Hexa­aqua­nickel(II) dinitrate bis­(hexa­methyl­enetetramine) tetrahydrate

In the title compound, [Ni(H₂O)₆](NO₃)₂·2C₆H₁₂N₄·4H₂O, the Ni atom lies on the crystallographic inversion center and is coordinated by six water mol­ecules in an octahedral environment. The coordinated water mol­ecules are involved in hydrogen bonding with the hexa­methyl­enetetr­amine, nitrate and lattice water mol­ecules, thus furnishing a three-dimensional network motif. The hexa­methyl­enetetr­amine entity is linked to three different [Ni(H₂O)₆]²⁺ octahedra, as well as to a lattice water mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-N) = 0.004 Å
• R factor = 0.043
• wR factor = 0.095
• Data-to-parameter ratio = 14.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.90
         From the CIF: _reflns_number_total               3095
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         3323
         Completeness (_total/calc)             93.14%
          Alert C: < 95% complete

PLAT_731  Alert C Bond    Calc     0.85(3), Rep   0.850(10) ....       3.00 s.u-Ratio
                     O5W  -H5W1    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.850(10) ....       3.00 s.u-Ratio
                     O4W  -H4W1    1.555   1.555

PLAT_735  Alert C D-H     Calc     0.85(3), Rep   0.850(10) ....       3.00 s.u-Ratio
                     O5W  -H5W1    1.555   1.555

PLAT_736  Alert C H...A   Calc     1.97(3), Rep   1.970(10) ....       3.00 s.u-Ratio
                     H4W1 -O5W     1.555   2.756

PLAT_736  Alert C H...A   Calc     2.06(3), Rep   2.060(10) ....       3.00 s.u-Ratio
                     H5W1 -O2      1.555   2.657


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 6 Alert Level C = Please check

---

S1. Comment

Hexamethylenetetramine, a nitrogen-donor ligand, functions as a bridging entity in a number of its complexes with metal salts (Carlucci et al., 1995; 1997); occasionally, it exists as a host molecule in inclusion compounds (Reddy et al., 1993, 1994). Both classes have been investigated in detail (Ganesh et al., 1990; Zheng et al., 2001). The reaction of nickel(II) acetate with this ligand furnished mixed crystal of dinickel tetraacetate with hexamethylenetetramine (Wang et al., 2002); the crystal adopts a chain architecture.

The analogous reaction with nickel nitrate in place of nickel acetate afforded the title hexaaquanickel dinitrate bis(hexamethylenetetramine) tetrahydrate, (I); each hexamethylenetetramine entity uses three of the four nitrogen sites to interact, indirectly, with the Ni atom through the coordinated water molecules. The Ni atom, which lies at the crystallographic inversion center, shows octahedral coordination (Fig. 1). The hexamethylenetetramine, nitrate and lattice water entities lie in general positions in the crystal structure. The ligand forms four hydrogen bonds, and each water molecule forms a pair of hydrogen bonds to give rise to a tightly-held three-dimensional structure.

S2. Experimental

10 ml of water solution of nickel nitrate tetrahydrate (0.26 g, 1 mmol) was mixed with 10 ml of water solution of hexamethylenetetramine (0.28 g, 2 mm mol). The mixture was filtered, and after the solution was set aside for several weeks, blue crystals precipitated.

S3. Refinement

The water-bound H atoms were located and refined, subject to O—H 0.85±0.01 Å and H···H = 1.39±0.01 Å; their displacement parameters were set to be 1.2 times those of the parent O atoms.

Computing details

Data collection: SMART (Siemens, 1997); cell refinement: SAINT (Siemens, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of the unit-cell contents at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

Hexaaquanickel dinitrate bis(hexamethylenetetramine) tetrahydrate

Crystal data

[Ni(H2O)6](NO3)2·2C6H12N4·4H2O	Z = 1
Mr = 643.28	F(000) = 342
Triclinic, P1	Dx = 1.536 Mg m^−3
a = 9.087 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.343 (2) Å	Cell parameters from 1562 reflections
c = 9.682 (2) Å	θ = 2.2–27.9°
α = 87.761 (3)°	µ = 0.78 mm^−1
β = 75.719 (2)°	T = 298 K
γ = 61.275 (2)°	Block, blue
V = 695.5 (2) Å^3	0.42 × 0.32 × 0.25 mm

Data collection

Siemens CCD area-detectorr diffractometer	3095 independent reflections
Radiation source: fine-focus sealed tube	2192 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 27.9°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
Tmin = 0.734, Tmax = 0.828	k = −9→11
4434 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 0.88	w = 1/[σ^2(Fo^2) + (0.044P)^2] where P = (Fo^2 + 2Fc^2)/3
3095 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.55 e Å^−3
15 restraints	Δρmin = −0.45 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.5000	0.5000	0.5000	0.0297 (2)
O1	0.3993 (4)	0.4270 (3)	0.9214 (3)	0.0918 (8)
O2	0.3654 (3)	0.3576 (3)	1.1353 (2)	0.0734 (7)
O3	0.5271 (5)	0.1806 (4)	0.9601 (4)	0.131 (1)
O1w	0.6070 (2)	0.3201 (2)	0.6311 (2)	0.0387 (4)
O2w	0.4917 (2)	0.6768 (2)	0.6270 (2)	0.0416 (5)
O3w	0.7427 (2)	0.4506 (2)	0.3926 (2)	0.0382 (4)
O4w	0.9808 (3)	0.2315 (3)	0.1767 (2)	0.0606 (6)
O5w	0.6961 (3)	−0.0916 (3)	0.7571 (3)	0.0736 (7)
N1	0.9521 (3)	0.2074 (3)	0.6605 (2)	0.0365 (5)
N2	1.0489 (3)	0.2021 (3)	0.8762 (2)	0.0394 (5)
N3	1.1527 (3)	0.3107 (3)	0.6625 (2)	0.0381 (5)
N4	1.2528 (3)	0.0167 (3)	0.6630 (2)	0.0371 (5)
N5	0.4321 (3)	0.3219 (4)	1.0049 (3)	0.0542 (7)
C1	0.9046 (3)	0.2235 (3)	0.8183 (3)	0.0420 (7)
C2	1.0059 (3)	0.3301 (3)	0.6099 (3)	0.0412 (7)
C3	1.1030 (3)	0.0435 (3)	0.6095 (3)	0.0385 (6)
C4	1.1972 (3)	0.0382 (3)	0.8210 (3)	0.0417 (7)
C5	1.0998 (4)	0.3253 (3)	0.8193 (3)	0.0451 (7)
C6	1.2986 (3)	0.1443 (3)	0.6126 (3)	0.0399 (6)
H1w1	0.550 (2)	0.343 (3)	0.718 (1)	0.046*
H1w2	0.714 (1)	0.281 (3)	0.626 (2)	0.046*
H2w1	0.531 (3)	0.657 (3)	0.701 (2)	0.050*
H2w2	0.426 (3)	0.780 (1)	0.628 (3)	0.050*
H3w1	0.802 (3)	0.381 (2)	0.320 (2)	0.046*
H3w2	0.764 (3)	0.530 (2)	0.385 (3)	0.046*
H4w1	1.079 (2)	0.183 (4)	0.195 (3)	0.073*
H4w2	0.992 (4)	0.225 (4)	0.088 (1)	0.073*
H5w1	0.666 (4)	−0.159 (3)	0.799 (3)	0.088*
H5w2	0.641 (4)	−0.001 (2)	0.808 (3)	0.088*
H1a	0.8705	0.1422	0.8528	0.050*
H1b	0.8054	0.3310	0.8532	0.050*
H2a	1.0390	0.3198	0.5061	0.049*
H2b	0.9083	0.4391	0.6423	0.049*
H3a	1.1369	0.0319	0.5057	0.046*
H3b	1.0704	−0.0394	0.6413	0.046*
H4a	1.1651	−0.0443	0.8558	0.050*
H4b	1.2940	0.0218	0.8576	0.050*
H5a	1.0026	0.4340	0.8535	0.054*
H5b	1.1952	0.3128	0.8558	0.054*
H6a	1.3340	0.1325	0.5088	0.048*
H6b	1.3965	0.1293	0.6466	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0289 (3)	0.0312 (3)	0.0259 (3)	−0.0125 (2)	−0.0059 (2)	0.0002 (2)
O1	0.105 (2)	0.095 (2)	0.058 (2)	−0.038 (2)	−0.021 (2)	0.021 (2)
O2	0.079 (2)	0.091 (2)	0.041 (1)	−0.036 (1)	−0.012 (1)	0.001 (2)
O3	0.142 (3)	0.070 (2)	0.109 (3)	−0.013 (2)	0.010 (2)	−0.026 (2)
O1w	0.035 (1)	0.045 (1)	0.034 (1)	−0.017 (1)	−0.012 (1)	0.010 (1)
O2w	0.049 (1)	0.032 (1)	0.041 (1)	−0.013 (1)	−0.021 (1)	−0.002 (1)
O3w	0.034 (1)	0.038 (1)	0.039 (1)	−0.019 (1)	0.001 (1)	−0.005 (1)
O4w	0.053 (1)	0.073 (2)	0.036 (1)	−0.021 (1)	0.002 (1)	−0.008 (1)
O5w	0.075 (2)	0.076 (2)	0.062 (2)	−0.033 (2)	−0.012 (1)	0.003 (1)
N1	0.034 (1)	0.041 (1)	0.037 (1)	−0.018 (1)	−0.012 (1)	0.006 (1)
N2	0.037 (1)	0.045 (1)	0.032 (1)	−0.018 (1)	−0.006 (1)	−0.003 (1)
N3	0.034 (1)	0.039 (1)	0.041 (1)	−0.020 (1)	−0.005 (1)	−0.001 (1)
N4	0.034 (1)	0.035 (1)	0.036 (1)	−0.011 (1)	−0.010 (1)	−0.002 (1)
N5	0.049 (2)	0.063 (2)	0.045 (2)	−0.022 (1)	−0.012 (1)	−0.002 (1)
C1	0.035 (2)	0.045 (2)	0.043 (2)	−0.019 (1)	−0.004 (1)	0.001 (1)
C2	0.038 (2)	0.036 (2)	0.045 (2)	−0.015 (1)	−0.010 (1)	0.007 (1)
C3	0.043 (2)	0.039 (2)	0.036 (2)	−0.021 (1)	−0.013 (1)	0.001 (1)
C4	0.041 (2)	0.045 (2)	0.038 (2)	−0.018 (1)	−0.017 (1)	0.007 (1)
C5	0.045 (2)	0.046 (2)	0.045 (2)	−0.022 (1)	−0.009 (1)	−0.010 (1)
C6	0.031 (1)	0.048 (2)	0.039 (2)	−0.019 (1)	−0.005 (1)	−0.003 (1)

Geometric parameters (Å, º)

Ni1—O1w	2.063 (2)	O1w—H1w2	0.85 (1)
Ni1—O1w^i	2.063 (2)	O2w—H2w1	0.85 (1)
Ni1—O2w	2.059 (2)	O2w—H2w2	0.85 (1)
Ni1—O2w^i	2.059 (2)	O3w—H3w1	0.85 (1)
Ni1—O3w	2.022 (2)	O3w—H3w2	0.85 (1)
Ni1—O3w^i	2.022 (2)	O4w—H4w1	0.85 (1)
O1—N5	1.218 (3)	O4w—H4w2	0.84 (1)
O2—N5	1.239 (3)	O5w—H5w1	0.85 (1)
O3—N5	1.200 (3)	O5w—H5w2	0.85 (1)
N1—C1	1.474 (3)	C1—H1a	0.9700
N1—C2	1.473 (3)	C1—H1b	0.9700
N1—C3	1.475 (3)	C2—H2a	0.9700
N2—C1	1.475 (3)	C2—H2b	0.9700
N2—C4	1.473 (3)	C3—H3a	0.9700
N2—C5	1.476 (3)	C3—H3b	0.9700
N3—C2	1.472 (3)	C4—H4a	0.9700
N3—C5	1.466 (3)	C4—H4b	0.9700
N3—C6	1.473 (3)	C5—H5a	0.9700
N4—C3	1.481 (3)	C5—H5b	0.9700
N4—C4	1.477 (3)	C6—H6a	0.9700
N4—C6	1.472 (3)	C6—H6b	0.9700
O1w—H1w1	0.84 (1)
O1w—Ni1—O1w^i	180.0	Ni1—O2w—H2w1	123 (2)
O1w—Ni1—O2w	92.5 (1)	Ni1—O2w—H2w2	125 (2)
O1w—Ni1—O2w^i	87.5 (1)	H2w1—O2w—H2w2	110 (2)
O1w—Ni1—O3w	88.8 (1)	Ni1—O3w—H3w1	123 (2)
O1w—Ni1—O3w^i	91.2 (1)	Ni1—O3w—H3w2	117 (2)
O1w^i—Ni1—O2w	87.5 (1)	H3w1—O3w—H3w2	111 (2)
O1w^i—Ni1—O2w^i	92.5 (1)	H4w1—O4w—H4w2	111 (2)
O1w^i—Ni1—O3w	91.2 (1)	H5w1—O5w—H5w2	110 (2)
O1w^i—Ni1—O3w^i	88.8 (1)	N1—C1—H1a	109.2
O2w—Ni1—O2w^i	180.0 (1)	N2—C1—H1a	109.2
O2w—Ni1—O3w	87.8 (1)	N1—C1—H1b	109.2
O2w—Ni1—O3w^i	92.2 (1)	N2—C1—H1b	109.2
O2w^i—Ni1—O3w	92.2 (1)	H1a—C1—H1b	107.9
O2w^i—Ni1—O2w^i	87.8 (1)	N3—C2—H2a	109.2
O3w—Ni1—O3w^i	180.0	N1—C2—H2a	109.2
C3—N1—C1	108.4 (2)	N3—C2—H2b	109.2
C3—N1—C2	107.8 (2)	N1—C2—H2b	109.2
C1—N1—C2	108.4 (2)	H2a—C2—H2b	107.9
C4—N2—C1	107.8 (2)	N1—C3—H3a	109.3
C4—N2—C5	108.1 (2)	N4—C3—H3a	109.3
C1—N2—C5	107.7 (2)	N1—C3—H3b	109.3
C5—N3—C2	108.0 (2)	N4—C3—H3b	109.3
C5—N3—C6	108.3 (2)	H3a—C3—H3b	107.9
C2—N3—C6	108.1 (2)	N2—C4—H4a	109.2
C6—N4—C4	108.3 (2)	N4—C4—H4a	109.2
C6—N4—C3	107.7 (2)	N2—C4—H4b	109.2
C4—N4—C3	108.3 (2)	N4—C4—H4b	109.2
O3—N5—O1	119.6 (3)	H4a—C4—H4b	107.9
O3—N5—O2	119.2 (3)	N3—C5—H5a	109.1
O1—N5—O2	121.2 (3)	N2—C5—H5a	109.1
N1—C1—N2	112.2 (2)	N3—C5—H5b	109.1
N3—C2—N1	112.0 (2)	N2—C5—H5b	109.1
N1—C3—N4	111.8 (2)	H5a—C5—H5b	107.8
N2—C4—N4	112.2 (2)	N4—C6—H6a	109.2
N3—C5—N2	112.7 (2)	N3—C6—H6a	109.2
N4—C6—N3	112.2 (2)	N4—C6—H6b	109.2
Ni1—O1w—H1w1	114 (2)	N3—C6—H6b	109.2
Ni1—O1w—H1w2	118 (2)	H6a—C6—H6b	107.9
H1w1—O1w—H1w2	110 (2)
C3—N1—C1—N2	58.8 (3)	C1—N2—C4—N4	58.6 (3)
C2—N1—C1—N2	−58.0 (3)	C5—N2—C4—N4	−57.6 (3)
C4—N2—C1—N1	−58.7 (3)	C6—N4—C4—N2	58.1 (3)
C5—N2—C1—N1	57.7 (3)	C3—N4—C4—N2	−58.4 (3)
C5—N3—C2—N1	−58.3 (3)	C2—N3—C5—N2	58.8 (3)
C6—N3—C2—N1	58.6 (3)	C6—N3—C5—N2	−58.0 (3)
C3—N1—C2—N3	−59.0 (3)	C4—N2—C5—N3	57.8 (3)
C1—N1—C2—N3	58.2 (3)	C1—N2—C5—N3	−58.4 (3)
C1—N1—C3—N4	−58.1 (3)	C4—N4—C6—N3	−58.1 (3)
C2—N1—C3—N4	59.1 (3)	C3—N4—C6—N3	58.8 (3)
C6—N4—C3—N1	−59.0 (3)	C5—N3—C6—N4	58.1 (3)
C4—N4—C3—N1	57.9 (3)	C2—N3—C6—N4	−58.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H1w1···O1	0.84 (1)	2.03 (1)	2.872 (3)	173 (3)
O1w—H1w2···N1	0.85 (1)	2.04 (1)	2.875 (3)	167 (2)
O2w—H2w1···O2^ii	0.85 (1)	2.01 (1)	2.846 (3)	169 (2)
O2w—H2w2···N4^iii	0.85 (1)	1.99 (1)	2.829 (3)	171 (3)
O3w—H3w1···O4w	0.85 (1)	1.84 (1)	2.662 (3)	164 (3)
O3w—H3w2···N3^iv	0.85 (1)	1.97 (1)	2.802 (3)	170 (2)
O4w—H4w1···O5w^v	0.85 (1)	1.97 (1)	2.813 (3)	174 (3)
O4w—H4w2···N2^vi	0.84 (1)	1.98 (1)	2.817 (3)	173 (3)
O5w—H5w1···O2^vii	0.85 (1)	2.06 (1)	2.901 (4)	168 (3)
O5w—H5w2···O3	0.85 (1)	1.96 (1)	2.799 (4)	168 (3)

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