catena-Poly[[[triaqua­sulfatozinc(II)]-μ-3,3′-bis­(3-pyrid­yl)-1,1′-(m-phenyl­ene)diurea] methanol solvate monohydrate]

Adarsh, N.N.; Dastidar, P.

doi:10.1107/S1600536810009268

catena-Poly[[[triaquasulfatozinc(II)]-μ-3,3′-bis(3-pyridyl)-1,1′-(m-phenylene)diurea] methanol solvate monohydrate]

In the title coordination polymer, {[Zn(SO₄)(C₁₈H₁₆N₆O₂)(H₂O)₃]·CH₃OH·H₂O}_n, the Zn²⁺ ion adopts a slightly distorted cis-ZnN₂O₄ octahedral geometry arising from three coordinated water molecules, one sulfate ion and two bridging 3,3′-bis(3-pyridyl)-1,1′-(m-phenylene)diurea (bpmpbu) ligands. The dihedral angles between the central benzene ring and two terminal pyridine rings of the bpmbpu molecule are 10.58 (17) and 34.63 (16)°. In the crystal, the ligands bridge the Zn^II ions, thus generating a one-dimensional zigzag coordination polymer propagating in [010]. The crystal structure features extensive N—H

O and O—H

O hydrogen-bonding interactions.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810009268/hb5311sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810009268/hb5311Isup2.hkl Contains datablock I

CCDC reference: 774139

checkCIF report

Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.005 Å
R factor = 0.031
wR factor = 0.068
Data-to-parameter ratio = 10.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT417_ALERT_2_B Short Inter D-H..H-D       H34B   ..  H35     ..       2.07 Ang.

Alert level C
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.09
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          2
PLAT915_ALERT_3_C Low Friedel Pair Coverage ......................      87.07 Perc.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               3968
           Count of symmetry unique reflns         2186
           Completeness (_total/calc)            181.52%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1782
           Fraction of Friedel pairs measured     0.815
           Are heavy atom types Z>Si present        yes
PLAT917_ALERT_2_G The FCF is likely NOT based on a BASF/TWIN Flack          !

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

As part of our ongoing studies of functional coordination polymers (CPs) and metal-organic frameworks (MOF) (Adarsh et al., 2008, 2009), we now report a coordination polymer derived from a newly synthesized bis-pyridyl-bis-urea ligand N,N'-bis(3-pyridyl)meta-phenylene-bis-urea (BPMPBU). Suitable single crystals of [{Zn(H₂O)₃(SO₄)(µ-BPMPBU)}.H₂O.MeOH]_∞, (I), were obtained by layering an methanolic solution of BPMPBU over aqueous solution of ZnSO₄ in 1:2 metal–ligand ratio (see experimental). It was crystallized in the monoclinic non centrosymmetric space group P2₁. In the asymmetric unit, the metal center Zn(II) is found to be hexacoordinated; while euqatorial positions are occupied by pyridyl N atoms of the ligand and water molecules, the apical positions are coordinated by O atoms of water and sulfate. The ORTEP diagram of 1 with 50% probability is given in Fig. 1. The metal center Zn(II) displayed a distorted octahedral geometry [N—Zn—N = 94.72?(12)°; O—Zn—N = 87.4)(12)-93.83 (10)°; O—Zn—O = 87.01 (11)-91.12 (12)°]. In the crystal structure, the ligand BPMPBU which displayed syn-syn-syn conformation (scheme 1) coordinated to the adjacent Zn(II) metal centres via pyridyl N atoms leading to the formation of a 1D zigzag polymeric chain (Fig. 2). The polymeric chains are further packed in parallel fashion sustained by N–H···O hydrogen bonding interactions involving sulfate and the urea moieties [N···O = 2.875 (4)–3.044 (4) Å; N–H···O =154–164°]. Both the lattice included water and MeOH are occupied within the interstitial space of the chains and are involved in O—H···O hydrogen bonding interactions [O···O = 2.633 (3)–2.942 (3) Å; O–H···O] (Fig. 3).

Related literature top

For our previous work on related compounds, see: Adarsh et al. (2008, 2009),

Experimental top

3-Aminopyridine (1 g, 10.6 mmol) and triethylamine (3 ml) were stirred under nitrogen in 150 ml of anhydrous dichloromethane in ice cold condition for 20 min. To this stirring solution, triphosgene (1.57 g, 5.3 mmol) was added and kept stirring for another 20 min at 0°C and to the resultant solution, meta-phenylenediamine (574 mg, 5.3 mmol) in 10 ml of dichloromethane was added dropwise. White precipitate was obtained after 24 hour of stirring at room temperature. The precipitate was filtered, air dried, treated with 5% NaHCO₃ solution and washed with distilled water. Pale yellow coloured microcrystalline material of the BPMPBU ligand was obtained (880 mg, 55% yield) after recrystallization from H₂O/MeOH (1 : 2 v/v) (880 mg, 55% yield) . mp 265-267°C Anal. data calc. for C₁₈H₁₆N₆O₂: C, 62.06; H, 4.63; N, 24.12. Found: C, 61.86, H, 4.24, N, 24.32. ¹H NMR (300 MHz, DMSO-d6): δ = 7.09-7.12 (2H, d, J = 9 Hz, Ar—H); 7.23-7.18 (1H, t, J = 9, 9 Hz, Ar—H); 7.34-7.30 (2H, dd, J = 6, 9 Hz, Py—H); 7.70 (1H, s, Ar—H); 7.96-7.93 (2H, d, J = 9 Hz, Py—H); 8.20-8.19 (2H, d, J = 3 Hz, Py—H); 8.62 (2H, s, Py—H); 8.78 (2H, s, urea N—H); 8.87 (2H, s, urea N—H). HRMS(ESI) calcd for C₁₈H₁₆N₆O₂ 349.14; found: [M + Na]+ 349.12 F T—IR (KBr, cm-1): 3346 (s, N–H stretch), 3242 (s, O–H stretch), 3059, 3022 (s, aromatic C–H stretch), 2908, 2827 (s, aliphatic C–H stretch), 1710, 1647 (s, urea C=O stretch), 1641 (s, urea N–H bend), 1608, 1595, 1535, 1485, 1425, 1421, 1408, 1327, 1294, 1209, 1186, 1122, 1103, 854, 786, 767, 734, 700, 626, 551.

The title compound was synthesized by layering a methanolic solution of BPMPBU (40 mg, 0.1149 mmol) over an aqueous solution of ZnSO₄.7H₂O (16.5 mg, 0.0575 mmol). After three days, colourless blocks of (I) were obtained (yield = 20 mg, 57 %). Anal. data calc. for C₁₉H₂₈N₆O₁₁SZn: C, 37.17; H, 4.60; N, 13.69, found: C, 37.12, H, 4.28, N, 13.66. F T—IR (KBr, cm-1): 3323 (b, N–H stretch), 3219 (b, O–H stretch), 3090 (b, aromatic C–H stretch), 1693 (s, urea C=O stretch), 1610 (s, urea N–H bend), 1589, 1570, 1552, 1496, 1483, 1431, 1330, 1294, 1217, 1193, 1130, 1089, 1066, 1035, 945, 900, 850, 819, 775, 704.

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Fragment of the structure of (I) with displacement ellipsoids drawn at 50% probability level
	Fig. 2. 1D zig-zag coordination polymer in (I).
	Fig. 3. Parallel packing of 1D zigzag chains in (I) (shown in orange and purple colour) displaying various hydrogen bonding (dotted lines) intearctions (dotted lines).

catena-Poly[[[triaquasulfatozinc(II)]-µ-3,3'-bis(3-pyridyl)- 1,1'-(m-phenylene)diurea] methanol solvate monohydrate] top

Crystal data top

[Zn(SO₄)(C₁₈H₁₆N₆O₂)(H₂O)₃]·CH₄O·H₂O	F(000) = 636
M_r = 613.90	D_x = 1.702 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 144 reflections
a = 6.4831 (7) Å	θ = 2.3–26.0°
b = 19.265 (2) Å	µ = 1.19 mm⁻¹
c = 9.7062 (11) Å	T = 100 K
β = 98.848 (2)°	Block, colourless
V = 1197.8 (2) Å³	0.28 × 0.22 × 0.12 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3968 independent reflections
Radiation source: fine-focus sealed tube	3823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
Detector resolution: 3 pixels mm^-1	θ_max = 25.0°, θ_min = 2.1°
ϕ and ω scans	h = −7→6
Absorption correction: multi-scan (SADABS; Bruker, 2006)	k = −22→22
T_min = 0.732, T_max = 0.871	l = −7→11
5989 measured reflections

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) + (0.0188P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3968 reflections	Δρ_max = 0.54 e Å⁻³
369 parameters	Δρ_min = −0.26 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1782 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.049 (10)

Crystal data top

[Zn(SO₄)(C₁₈H₁₆N₆O₂)(H₂O)₃]·CH₄O·H₂O	V = 1197.8 (2) Å³
M_r = 613.90	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.4831 (7) Å	µ = 1.19 mm⁻¹
b = 19.265 (2) Å	T = 100 K
c = 9.7062 (11) Å	0.28 × 0.22 × 0.12 mm
β = 98.848 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3968 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	3823 reflections with I > 2σ(I)
T_min = 0.732, T_max = 0.871	R_int = 0.025
5989 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.068	Δρ_max = 0.54 e Å⁻³
S = 1.02	Δρ_min = −0.26 e Å⁻³
3968 reflections	Absolute structure: Flack (1983), 1782 Friedel pairs
369 parameters	Absolute structure parameter: 0.049 (10)
1 restraint

Special details top

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.

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	1.01818 (5)	0.83531 (2)	0.15530 (4)	0.01276 (10)
S1	0.59561 (13)	0.76119 (4)	−0.03921 (8)	0.01383 (19)
N1	0.9621 (4)	0.84335 (19)	0.3638 (3)	0.0137 (6)
C2	0.7909 (5)	0.81484 (16)	0.4027 (3)	0.0159 (8)
H2	0.6967	0.7916	0.3365	0.019*
C3	0.7500 (5)	0.81905 (15)	0.5399 (3)	0.0133 (8)
C4	0.8923 (5)	0.85448 (16)	0.6356 (4)	0.0157 (8)
H4	0.8676	0.8592	0.7270	0.019*
C5	1.0682 (5)	0.88257 (18)	0.5975 (4)	0.0159 (8)
H5	1.1653	0.9056	0.6622	0.019*
C6	1.0987 (5)	0.87587 (18)	0.4585 (4)	0.0164 (8)
H6	1.2183	0.8947	0.4315	0.020*
N7	0.5748 (4)	0.79042 (15)	0.5860 (3)	0.0174 (7)
H7	0.5445	0.8065	0.6631	0.021*
C8	0.4459 (5)	0.73982 (18)	0.5225 (4)	0.0147 (8)
O9	0.4570 (4)	0.71652 (12)	0.4060 (2)	0.0177 (5)
N10	0.3052 (5)	0.71747 (15)	0.6036 (3)	0.0165 (6)
H10	0.3019	0.7402	0.6796	0.020*
C11	0.1645 (5)	0.66159 (17)	0.5776 (3)	0.0138 (7)
C12	0.1858 (6)	0.60887 (19)	0.4839 (4)	0.0185 (8)
H12	0.2956	0.6091	0.4325	0.022*
C13	0.0411 (6)	0.5561 (2)	0.4683 (4)	0.0248 (9)
H13	0.0552	0.5208	0.4051	0.030*
C14	−0.1251 (6)	0.55336 (19)	0.5430 (4)	0.0193 (9)
H14	−0.2232	0.5179	0.5282	0.023*
C15	−0.1405 (5)	0.60492 (17)	0.6399 (3)	0.0145 (7)
C16	0.0004 (5)	0.65929 (17)	0.6551 (3)	0.0142 (7)
H16	−0.0144	0.6948	0.7178	0.017*
N17	−0.2982 (4)	0.60722 (14)	0.7258 (3)	0.0164 (6)
H17	−0.3135	0.6464	0.7656	0.020*
C18	−0.4296 (5)	0.55496 (17)	0.7538 (4)	0.0144 (8)
O19	−0.4347 (4)	0.49686 (12)	0.7017 (2)	0.0166 (5)
N20	−0.5554 (4)	0.57575 (15)	0.8485 (3)	0.0154 (6)
H20	−0.5270	0.6156	0.8867	0.018*
C21	−0.7245 (6)	0.54001 (18)	0.8903 (4)	0.0144 (7)
C22	−0.7849 (5)	0.47290 (18)	0.8489 (3)	0.0140 (7)
H22	−0.7116	0.4495	0.7879	0.017*
N23	−0.9455 (4)	0.44088 (14)	0.8943 (3)	0.0129 (6)
C24	−1.0544 (5)	0.47467 (19)	0.9809 (4)	0.0181 (8)
H24	−1.1646	0.4523	1.0134	0.022*
C25	−1.0052 (6)	0.54219 (19)	1.0225 (4)	0.0197 (8)
H25	−1.0843	0.5653	1.0803	0.024*
C26	−0.8391 (5)	0.57487 (18)	0.9779 (4)	0.0185 (8)
H26	−0.8039	0.6200	1.0063	0.022*
O27	0.6905 (4)	0.80524 (12)	0.0790 (2)	0.0142 (5)
O28	0.7580 (4)	0.73351 (12)	−0.1150 (3)	0.0204 (6)
O29	0.4479 (4)	0.80304 (13)	−0.1355 (2)	0.0198 (6)
O30	0.4820 (4)	0.70339 (12)	0.0130 (3)	0.0231 (6)
O31	1.0881 (4)	0.72757 (13)	0.1965 (3)	0.0185 (6)
O32	1.3440 (4)	0.86231 (13)	0.2068 (3)	0.0167 (6)
O33	1.0745 (4)	0.81868 (13)	−0.0455 (2)	0.0175 (6)
O34	0.7276 (5)	0.64800 (13)	0.2427 (3)	0.0277 (7)
O35	0.6380 (5)	0.50133 (16)	0.2090 (3)	0.0393 (8)
H35	0.6448	0.5437	0.2152	0.059*
C36	0.4550 (7)	0.4779 (2)	0.2561 (5)	0.0385 (11)
H36A	0.4866	0.4655	0.3529	0.058*
H36B	0.4017	0.4380	0.2029	0.058*
H36C	0.3522	0.5141	0.2446	0.058*
H31A	1.194 (7)	0.722 (2)	0.251 (4)	0.027*
H31B	1.000 (7)	0.704 (2)	0.220 (4)	0.027*
H32A	1.445 (6)	0.846 (2)	0.170 (4)	0.026*
H32B	1.386 (7)	0.898 (2)	0.215 (4)	0.026*
H33A	1.198 (7)	0.8143 (19)	−0.063 (4)	0.027*
H33B	0.995 (6)	0.786 (2)	−0.063 (4)	0.027*
H34A	0.691 (7)	0.667 (2)	0.320 (5)	0.043*
H34B	0.615 (7)	0.648 (2)	0.163 (5)	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.01308 (19)	0.01284 (18)	0.01308 (19)	0.00027 (18)	0.00425 (13)	−0.00021 (18)
S1	0.0139 (4)	0.0144 (4)	0.0138 (4)	−0.0007 (3)	0.0043 (3)	−0.0030 (3)
N1	0.0149 (14)	0.0138 (16)	0.0132 (14)	0.0001 (14)	0.0047 (10)	0.0015 (14)
C2	0.0147 (18)	0.019 (2)	0.0137 (18)	−0.0010 (14)	−0.0003 (14)	0.0010 (13)
C3	0.0111 (17)	0.014 (2)	0.0162 (17)	0.0010 (13)	0.0056 (13)	0.0011 (13)
C4	0.0222 (19)	0.014 (2)	0.0119 (17)	0.0028 (14)	0.0068 (14)	0.0002 (13)
C5	0.0147 (19)	0.0166 (18)	0.0159 (19)	−0.0050 (15)	0.0007 (14)	−0.0001 (15)
C6	0.017 (2)	0.0138 (18)	0.0197 (19)	−0.0057 (15)	0.0074 (15)	−0.0018 (15)
N7	0.0183 (17)	0.0237 (17)	0.0119 (15)	−0.0061 (14)	0.0076 (12)	−0.0029 (13)
C8	0.0115 (18)	0.0167 (19)	0.0166 (19)	0.0038 (14)	0.0046 (14)	0.0024 (15)
O9	0.0190 (14)	0.0218 (13)	0.0133 (13)	−0.0022 (11)	0.0054 (10)	−0.0024 (11)
N10	0.0210 (17)	0.0184 (16)	0.0115 (15)	−0.0037 (13)	0.0073 (12)	−0.0062 (12)
C11	0.0122 (18)	0.0136 (17)	0.0165 (18)	0.0018 (14)	0.0048 (14)	0.0049 (14)
C12	0.0171 (19)	0.020 (2)	0.022 (2)	−0.0037 (16)	0.0133 (15)	−0.0011 (16)
C13	0.031 (2)	0.020 (2)	0.027 (2)	−0.0029 (17)	0.0151 (17)	−0.0104 (16)
C14	0.022 (2)	0.019 (2)	0.017 (2)	−0.0087 (17)	0.0053 (16)	−0.0029 (15)
C15	0.0135 (18)	0.0158 (18)	0.0150 (18)	0.0028 (15)	0.0047 (14)	0.0023 (14)
C16	0.0176 (19)	0.0125 (17)	0.0134 (18)	0.0012 (15)	0.0051 (14)	−0.0008 (14)
N17	0.0162 (16)	0.0114 (15)	0.0239 (17)	−0.0034 (13)	0.0102 (13)	−0.0023 (12)
C18	0.0135 (18)	0.0132 (19)	0.0168 (19)	0.0010 (15)	0.0027 (14)	0.0008 (14)
O19	0.0187 (14)	0.0123 (13)	0.0197 (13)	−0.0020 (10)	0.0051 (10)	−0.0012 (10)
N20	0.0152 (16)	0.0118 (15)	0.0206 (16)	−0.0075 (12)	0.0069 (12)	−0.0046 (12)
C21	0.0097 (17)	0.0181 (19)	0.0159 (19)	−0.0002 (14)	0.0032 (13)	0.0028 (15)
C22	0.0135 (18)	0.0140 (18)	0.0159 (18)	0.0023 (15)	0.0063 (14)	0.0017 (15)
N23	0.0130 (15)	0.0109 (14)	0.0150 (15)	−0.0010 (12)	0.0026 (12)	−0.0008 (12)
C24	0.0160 (19)	0.0206 (19)	0.0182 (19)	−0.0010 (16)	0.0041 (15)	0.0009 (16)
C25	0.020 (2)	0.0181 (19)	0.023 (2)	−0.0019 (16)	0.0102 (16)	−0.0044 (16)
C26	0.019 (2)	0.0146 (18)	0.023 (2)	−0.0004 (16)	0.0061 (15)	−0.0043 (15)
O27	0.0123 (12)	0.0171 (12)	0.0134 (12)	−0.0012 (10)	0.0022 (9)	−0.0033 (10)
O28	0.0161 (13)	0.0223 (13)	0.0242 (14)	−0.0026 (11)	0.0076 (10)	−0.0102 (11)
O29	0.0218 (14)	0.0253 (13)	0.0132 (13)	0.0031 (11)	0.0055 (10)	−0.0013 (10)
O30	0.0283 (15)	0.0196 (14)	0.0234 (15)	−0.0081 (12)	0.0100 (11)	−0.0030 (11)
O31	0.0189 (15)	0.0168 (14)	0.0195 (14)	0.0026 (11)	0.0018 (11)	0.0012 (11)
O32	0.0122 (13)	0.0132 (12)	0.0259 (15)	−0.0036 (10)	0.0070 (10)	−0.0049 (11)
O33	0.0133 (13)	0.0229 (17)	0.0177 (13)	−0.0032 (11)	0.0073 (10)	−0.0038 (10)
O34	0.0349 (17)	0.0226 (15)	0.0268 (16)	0.0016 (13)	0.0088 (13)	−0.0024 (12)
O35	0.0384 (19)	0.0336 (17)	0.050 (2)	0.0036 (15)	0.0193 (15)	0.0041 (15)
C36	0.031 (3)	0.039 (3)	0.049 (3)	0.003 (2)	0.015 (2)	0.010 (2)

Geometric parameters (Å, º) top

Zn1—N1	2.116 (3)	C14—H14	0.9300
Zn1—N23ⁱ	2.126 (3)	C15—C16	1.383 (5)
Zn1—O33	2.062 (2)	C15—N17	1.416 (4)
Zn1—O31	2.149 (3)	C16—H16	0.9300
Zn1—O32	2.158 (3)	N17—C18	1.373 (4)
Zn1—O27	2.217 (2)	N17—H17	0.8600
S1—O30	1.468 (3)	C18—O19	1.227 (4)
S1—O29	1.471 (2)	C18—N20	1.379 (4)
S1—O28	1.474 (3)	N20—C21	1.406 (5)
S1—O27	1.482 (2)	N20—H20	0.8600
N1—C6	1.331 (4)	C21—C26	1.386 (5)
N1—C2	1.344 (4)	C21—C22	1.392 (5)
C2—C3	1.399 (4)	C22—N23	1.342 (4)
C2—H2	0.9300	C22—H22	0.9300
C3—C4	1.384 (4)	N23—C24	1.346 (5)
C3—N7	1.397 (4)	N23—Zn1ⁱⁱ	2.126 (3)
C4—C5	1.364 (5)	C24—C25	1.384 (5)
C4—H4	0.9300	C24—H24	0.9300
C5—C6	1.399 (5)	C25—C26	1.373 (5)
C5—H5	0.9300	C25—H25	0.9300
C6—H6	0.9300	C26—H26	0.9300
N7—C8	1.367 (4)	O31—H31A	0.81 (4)
N7—H7	0.8600	O31—H31B	0.79 (4)
C8—O9	1.230 (4)	O32—H32A	0.85 (4)
C8—O9	1.230 (4)	O32—H32B	0.73 (4)
C8—N10	1.363 (4)	O33—H33A	0.85 (4)
N10—C11	1.409 (4)	O33—H33B	0.82 (4)
N10—H10	0.8600	O34—H34A	0.90 (5)
C11—C12	1.384 (5)	O34—H34B	0.98 (5)
C11—C16	1.394 (5)	O35—C36	1.409 (5)
C12—C13	1.375 (5)	O35—H35	0.8200
C12—H12	0.9300	C36—H36A	0.9600
C13—C14	1.389 (5)	C36—H36B	0.9600
C13—H13	0.9300	C36—H36C	0.9600
C14—C15	1.382 (5)

O33—Zn1—N1	175.25 (12)	C12—C13—H13	118.6
O33—Zn1—N23ⁱ	89.98 (10)	C14—C13—H13	118.6
N1—Zn1—N23ⁱ	94.71 (12)	C15—C14—C13	118.1 (3)
O33—Zn1—O31	87.88 (10)	C15—C14—H14	121.0
N1—Zn1—O31	87.42 (12)	C13—C14—H14	121.0
N23ⁱ—Zn1—O31	177.64 (11)	C16—C15—C14	120.1 (3)
O33—Zn1—O32	86.97 (10)	C16—C15—N17	116.0 (3)
N1—Zn1—O32	93.83 (10)	C14—C15—N17	123.9 (3)
N23ⁱ—Zn1—O32	89.81 (10)	C15—C16—C11	120.8 (3)
O31—Zn1—O32	91.08 (10)	C15—C16—H16	119.6
O33—Zn1—O27	86.75 (9)	C11—C16—H16	119.6
N1—Zn1—O27	92.41 (10)	C18—N17—C15	128.3 (3)
N23ⁱ—Zn1—O27	90.39 (10)	C18—N17—H17	115.8
O31—Zn1—O27	88.50 (10)	C15—N17—H17	115.8
O32—Zn1—O27	173.72 (9)	O19—C18—N17	124.4 (3)
O30—S1—O29	108.84 (15)	O19—C18—N20	124.0 (3)
O30—S1—O28	109.45 (14)	N17—C18—N20	111.6 (3)
O29—S1—O28	109.04 (15)	C18—N20—C21	128.1 (3)
O30—S1—O27	109.73 (14)	C18—N20—H20	115.9
O29—S1—O27	109.25 (14)	C21—N20—H20	115.9
O28—S1—O27	110.50 (14)	C26—C21—C22	118.3 (3)
C6—N1—C2	119.2 (3)	C26—C21—N20	117.1 (3)
C6—N1—Zn1	120.1 (2)	C22—C21—N20	124.6 (3)
C2—N1—Zn1	120.7 (2)	N23—C22—C21	122.0 (3)
N1—C2—C3	122.0 (3)	N23—C22—H22	119.0
N1—C2—H2	119.0	C21—C22—H22	119.0
C3—C2—H2	119.0	C22—N23—C24	119.4 (3)
C4—C3—N7	118.1 (3)	C22—N23—Zn1ⁱⁱ	121.4 (2)
C4—C3—C2	117.6 (3)	C24—N23—Zn1ⁱⁱ	119.0 (2)
N7—C3—C2	124.3 (3)	N23—C24—C25	121.1 (3)
C5—C4—C3	120.8 (3)	N23—C24—H24	119.4
C5—C4—H4	119.6	C25—C24—H24	119.4
C3—C4—H4	119.6	C26—C25—C24	119.7 (3)
C4—C5—C6	118.2 (3)	C26—C25—H25	120.1
C4—C5—H5	120.9	C24—C25—H25	120.1
C6—C5—H5	120.9	C25—C26—C21	119.4 (3)
N1—C6—C5	122.1 (3)	C25—C26—H26	120.3
N1—C6—H6	118.9	C21—C26—H26	120.3
C5—C6—H6	118.9	S1—O27—Zn1	132.11 (14)
C8—N7—C3	127.4 (3)	Zn1—O31—H31A	113 (3)
C8—N7—H7	116.3	Zn1—O31—H31B	117 (3)
C3—N7—H7	116.3	H31A—O31—H31B	108 (4)
O9—C8—N10	123.7 (3)	Zn1—O32—H32A	127 (3)
O9—C8—N10	123.7 (3)	Zn1—O32—H32B	126 (3)
O9—C8—N7	123.8 (3)	H32A—O32—H32B	95 (4)
O9—C8—N7	123.8 (3)	Zn1—O33—H33A	121 (2)
N10—C8—N7	112.4 (3)	Zn1—O33—H33B	97 (3)
C8—N10—C11	127.6 (3)	H33A—O33—H33B	118 (4)
C8—N10—H10	116.2	H34A—O34—H34B	113 (4)
C11—N10—H10	116.2	C36—O35—H35	109.5
C12—C11—C16	119.5 (3)	O35—C36—H36A	109.5
C12—C11—N10	123.4 (3)	O35—C36—H36B	109.5
C16—C11—N10	117.0 (3)	H36A—C36—H36B	109.5
C13—C12—C11	118.6 (3)	O35—C36—H36C	109.5
C13—C12—H12	120.7	H36A—C36—H36C	109.5
C11—C12—H12	120.7	H36B—C36—H36C	109.5
C12—C13—C14	122.8 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O29ⁱⁱⁱ	0.86	2.14	2.954 (4)	157
N10—H10···O29ⁱⁱⁱ	0.86	2.25	3.044 (4)	154
N17—H17···O28^iv	0.86	2.05	2.875 (4)	160
N20—H20···O30^iv	0.86	2.08	2.922 (4)	164
O35—H35···O34	0.82	2.09	2.893 (4)	168
O32—H32A···O27^v	0.85 (4)	2.09 (4)	2.942 (3)	179 (4)
O31—H31A···O9^v	0.81 (4)	2.09 (4)	2.899 (4)	173 (4)
O33—H33A···O29^v	0.85 (4)	1.87 (4)	2.714 (4)	170 (4)
O34—H34A···O9	0.90 (5)	2.08 (5)	2.861 (4)	146 (4)
O32—H32B···O19^vi	0.73 (4)	2.08 (4)	2.774 (3)	158 (5)
O31—H31B···O34	0.79 (4)	2.11 (4)	2.887 (4)	168 (4)
O33—H33B···O28	0.82 (4)	1.84 (4)	2.633 (3)	162 (4)
O34—H34B···O30	0.98 (5)	1.90 (5)	2.748 (4)	144 (4)

Symmetry codes: (iii) x, y, z+1; (iv) x−1, y, z+1; (v) x+1, y, z; (vi) −x+1, y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn(SO₄)(C₁₈H₁₆N₆O₂)(H₂O)₃]·CH₄O·H₂O
M_r	613.90
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	6.4831 (7), 19.265 (2), 9.7062 (11)
β (°)	98.848 (2)
V (Å³)	1197.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.19
Crystal size (mm)	0.28 × 0.22 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.732, 0.871
No. of measured, independent and observed [I > 2σ(I)] reflections	5989, 3968, 3823
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.068, 1.02
No. of reflections	3968
No. of parameters	369
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.26
Absolute structure	Flack (1983), 1782 Friedel pairs
Absolute structure parameter	0.049 (10)

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Selected bond lengths (Å) top

Zn1—N1	2.116 (3)	Zn1—O31	2.149 (3)
Zn1—N23ⁱ	2.126 (3)	Zn1—O32	2.158 (3)
Zn1—O33	2.062 (2)	Zn1—O27	2.217 (2)

Symmetry code: (i) −x, y+1/2, −z+1.