Aqua­(hexa­methyl­enetetra­mine-κN)bis­(methanol)bis­(thio­cyanato-κN)nickel(II)

The Ni atom in the title complex, [Ni(SCN)₂(C₆H₁₄N₄)(CH₄O)₂(H₂O)], is six-coordinate in a slightly distorted octa­hedral environment. The hexa­methyl­enetetra­mine ligand binds to the Ni atom through only one of its N atoms, trans to the coordinated water mol­ecule. The thio­cyanate and methanol ligands are also mutually trans. In the crystal structure, complex mol­ecules are linked by four different kinds of hydrogen bonds (O—H...S, O—H...N, C—H...N and C—H...O) to form a three-dimensional network structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](N-C) = 0.003 Å
• R factor = 0.031
• wR factor = 0.077
• Data-to-parameter ratio = 19.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        300 Ang.
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.64 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.32 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     -   C1      ..       6.31 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   O1W     ..       5.99 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N1      ..       6.68 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N2      ..       5.45 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C1
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

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S1. Comment

During the past decade, the self-assembly of transition metal ions and organic molecules has become a powerful methodology for the construction of different supramolecular architectures with unusual and interesting properties either by strong metal-ligand bonding or by weaker bonding forces such as hydrogen bonding and π—π interactions (Guo, et al., 2002; Kumar, Das et al., 2007; Venkateswaran et al., 2007). Among the ligands, hexamethylenetetramine (hmt) as a potential tetradentate ligand or hydrogen bond acceptor seems quite suitable in self-assembly systems. Several groups have reported that Co(II), Mn(II) or Ni(II) complexes with hmt and SCN^- as ligands form two- or three-dimensional networks (Liu et al., 2006; Zhang et al., 1999; Meng et al., 2001; Li et al., 2002). Herein, we present a new hmt complex, (I), of nickel(II) with SCN^-, Fig 1. The title complex, which contains one nickel center, one hmt, two NCS^-, two coordinated methanol molecules and one coordinated water molecule, forms a mononuclear complex (Fig.1). The Ni²⁺ atom has a distorted octahedral coordination geometry. The N atom of hmt and the O atom of the water molecule, the N atoms of the two isothiocyanates and the O atoms of both methanol molecules are each mutually trans to each other. Intramolecular C—H···N and C—H···O hydrogen bonds (Table 2) are important factors in the stabilization of the molecule.

In the crystal structure, molecules interact with each other, forming a three-dimensional supramolecular network through multiform intermolecular hydrogen bonds (Fig. 2 and Table 1). The O₁, O₂ and O_1w atoms form three O—H···N hydrogen bonds with the N₆, N₄ and N₅ atoms of the adjacent hmt ligand, respectively. In addition, an O_1w—H···S₂ hydrogen bond is also found in the solid state.

Related literature

For information on the self-assembly of transition-metal complexes see Guo et al. (2002); Kumar et al. (2007); Venkateswaran et al. (2007). For complexes of the hexamethylenetetramine (hmt) ligand see Liu et al. (2006); Zhang et al. (1999); Meng et al. (2001); Li et al. (2002).

S2. Experimental

All chemicals were of reagent grade quality obtained from commercial sources and used without further purification. The hexamethylenetetramine (0.50 mmol, 0.07 g), KSCN (2 mmol, 0.19 g) and NiCl₂.6H₂O (0.50 mmol, 0.12 g) were mixed in methanol (25 ml). The green solution was left for several weeks at room temperature to afford green crystals (yield 68%).

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.97 Å, U_iso = 1.2U_eq (C) for CH₂, 0.96 Å, U_iso = 1.5U_eq (C) for CH₃ atoms and 0.85 Å, U_iso = 1.2U_eq (O) for the OH groups.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures

	Fig. 1. The molecular structure of the title complex, with displacement ellipsoids drawn at the 50% probability level. The hydrogen atoms are omitted for clarity.
	Fig. 2. Perspective view of the three-dimensional showing the intermolecular hydrogen bonds as dashed lines.

Aqua(hexamethylenetetramine-κN)bis(methanol)bis(thiocyanato-κN)nickel(II)

Crystal data

[Ni(SCN)2(C6H14N4)(CH4O)2(H2O)]	F(000) = 1664
Mr = 397.17	Dx = 1.527 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5794 reflections
a = 14.069 (3) Å	θ = 2.3–27.0°
b = 15.312 (3) Å	µ = 1.38 mm^−1
c = 16.036 (3) Å	T = 293 K
V = 3454.6 (12) Å^3	Block, green
Z = 8	0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3102 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.037
Graphite monochromator	θmax = 27.5°, θmin = 2.3°
φ and ω scans	h = −17→18
20196 measured reflections	k = −19→19
3954 independent reflections	l = −15→20

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0346P)^2 + 1.4403P] where P = (Fo^2 + 2Fc^2)/3
3954 reflections	(Δ/σ)max = 0.002
201 parameters	Δρmax = 0.63 e Å^−3
0 restraints	Δρmin = −0.53 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
Ni1	1.051115 (17)	1.037270 (16)	0.284126 (16)	0.02737 (9)
N1	1.15174 (12)	0.97450 (11)	0.35135 (12)	0.0348 (4)
C1	1.21094 (14)	0.94091 (13)	0.38983 (13)	0.0298 (4)
S1	1.29502 (5)	0.89385 (4)	0.44312 (5)	0.0560 (2)
N2	0.95730 (13)	1.10636 (13)	0.21696 (12)	0.0379 (4)
C2	0.90475 (15)	1.14612 (13)	0.17719 (13)	0.0308 (4)
S2	0.83037 (4)	1.20509 (4)	0.12261 (4)	0.04665 (16)
N3	0.94070 (11)	0.94372 (10)	0.32743 (10)	0.0248 (3)
N4	0.88319 (12)	0.86786 (11)	0.45339 (11)	0.0319 (4)
N5	0.88039 (12)	0.79295 (11)	0.31899 (10)	0.0307 (4)
N6	0.77062 (11)	0.91318 (11)	0.34617 (11)	0.0294 (4)
C3	0.95225 (14)	0.93031 (14)	0.41893 (12)	0.0301 (4)
H3A	1.0160	0.9092	0.4299	0.036*
H3B	0.9450	0.9860	0.4471	0.036*
C4	0.89509 (16)	0.78346 (14)	0.40984 (13)	0.0353 (5)
H4A	0.9585	0.7611	0.4202	0.042*
H4B	0.8498	0.7416	0.4318	0.042*
C5	0.78700 (15)	0.90098 (15)	0.43675 (13)	0.0346 (5)
H5A	0.7784	0.9563	0.4652	0.042*
H5B	0.7406	0.8601	0.4586	0.042*
C6	0.78424 (15)	0.82792 (14)	0.30448 (14)	0.0338 (5)
H6A	0.7376	0.7867	0.3253	0.041*
H6B	0.7740	0.8347	0.2450	0.041*
C7	0.94994 (14)	0.85635 (13)	0.28606 (13)	0.0290 (4)
H7A	0.9404	0.8630	0.2265	0.035*
H7B	1.0137	0.8341	0.2948	0.035*
C8	0.84141 (13)	0.97490 (13)	0.31293 (13)	0.0284 (4)
H8A	0.8330	1.0313	0.3395	0.034*
H8B	0.8311	0.9824	0.2535	0.034*
O1	1.08313 (10)	0.95834 (10)	0.18127 (9)	0.0344 (3)
H1A	1.1430	0.9511	0.1796	0.041*
C9	1.05023 (17)	0.9745 (2)	0.09820 (15)	0.0551 (7)
H9A	1.0726	0.9291	0.0619	0.083*
H9B	1.0740	1.0298	0.0793	0.083*
H9C	0.9820	0.9754	0.0977	0.083*
O2	1.02424 (11)	1.12126 (9)	0.38967 (9)	0.0396 (4)
H2A	1.0708	1.1218	0.4234	0.048*
C10	0.9735 (3)	1.20139 (19)	0.39099 (19)	0.0753 (10)
H10A	0.9296	1.2013	0.4369	0.113*
H10B	0.9390	1.2081	0.3397	0.113*
H10C	1.0173	1.2489	0.3973	0.113*
O1W	1.15882 (11)	1.12462 (9)	0.24620 (10)	0.0408 (4)
H1WB	1.1952	1.1361	0.2871	0.049*
H1WD	1.1343	1.1721	0.2292	0.049*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02452 (14)	0.02876 (15)	0.02882 (15)	0.00163 (10)	−0.00440 (10)	0.00596 (10)
N1	0.0296 (10)	0.0369 (10)	0.0378 (10)	0.0010 (8)	−0.0052 (8)	0.0060 (8)
C1	0.0302 (11)	0.0277 (10)	0.0315 (11)	−0.0021 (8)	−0.0029 (9)	−0.0016 (8)
S1	0.0549 (4)	0.0463 (4)	0.0668 (5)	0.0131 (3)	−0.0356 (3)	−0.0032 (3)
N2	0.0335 (10)	0.0405 (10)	0.0398 (11)	0.0044 (8)	−0.0047 (8)	0.0108 (8)
C2	0.0303 (11)	0.0308 (11)	0.0313 (11)	0.0006 (9)	−0.0006 (9)	0.0019 (9)
S2	0.0430 (3)	0.0513 (4)	0.0457 (4)	0.0130 (3)	−0.0128 (3)	0.0088 (3)
N3	0.0241 (8)	0.0275 (8)	0.0228 (8)	0.0004 (6)	−0.0025 (6)	0.0015 (6)
N4	0.0333 (10)	0.0356 (10)	0.0269 (9)	−0.0019 (7)	0.0003 (7)	0.0042 (7)
N5	0.0342 (10)	0.0263 (9)	0.0318 (9)	−0.0009 (7)	0.0025 (7)	−0.0004 (7)
N6	0.0247 (9)	0.0318 (9)	0.0318 (9)	−0.0007 (7)	0.0004 (7)	−0.0013 (7)
C3	0.0296 (11)	0.0368 (11)	0.0239 (10)	−0.0031 (9)	−0.0032 (8)	0.0019 (8)
C4	0.0357 (12)	0.0318 (11)	0.0385 (12)	0.0014 (9)	0.0007 (9)	0.0079 (9)
C5	0.0303 (11)	0.0443 (13)	0.0294 (11)	0.0001 (9)	0.0062 (9)	−0.0017 (9)
C6	0.0310 (11)	0.0348 (11)	0.0356 (12)	−0.0055 (9)	−0.0019 (9)	−0.0024 (9)
C7	0.0296 (10)	0.0289 (10)	0.0285 (10)	0.0022 (8)	0.0041 (8)	−0.0016 (8)
C8	0.0250 (10)	0.0297 (10)	0.0307 (10)	0.0021 (8)	−0.0025 (8)	0.0006 (8)
O1	0.0246 (7)	0.0492 (9)	0.0292 (8)	−0.0004 (6)	−0.0002 (6)	0.0020 (7)
C9	0.0417 (15)	0.091 (2)	0.0326 (13)	0.0067 (14)	−0.0027 (10)	−0.0001 (13)
O2	0.0487 (9)	0.0349 (8)	0.0352 (9)	0.0078 (7)	−0.0121 (7)	−0.0017 (7)
C10	0.115 (3)	0.0549 (18)	0.0561 (18)	0.0408 (18)	−0.0207 (18)	−0.0111 (14)
O1W	0.0380 (9)	0.0340 (8)	0.0504 (10)	−0.0035 (7)	−0.0073 (7)	0.0114 (7)

Geometric parameters (Å, º)

Ni1—N2	2.005 (2)	C3—H3B	0.9700
Ni1—N1	2.022 (2)	C4—H4A	0.9700
Ni1—O1	2.094 (2)	C4—H4B	0.9700
Ni1—O1W	2.111 (2)	C5—H5A	0.9700
Ni1—O2	2.159 (2)	C5—H5B	0.9700
Ni1—N3	2.224 (2)	C6—H6A	0.9700
N1—C1	1.157 (3)	C6—H6B	0.9700
C1—S1	1.627 (2)	C7—H7A	0.9700
N2—C2	1.151 (3)	C7—H7B	0.9700
C2—S2	1.636 (2)	C8—H8A	0.9700
N3—C3	1.490 (2)	C8—H8B	0.9700
N3—C8	1.494 (2)	O1—C9	1.432 (3)
N3—C7	1.499 (2)	O1—H1A	0.8500
N4—C5	1.470 (3)	C9—H9A	0.9600
N4—C3	1.471 (3)	C9—H9B	0.9600
N4—C4	1.479 (3)	C9—H9C	0.9600
N5—C6	1.473 (3)	O2—C10	1.420 (3)
N5—C7	1.476 (3)	O2—H2A	0.8500
N5—C4	1.479 (3)	C10—H10A	0.9600
N6—C8	1.473 (2)	C10—H10B	0.9600
N6—C6	1.479 (3)	C10—H10C	0.9600
N6—C5	1.482 (3)	O1W—H1WB	0.8500
C3—H3A	0.9700	O1W—H1WD	0.8500
N2—Ni1—N1	176.16 (7)	N4—C5—N6	111.39 (16)
N2—Ni1—O1	91.32 (7)	N4—C5—H5A	109.4
N1—Ni1—O1	89.71 (7)	N6—C5—H5A	109.4
N2—Ni1—O1W	89.05 (7)	N4—C5—H5B	109.4
N1—Ni1—O1W	87.26 (7)	N6—C5—H5B	109.4
O1—Ni1—O1W	89.10 (6)	H5A—C5—H5B	108.0
N2—Ni1—O2	89.51 (7)	N5—C6—N6	111.62 (16)
N1—Ni1—O2	89.31 (7)	N5—C6—H6A	109.3
O1—Ni1—O2	177.47 (6)	N6—C6—H6A	109.3
O1W—Ni1—O2	88.52 (6)	N5—C6—H6B	109.3
N2—Ni1—N3	92.74 (7)	N6—C6—H6B	109.3
N1—Ni1—N3	90.94 (7)	H6A—C6—H6B	108.0
O1—Ni1—N3	91.40 (6)	N5—C7—N3	111.79 (15)
O1W—Ni1—N3	178.13 (6)	N5—C7—H7A	109.3
O2—Ni1—N3	90.95 (6)	N3—C7—H7A	109.3
C1—N1—Ni1	177.90 (17)	N5—C7—H7B	109.3
N1—C1—S1	179.4 (2)	N3—C7—H7B	109.3
C2—N2—Ni1	178.66 (19)	H7A—C7—H7B	107.9
N2—C2—S2	178.3 (2)	N6—C8—N3	111.76 (15)
C3—N3—C8	107.41 (15)	N6—C8—H8A	109.3
C3—N3—C7	107.66 (15)	N3—C8—H8A	109.3
C8—N3—C7	107.29 (15)	N6—C8—H8B	109.3
C3—N3—Ni1	108.66 (11)	N3—C8—H8B	109.3
C8—N3—Ni1	113.48 (11)	H8A—C8—H8B	107.9
C7—N3—Ni1	112.09 (11)	C9—O1—Ni1	124.31 (15)
C5—N4—C3	108.40 (16)	C9—O1—H1A	108.3
C5—N4—C4	108.67 (17)	Ni1—O1—H1A	108.3
C3—N4—C4	108.42 (16)	O1—C9—H9A	109.5
C6—N5—C7	108.24 (16)	O1—C9—H9B	109.5
C6—N5—C4	108.65 (16)	H9A—C9—H9B	109.5
C7—N5—C4	108.93 (16)	O1—C9—H9C	109.5
C8—N6—C6	108.37 (16)	H9A—C9—H9C	109.5
C8—N6—C5	109.29 (16)	H9B—C9—H9C	109.5
C6—N6—C5	108.14 (16)	C10—O2—Ni1	127.92 (15)
N4—C3—N3	112.79 (16)	C10—O2—H2A	111.7
N4—C3—H3A	109.0	Ni1—O2—H2A	111.7
N3—C3—H3A	109.0	O2—C10—H10A	109.5
N4—C3—H3B	109.0	O2—C10—H10B	109.5
N3—C3—H3B	109.0	H10A—C10—H10B	109.5
H3A—C3—H3B	107.8	O2—C10—H10C	109.5
N5—C4—N4	111.32 (16)	H10A—C10—H10C	109.5
N5—C4—H4A	109.4	H10B—C10—H10C	109.5
N4—C4—H4A	109.4	Ni1—O1W—H1WB	109.9
N5—C4—H4B	109.4	Ni1—O1W—H1WD	110.0
N4—C4—H4B	109.4	H1WB—O1W—H1WD	108.3
H4A—C4—H4B	108.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WB···S2^i	0.85	2.61	3.431 (2)	162
O1—H1A···N6^i	0.85	1.93	2.762 (2)	165
O1W—H1WD···N5^ii	0.85	2.02	2.836 (2)	162
O2—H2A···N4^iii	0.85	2.09	2.839 (2)	148
C3—H3A···N1	0.97	2.50	3.084 (3)	119
C3—H3B···O2	0.97	2.53	3.130 (3)	120
C7—H7A···O1	0.97	2.59	2.962 (3)	103
C10—H10B···N2	0.96	2.52	3.156 (4)	123

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