Diaqua­[(1R,2S,4R,8R,9S,11R)-2,9-di­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane]nickel(II) dichloride dihydrate

Townsend, J.A.; Desper, J.

doi:10.1107/S160053681203276X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1111-m1112

https://doi.org/10.1107/S160053681203276X

Open

access

Diaqua[(1R,2S,4R,8R,9S,11R)-2,9-dimethyl-1,4,8,11-tetraazacyclotetradecane]nickel(II) dichloride dihydrate

James Alan Townsend ^a ^* and John Desper ^b

^aKansas Wesleyan University, 100 East Claflin, Salina, Kansas 67401, USA, and ^bKansas State University, Manhattan, Kansas 66502, USA
^*Correspondence e-mail: James.Townsend@kwu.edu

(Received 28 June 2012; accepted 19 July 2012; online 25 July 2012)

The crystal structure of the title complex, [Ni(C₁₂H₂₈N₄)(H₂O)₂]Cl₂·2H₂O, displays O—H⋯Cl and O—H⋯O hydrogen bonding. The tetraazacyclotetradecane ligand interacts with the Ni^II atom in the cis V configuration and the final two ligand binding sites are occupied by water.

Related literature

For uses of the title compound, see: Kimura et al. (1992 ); Liang et al. (2002 ); Burrows et al. (1992 , 1988 ); Kelly et al. (1999 ); Churchard et al. (2010 ). For the synthesis of the ligand, see: Beck & Lang (2003 ); Beck et al. (1998 , 2003 ). For metal complex formation, see: Sadler et al. (2007 ); Voelcker et al. (2008 ). For nickel cyclam complex crystal structures with a cis-V configuration, see: Sadler et al. (2007); Ito et al. (1981 , 1982 ); Allen (2002 ). For details of peptide racemization, see: Liardon & Ledermann (1986 ).

Experimental

Crystal data

[Ni(C₁₂H₂₈N₄)(H₂O)₂]Cl₂·2H₂O
M_r = 430.06
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.7309 (8) Å
b = 14.0994 (11) Å
c = 14.6000 (11) Å
V = 2003.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.26 mm⁻¹
T = 120 K
0.28 × 0.24 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.720, T_max = 0.864
25180 measured reflections
7454 independent reflections
6563 reflections with I > σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.083
S = 1.04
7454 reflections
246 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.38 e Å⁻³
Absolute structure: Flack (1983 ), 3205 Friedel pairs
Flack parameter: −0.006 (7)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯Cl1	0.73 (2)	2.44 (2)	3.1580 (12)	172 (2)
O1—H1B⋯O3	0.85 (2)	1.84 (2)	2.6912 (17)	176 (2)
O2—H2A⋯Cl2	0.74 (2)	2.38 (2)	3.1192 (13)	176 (2)
O2—H2B⋯O4	0.80 (2)	1.88 (2)	2.6767 (18)	177 (2)
O3—H3A⋯Cl2	0.81 (2)	2.50 (3)	3.2587 (15)	156 (2)
O3—H3B⋯Cl1ⁱ	0.78 (2)	2.48 (2)	3.2256 (14)	160 (2)
O4—H4A⋯Cl1	0.75 (3)	2.50 (3)	3.1971 (18)	154 (2)
O4—H4B⋯Cl1ⁱⁱ	0.72 (3)	2.50 (3)	3.2227 (16)	173 (3)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XCIF in SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S160053681203276X/pk2429sup1.cif

Supporting information file. DOI: https://doi.org/10.1107/S160053681203276X/pk2429Isup2.mol

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681203276X/pk2429Isup3.hkl

checkCIF report

Comment top

The ligand in the title compound was synthesized by base-catalyzed metal-templated cyclization of dipeptides, metal removal using HCl and finally amide reduction to yield a C-functionalized cyclam molecule (Beck & Lang, 2003). The stereochemical integrity of the ligands previously synthesized, however, was never established. Strong bases such as NaOMe, which is used in the ligand synthesis, have the ability to racemize peptides Liardon et al. (1986). The crystal structure of the title compound shows that the stereochemical integrity of the (2S,9S)-2,9-dimethyl-1,4,8,11-tetraazacyclotetradecane ligand is maintained throughout the synthesis.

Cyclam metal complexes have 6 possible configurations: trans I—V and cis V (Liang et al., 2002). Typically the structure of cyclam metal complexes tends to favor the thermodynamically most stable trans III configuration in the solid state (Liang et al., 2002). However, in this case the compound has adopted the cis V configuration with two water molecules acting as ligands to the metal center. The chloride counter ions interact with the water ligands through O—H···Cl hydrogen bonds. Similarly configured nickel cyclam complexes were reported by Ito et al. (1981, 1982). A recent crystal structure search in the CCDC database has shown that only 4% of cyclam complexes without nitrogen functionalization, utilizing halogen containing counter ions and monodentate ligands for the final two coordination sites, adopt a cis V configuration (Allen, 2002).

When chiral carbons are present in the cyclam it is possible to generate two stereoisomers for each metal complex configuration. The diastereomers for each configuration are dependent on the chirality around the N atoms in the complex as the carbon chirality in the cyclam ligand is both encoded and maintained during synthesis. The title compound has adopted a diastereomer that places the methyl side arms into the equatorial plane of the 5 membered rings. This minimizes steric interactions with the remainder of the cyclam and the water ligands attached to the nickel center.

Related literature top

For uses of the title compound, see: Kimura et al. (1992); Liang et al. (2002); Burrows et al. (1992, 1988); Kelly et al. (1999); Churchard et al. (2010). For the synthesis of the ligand, see: Beck & Lang (2003); Beck et al. (1998, 2003). For metal complex formation, see: Sadler et al. (2007); Voelcker et al. (2008). For nickel cyclam complex crystal structures with a cis-V configuration, see: Sadler et al. (2007); Ito et al. (1981, 1982); Allen (2002). For details of peptide racemization, see: Liardon et al. (1986).

Experimental top

The (2S,9S)-2,9-dimethyl-1,4,8,11-tetraazacyclotetradecane (100 mg, 0.44 mmol) was dissolved in methanol (2 ml) and the NiCl_2.6H₂O (105 mg, 0.44 mmol) was added in methanol (2 ml). The reaction mixture was heated to reflux for ten minutes and allowed to cool. A purple crystalline solid was isolated for X-ray analysis after 4 months of crystallization via slow evaporation at RT.

Structure description top

For uses of the title compound, see: Kimura et al. (1992); Liang et al. (2002); Burrows et al. (1992, 1988); Kelly et al. (1999); Churchard et al. (2010). For the synthesis of the ligand, see: Beck & Lang (2003); Beck et al. (1998, 2003). For metal complex formation, see: Sadler et al. (2007); Voelcker et al. (2008). For nickel cyclam complex crystal structures with a cis-V configuration, see: Sadler et al. (2007); Ito et al. (1981, 1982); Allen (2002). For details of peptide racemization, see: Liardon et al. (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XCIF in SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids.

Diaqua[(1R,2S,4R,8R,9S,11R)-2,9- dimethyl-1,4,8,11-tetraazacyclotetradecane]nickel(II) dichloride dihydrate top

Crystal data top

[Ni(C₁₂H₂₈N₄)(H₂O)₂]Cl₂·2H₂O	F(000) = 920
M_r = 430.06	D_x = 1.426 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9955 reflections
a = 9.7309 (8) Å	θ = 3.1–33.2°
b = 14.0994 (11) Å	µ = 1.26 mm⁻¹
c = 14.6000 (11) Å	T = 120 K
V = 2003.1 (3) Å³	Plate, purple
Z = 4	0.28 × 0.24 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	7454 independent reflections
Radiation source: fine-focus sealed tube	6563 reflections with I > σ(I)
Graphite monochromator	R_int = 0.061
φ and ω scans	θ_max = 33.1°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.720, T_max = 0.864	k = −20→21
25180 measured reflections	l = −22→21

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)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	w = 1/[σ²(F_o²) + (0.035P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
7454 reflections	Δρ_max = 0.29 e Å⁻³
246 parameters	Δρ_min = −0.38 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 3205 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.006 (7)

Crystal data top

[Ni(C₁₂H₂₈N₄)(H₂O)₂]Cl₂·2H₂O	V = 2003.1 (3) Å³
M_r = 430.06	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.7309 (8) Å	µ = 1.26 mm⁻¹
b = 14.0994 (11) Å	T = 120 K
c = 14.6000 (11) Å	0.28 × 0.24 × 0.12 mm

Data collection top

Bruker APEXII CCD diffractometer	7454 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	6563 reflections with I > σ(I)
T_min = 0.720, T_max = 0.864	R_int = 0.061
25180 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.083	Δρ_max = 0.29 e Å⁻³
S = 1.03	Δρ_min = −0.38 e Å⁻³
7454 reflections	Absolute structure: Flack (1983), 3205 Friedel pairs
246 parameters	Absolute structure parameter: −0.006 (7)
0 restraints

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
Cl1	0.71927 (4)	0.16329 (3)	0.06960 (2)	0.02112 (8)
Cl2	0.79391 (5)	0.60262 (3)	0.074484 (19)	0.02032 (8)
Ni1	0.749450 (19)	0.382317 (11)	0.280156 (10)	0.01238 (5)
O1	0.87944 (13)	0.32002 (8)	0.18131 (7)	0.0182 (2)
H1A	0.841 (2)	0.2877 (15)	0.1520 (12)	0.022*
H1B	0.925 (2)	0.3587 (13)	0.1483 (12)	0.022*
O2	0.63308 (14)	0.43853 (8)	0.16958 (6)	0.0188 (2)
H2A	0.670 (3)	0.4766 (14)	0.1447 (12)	0.023*
H2B	0.590 (2)	0.4070 (14)	0.1346 (13)	0.023*
O3	1.03357 (16)	0.44143 (10)	0.08293 (8)	0.0264 (3)
H3A	0.985 (3)	0.4846 (15)	0.0655 (13)	0.032*
H3B	1.069 (3)	0.4260 (15)	0.0375 (15)	0.032*
O4	0.49336 (18)	0.32714 (12)	0.05395 (10)	0.0389 (4)
H4A	0.538 (3)	0.2856 (19)	0.0410 (16)	0.047*
H4B	0.436 (3)	0.3292 (19)	0.0224 (16)	0.047*
N11	0.87279 (15)	0.31679 (9)	0.37995 (8)	0.0157 (2)
H11	0.838 (2)	0.3325 (13)	0.4315 (10)	0.019*
C12	1.02074 (17)	0.33903 (11)	0.37783 (10)	0.0191 (3)
H12A	1.0595	0.3182	0.3185	0.023*
H12B	1.0678	0.3032	0.4270	0.023*
C13	1.04857 (18)	0.44409 (11)	0.39043 (10)	0.0200 (3)
H13A	1.1473	0.4528	0.4045	0.024*
H13B	0.9956	0.4669	0.4440	0.024*
C14	1.01209 (17)	0.50543 (11)	0.30776 (9)	0.0181 (3)
H14A	1.0482	0.5702	0.3178	0.022*
H14B	1.0581	0.4792	0.2528	0.022*
N15	0.86136 (14)	0.51134 (9)	0.28990 (7)	0.0151 (2)
H15	0.849 (2)	0.5386 (13)	0.2377 (11)	0.018*
C16	0.79010 (17)	0.57511 (10)	0.35683 (9)	0.0153 (3)
H16A	0.8226	0.5585	0.4198	0.018*
C17	0.63766 (18)	0.55513 (10)	0.35165 (9)	0.0168 (3)
H17A	0.5890	0.5921	0.3993	0.020*
H17B	0.6020	0.5749	0.2911	0.020*
N18	0.61136 (14)	0.45273 (8)	0.36543 (7)	0.0143 (2)
H18	0.634 (2)	0.4368 (13)	0.4203 (11)	0.017*
C19	0.46435 (17)	0.43027 (11)	0.35336 (10)	0.0186 (3)
H19A	0.4358	0.4481	0.2906	0.022*
H19B	0.4096	0.4684	0.3971	0.022*
C20	0.43414 (18)	0.32571 (11)	0.36862 (10)	0.0192 (3)
H20A	0.3335	0.3175	0.3747	0.023*
H20B	0.4765	0.3060	0.4273	0.023*
C21	0.48560 (17)	0.26014 (11)	0.29316 (10)	0.0187 (3)
H21A	0.4471	0.1960	0.3034	0.022*
H21B	0.4504	0.2833	0.2336	0.022*
N22	0.63722 (14)	0.25275 (9)	0.28777 (7)	0.0149 (2)
H22	0.662 (2)	0.2237 (13)	0.2382 (11)	0.018*
C23	0.69697 (18)	0.19430 (10)	0.36349 (9)	0.0174 (3)
H23A	0.6546	0.2156	0.4224	0.021*
C24	0.84928 (18)	0.21402 (10)	0.36830 (9)	0.0170 (3)
H24A	0.8900	0.1791	0.4205	0.020*
H24B	0.8943	0.1919	0.3114	0.020*
C25	0.8201 (2)	0.67969 (11)	0.34008 (10)	0.0228 (3)
H25A	0.9188	0.6913	0.3471	0.034*
H25B	0.7692	0.7182	0.3845	0.034*
H25C	0.7916	0.6968	0.2779	0.034*
C26	0.6686 (2)	0.08823 (11)	0.35262 (11)	0.0266 (4)
H26A	0.5693	0.0770	0.3544	0.040*
H26B	0.7130	0.0534	0.4027	0.040*
H26C	0.7055	0.0663	0.2939	0.040*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0206 (2)	0.02300 (17)	0.01969 (14)	−0.00200 (14)	−0.00002 (13)	−0.00204 (11)
Cl2	0.0262 (2)	0.02052 (16)	0.01430 (13)	−0.00036 (15)	0.00089 (13)	0.00095 (11)
Ni1	0.01140 (10)	0.01451 (8)	0.01122 (7)	−0.00030 (8)	−0.00007 (7)	−0.00057 (5)
O1	0.0176 (6)	0.0210 (5)	0.0159 (4)	−0.0025 (5)	0.0020 (4)	−0.0034 (4)
O2	0.0185 (6)	0.0224 (5)	0.0155 (4)	−0.0030 (5)	−0.0025 (4)	0.0017 (4)
O3	0.0282 (8)	0.0289 (6)	0.0221 (5)	0.0022 (6)	0.0062 (5)	0.0027 (4)
O4	0.0328 (9)	0.0410 (8)	0.0428 (7)	0.0097 (7)	−0.0187 (6)	−0.0186 (6)
N11	0.0148 (6)	0.0176 (5)	0.0146 (4)	0.0005 (5)	−0.0009 (4)	−0.0020 (4)
C12	0.0134 (7)	0.0229 (7)	0.0210 (6)	0.0025 (6)	−0.0025 (5)	−0.0015 (5)
C13	0.0148 (8)	0.0225 (7)	0.0225 (6)	−0.0013 (6)	−0.0054 (6)	−0.0016 (5)
C14	0.0129 (7)	0.0220 (7)	0.0193 (6)	−0.0025 (6)	0.0014 (5)	−0.0002 (5)
N15	0.0149 (6)	0.0177 (5)	0.0128 (4)	0.0003 (5)	0.0005 (4)	−0.0009 (4)
C16	0.0150 (7)	0.0164 (6)	0.0145 (5)	−0.0011 (5)	0.0003 (5)	−0.0017 (4)
C17	0.0173 (8)	0.0145 (6)	0.0186 (5)	0.0008 (6)	0.0005 (5)	−0.0004 (5)
N18	0.0131 (6)	0.0147 (5)	0.0150 (5)	−0.0004 (5)	−0.0008 (4)	0.0002 (4)
C19	0.0126 (8)	0.0216 (7)	0.0215 (6)	0.0009 (6)	0.0014 (5)	−0.0012 (5)
C20	0.0151 (8)	0.0198 (7)	0.0228 (6)	−0.0015 (6)	0.0036 (6)	−0.0020 (5)
C21	0.0135 (7)	0.0214 (7)	0.0211 (6)	−0.0022 (6)	−0.0015 (5)	−0.0024 (5)
N22	0.0150 (6)	0.0178 (5)	0.0119 (4)	0.0002 (5)	−0.0005 (4)	−0.0009 (4)
C23	0.0191 (8)	0.0184 (6)	0.0146 (5)	−0.0002 (6)	−0.0006 (5)	0.0016 (4)
C24	0.0163 (8)	0.0151 (6)	0.0195 (6)	0.0001 (6)	−0.0019 (5)	0.0016 (5)
C25	0.0216 (9)	0.0175 (7)	0.0294 (7)	−0.0043 (6)	−0.0001 (6)	−0.0024 (5)
C26	0.0250 (10)	0.0188 (7)	0.0359 (8)	−0.0032 (7)	−0.0037 (7)	0.0062 (6)

Geometric parameters (Å, º) top

Ni1—N18	2.0836 (12)	C16—C25	1.523 (2)
Ni1—N11	2.1017 (13)	C16—H16A	1.0000
Ni1—O1	2.1105 (11)	C17—N18	1.4800 (19)
Ni1—N15	2.1249 (13)	C17—H17A	0.9900
Ni1—O2	2.1253 (11)	C17—H17B	0.9900
Ni1—N22	2.1312 (13)	N18—C19	1.476 (2)
O1—H1A	0.73 (2)	N18—H18	0.861 (16)
O1—H1B	0.85 (2)	C19—C20	1.520 (2)
O2—H2A	0.74 (2)	C19—H19A	0.9900
O2—H2B	0.80 (2)	C19—H19B	0.9900
O3—H3A	0.81 (2)	C20—C21	1.523 (2)
O3—H3B	0.78 (2)	C20—H20A	0.9900
O4—H4A	0.75 (3)	C20—H20B	0.9900
O4—H4B	0.72 (3)	C21—N22	1.481 (2)
N11—C12	1.474 (2)	C21—H21A	0.9900
N11—C24	1.4767 (19)	C21—H21B	0.9900
N11—H11	0.853 (15)	N22—C23	1.4965 (18)
C12—C13	1.517 (2)	N22—H22	0.864 (17)
C12—H12A	0.9900	C23—C24	1.510 (3)
C12—H12B	0.9900	C23—C26	1.529 (2)
C13—C14	1.527 (2)	C23—H23A	1.0000
C13—H13A	0.9900	C24—H24A	0.9900
C13—H13B	0.9900	C24—H24B	0.9900
C14—N15	1.492 (2)	C25—H25A	0.9800
C14—H14A	0.9900	C25—H25B	0.9800
C14—H14B	0.9900	C25—H25C	0.9800
N15—C16	1.4980 (18)	C26—H26A	0.9800
N15—H15	0.861 (17)	C26—H26B	0.9800
C16—C17	1.512 (2)	C26—H26C	0.9800

N18—Ni1—N11	99.41 (5)	N18—C17—H17A	109.6
N18—Ni1—O1	173.42 (4)	C16—C17—H17A	109.6
N11—Ni1—O1	87.06 (4)	N18—C17—H17B	109.6
N18—Ni1—N15	83.26 (5)	C16—C17—H17B	109.6
N11—Ni1—N15	92.14 (5)	H17A—C17—H17B	108.1
O1—Ni1—N15	95.45 (5)	C19—N18—C17	111.14 (12)
N18—Ni1—O2	86.14 (5)	C19—N18—Ni1	116.84 (9)
N11—Ni1—O2	174.18 (5)	C17—N18—Ni1	105.79 (9)
O1—Ni1—O2	87.43 (5)	C19—N18—H18	107.6 (14)
N15—Ni1—O2	90.27 (5)	C17—N18—H18	109.7 (13)
N18—Ni1—N22	92.68 (5)	Ni1—N18—H18	105.5 (13)
N11—Ni1—N22	83.09 (5)	N18—C19—C20	112.22 (13)
O1—Ni1—N22	89.20 (5)	N18—C19—H19A	109.2
N15—Ni1—N22	173.17 (5)	C20—C19—H19A	109.2
O2—Ni1—N22	94.95 (5)	N18—C19—H19B	109.2
Ni1—O1—H1A	110.9 (18)	C20—C19—H19B	109.2
Ni1—O1—H1B	115.6 (13)	H19A—C19—H19B	107.9
H1A—O1—H1B	109.4 (19)	C19—C20—C21	114.79 (12)
Ni1—O2—H2A	112.7 (18)	C19—C20—H20A	108.6
Ni1—O2—H2B	124.1 (14)	C21—C20—H20A	108.6
H2A—O2—H2B	110 (2)	C19—C20—H20B	108.6
H3A—O3—H3B	102 (2)	C21—C20—H20B	108.6
H4A—O4—H4B	108 (3)	H20A—C20—H20B	107.5
C12—N11—C24	110.96 (13)	N22—C21—C20	114.12 (13)
C12—N11—Ni1	116.73 (9)	N22—C21—H21A	108.7
C24—N11—Ni1	105.25 (9)	C20—C21—H21A	108.7
C12—N11—H11	110.4 (14)	N22—C21—H21B	108.7
C24—N11—H11	107.2 (13)	C20—C21—H21B	108.7
Ni1—N11—H11	105.8 (13)	H21A—C21—H21B	107.6
N11—C12—C13	112.31 (14)	C21—N22—C23	112.74 (12)
N11—C12—H12A	109.1	C21—N22—Ni1	116.93 (9)
C13—C12—H12A	109.1	C23—N22—Ni1	108.15 (9)
N11—C12—H12B	109.1	C21—N22—H22	110.6 (15)
C13—C12—H12B	109.1	C23—N22—H22	104.5 (12)
H12A—C12—H12B	107.9	Ni1—N22—H22	102.7 (13)
C12—C13—C14	114.56 (12)	N22—C23—C24	108.32 (12)
C12—C13—H13A	108.6	N22—C23—C26	113.08 (13)
C14—C13—H13A	108.6	C24—C23—C26	111.22 (14)
C12—C13—H13B	108.6	N22—C23—H23A	108.0
C14—C13—H13B	108.6	C24—C23—H23A	108.0
H13A—C13—H13B	107.6	C26—C23—H23A	108.0
N15—C14—C13	113.47 (13)	N11—C24—C23	109.77 (13)
N15—C14—H14A	108.9	N11—C24—H24A	109.7
C13—C14—H14A	108.9	C23—C24—H24A	109.7
N15—C14—H14B	108.9	N11—C24—H24B	109.7
C13—C14—H14B	108.9	C23—C24—H24B	109.7
H14A—C14—H14B	107.7	H24A—C24—H24B	108.2
C14—N15—C16	112.00 (11)	C16—C25—H25A	109.5
C14—N15—Ni1	117.88 (9)	C16—C25—H25B	109.5
C16—N15—Ni1	108.68 (9)	H25A—C25—H25B	109.5
C14—N15—H15	108.2 (15)	C16—C25—H25C	109.5
C16—N15—H15	104.2 (13)	H25A—C25—H25C	109.5
Ni1—N15—H15	104.7 (13)	H25B—C25—H25C	109.5
N15—C16—C17	108.04 (11)	C23—C26—H26A	109.5
N15—C16—C25	112.81 (12)	C23—C26—H26B	109.5
C17—C16—C25	111.14 (13)	H26A—C26—H26B	109.5
N15—C16—H16A	108.2	C23—C26—H26C	109.5
C17—C16—H16A	108.2	H26A—C26—H26C	109.5
C25—C16—H16A	108.2	H26B—C26—H26C	109.5
N18—C17—C16	110.16 (13)

N18—Ni1—N11—C12	−122.05 (10)	N11—Ni1—N18—C19	−122.13 (10)
O1—Ni1—N11—C12	56.81 (10)	N15—Ni1—N18—C19	146.81 (10)
N15—Ni1—N11—C12	−38.54 (10)	O2—Ni1—N18—C19	56.08 (10)
N22—Ni1—N11—C12	146.36 (11)	N22—Ni1—N18—C19	−38.70 (10)
N18—Ni1—N11—C24	114.41 (10)	N11—Ni1—N18—C17	113.58 (9)
O1—Ni1—N11—C24	−66.72 (10)	N15—Ni1—N18—C17	22.53 (9)
N15—Ni1—N11—C24	−162.07 (10)	O2—Ni1—N18—C17	−68.20 (9)
N22—Ni1—N11—C24	22.83 (10)	N22—Ni1—N18—C17	−162.98 (9)
C24—N11—C12—C13	−179.52 (11)	C17—N18—C19—C20	−179.10 (11)
Ni1—N11—C12—C13	59.94 (14)	Ni1—N18—C19—C20	59.39 (13)
N11—C12—C13—C14	−72.87 (18)	N18—C19—C20—C21	−71.94 (17)
C12—C13—C14—N15	68.35 (18)	C19—C20—C21—N22	68.51 (18)
C13—C14—N15—C16	75.20 (15)	C20—C21—N22—C23	74.12 (15)
C13—C14—N15—Ni1	−52.00 (14)	C20—C21—N22—Ni1	−52.15 (14)
N18—Ni1—N15—C14	134.12 (9)	N18—Ni1—N22—C21	35.07 (10)
N11—Ni1—N15—C14	34.89 (9)	N11—Ni1—N22—C21	134.24 (10)
O1—Ni1—N15—C14	−52.36 (9)	O1—Ni1—N22—C21	−138.62 (10)
O2—Ni1—N15—C14	−139.80 (9)	O2—Ni1—N22—C21	−51.28 (10)
N18—Ni1—N15—C16	5.35 (9)	N18—Ni1—N22—C23	−93.44 (9)
N11—Ni1—N15—C16	−93.88 (9)	N11—Ni1—N22—C23	5.72 (9)
O1—Ni1—N15—C16	178.86 (9)	O1—Ni1—N22—C23	92.86 (9)
O2—Ni1—N15—C16	91.42 (9)	O2—Ni1—N22—C23	−179.79 (9)
C14—N15—C16—C17	−163.86 (11)	C21—N22—C23—C24	−163.87 (12)
Ni1—N15—C16—C17	−31.87 (12)	Ni1—N22—C23—C24	−33.01 (13)
C14—N15—C16—C25	72.87 (16)	C21—N22—C23—C26	72.38 (17)
Ni1—N15—C16—C25	−155.13 (11)	Ni1—N22—C23—C26	−156.76 (12)
N15—C16—C17—N18	54.08 (14)	C12—N11—C24—C23	−175.69 (11)
C25—C16—C17—N18	178.35 (10)	Ni1—N11—C24—C23	−48.56 (12)
C16—C17—N18—C19	−175.47 (11)	N22—C23—C24—N11	55.86 (14)
C16—C17—N18—Ni1	−47.70 (12)	C26—C23—C24—N11	−179.28 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.73 (2)	2.44 (2)	3.1580 (12)	172 (2)
O1—H1B···O3	0.85 (2)	1.84 (2)	2.6912 (17)	176 (2)
O2—H2A···Cl2	0.74 (2)	2.38 (2)	3.1192 (13)	176 (2)
O2—H2B···O4	0.80 (2)	1.88 (2)	2.6767 (18)	177 (2)
O3—H3A···Cl2	0.81 (2)	2.50 (3)	3.2587 (15)	156 (2)
O3—H3B···Cl1ⁱ	0.78 (2)	2.48 (2)	3.2256 (14)	160 (2)
O4—H4A···Cl1	0.75 (3)	2.50 (3)	3.1971 (18)	154 (2)
O4—H4B···Cl1ⁱⁱ	0.72 (3)	2.50 (3)	3.2227 (16)	173 (3)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₁₂H₂₈N₄)(H₂O)₂]Cl₂·2H₂O
M_r	430.06
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	120
a, b, c (Å)	9.7309 (8), 14.0994 (11), 14.6000 (11)
V (Å³)	2003.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.26
Crystal size (mm)	0.28 × 0.24 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.720, 0.864
No. of measured, independent and observed [I > σ(I)] reflections	25180, 7454, 6563
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.769

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.083, 1.03
No. of reflections	7454
No. of parameters	246
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.38
Absolute structure	Flack (1983), 3205 Friedel pairs
Absolute structure parameter	−0.006 (7)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), XCIF in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Cl1	0.73 (2)	2.44 (2)	3.1580 (12)	172 (2)
O1—H1B···O3	0.85 (2)	1.84 (2)	2.6912 (17)	176 (2)
O2—H2A···Cl2	0.74 (2)	2.38 (2)	3.1192 (13)	176 (2)
O2—H2B···O4	0.80 (2)	1.88 (2)	2.6767 (18)	177 (2)
O3—H3A···Cl2	0.81 (2)	2.50 (3)	3.2587 (15)	156 (2)
O3—H3B···Cl1ⁱ	0.78 (2)	2.48 (2)	3.2256 (14)	160 (2)
O4—H4A···Cl1	0.75 (3)	2.50 (3)	3.1971 (18)	154 (2)
O4—H4B···Cl1ⁱⁱ	0.72 (3)	2.50 (3)	3.2227 (16)	173 (3)

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

Acknowledgements

We would like to thank Kansas State University for the generous use of their spectroscopy equipment.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Beck, W., Hass, K., Ponikwar, W. & Noth, H. (1998). Angew. Chem. Int. Ed. 37, 1086–1089. Google Scholar
Beck, W. & Lang, M. A. (2003). Z. Naturforsch. Teil B, 58, 447–450. Google Scholar
Beck, W., Schapp, J., Hass, K. & Sunkel, K. (2003). Eur. J. Inorg. Chem. 20, 3745–3751. Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burrows, C. J., Kinneary, J. F. & Albert, J. S. (1988). J. Am. Chem. Soc. 110, 6124–6129. PubMed Web of Science Google Scholar
Burrows, C. J., Rokita, S. E., Muller, J. G., Chen, X. & Dadiz, A. C. (1992). J. Am. Chem. Soc. 114, 6407–6411. Google Scholar
Churchard, A. J., Cyanski, M. K., Dobrzycki, K., Budzianowski, A. & Grochala, W. (2010). Energy Environ. 3, 1973–1978. CrossRef CAS Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Ito, T., Sugimoto, M. & Ito, H. (1982). Bull. Chem. Soc. Jpn, 55, 1971–1972. CrossRef CAS Web of Science Google Scholar
Ito, T., Toriumi, K. & Ito, H. (1981). Bull. Chem. Soc. Jpn, 54, 1096–1100. CrossRef CAS Web of Science Google Scholar
Kelly, C. A., Blinn, E. L., Camaioni, N., D'Angelantonio, M. & Mulazzani, Q. G. (1999). Inorg. Chem. 38, 1579–1584. Web of Science CrossRef CAS Google Scholar
Kimura, E., Bu, X., Shionoya, M., Wada, S. & Maruyama, S. (1992). Inorg. Chem. 31, 4542–4546. CrossRef CAS Web of Science Google Scholar
Liang, X., Parkinson, J. A., Weishaupl, M., Gould, R. O., Paisey, S. J., Park, H., Hunter, T. M., Blindauer, C. A. & Parsons, S. (2002). J. Am. Chem. Soc. 124, 9105–9112. Web of Science CSD CrossRef PubMed CAS Google Scholar
Liardon, R. & Ledermann, S. (1986). Inorg. Chem. 34, 557–565. CAS Google Scholar
Sadler, P. J., Hunter, T. M., McNae, I. W., Simpson, D. P., Smith, S. M., Moggach, S., White, F., Walkinshaw, M. D. & Parsons, S. (2007). Chem. Eur. J. 13, 40–50. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Voelcker, N. H., Alfonso, I. & Ghadiri, M. R. (2008). ChemBioChem, 9, 1776–1786. Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages m1111-m1112

https://doi.org/10.1107/S160053681203276X

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­aqua­[(1R,2S,4R,8R,9S,11R)-2,9-di­methyl-1,4,8,11-tetra­aza­cyclo­tetra­decane]nickel(II) dichloride dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Diaqua[(1R,2S,4R,8R,9S,11R)-2,9-dimethyl-1,4,8,11-tetraazacyclotetradecane]nickel(II) dichloride dihydrate