Bis[μ-1,3-bis­(1H-imidazol-1-yl)propane-κ2N3:N3′]bis­(di­chlorido­zinc) dihydrate

Wang, X.-J.; Feng, Y.-L.

doi:10.1107/S1600536814008162

metal-organic compounds

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Volume 70| Part 5| May 2014| Page m184

doi:10.1107/S1600536814008162

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Bis[μ-1,3-bis(1H-imidazol-1-yl)propane-κ²N³:N^3′]bis(dichloridozinc) dihydrate

Xiao-Juan Wang ^a ^* and Yun-Long Feng ^a

^aCollege of Chemistry and Life Science, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's Republic of China
^*Correspondence e-mail: wangxj@zjnu.cn

(Received 24 March 2014; accepted 11 April 2014; online 16 April 2014)

The title hydrated complex, [Zn₂Cl₄(C₉H₁₂N₄)₂]·2H₂O, is a discrete dinuclear zinc complex with 1,3-bis(1H-imidazol-1-yl)propane as the bridging ligand. The complex molecule lies about a crystallographic inversion centre. The Zn^II atom exhibits a distorted tetrahedral coordination geometry defined by two imidazole N atoms and two Cl atoms. O—H⋯Cl hydrogen bonding between the lattice water molecules and the terminal Cl atoms of the molecule lead to a two-dimensional structure extending parallel to (100).

CCDC reference: 996742

Related literature

For related structures containing the 1,3-bis(imidazol)propane ligand, see: Ma et al. (2012 ); Kan et al. (2012 ); Jiang et al. (2011 ); Shen & Lin (2012 ).

Experimental

Crystal data

[Zn₂Cl₄(C₉H₁₂N₄)₂]·2H₂O
M_r = 661.02
Monoclinic, P 2₁ /c
a = 10.1378 (4) Å
b = 9.7173 (4) Å
c = 13.8801 (6) Å
β = 93.704 (2)°
V = 1364.50 (10) Å³
Z = 2
Mo Kα radiation
μ = 2.18 mm⁻¹
T = 296 K
0.25 × 0.18 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.631, T_max = 0.770
21184 measured reflections
3162 independent reflections
2473 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.087
S = 1.04
3162 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯Cl1	0.85	2.47	3.282 (3)	160
O1W—H1WB⋯Cl2ⁱ	0.85	2.76	3.473 (4)	143
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 996742

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814008162/wm5017sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814008162/wm5017Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814008162/wm5017Isup3.mol

checkCIF report

Comment top

In the past few years, complexes based on the 1,3-bis(imidazol)propane (1,3-bip) ligand have been reported, such as [Mn₄(tbip)₄(1,3-bip)]_n^.2nH₂O (H₂tbip = (5-tert-butyl isophthalic acid) (Ma et al., 2012), [Cd(HL)(1,3-bip)]_n^.5nH₂O (H₃L = 5-(2-carboxybenzyloxy)isophthalic acid) (Kan et al., 2012), [Zn(L)(1,3-bip)]_n (H₂L = 5-methylisophthalic acid) (Jiang et al., 2011), [Cd(1,3-bip)Cl₂]_n (Shen et al., 2012). In order to extend our knowledge in this field, we report here the syntheses and structure of a new complex, [ZnCl₂(C₉H₁₂N₄]₂^.2H₂O, (I).

The asymmetric unit of (I) consists of one Zn²⁺ ion, one 1,3-bip ligand, two Cl^- ions, and one lattice water molecules. A perspective view of the molecular entities of complex (I) is presented in Fig. 1. The complex contains centrosymmetric dimers with bridging 1,3-bip ligands. The Zn(II) atom is four-coordinated in a distorted tetrahedral coordination. O—H···Cl hydrogen bonds between the lattice water molecules and Cl atoms lead to a layered structure extending parallel to (100) (Fig. 2).

Related literature top

For related structures containing the 1,3-bis(imidazol)propane ligand, see: Ma et al. (2012); Kan et al. (2012); Jiang et al. (2011); Shen & Lin (2012).

Experimental top

A mixture of 1,3-bis(imidazol)propane (0.088 g, 0.5 mmol), ZnCl₂ (0.204 g, 1.5 mmol), and Na₂CO₃ (0.060 g, 0.5 mmol) in H₂O (16 ml)/C₂H₅OH (2 ml) was placed in a 25 ml Teflon-lined stainless steel vessel and heated at 433 K for 72 h, then cooled to room temperature over a period of 24 h. Colourless crystals suitable for X-ray analysis were obtained.

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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Perspective view of the molecular entities of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (A) -x + 1,-y + 1,-z + 1.]
	Fig. 2. The layer structure of (I) viewed along [100]. Dashed lines indicate O—H···Cl hydrogen bonds.

Bis[µ-1,3-bis(1H-imidazol-1-yl)propane-κ²N³:N^3']bis(dichloridozinc) dihydrate top

Crystal data top

[Zn₂Cl₄(C₉H₁₂N₄)₂]·2H₂O	F(000) = 672
M_r = 661.02	D_x = 1.609 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6173 reflections
a = 10.1378 (4) Å	θ = 2.0–27.6°
b = 9.7173 (4) Å	µ = 2.18 mm⁻¹
c = 13.8801 (6) Å	T = 296 K
β = 93.704 (2)°	Block, colourless
V = 1364.50 (10) Å³	0.25 × 0.18 × 0.12 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3162 independent reflections
Radiation source: fine-focus sealed tube	2473 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω and ϕ–scans	θ_max = 27.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −13→13
T_min = 0.631, T_max = 0.770	k = −11→12
21184 measured reflections	l = −18→18

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0432P)² + 0.5084P] where P = (F_o² + 2F_c²)/3
3162 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[Zn₂Cl₄(C₉H₁₂N₄)₂]·2H₂O	V = 1364.50 (10) Å³
M_r = 661.02	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.1378 (4) Å	µ = 2.18 mm⁻¹
b = 9.7173 (4) Å	T = 296 K
c = 13.8801 (6) Å	0.25 × 0.18 × 0.12 mm
β = 93.704 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3162 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	2473 reflections with I > 2σ(I)
T_min = 0.631, T_max = 0.770	R_int = 0.033
21184 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.04	Δρ_max = 0.55 e Å⁻³
3162 reflections	Δρ_min = −0.23 e Å⁻³
154 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Zn1	0.34226 (3)	0.80572 (3)	0.74784 (2)	0.04641 (11)
Cl1	0.39773 (7)	0.82340 (8)	0.90676 (5)	0.0634 (2)
Cl2	0.19959 (7)	0.97104 (7)	0.69087 (6)	0.0684 (2)
O1W	0.1166 (3)	0.7064 (4)	0.9784 (2)	0.1265 (12)
H1WA	0.1788	0.7355	0.9456	0.152*
H1WB	0.1429	0.7043	1.0377	0.152*
N1	0.25814 (18)	0.6260 (2)	0.70857 (13)	0.0443 (4)
N2	0.21115 (19)	0.43655 (19)	0.62798 (13)	0.0430 (4)
N3	0.29331 (19)	0.1944 (2)	0.37271 (14)	0.0452 (4)
N4	0.49316 (19)	0.1728 (2)	0.32351 (14)	0.0458 (5)
C1	0.1371 (2)	0.5783 (3)	0.73318 (17)	0.0474 (6)
H1A	0.0841	0.6199	0.7771	0.057*
C2	0.2989 (2)	0.5376 (2)	0.64438 (16)	0.0449 (5)
H2A	0.3782	0.5449	0.6146	0.054*
C3	0.1072 (2)	0.4622 (3)	0.68377 (17)	0.0481 (6)
H3A	0.0310	0.4096	0.6869	0.058*
C4	0.2215 (3)	0.3244 (2)	0.55803 (18)	0.0505 (6)
H4A	0.1746	0.2443	0.5797	0.061*
H4B	0.3137	0.2993	0.5542	0.061*
C5	0.1646 (2)	0.3666 (3)	0.45951 (16)	0.0489 (5)
H5A	0.2165	0.4420	0.4363	0.059*
H5B	0.0752	0.3999	0.4651	0.059*
C6	0.1616 (2)	0.2514 (3)	0.3861 (2)	0.0555 (6)
H6A	0.1046	0.1785	0.4068	0.067*
H6B	0.1241	0.2858	0.3247	0.067*
C7	0.3435 (3)	0.0752 (3)	0.41050 (19)	0.0571 (6)
H7A	0.3011	0.0141	0.4498	0.069*
C8	0.3855 (2)	0.2498 (3)	0.32038 (17)	0.0489 (6)
H8A	0.3753	0.3318	0.2862	0.059*
C9	0.4668 (3)	0.0622 (3)	0.38023 (18)	0.0533 (6)
H9A	0.5245	−0.0101	0.3955	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.04298 (17)	0.04543 (18)	0.05161 (18)	0.00076 (12)	0.00928 (12)	−0.00741 (12)
Cl1	0.0657 (4)	0.0750 (5)	0.0500 (4)	−0.0032 (3)	0.0081 (3)	−0.0131 (3)
Cl2	0.0546 (4)	0.0569 (4)	0.0943 (5)	0.0137 (3)	0.0087 (4)	0.0021 (4)
O1W	0.0764 (17)	0.190 (4)	0.116 (2)	0.0006 (18)	0.0274 (16)	−0.022 (2)
N1	0.0451 (10)	0.0451 (11)	0.0431 (10)	0.0013 (9)	0.0051 (8)	−0.0024 (8)
N2	0.0450 (10)	0.0398 (10)	0.0437 (10)	0.0030 (8)	0.0000 (8)	−0.0004 (8)
N3	0.0391 (10)	0.0488 (12)	0.0480 (11)	−0.0025 (8)	0.0062 (8)	−0.0095 (9)
N4	0.0453 (11)	0.0478 (12)	0.0451 (11)	0.0026 (9)	0.0088 (8)	−0.0006 (8)
C1	0.0415 (12)	0.0553 (15)	0.0462 (12)	0.0047 (11)	0.0082 (10)	0.0008 (10)
C2	0.0439 (12)	0.0435 (13)	0.0477 (12)	−0.0006 (10)	0.0070 (10)	−0.0029 (10)
C3	0.0403 (12)	0.0522 (15)	0.0518 (13)	−0.0034 (10)	0.0029 (10)	0.0065 (11)
C4	0.0585 (15)	0.0388 (13)	0.0536 (14)	0.0029 (11)	−0.0008 (11)	−0.0051 (10)
C5	0.0466 (13)	0.0520 (14)	0.0486 (13)	0.0060 (11)	0.0062 (10)	−0.0028 (11)
C6	0.0366 (12)	0.0696 (17)	0.0604 (15)	0.0003 (12)	0.0040 (11)	−0.0170 (13)
C7	0.0603 (16)	0.0513 (15)	0.0614 (15)	−0.0057 (12)	0.0171 (12)	0.0044 (12)
C8	0.0467 (13)	0.0493 (14)	0.0514 (14)	0.0031 (11)	0.0094 (11)	0.0013 (11)
C9	0.0574 (15)	0.0461 (14)	0.0570 (14)	0.0063 (11)	0.0088 (12)	0.0011 (11)

Geometric parameters (Å, º) top

Zn1—N1	2.0038 (19)	C1—C3	1.345 (3)
Zn1—N4ⁱ	2.0053 (19)	C1—H1A	0.9300
Zn1—Cl1	2.2476 (7)	C2—H2A	0.9300
Zn1—Cl2	2.2694 (7)	C3—H3A	0.9300
O1W—H1WA	0.8500	C4—C5	1.507 (3)
O1W—H1WB	0.8500	C4—H4A	0.9700
N1—C2	1.323 (3)	C4—H4B	0.9700
N1—C1	1.375 (3)	C5—C6	1.513 (3)
N2—C2	1.334 (3)	C5—H5A	0.9700
N2—C3	1.370 (3)	C5—H5B	0.9700
N2—C4	1.468 (3)	C6—H6A	0.9700
N3—C8	1.333 (3)	C6—H6B	0.9700
N3—C7	1.357 (3)	C7—C9	1.350 (4)
N3—C6	1.468 (3)	C7—H7A	0.9300
N4—C8	1.322 (3)	C8—H8A	0.9300
N4—C9	1.369 (3)	C9—H9A	0.9300
N4—Zn1ⁱ	2.0053 (19)

N1—Zn1—N4ⁱ	108.03 (8)	N2—C4—C5	111.01 (19)
N1—Zn1—Cl1	114.12 (6)	N2—C4—H4A	109.4
N4ⁱ—Zn1—Cl1	108.26 (6)	C5—C4—H4A	109.4
N1—Zn1—Cl2	105.77 (6)	N2—C4—H4B	109.4
N4ⁱ—Zn1—Cl2	106.63 (6)	C5—C4—H4B	109.4
Cl1—Zn1—Cl2	113.66 (3)	H4A—C4—H4B	108.0
H1WA—O1W—H1WB	109.3	C4—C5—C6	113.6 (2)
C2—N1—C1	105.7 (2)	C4—C5—H5A	108.8
C2—N1—Zn1	127.09 (16)	C6—C5—H5A	108.8
C1—N1—Zn1	126.64 (16)	C4—C5—H5B	108.8
C2—N2—C3	107.35 (19)	C6—C5—H5B	108.8
C2—N2—C4	125.7 (2)	H5A—C5—H5B	107.7
C3—N2—C4	126.8 (2)	N3—C6—C5	112.65 (19)
C8—N3—C7	107.2 (2)	N3—C6—H6A	109.1
C8—N3—C6	126.3 (2)	C5—C6—H6A	109.1
C7—N3—C6	126.5 (2)	N3—C6—H6B	109.1
C8—N4—C9	105.8 (2)	C5—C6—H6B	109.1
C8—N4—Zn1ⁱ	129.55 (17)	H6A—C6—H6B	107.8
C9—N4—Zn1ⁱ	124.41 (16)	C9—C7—N3	106.9 (2)
C3—C1—N1	109.3 (2)	C9—C7—H7A	126.5
C3—C1—H1A	125.3	N3—C7—H7A	126.5
N1—C1—H1A	125.3	N4—C8—N3	111.1 (2)
N1—C2—N2	111.0 (2)	N4—C8—H8A	124.4
N1—C2—H2A	124.5	N3—C8—H8A	124.4
N2—C2—H2A	124.5	C7—C9—N4	108.9 (2)
C1—C3—N2	106.6 (2)	C7—C9—H9A	125.5
C1—C3—H3A	126.7	N4—C9—H9A	125.5
N2—C3—H3A	126.7

N4ⁱ—Zn1—N1—C2	−2.4 (2)	C2—N2—C4—C5	−86.8 (3)
Cl1—Zn1—N1—C2	−122.86 (18)	C3—N2—C4—C5	88.8 (3)
Cl2—Zn1—N1—C2	111.46 (19)	N2—C4—C5—C6	−175.0 (2)
N4ⁱ—Zn1—N1—C1	−172.98 (18)	C8—N3—C6—C5	−78.9 (3)
Cl1—Zn1—N1—C1	66.57 (19)	C7—N3—C6—C5	101.8 (3)
Cl2—Zn1—N1—C1	−59.12 (19)	C4—C5—C6—N3	−58.6 (3)
C2—N1—C1—C3	0.2 (3)	C8—N3—C7—C9	0.5 (3)
Zn1—N1—C1—C3	172.38 (16)	C6—N3—C7—C9	180.0 (2)
C1—N1—C2—N2	−0.6 (3)	C9—N4—C8—N3	0.6 (3)
Zn1—N1—C2—N2	−172.77 (14)	Zn1ⁱ—N4—C8—N3	174.77 (15)
C3—N2—C2—N1	0.8 (3)	C7—N3—C8—N4	−0.7 (3)
C4—N2—C2—N1	177.2 (2)	C6—N3—C8—N4	179.8 (2)
N1—C1—C3—N2	0.3 (3)	N3—C7—C9—N4	−0.2 (3)
C2—N2—C3—C1	−0.7 (2)	C8—N4—C9—C7	−0.2 (3)
C4—N2—C3—C1	−177.0 (2)	Zn1ⁱ—N4—C9—C7	−174.79 (17)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Cl1	0.85	2.47	3.282 (3)	160
O1W—H1WB···Cl2ⁱⁱ	0.85	2.76	3.473 (4)	143

Symmetry code: (ii) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···Cl1	0.85	2.47	3.282 (3)	160.1
O1W—H1WB···Cl2ⁱ	0.85	2.76	3.473 (4)	143.1

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

This work was supported by the Youth Foundation of Zhejiang Normal University (No. KYJ06Y12144).

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