catena-Poly[[[(5,5,7,12,12,14-hexa­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane-κ4N)nickel(II)]-μ-oxido-[dioxidotungstate(VI)]-μ-oxido] tetra­hydrate]

Ou, G.-C.; Yuan, X.-Y.; Li, Z.-Z.

doi:10.1107/S1600536812034538

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1173

doi:10.1107/S1600536812034538

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catena-Poly[[[(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ⁴N)nickel(II)]-μ-oxido-[dioxidotungstate(VI)]-μ-oxido] tetrahydrate]

Guang-Chuan Ou,^a ^* Xian-You Yuan ^a and Zhi-Zhang Li ^a

^aDepartment of Biology and Chemistry, Hunan University of Science and Engineering, Yongzhou Hunan 425100, People's Republic of China
^*Correspondence e-mail: ouguangchuan@yahoo.com.cn

(Received 27 July 2012; accepted 3 August 2012; online 11 August 2012)

In the title compound, {[NiWO₄(C₁₆H₃₆N₄)]·4H₂O}_n, the Ni^II ion lies on an inversion center and is octahedrally coordinated by four N atoms of the tetradentate macrocyclic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) ligand in the equatorial plane and two O atoms of [WO₄]²⁻ anions in axial positions. Each [WO₄]²⁻ anion bridges two adjacent [NiL]²⁺ cations, forming a chain along [001]. The chains are further connected via N—H⋯O, O—H⋯O and C—H⋯O hydrogen-bonding interactions, generating a three-dimensional structure.

Related literature

For a related structure, see: Ou et al. (2011 ).

Experimental

Crystal data

[NiWO₄(C₁₆H₃₆N₄)]·4H₂O
M_r = 663.11
Triclinic, $[P \overline 1]$
a = 8.8402 (14) Å
b = 11.7653 (18) Å
c = 13.931 (2) Å
α = 107.163 (2)°
β = 102.529 (3)°
γ = 104.984 (3)°
V = 1268.1 (3) Å³
Z = 2
Mo Kα radiation
μ = 5.32 mm⁻¹
T = 173 K
0.31 × 0.11 × 0.02 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.289, T_max = 0.901
7631 measured reflections
5397 independent reflections
4330 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.096
S = 1.02
5397 reflections
304 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.33 e Å⁻³
Δρ_min = −1.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O2ⁱ	0.93	2.32	3.253 (7)	180
N2—H2C⋯O4Wⁱ	0.93	2.21	3.040 (8)	149
O4W—H4WB⋯O3W	0.85 (2)	2.12 (5)	2.720 (8)	128 (6)
O4W—H4WA⋯O3	0.86 (2)	2.05 (3)	2.900 (7)	168 (6)
O2W—H2WA⋯O1Wⁱⁱ	0.85 (2)	1.94 (2)	2.790 (8)	175 (7)
O3W—H3WA⋯O2ⁱⁱⁱ	0.87 (2)	2.01 (5)	2.784 (7)	148 (8)
O1W—H1WA⋯O2	0.86 (2)	1.95 (2)	2.801 (7)	172 (8)
O2W—H2WB⋯O3	0.86 (2)	1.99 (3)	2.811 (7)	160 (8)
O3W—H3WB⋯O2W	0.86 (2)	2.08 (4)	2.834 (8)	145 (6)
O1W—H1WB⋯O2W	0.85 (2)	2.10 (4)	2.895 (9)	157 (7)
C16—H16A⋯O1^iv	0.98	2.40	3.241 (9)	144
Symmetry codes: (i) -x+2, -y+2, -z+2; (ii) -x+1, -y+1, -z+1; (iii) x-1, y, z; (iv) -x+2, -y+2, -z+1.

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812034538/pv2574sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812034538/pv2574Isup2.hkl

checkCIF report

Comment top

Continuing our research (Ou et al., 2011), we now report the crystal structure of the title complex. The asymmetric unit of the title complex contains one cation [NiL]²⁺, one anion [WO₄]^2-, and four water molecules of hydration. Each Ni^II ion displays a distorted octahedral coordination geometry by coordination with four nitrogen atoms of L in in the equatorial plane, and two oxygen atoms of [WO₄]^2- anions in the axial positions. Each [WO₄]^2- anion bridges two adjacent [NiL]²⁺cations to form a one-dimensional chain. The one-dimensional chains are further connected through O···O (2.720 (8)–2.900 (8) Å) and N···O (3.040 (8) and 3.253 (7) Å) hydrogen bonding interactions between the oxygen atoms of [WO₄]^2- anions, free water molecules and the secondary amine of [NiL]²⁺, forming a three-dimensional supramolecular structure (Tab. 2, Figs. 2, 3).

Related literature top

For a related structure, see: Ou et al. (2011).

Experimental top

A glass tube was charged with an aqueous solution of K₂WO₄ (0.033 g, 0.1 mmol) in water (20 ml), and a mixture of methanol and H₂O (1/1, 20 ml) was gently added as an upper layer. A solution of NiL (ClO₄)₂ (0.054 g, 0.1 mmol) (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in methanol (20 ml) was added carefully as a third layer, and then the tube was sealed. After several weeks, yellow prism-shaped crystals were obtained.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex, with atom labels and 50% probability displacement ellipsoids for non-H atoms. Symmetry codes for the generated atoms: A: 2 - x, 2 - y, 1 - z; B: 2 - x, 2 - y, 2 - z.
	Fig. 2. A view of the hydrogen bonds (dotted lines) in the crystal structure of the title compound. H atoms non-participating in hydrogen- bonding were omitted for clarity.
	Fig. 3. Hydrogen bonding (dashed lines) in the title compound. Symmetry codes for the generated atoms: A: 1 - x, 1 - y, 1 - z; B: -1 + x, y, z; C: - x, 1 - y, 1 - z.

catena-Poly[[[(5,5,7,12,12,14-hexamethyl-1,4,8,11- tetraazacyclotetradecane-κ⁴N)nickel(II)]-µ-oxido- [dioxidotungstate(VI)]-µ-oxido] tetrahydrate] top

Crystal data top

[NiWO₄(C₁₆H₃₆N₄)]·4H₂O	Z = 2
M_r = 663.11	F(000) = 668
Triclinic, P1	D_x = 1.737 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8402 (14) Å	Cell parameters from 3766 reflections
b = 11.7653 (18) Å	θ = 1.9–27.1°
c = 13.931 (2) Å	µ = 5.32 mm⁻¹
α = 107.163 (2)°	T = 173 K
β = 102.529 (3)°	Prism, yellow
γ = 104.984 (3)°	0.31 × 0.11 × 0.02 mm
V = 1268.1 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	5397 independent reflections
Radiation source: fine-focus sealed tube	4330 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 27.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→4
T_min = 0.289, T_max = 0.901	k = −14→15
7631 measured reflections	l = −17→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0498P)²] where P = (F_o² + 2F_c²)/3
5397 reflections	(Δ/σ)_max = 0.001
304 parameters	Δρ_max = 2.33 e Å⁻³
13 restraints	Δρ_min = −1.48 e Å⁻³

Crystal data top

[NiWO₄(C₁₆H₃₆N₄)]·4H₂O	γ = 104.984 (3)°
M_r = 663.11	V = 1268.1 (3) Å³
Triclinic, P1	Z = 2
a = 8.8402 (14) Å	Mo Kα radiation
b = 11.7653 (18) Å	µ = 5.32 mm⁻¹
c = 13.931 (2) Å	T = 173 K
α = 107.163 (2)°	0.31 × 0.11 × 0.02 mm
β = 102.529 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5397 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4330 reflections with I > 2σ(I)
T_min = 0.289, T_max = 0.901	R_int = 0.030
7631 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	13 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 2.33 e Å⁻³
5397 reflections	Δρ_min = −1.48 e Å⁻³
304 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
W1	0.86432 (3)	0.90496 (2)	0.70182 (2)	0.01423 (9)
O4	0.9085 (5)	0.9844 (4)	0.8399 (3)	0.0187 (9)
O1	0.9900 (5)	0.9988 (4)	0.6505 (3)	0.0201 (10)
O3	0.6535 (5)	0.8719 (4)	0.6342 (4)	0.0231 (10)
O2	0.9049 (6)	0.7611 (4)	0.6806 (4)	0.0258 (11)
Ni1	1.0000	1.0000	1.0000	0.0130 (2)
Ni2	1.0000	1.0000	0.5000	0.0139 (2)
N1	0.9427 (7)	1.1622 (5)	1.0653 (4)	0.0170 (11)
H1C	0.9860	1.1842	1.1380	0.020*
N2	1.2351 (6)	1.1000 (5)	1.0097 (4)	0.0158 (11)
H2C	1.3028	1.1227	1.0785	0.019*
N4	0.7426 (6)	0.9212 (5)	0.4386 (4)	0.0183 (11)
H4D	0.7043	0.9048	0.4920	0.022*
N3	1.0343 (7)	0.8257 (5)	0.4733 (4)	0.0195 (12)
H3A	1.0258	0.8088	0.5334	0.023*
C6	1.0127 (9)	1.2828 (6)	1.0490 (5)	0.0219 (15)
C11	0.6783 (9)	0.7997 (7)	0.3458 (6)	0.0298 (17)
H11	0.7226	0.8148	0.2887	0.036*
C5	1.1979 (9)	1.3084 (6)	1.0670 (6)	0.0264 (16)
H5A	1.2466	1.3084	1.1380	0.032*
H5B	1.2477	1.3953	1.0694	0.032*
C9	1.2125 (8)	0.8541 (7)	0.4833 (6)	0.0271 (16)
H9A	1.2321	0.8652	0.4188	0.033*
H9B	1.2474	0.7833	0.4922	0.033*
C10	0.6896 (9)	1.0242 (7)	0.4200 (6)	0.0295 (17)
H10A	0.5698	1.0036	0.4095	0.035*
H10B	0.7109	1.0349	0.3558	0.035*
C14	0.9159 (9)	0.7086 (6)	0.3836 (6)	0.0266 (16)
C16	0.9464 (10)	0.7001 (7)	0.2778 (6)	0.0359 (19)
H16A	0.9446	0.7773	0.2649	0.054*
H16B	0.8597	0.6263	0.2204	0.054*
H16C	1.0543	0.6912	0.2805	0.054*
C13	0.7386 (9)	0.7023 (6)	0.3763 (6)	0.0313 (18)
H13A	0.6640	0.6175	0.3245	0.038*
H13B	0.7252	0.7078	0.4461	0.038*
C15	0.9397 (11)	0.5905 (7)	0.4055 (7)	0.041 (2)
H15A	0.8627	0.5129	0.3469	0.061*
H15B	0.9180	0.5911	0.4717	0.061*
H15C	1.0533	0.5934	0.4117	0.061*
C12	0.4873 (10)	0.7496 (8)	0.3017 (7)	0.045 (2)
H12A	0.4416	0.7344	0.3568	0.068*
H12B	0.4495	0.6701	0.2403	0.068*
H12C	0.4499	0.8125	0.2803	0.068*
C3	1.2531 (9)	1.2195 (6)	0.9881 (6)	0.0256 (16)
H3	1.1785	1.1969	0.9150	0.031*
C8	0.9959 (10)	1.3946 (6)	1.1322 (6)	0.0283 (16)
H8A	0.8787	1.3813	1.1227	0.042*
H8B	1.0477	1.4736	1.1233	0.042*
H8C	1.0506	1.4000	1.2034	0.042*
C7	0.9231 (9)	1.2735 (7)	0.9384 (6)	0.0298 (17)
H7A	0.9179	1.1950	0.8854	0.045*
H7B	0.9832	1.3464	0.9246	0.045*
H7C	0.8109	1.2731	0.9343	0.045*
C4	1.4286 (10)	1.2865 (8)	0.9937 (8)	0.051 (3)
H4A	1.5007	1.3220	1.0674	0.077*
H4B	1.4304	1.3550	0.9671	0.077*
H4C	1.4677	1.2257	0.9504	0.077*
C1	0.7623 (8)	1.1146 (6)	1.0442 (5)	0.0213 (14)
H1A	0.7047	1.1009	0.9702	0.026*
H1B	0.7301	1.1780	1.0919	0.026*
C2	1.2872 (8)	1.0076 (6)	0.9384 (5)	0.0188 (14)
H2A	1.4084	1.0407	0.9539	0.023*
H2B	1.2336	0.9936	0.8636	0.023*
O2W	0.3988 (7)	0.6388 (5)	0.5720 (5)	0.0422 (14)
H2WA	0.389 (10)	0.589 (5)	0.510 (3)	0.051*
H2WB	0.458 (9)	0.714 (3)	0.582 (5)	0.051*
O4W	0.5200 (7)	0.9166 (6)	0.8089 (4)	0.0441 (15)
H4WB	0.461 (7)	0.842 (3)	0.797 (4)	0.053*
H4WA	0.564 (9)	0.915 (6)	0.759 (5)	0.053*
O1W	0.6501 (8)	0.5326 (5)	0.6291 (5)	0.0447 (15)
H1WA	0.729 (5)	0.599 (5)	0.639 (7)	0.054*
H1WB	0.560 (4)	0.547 (7)	0.617 (7)	0.054*
O3W	0.2150 (7)	0.7401 (6)	0.6956 (5)	0.0504 (17)
H3WA	0.109 (3)	0.714 (8)	0.681 (5)	0.061*
H3WB	0.234 (7)	0.706 (8)	0.638 (3)	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
W1	0.01641 (14)	0.01438 (14)	0.01496 (14)	0.00471 (10)	0.00913 (10)	0.00725 (10)
O4	0.021 (2)	0.019 (2)	0.017 (2)	0.0070 (19)	0.0074 (19)	0.0073 (19)
O1	0.014 (2)	0.023 (2)	0.021 (3)	0.0006 (19)	0.0067 (19)	0.010 (2)
O3	0.015 (2)	0.028 (3)	0.022 (3)	0.003 (2)	0.007 (2)	0.004 (2)
O2	0.029 (3)	0.018 (2)	0.034 (3)	0.012 (2)	0.010 (2)	0.011 (2)
Ni1	0.0154 (6)	0.0136 (5)	0.0142 (6)	0.0060 (4)	0.0092 (5)	0.0070 (4)
Ni2	0.0161 (6)	0.0127 (5)	0.0161 (6)	0.0038 (4)	0.0092 (5)	0.0077 (4)
N1	0.027 (3)	0.016 (3)	0.019 (3)	0.011 (2)	0.016 (2)	0.012 (2)
N2	0.020 (3)	0.016 (3)	0.017 (3)	0.008 (2)	0.009 (2)	0.011 (2)
N4	0.019 (3)	0.021 (3)	0.018 (3)	0.006 (2)	0.008 (2)	0.010 (2)
N3	0.023 (3)	0.021 (3)	0.021 (3)	0.010 (2)	0.010 (2)	0.012 (2)
C6	0.039 (4)	0.015 (3)	0.021 (4)	0.016 (3)	0.017 (3)	0.010 (3)
C11	0.020 (4)	0.031 (4)	0.029 (4)	−0.001 (3)	0.007 (3)	0.008 (3)
C5	0.036 (4)	0.016 (3)	0.032 (4)	0.008 (3)	0.022 (3)	0.010 (3)
C9	0.024 (4)	0.038 (4)	0.030 (4)	0.020 (3)	0.013 (3)	0.017 (3)
C10	0.026 (4)	0.032 (4)	0.045 (5)	0.015 (3)	0.019 (4)	0.023 (4)
C14	0.042 (5)	0.015 (3)	0.024 (4)	0.007 (3)	0.020 (3)	0.007 (3)
C16	0.047 (5)	0.029 (4)	0.028 (4)	0.010 (4)	0.018 (4)	0.005 (3)
C13	0.042 (5)	0.013 (3)	0.029 (4)	−0.004 (3)	0.012 (4)	0.004 (3)
C15	0.059 (6)	0.018 (4)	0.046 (5)	0.013 (4)	0.024 (4)	0.010 (4)
C12	0.038 (5)	0.032 (5)	0.045 (5)	0.002 (4)	0.001 (4)	0.004 (4)
C3	0.028 (4)	0.017 (3)	0.041 (5)	0.009 (3)	0.024 (3)	0.015 (3)
C8	0.044 (5)	0.019 (4)	0.032 (4)	0.017 (3)	0.021 (4)	0.011 (3)
C7	0.044 (5)	0.032 (4)	0.027 (4)	0.021 (4)	0.016 (4)	0.020 (3)
C4	0.039 (5)	0.029 (5)	0.098 (8)	0.008 (4)	0.041 (5)	0.032 (5)
C1	0.024 (4)	0.021 (3)	0.025 (4)	0.012 (3)	0.013 (3)	0.010 (3)
C2	0.016 (3)	0.019 (3)	0.025 (4)	0.007 (3)	0.015 (3)	0.006 (3)
O2W	0.031 (3)	0.029 (3)	0.055 (4)	0.001 (3)	0.020 (3)	0.003 (3)
O4W	0.027 (3)	0.071 (4)	0.029 (3)	0.012 (3)	0.015 (3)	0.012 (3)
O1W	0.041 (3)	0.027 (3)	0.048 (4)	−0.003 (3)	0.000 (3)	0.011 (3)
O3W	0.032 (3)	0.044 (4)	0.060 (4)	0.007 (3)	0.025 (3)	−0.005 (3)

Geometric parameters (Å, º) top

W1—O1	1.772 (4)	C10—H10A	0.9900
W1—O2	1.773 (4)	C10—H10B	0.9900
W1—O4	1.775 (4)	C14—C13	1.529 (10)
W1—O3	1.778 (4)	C14—C16	1.534 (9)
O4—Ni1	2.135 (4)	C14—C15	1.563 (9)
O1—Ni2	2.121 (4)	C16—H16A	0.9800
Ni1—N2	2.059 (5)	C16—H16B	0.9800
Ni1—N2ⁱ	2.059 (5)	C16—H16C	0.9800
Ni1—N1ⁱ	2.098 (5)	C13—H13A	0.9900
Ni1—N1	2.098 (5)	C13—H13B	0.9900
Ni1—O4ⁱ	2.135 (4)	C15—H15A	0.9800
Ni2—N3ⁱⁱ	2.087 (5)	C15—H15B	0.9800
Ni2—N3	2.087 (5)	C15—H15C	0.9800
Ni2—N4ⁱⁱ	2.089 (5)	C12—H12A	0.9800
Ni2—N4	2.089 (5)	C12—H12B	0.9800
Ni2—O1ⁱⁱ	2.121 (4)	C12—H12C	0.9800
N1—C1	1.477 (8)	C3—C4	1.521 (10)
N1—C6	1.498 (8)	C3—H3	1.0000
N1—H1C	0.9300	C8—H8A	0.9800
N2—C2	1.484 (7)	C8—H8B	0.9800
N2—C3	1.499 (8)	C8—H8C	0.9800
N2—H2C	0.9300	C7—H7A	0.9800
N4—C10	1.478 (8)	C7—H7B	0.9800
N4—C11	1.486 (8)	C7—H7C	0.9800
N4—H4D	0.9300	C4—H4A	0.9800
N3—C9	1.490 (8)	C4—H4B	0.9800
N3—C14	1.492 (8)	C4—H4C	0.9800
N3—H3A	0.9300	C1—C2ⁱ	1.498 (8)
C6—C7	1.530 (9)	C1—H1A	0.9900
C6—C5	1.535 (10)	C1—H1B	0.9900
C6—C8	1.539 (9)	C2—C1ⁱ	1.498 (8)
C11—C13	1.511 (10)	C2—H2A	0.9900
C11—C12	1.548 (10)	C2—H2B	0.9900
C11—H11	1.0000	O2W—H2WA	0.85 (2)
C5—C3	1.536 (9)	O2W—H2WB	0.86 (2)
C5—H5A	0.9900	O4W—H4WB	0.845 (19)
C5—H5B	0.9900	O4W—H4WA	0.86 (2)
C9—C10ⁱⁱ	1.526 (10)	O1W—H1WA	0.86 (2)
C9—H9A	0.9900	O1W—H1WB	0.85 (2)
C9—H9B	0.9900	O3W—H3WA	0.87 (2)
C10—C9ⁱⁱ	1.526 (10)	O3W—H3WB	0.863 (19)

O1—W1—O2	108.7 (2)	N3—C9—H9A	110.2
O1—W1—O4	110.9 (2)	C10ⁱⁱ—C9—H9A	110.2
O2—W1—O4	108.7 (2)	N3—C9—H9B	110.2
O1—W1—O3	108.9 (2)	C10ⁱⁱ—C9—H9B	110.2
O2—W1—O3	109.7 (2)	H9A—C9—H9B	108.5
O4—W1—O3	109.9 (2)	N4—C10—C9ⁱⁱ	108.0 (6)
W1—O4—Ni1	151.1 (2)	N4—C10—H10A	110.1
W1—O1—Ni2	137.9 (2)	C9ⁱⁱ—C10—H10A	110.1
N2—Ni1—N2ⁱ	180.000 (1)	N4—C10—H10B	110.1
N2—Ni1—N1ⁱ	85.46 (19)	C9ⁱⁱ—C10—H10B	110.1
N2ⁱ—Ni1—N1ⁱ	94.5 (2)	H10A—C10—H10B	108.4
N2—Ni1—N1	94.5 (2)	N3—C14—C13	109.8 (5)
N2ⁱ—Ni1—N1	85.46 (19)	N3—C14—C16	112.3 (6)
N1ⁱ—Ni1—N1	180.000 (3)	C13—C14—C16	110.8 (6)
N2—Ni1—O4	90.57 (18)	N3—C14—C15	108.7 (6)
N2ⁱ—Ni1—O4	89.43 (18)	C13—C14—C15	108.1 (6)
N1ⁱ—Ni1—O4	85.20 (18)	C16—C14—C15	106.9 (6)
N1—Ni1—O4	94.80 (18)	C14—C16—H16A	109.5
N2—Ni1—O4ⁱ	89.43 (18)	C14—C16—H16B	109.5
N2ⁱ—Ni1—O4ⁱ	90.57 (18)	H16A—C16—H16B	109.5
N1ⁱ—Ni1—O4ⁱ	94.80 (18)	C14—C16—H16C	109.5
N1—Ni1—O4ⁱ	85.20 (18)	H16A—C16—H16C	109.5
O4—Ni1—O4ⁱ	180.000 (2)	H16B—C16—H16C	109.5
N3ⁱⁱ—Ni2—N3	180.000 (2)	C11—C13—C14	118.9 (6)
N3ⁱⁱ—Ni2—N4ⁱⁱ	94.6 (2)	C11—C13—H13A	107.6
N3—Ni2—N4ⁱⁱ	85.4 (2)	C14—C13—H13A	107.6
N3ⁱⁱ—Ni2—N4	85.4 (2)	C11—C13—H13B	107.6
N3—Ni2—N4	94.6 (2)	C14—C13—H13B	107.6
N4ⁱⁱ—Ni2—N4	180.000 (1)	H13A—C13—H13B	107.0
N3ⁱⁱ—Ni2—O1ⁱⁱ	86.13 (19)	C14—C15—H15A	109.5
N3—Ni2—O1ⁱⁱ	93.87 (19)	C14—C15—H15B	109.5
N4ⁱⁱ—Ni2—O1ⁱⁱ	90.23 (18)	H15A—C15—H15B	109.5
N4—Ni2—O1ⁱⁱ	89.77 (18)	C14—C15—H15C	109.5
N3ⁱⁱ—Ni2—O1	93.87 (19)	H15A—C15—H15C	109.5
N3—Ni2—O1	86.13 (19)	H15B—C15—H15C	109.5
N4ⁱⁱ—Ni2—O1	89.77 (18)	C11—C12—H12A	109.5
N4—Ni2—O1	90.23 (18)	C11—C12—H12B	109.5
O1ⁱⁱ—Ni2—O1	180.000 (2)	H12A—C12—H12B	109.5
C1—N1—C6	116.7 (5)	C11—C12—H12C	109.5
C1—N1—Ni1	104.6 (4)	H12A—C12—H12C	109.5
C6—N1—Ni1	122.1 (4)	H12B—C12—H12C	109.5
C1—N1—H1C	103.7	N2—C3—C4	112.5 (6)
C6—N1—H1C	103.7	N2—C3—C5	109.4 (5)
Ni1—N1—H1C	103.7	C4—C3—C5	110.3 (6)
C2—N2—C3	113.8 (5)	N2—C3—H3	108.2
C2—N2—Ni1	105.4 (4)	C4—C3—H3	108.2
C3—N2—Ni1	115.3 (4)	C5—C3—H3	108.2
C2—N2—H2C	107.3	C6—C8—H8A	109.5
C3—N2—H2C	107.3	C6—C8—H8B	109.5
Ni1—N2—H2C	107.3	H8A—C8—H8B	109.5
C10—N4—C11	115.2 (5)	C6—C8—H8C	109.5
C10—N4—Ni2	104.7 (4)	H8A—C8—H8C	109.5
C11—N4—Ni2	114.5 (4)	H8B—C8—H8C	109.5
C10—N4—H4D	107.3	C6—C7—H7A	109.5
C11—N4—H4D	107.3	C6—C7—H7B	109.5
Ni2—N4—H4D	107.3	H7A—C7—H7B	109.5
C9—N3—C14	116.5 (5)	C6—C7—H7C	109.5
C9—N3—Ni2	104.7 (4)	H7A—C7—H7C	109.5
C14—N3—Ni2	121.3 (4)	H7B—C7—H7C	109.5
C9—N3—H3A	104.1	C3—C4—H4A	109.5
C14—N3—H3A	104.1	C3—C4—H4B	109.5
Ni2—N3—H3A	104.1	H4A—C4—H4B	109.5
N1—C6—C7	110.9 (6)	C3—C4—H4C	109.5
N1—C6—C5	107.7 (5)	H4A—C4—H4C	109.5
C7—C6—C5	111.8 (6)	H4B—C4—H4C	109.5
N1—C6—C8	110.2 (5)	N1—C1—C2ⁱ	109.7 (5)
C7—C6—C8	108.9 (5)	N1—C1—H1A	109.7
C5—C6—C8	107.4 (6)	C2ⁱ—C1—H1A	109.7
N4—C11—C13	109.7 (6)	N1—C1—H1B	109.7
N4—C11—C12	111.8 (6)	C2ⁱ—C1—H1B	109.7
C13—C11—C12	110.3 (6)	H1A—C1—H1B	108.2
N4—C11—H11	108.3	N2—C2—C1ⁱ	108.5 (5)
C13—C11—H11	108.3	N2—C2—H2A	110.0
C12—C11—H11	108.3	C1ⁱ—C2—H2A	110.0
C6—C5—C3	119.3 (6)	N2—C2—H2B	110.0
C6—C5—H5A	107.5	C1ⁱ—C2—H2B	110.0
C3—C5—H5A	107.5	H2A—C2—H2B	108.4
C6—C5—H5B	107.5	H2WA—O2W—H2WB	109 (3)
C3—C5—H5B	107.5	H4WB—O4W—H4WA	109 (3)
H5A—C5—H5B	107.0	H3WA—O3W—H3WB	107 (3)
N3—C9—C10ⁱⁱ	107.7 (5)

O1—W1—O4—Ni1	−113.9 (5)	N4ⁱⁱ—Ni2—N3—C14	−149.8 (5)
O2—W1—O4—Ni1	5.5 (6)	N4—Ni2—N3—C14	30.2 (5)
O3—W1—O4—Ni1	125.6 (5)	O1ⁱⁱ—Ni2—N3—C14	−59.9 (5)
O2—W1—O1—Ni2	73.4 (4)	O1—Ni2—N3—C14	120.1 (5)
O4—W1—O1—Ni2	−167.2 (3)	C1—N1—C6—C7	−53.1 (7)
O3—W1—O1—Ni2	−46.1 (4)	Ni1—N1—C6—C7	77.3 (6)
W1—O4—Ni1—N2	87.9 (5)	C1—N1—C6—C5	−175.7 (5)
W1—O4—Ni1—N2ⁱ	−92.1 (5)	Ni1—N1—C6—C5	−45.2 (7)
W1—O4—Ni1—N1ⁱ	2.5 (5)	C1—N1—C6—C8	67.5 (7)
W1—O4—Ni1—N1	−177.5 (5)	Ni1—N1—C6—C8	−162.1 (5)
W1—O1—Ni2—N3ⁱⁱ	117.7 (4)	C10—N4—C11—C13	−178.8 (5)
W1—O1—Ni2—N3	−62.3 (4)	Ni2—N4—C11—C13	59.7 (6)
W1—O1—Ni2—N4ⁱⁱ	−147.8 (4)	C10—N4—C11—C12	−56.2 (8)
W1—O1—Ni2—N4	32.2 (4)	Ni2—N4—C11—C12	−177.7 (5)
N2—Ni1—N1—C1	167.3 (4)	N1—C6—C5—C3	67.8 (7)
N2ⁱ—Ni1—N1—C1	−12.7 (4)	C7—C6—C5—C3	−54.3 (8)
O4—Ni1—N1—C1	76.4 (4)	C8—C6—C5—C3	−173.6 (6)
O4ⁱ—Ni1—N1—C1	−103.6 (4)	C14—N3—C9—C10ⁱⁱ	−179.4 (5)
N2—Ni1—N1—C6	32.0 (5)	Ni2—N3—C9—C10ⁱⁱ	43.7 (6)
N2ⁱ—Ni1—N1—C6	−148.0 (5)	C11—N4—C10—C9ⁱⁱ	−171.2 (5)
O4—Ni1—N1—C6	−58.9 (5)	Ni2—N4—C10—C9ⁱⁱ	−44.5 (6)
O4ⁱ—Ni1—N1—C6	121.1 (5)	C9—N3—C14—C13	−172.9 (5)
N1ⁱ—Ni1—N2—C2	16.8 (4)	Ni2—N3—C14—C13	−43.5 (7)
N1—Ni1—N2—C2	−163.2 (4)	C9—N3—C14—C16	−49.2 (8)
O4—Ni1—N2—C2	−68.4 (4)	Ni2—N3—C14—C16	80.2 (7)
O4ⁱ—Ni1—N2—C2	111.6 (4)	C9—N3—C14—C15	69.0 (7)
N1ⁱ—Ni1—N2—C3	143.2 (5)	Ni2—N3—C14—C15	−161.6 (5)
N1—Ni1—N2—C3	−36.8 (5)	N4—C11—C13—C14	−78.2 (8)
O4—Ni1—N2—C3	58.0 (4)	C12—C11—C13—C14	158.4 (6)
O4ⁱ—Ni1—N2—C3	−122.0 (4)	N3—C14—C13—C11	66.9 (8)
N3ⁱⁱ—Ni2—N4—C10	16.1 (4)	C16—C14—C13—C11	−57.8 (8)
N3—Ni2—N4—C10	−163.9 (4)	C15—C14—C13—C11	−174.6 (6)
O1ⁱⁱ—Ni2—N4—C10	−70.1 (4)	C2—N2—C3—C4	−56.5 (8)
O1—Ni2—N4—C10	109.9 (4)	Ni1—N2—C3—C4	−178.5 (5)
N3ⁱⁱ—Ni2—N4—C11	143.2 (5)	C2—N2—C3—C5	−179.3 (5)
N3—Ni2—N4—C11	−36.8 (5)	Ni1—N2—C3—C5	58.7 (7)
O1ⁱⁱ—Ni2—N4—C11	57.1 (4)	C6—C5—C3—N2	−77.9 (8)
O1—Ni2—N4—C11	−122.9 (4)	C6—C5—C3—C4	157.9 (6)
N4ⁱⁱ—Ni2—N3—C9	−15.4 (4)	C6—N1—C1—C2ⁱ	178.6 (5)
N4—Ni2—N3—C9	164.6 (4)	Ni1—N1—C1—C2ⁱ	40.5 (6)
O1ⁱⁱ—Ni2—N3—C9	74.5 (4)	C3—N2—C2—C1ⁱ	−170.8 (6)
O1—Ni2—N3—C9	−105.5 (4)	Ni1—N2—C2—C1ⁱ	−43.5 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2ⁱ	0.93	2.32	3.253 (7)	180
N2—H2C···O4Wⁱ	0.93	2.21	3.040 (8)	149
O4W—H4WB···O3W	0.85 (2)	2.12 (5)	2.720 (8)	128 (6)
O4W—H4WA···O3	0.86 (2)	2.05 (3)	2.900 (7)	168 (6)
O2W—H2WA···O1Wⁱⁱⁱ	0.85 (2)	1.94 (2)	2.790 (8)	175 (7)
O3W—H3WA···O2^iv	0.87 (2)	2.01 (5)	2.784 (7)	148 (8)
O1W—H1WA···O2	0.86 (2)	1.95 (2)	2.801 (7)	172 (8)
O2W—H2WB···O3	0.86 (2)	1.99 (3)	2.811 (7)	160 (8)
O3W—H3WB···O2W	0.86 (2)	2.08 (4)	2.834 (8)	145 (6)
O1W—H1WB···O2W	0.85 (2)	2.10 (4)	2.895 (9)	157 (7)
C16—H16A···O1ⁱⁱ	0.98	2.40	3.241 (9)	144

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

Experimental details

Crystal data
Chemical formula	[NiWO₄(C₁₆H₃₆N₄)]·4H₂O
M_r	663.11
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.8402 (14), 11.7653 (18), 13.931 (2)
α, β, γ (°)	107.163 (2), 102.529 (3), 104.984 (3)
V (Å³)	1268.1 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.32
Crystal size (mm)	0.31 × 0.11 × 0.02

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.289, 0.901
No. of measured, independent and observed [I > 2σ(I)] reflections	7631, 5397, 4330
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.096, 1.02
No. of reflections	5397
No. of parameters	304
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.33, −1.48

Computer programs: SMART (Bruker, 1999), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2ⁱ	0.93	2.32	3.253 (7)	179.7
N2—H2C···O4Wⁱ	0.93	2.21	3.040 (8)	149.0
O4W—H4WB···O3W	0.845 (19)	2.12 (5)	2.720 (8)	128 (6)
O4W—H4WA···O3	0.86 (2)	2.05 (3)	2.900 (7)	168 (6)
O2W—H2WA···O1Wⁱⁱ	0.85 (2)	1.94 (2)	2.790 (8)	175 (7)
O3W—H3WA···O2ⁱⁱⁱ	0.87 (2)	2.01 (5)	2.784 (7)	148 (8)
O1W—H1WA···O2	0.86 (2)	1.95 (2)	2.801 (7)	172 (8)
O2W—H2WB···O3	0.86 (2)	1.99 (3)	2.811 (7)	160 (8)
O3W—H3WB···O2W	0.863 (19)	2.08 (4)	2.834 (8)	145 (6)
O1W—H1WB···O2W	0.85 (2)	2.10 (4)	2.895 (9)	157 (7)
C16—H16A···O1^iv	0.98	2.40	3.241 (9)	143.8

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

Acknowledgements

The authors thank the Science and Technology Planning Project of Hunan Province (2012 F J3050, 2012 N K3067), the Construct Program of the Key Discipline in Hunan Province (2011–76) and the Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province (2012–318) for financial support.

References

Bruker (1999). SMART and SAINT-Plus. Bruker AXS Inc, Madison, Wisconsin, USA. Google Scholar
Ou, G. C., Zou, L. S. & Yuan, Z. H. (2011). Z. Kristallogr. New Cryst. Struct. 226, 543–544. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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