)	0.0376 (13)	0.0064 (11)	−0.0032 (10)	0.0081 (11)
N1B	0.0280 (11)	0.0372 (12)	0.0299 (11)	0.0070 (10)	0.0008 (9)	0.0123 (10)
N2B	0.0293 (12)	0.0325 (13)	0.0351 (12)	0.0083 (10)	−0.0018 (10)	0.0109 (10)
N3B	0.0281 (11)	0.0474 (14)	0.0318 (12)	0.0092 (10)	0.0002 (9)	0.0192 (11)
C1A	0.0309 (14)	0.0390 (16)	0.0417 (16)	0.0099 (12)	0.0029 (12)	0.0108 (13)
C2A	0.0346 (15)	0.0411 (16)	0.0329 (14)	0.0120 (12)	0.0046 (12)	0.0131 (12)
C3A	0.0288 (13)	0.0432 (16)	0.0303 (14)	0.0108 (12)	0.0056 (11)	0.0147 (12)
C4A	0.0286 (13)	0.0459 (16)	0.0292 (13)	0.0141 (12)	0.0068 (11)	0.0149 (12)
C5A	0.0355 (15)	0.0454 (17)	0.0315 (14)	0.0123 (13)	0.0098 (12)	0.0146 (13)
C6A	0.0302 (14)	0.0538 (18)	0.0302 (14)	0.0070 (13)	0.0049 (11)	0.0129 (13)
C7A	0.0305 (15)	0.061 (2)	0.0365 (15)	0.0159 (14)	0.0002 (12)	0.0190 (14)
C8A	0.0364 (15)	0.0487 (17)	0.0365 (15)	0.0168 (13)	0.0044 (12)	0.0177 (13)
C9A	0.0315 (15)	0.0401 (16)	0.0526 (19)	0.0124 (13)	−0.0024 (13)	0.0081 (14)
C10A	0.054 (2)	0.078 (3)	0.064 (2)	0.029 (2)	−0.0094 (18)	0.027 (2)
C11A	0.046 (2)	0.054 (2)	0.096 (3)	−0.0037 (18)	−0.015 (2)	0.003 (2)
C12A	0.048 (2)	0.129 (4)	0.041 (2)	0.008 (2)	0.0077 (17)	0.019 (2)
C1B	0.0295 (13)	0.0395 (16)	0.0304 (13)	0.0096 (12)	0.0018 (11)	0.0126 (12)
C2B	0.0329 (14)	0.0347 (14)	0.0302 (14)	0.0123 (11)	0.0061 (11)	0.0101 (11)
C3B	0.0273 (13)	0.0377 (14)	0.0278 (13)	0.0101 (11)	0.0057 (10)	0.0131 (11)
C4B	0.0277 (13)	0.0418 (15)	0.0299 (13)	0.0107 (11)	0.0049 (11)	0.0182 (12)
C5B	0.0359 (15)	0.0365 (15)	0.0304 (14)	0.0079 (12)	0.0036 (11)	0.0143 (12)
C6B	0.0306 (14)	0.0435 (16)	0.0238 (13)	0.0063 (12)	0.0030 (11)	0.0096 (12)
C7B	0.0307 (14)	0.0494 (17)	0.0338 (14)	0.0165 (13)	0.0029 (11)	0.0148 (13)
C8B	0.0365 (15)	0.0371 (15)	0.0343 (14)	0.0156 (12)	0.0045 (12)	0.0126 (12)
C9B	0.0318 (14)	0.0387 (15)	0.0370 (15)	0.0123 (12)	−0.0016 (12)	0.0121 (12)
C10B	0.0419 (17)	0.068 (2)	0.0420 (17)	0.0188 (16)	0.0038 (14)	0.0324 (16)
C11B	0.0422 (18)	0.058 (2)	0.058 (2)	−0.0027 (16)	−0.0138 (16)	0.0210 (18)
C12B	0.0444 (18)	0.073 (2)	0.0389 (17)	0.0214 (17)	0.0149 (14)	0.0230 (16)
C13	0.108 (4)	0.094 (4)	0.089 (4)	0.060 (3)	0.002 (3)	0.009 (3)

Geometric parameters (Å, º) top

Zn1—Cl3	2.2467 (13)	O4B—C4B	1.357 (3)
Zn1—Cl1	2.2661 (11)	O4B—H4B	0.80 (4)
Zn1—Cl2	2.2731 (18)	O5B—C5B	1.371 (4)
Zn1—Cl4	2.2870 (12)	O5B—H5B	0.77 (5)
O1A—C1A	1.208 (4)	O6B—C6B	1.359 (4)
O4A—C4A	1.356 (3)	O6B—H6B	0.85 (5)
O4A—H4A	0.84 (4)	N1B—C2B	1.276 (4)
O5A—C5A	1.369 (4)	N1B—N2B	1.366 (3)
O5A—H5A	0.82 (5)	N2B—C1B	1.352 (4)
O6A—C6A	1.362 (4)	N2B—H2NB	0.79 (3)
O6A—H6A	0.82 (6)	N3B—C11B	1.493 (4)
N1A—C2A	1.285 (4)	N3B—C10B	1.495 (4)
N1A—N2A	1.373 (4)	N3B—C12B	1.504 (4)
N2A—C1A	1.346 (4)	N3B—C9B	1.506 (4)
N2A—H2NA	0.75 (4)	C1B—C9B	1.523 (4)
N3A—C12A	1.484 (5)	C2B—C3B	1.454 (4)
N3A—C9A	1.494 (4)	C2B—H2B	0.9300
N3A—C11A	1.497 (5)	C3B—C4B	1.396 (4)
N3A—C10A	1.505 (5)	C3B—C8B	1.397 (4)
C1A—C9A	1.513 (4)	C4B—C5B	1.390 (4)
C2A—C3A	1.441 (4)	C5B—C6B	1.389 (4)
C2A—H2A	0.9300	C6B—C7B	1.388 (4)
C3A—C4A	1.405 (4)	C7B—C8B	1.373 (4)
C3A—C8A	1.407 (4)	C7B—H7B	0.9300
C4A—C5A	1.382 (4)	C8B—H8B	0.9300
C5A—C6A	1.390 (4)	C9B—H9B2	0.9700
C6A—C7A	1.378 (5)	C9B—H9B1	0.9700
C7A—C8A	1.371 (5)	C10B—H10D	0.9600
C7A—H7A	0.9300	C10B—H10F	0.9600
C8A—H9A	0.9300	C10B—H10E	0.9600
C9A—H9A1	0.9700	C11B—H11D	0.9600
C9A—H9A2	0.9700	C11B—H11E	0.9600
C10A—H10B	0.9600	C11B—H11F	0.9600
C10A—H10A	0.9600	C12B—H12D	0.9600
C10A—H10C	0.9600	C12B—H12E	0.9600
C11A—H11A	0.9600	C12B—H12F	0.9600
C11A—H11C	0.9600	C13—O7	1.355 (6)
C11A—H11B	0.9600	O7—H7O	0.8200
C12A—H12C	0.9600	C13—H13A	0.9600
C12A—H12A	0.9600	C13—H13B	0.9600
C12A—H12B	0.9600	C13—H13C	0.9600
O1B—C1B	1.203 (4)

Cl3—Zn1—Cl1	109.97 (5)	H10A—C10A—H10C	109.5
Cl3—Zn1—Cl2	110.89 (5)	N3A—C11A—H11A	109.5
Cl1—Zn1—Cl2	107.16 (5)	N3A—C11A—H11C	109.5
Cl3—Zn1—Cl4	113.17 (6)	H11A—C11A—H11C	109.5
Cl1—Zn1—Cl4	105.36 (5)	N3A—C11A—H11B	109.5
Cl2—Zn1—Cl4	109.97 (6)	H11A—C11A—H11B	109.5
C4A—O4A—H4A	103 (3)	H11C—C11A—H11B	109.5
C5A—O5A—H5A	108 (3)	N3A—C12A—H12C	109.5
C6A—O6A—H6A	113 (4)	N3A—C12A—H12A	109.5
C4B—O4B—H4B	102 (3)	H12C—C12A—H12A	109.5
C5B—O5B—H5B	106 (4)	N3A—C12A—H12B	109.5
C6B—O6B—H6B	112 (3)	H12C—C12A—H12B	109.5
C13—O7—H7O	109.5	H12A—C12A—H12B	109.5
C2A—N1A—N2A	116.7 (3)	O1B—C1B—N2B	124.5 (3)
C1A—N2A—N1A	118.6 (3)	O1B—C1B—C9B	124.6 (3)
C1A—N2A—H2NA	126 (3)	N2B—C1B—C9B	110.9 (2)
N1A—N2A—H2NA	116 (3)	N1B—C2B—C3B	120.2 (3)
C12A—N3A—C9A	112.0 (3)	N1B—C2B—H2B	119.9
C12A—N3A—C11A	110.4 (3)	C3B—C2B—H2B	119.9
C9A—N3A—C11A	106.7 (3)	C4B—C3B—C8B	118.9 (3)
C12A—N3A—C10A	108.2 (3)	C4B—C3B—C2B	120.9 (2)
C9A—N3A—C10A	112.0 (3)	C8B—C3B—C2B	120.2 (3)
C11A—N3A—C10A	107.4 (3)	O4B—C4B—C5B	116.0 (3)
C2B—N1B—N2B	117.1 (2)	O4B—C4B—C3B	124.0 (3)
C1B—N2B—N1B	118.6 (3)	C5B—C4B—C3B	120.0 (3)
C1B—N2B—H2NB	124 (2)	O5B—C5B—C6B	117.4 (3)
N1B—N2B—H2NB	116 (2)	O5B—C5B—C4B	122.5 (3)
C11B—N3B—C10B	109.3 (2)	C6B—C5B—C4B	120.1 (3)
C11B—N3B—C12B	108.3 (3)	O6B—C6B—C7B	118.6 (3)
C10B—N3B—C12B	109.5 (3)	O6B—C6B—C5B	121.4 (3)
C11B—N3B—C9B	107.3 (2)	C7B—C6B—C5B	120.1 (3)
C10B—N3B—C9B	111.6 (2)	C8B—C7B—C6B	119.7 (3)
C12B—N3B—C9B	110.8 (2)	C8B—C7B—H7B	120.1
O1A—C1A—N2A	123.6 (3)	C6B—C7B—H7B	120.1
O1A—C1A—C9A	124.5 (3)	C7B—C8B—C3B	121.2 (3)
N2A—C1A—C9A	112.0 (3)	C7B—C8B—H8B	119.4
N1A—C2A—C3A	119.6 (3)	C3B—C8B—H8B	119.4
N1A—C2A—H2A	120.2	N3B—C9B—C1B	114.8 (2)
C3A—C2A—H2A	120.2	N3B—C9B—H9B2	108.6
C4A—C3A—C8A	118.3 (3)	C1B—C9B—H9B2	108.6
C4A—C3A—C2A	122.4 (3)	N3B—C9B—H9B1	108.6
C8A—C3A—C2A	119.2 (3)	C1B—C9B—H9B1	108.6
O4A—C4A—C5A	117.7 (3)	H9B2—C9B—H9B1	107.5
O4A—C4A—C3A	122.1 (3)	N3B—C10B—H10D	109.5
C5A—C4A—C3A	120.2 (3)	N3B—C10B—H10F	109.5
O5A—C5A—C4A	122.5 (3)	H10D—C10B—H10F	109.5
O5A—C5A—C6A	117.6 (3)	N3B—C10B—H10E	109.5
C4A—C5A—C6A	119.8 (3)	H10D—C10B—H10E	109.5
O6A—C6A—C7A	119.7 (3)	H10F—C10B—H10E	109.5
O6A—C6A—C5A	119.4 (3)	N3B—C11B—H11D	109.5
C7A—C6A—C5A	121.0 (3)	N3B—C11B—H11E	109.5
C8A—C7A—C6A	119.5 (3)	H11D—C11B—H11E	109.5
C8A—C7A—H7A	120.3	N3B—C11B—H11F	109.5
C6A—C7A—H7A	120.3	H11D—C11B—H11F	109.5
C7A—C8A—C3A	121.3 (3)	H11E—C11B—H11F	109.5
C7A—C8A—H9A	119.4	N3B—C12B—H12D	109.5
C3A—C8A—H9A	119.4	N3B—C12B—H12E	109.5
N3A—C9A—C1A	115.2 (3)	H12D—C12B—H12E	109.5
N3A—C9A—H9A1	108.5	N3B—C12B—H12F	109.5
C1A—C9A—H9A1	108.5	H12D—C12B—H12F	109.5
N3A—C9A—H9A2	108.5	H12E—C12B—H12F	109.5
C1A—C9A—H9A2	108.5	O7—C13—H13A	109.5
H9A1—C9A—H9A2	107.5	O7—C13—H13B	109.5
N3A—C10A—H10B	109.5	H13A—C13—H13B	109.5
N3A—C10A—H10A	109.5	O7—C13—H13C	109.5
H10B—C10A—H10A	109.5	H13A—C13—H13C	109.5
N3A—C10A—H10C	109.5	H13B—C13—H13C	109.5
H10B—C10A—H10C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4A—H4A···N1A	0.84 (5)	1.82 (5)	2.592 (4)	153 (5)
O5A—H5A···Cl2ⁱ	0.83 (5)	2.29 (5)	3.094 (4)	167 (3)
O6A—H6A···O5A	0.82 (7)	2.30 (6)	2.693 (4)	110 (5)
O6A—H6A···Cl4ⁱ	0.82 (7)	2.64 (6)	3.317 (3)	141 (5)
O4B—H4B···N1B	0.80 (4)	1.86 (4)	2.599 (4)	155 (4)
O5B—H5B···O4B	0.77 (6)	2.28 (6)	2.721 (4)	118 (5)
O5B—H5B···Cl1ⁱⁱ	0.77 (6)	2.60 (5)	3.217 (3)	139 (5)
O6B—H6B···O5B	0.85 (5)	2.32 (5)	2.728 (4)	110 (4)
O6B—H6B···Cl4ⁱⁱⁱ	0.85 (5)	2.59 (5)	3.193 (3)	129 (4)
C10A—H10A···O1A	0.96	2.34	2.992 (5)	124
C10B—H10F···O1B	0.96	2.33	2.978 (4)	124
C10B—H10E···O4A	0.96	2.50	3.404 (5)	157
C10B—H10F···O1B	0.96	2.33	2.978 (4)	124
C12A—H12A···O6Aⁱ	0.96	2.60	3.307 (6)	131
C12A—H12B···O1A	0.96	2.41	3.043 (7)	123
C12B—H12E···O1B	0.96	2.40	3.028 (5)	123
C12A—H12C···Cl1ⁱⁱ	0.96	2.83	3.715 (5)	154
O7—H7O···Cl3^iv	0.82	2.44	3.251 (4)	169
N2A—H2NA···Cl1	0.77 (4)	2.59 (4)	3.287 (3)	154 (4)
N2B—H2NB···O7	0.78 (4)	2.05 (4)	2.826 (5)	175 (4)

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

Experimental details

Crystal data
Chemical formula	(C₁₂H₁₈N₃O₄)₂[ZnCl₄]·CH₄O
M_r	775.82
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.471 (3), 13.389 (4), 14.986 (5)
α, β, γ (°)	110.90 (4), 94.91 (4), 103.94 (5)
V (Å³)	1691.9 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.10
Crystal size (mm)	0.33 × 0.21 × 0.18

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7056, 6632, 5226
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.128, 1.05
No. of reflections	6632
No. of parameters	440
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.81, −0.58

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (cheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999), PLATON (Spek, 2009) and PARST (Nardelli, 1995).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4A—H4A···N1A	0.84 (5)	1.82 (5)	2.592 (4)	153 (5)
O5A—H5A···Cl2ⁱ	0.83 (5)	2.29 (5)	3.094 (4)	167 (3)
O6A—H6A···O5A	0.82 (7)	2.30 (6)	2.693 (4)	110 (5)
O6A—H6A···Cl4ⁱ	0.82 (7)	2.64 (6)	3.317 (3)	141 (5)
O4B—H4B···N1B	0.80 (4)	1.86 (4)	2.599 (4)	155 (4)
O5B—H5B···O4B	0.77 (6)	2.28 (6)	2.721 (4)	118 (5)
O5B—H5B···Cl1ⁱⁱ	0.77 (6)	2.60 (5)	3.217 (3)	139 (5)
O6B—H6B···O5B	0.85 (5)	2.32 (5)	2.728 (4)	110 (4)
O6B—H6B···Cl4ⁱⁱⁱ	0.85 (5)	2.59 (5)	3.193 (3)	129 (4)
C10A—H10A···O1A	0.96	2.34	2.992 (5)	124
C10B—H10F···O1B	0.96	2.33	2.978 (4)	124
C10B—H10E···O4A	0.96	2.50	3.404 (5)	157
C10B—H10F···O1B	0.96	2.33	2.978 (4)	124
C12A—H12A···O6Aⁱ	0.96	2.60	3.307 (6)	131
C12A—H12B···O1A	0.96	2.41	3.043 (7)	123
C12B—H12E···O1B	0.96	2.40	3.028 (5)	123
C12A—H12C···Cl1ⁱⁱ	0.96	2.83	3.715 (5)	154
O7—H7O···Cl3^iv	0.82	2.44	3.251 (4)	169
N2A—H2NA···Cl1	0.77 (4)	2.59 (4)	3.287 (3)	154 (4)
N2B—H2NB···O7	0.78 (4)	2.05 (4)	2.826 (5)	175 (4)

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

Footnotes

†Transition metal complexes with Girard reagent-based ligands. Part VI.

Acknowledgements

This work was supported by the Ministry of Science and Technological Development of the Republic of Serbia (Project No 142028) and Provincial Secretariat for Science and Technological Development of Vojvodina.

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages m328-m329

doi:10.1107/S160053681000615X

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis{N,N,N-tri­methyl-2-oxo-2-[2-(2,3,4- tri­hydroxy­benzyl­­idene)hydrazin­yl]ethanaminium} tetra­chlorido­zincate(II) methanol solvate†

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

metal-organic compounds

Bis{N,N,N-trimethyl-2-oxo-2-[2-(2,3,4- trihydroxybenzylidene)hydrazinyl]ethanaminium} tetrachloridozincate(II) methanol solvate †