Diaqua­(1,4,8,11-tetra­aza­cyclo­tetra­deca­ne)nickel(II) fumarate tetra­hydrate

The asymmetric unit of the title complex salt, [Ni(C₁₀H₂₄N₄)(H₂O)₂](C₄H₂O₄)·4H₂O, comprises half of a nickel(II) complex dication, half of a fumarate dianion and two water mol­ecules. Both the Ni^II cation and fumarate anion lie on a crystallographic inversion center. The Ni^II ion in the cyclam complex is six-coordinated within a distorted N₄O₂ octa­hedral geometry, with the four cyclam N atoms in the equatorial plane and the two water mol­ecules in apical positions. The six-membered metalla ring adopts a chair conformation, whereas the five-membered ring exists in a twisted form. In the crystal packing, inter­molecular O—H...O hydrogen bonds between the water molecules and the carboxyl groups of the fumarate anions lead to the formation of layers with R₄²(8) ring motifs. Ni^II complex cations are sandwiched between two such layers, being held in place by O—H...O, N—H...O and C—H...O hydrogen bonds, consolidating a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.133
• Data-to-parameter ratio = 30.2

checkCIF/PLATON results

No syntax errors found



Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    --  N1      ..       5.90 su
PLAT314_ALERT_2_C Check Small Angle for H2O: Metal-O1W    -H2W1         76.99 Deg.
PLAT414_ALERT_2_C Short Intra D-H..H-X       H1A    ..  H2W1    ..       1.95 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         62
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          8
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         31

Alert level G
PLAT960_ALERT_3_G Number of Intensities with I .LT. - 2*sig(I) ..           2
PLAT154_ALERT_1_G The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          8
PLAT793_ALERT_4_G The Model has Chirality at N1      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at N2      (Verify) ....          S

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The antiviral properties of cyclam (1,4,8,11-tetraazacyclotetradecane) have stimulated interest in metal complexes of this ligand (Kim et al., 2006). Besides its antiviral property, [Ni(cyclam)(OAc)₂] also has protein recognition potential (Hunter et al., 2006). Amongst the metal ions investigated, coordination of Ni^II to cyclam rings bridged by 1,4-dimethylene(phenylene) was reported to result in greatest enhancement of its antiviral property (Gerlach et al., 2003). However, the rate of complexation of Ni^II to cyclam is the poorest compared to Cu^II, Zn^II and Co^II (Paisey et al., 2004). In this paper, we report the crystal structure of the title compound, obtained by the reaction of a nickel(II) salt, cyclam and sodium fumarate.

The title compound, Fig. 1, consists of one nickel(II) complex cation, one fumarate anion and four water molecules. Both Ni^II ion and fumarate anion lie on a crystallographic inversion center, generated by the symmetry codes -x+2, -y+1, -z and -x+1, -y, -z+1, respectively. The Ni^II complex of cyclam has six-coordination in a distorted octahedral geometry, with the four ligand N atoms (N1/N2/N1A/N2A) almost coplanar with the Ni^II ion and the two water molecules (O1W & O1WA) in apical positions. The six-membered ring (Ni1/N1/C1–C3/N2) exists in a chair conformation with the puckering parameters (Cremer & Pople, 1975) Q = 0.5900 (14) Å; Θ = 9.05 (13)° and ϕ = 192.1 (9)°. In the five-membered ring, Ni1/N1/C5/C4A/N2A is twisted about the C5–C4A bond with the puckering parameters (Cremer & Pople, 1975) Q = 0.4382 (14) Å and ϕ = 271.34 (14)°. This structure is comparable to a closely related structure (Panneerselvam et al., 1999).

In the crystal packing (Fig. 2), intermolecular O_water—H···O_carboxylate, hydrogen bonds (Table 1) link with the carboxyl groups of the fumarate anions into a two-dimensional layers with R²₄(8) ring motifs (Bernstein et al., 1995). The Ni^II complex cations are linked to these layers by O_aquo—H···O_water, N_amine—H···O_water, C3—H3B···O_carboxylate hydrogen bonds (Table 1) to form a three-dimensional network.

Related literature

For the background to and the biological activity of cyclam, see: Kim et al. (2006); Hunter et al. (2006); Gerlach et al. (2003); Paisey et al. (2004). For a related structure, see: Panneerselvam et al. (1999). For puckering parameters, see: Cremer & Pople (1975). For hydrogen-bond motifs, see: Bernstein et al. (1995). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

S2. Experimental

Nickel chloride hexahydrate (0.24 g, 1 mmol), cyclam (0.22 g, 1 mmol) and sodium fumarate (0.16 g, 1 mmol) were dissolved in water and heated overnight in a water bath at 313 K. Purple crystals were obtained from the yellow solution.

S3. Refinement

N-bound H atoms (H1N1 & H2N1) were located from the difference map and refined freely. The O-bound H atoms were also located in a difference map but were then fixed in their as found positions with U_iso(H) = 1.5 U_eq(O). The remaining H atoms were positioned geometrically and refined using a riding model, with U_iso(H) = 1.2 or 1.5 U_eq(C) [C–H = 0.93 or 0.97 Å; N–H = 0.85 (2) to 0.86 (2) Å; O–H = 0.8482 to 0.8537 Å]. The maximum and minimum residual electron density peaks of 1.300 and -1.178 eÅ^-3, respectively, were located 0.36 Å and 0.94 Å from the N1 and Ni1 atoms, respectively.

Computing details

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

Figures

	Fig. 1. The molecular structure of the title complex, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Symmetry-related atoms of the Ni^II complex ion and fumarate anion are generated by the symmetry codes -x+2, -y+1, -z and -x+1, -y, -z+1, respectively.
	Fig. 2. The crystal packing of the title compound, viewed approximately along the a axis, showing the three-dimensional network. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

Diaqua(1,4,8,11-tetraazacyclotetradecane)nickel(II) fumarate tetrahydrate

Crystal data

[Ni(C10H24N4)(H2O)2](C4H2O4)·4H2O	Z = 1
Mr = 481.19	F(000) = 258
Triclinic, P1	Dx = 1.478 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9913 (5) Å	Cell parameters from 9982 reflections
b = 8.8313 (7) Å	θ = 3.8–35.1°
c = 9.3147 (8) Å	µ = 0.95 mm^−1
α = 73.165 (2)°	T = 100 K
β = 79.207 (2)°	Block, purple
γ = 85.227 (2)°	0.47 × 0.44 × 0.24 mm
V = 540.47 (7) Å^3

Data collection

Bruker APEXII DUO CCD area-detector diffractometer	4295 independent reflections
Radiation source: fine-focus sealed tube	4219 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scans	θmax = 34.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.665, Tmax = 0.805	k = −13→13
12800 measured reflections	l = −14→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.0892P)^2 + 0.062P] where P = (Fo^2 + 2Fc^2)/3
S = 1.30	(Δ/σ)max < 0.001
4295 reflections	Δρmax = 1.27 e Å^−3
142 parameters	Δρmin = −1.18 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.75 (4)

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	1.0000	0.5000	0.0000	0.00889 (11)
O1W	0.70136 (13)	0.43457 (11)	0.07879 (11)	0.01471 (17)
H1W1	0.5819	0.4284	0.1199	0.022*
H2W1	0.7631	0.3578	0.1313	0.022*
N1	0.90487 (15)	0.73294 (12)	−0.04325 (12)	0.01220 (18)
N2	0.97429 (15)	0.48188 (12)	−0.21216 (12)	0.01229 (18)
C1	0.97192 (19)	0.83674 (14)	−0.19756 (15)	0.0160 (2)
H1A	1.1117	0.8476	−0.2125	0.019*
H1B	0.9108	0.9411	−0.2068	0.019*
C2	0.9231 (2)	0.77130 (15)	−0.32091 (15)	0.0188 (2)
H2A	0.7853	0.7497	−0.2980	0.023*
H2B	0.9461	0.8528	−0.4173	0.023*
C3	1.0368 (2)	0.62134 (16)	−0.34023 (14)	0.0168 (2)
H3A	1.0178	0.6032	−0.4344	0.020*
H3B	1.1746	0.6357	−0.3474	0.020*
C4	1.08394 (18)	0.33580 (15)	−0.22827 (14)	0.0154 (2)
H4A	1.2220	0.3563	−0.2578	0.018*
H4B	1.0424	0.3011	−0.3070	0.018*
C5	0.95195 (18)	0.79227 (14)	0.07821 (15)	0.0144 (2)
H5A	0.8713	0.8855	0.0855	0.017*
H5B	1.0873	0.8217	0.0545	0.017*
O1	0.52695 (16)	0.26163 (11)	0.55707 (11)	0.01632 (18)
O2	0.52311 (19)	0.08177 (12)	0.78098 (11)	0.0224 (2)
C11	0.51455 (17)	0.12258 (13)	0.64080 (13)	0.0124 (2)
C12	0.48943 (17)	−0.00891 (13)	0.57443 (12)	0.0121 (2)
H12A	0.4574	−0.1080	0.6408	0.014*
O2W	0.52940 (14)	0.20503 (11)	0.01387 (11)	0.01441 (17)
H1W2	0.5831	0.1689	−0.0597	0.022*
H2W2	0.5251	0.1297	0.0954	0.022*
O3W	0.42354 (14)	0.50357 (11)	0.31238 (11)	0.01463 (18)
H1W3	0.4170	0.5898	0.3362	0.022*
H2W3	0.3993	0.4291	0.3948	0.022*
H1N1	0.779 (3)	0.719 (3)	−0.034 (3)	0.018 (5)*
H1N2	0.849 (3)	0.463 (3)	−0.210 (3)	0.015 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.00948 (13)	0.00806 (13)	0.00991 (13)	−0.00033 (7)	−0.00201 (7)	−0.00347 (8)
O1W	0.0114 (4)	0.0161 (4)	0.0187 (4)	−0.0023 (3)	−0.0003 (3)	−0.0089 (3)
N1	0.0115 (4)	0.0103 (4)	0.0151 (4)	−0.0006 (3)	−0.0026 (3)	−0.0038 (3)
N2	0.0125 (4)	0.0134 (4)	0.0120 (4)	−0.0008 (3)	−0.0025 (3)	−0.0047 (3)
C1	0.0183 (5)	0.0108 (4)	0.0175 (5)	−0.0020 (4)	−0.0043 (4)	−0.0006 (4)
C2	0.0237 (6)	0.0158 (5)	0.0163 (5)	−0.0013 (4)	−0.0087 (4)	−0.0003 (4)
C3	0.0212 (5)	0.0180 (5)	0.0111 (4)	−0.0034 (4)	−0.0030 (4)	−0.0029 (4)
C4	0.0170 (5)	0.0161 (5)	0.0153 (5)	−0.0003 (4)	−0.0011 (4)	−0.0089 (4)
C5	0.0143 (5)	0.0117 (4)	0.0193 (5)	−0.0008 (3)	−0.0023 (4)	−0.0080 (4)
O1	0.0251 (5)	0.0105 (4)	0.0131 (4)	−0.0020 (3)	−0.0028 (3)	−0.0029 (3)
O2	0.0434 (6)	0.0145 (4)	0.0110 (4)	−0.0018 (4)	−0.0080 (4)	−0.0041 (3)
C11	0.0158 (5)	0.0113 (4)	0.0110 (4)	−0.0002 (3)	−0.0017 (3)	−0.0050 (3)
C12	0.0153 (5)	0.0107 (4)	0.0105 (4)	−0.0004 (3)	−0.0019 (3)	−0.0037 (3)
O2W	0.0174 (4)	0.0131 (4)	0.0146 (4)	−0.0020 (3)	−0.0032 (3)	−0.0061 (3)
O3W	0.0175 (4)	0.0144 (4)	0.0134 (4)	−0.0017 (3)	−0.0034 (3)	−0.0052 (3)

Geometric parameters (Å, º)

Ni1—N1^i	2.0564 (10)	C2—H2B	0.9700
Ni1—N1	2.0565 (10)	C3—H3A	0.9700
Ni1—N2	2.0699 (10)	C3—H3B	0.9700
Ni1—N2^i	2.0699 (10)	C4—C5^i	1.5153 (18)
Ni1—O1W	2.1478 (9)	C4—H4A	0.9700
Ni1—O1W^i	2.1478 (9)	C4—H4B	0.9700
O1W—H1W1	0.8499	C5—C4^i	1.5153 (18)
O1W—H2W1	0.8506	C5—H5A	0.9700
N1—C5	1.4747 (16)	C5—H5B	0.9700
N1—C1	1.4772 (17)	O1—C11	1.2496 (14)
N1—H1N1	0.88 (2)	O2—C11	1.2615 (14)
N2—C3	1.4745 (16)	C11—C12	1.5007 (16)
N2—C4	1.4761 (16)	C12—C12^ii	1.330 (2)
N2—H1N2	0.90 (2)	C12—H12A	0.9300
C1—C2	1.5279 (19)	O2W—H1W2	0.8501
C1—H1A	0.9700	O2W—H2W2	0.8496
C1—H1B	0.9700	O3W—H1W3	0.8482
C2—C3	1.5253 (19)	O3W—H2W3	0.8537
C2—H2A	0.9700
N1^i—Ni1—N1	180.0	C2—C1—H1B	109.2
N1^i—Ni1—N2	85.49 (4)	H1A—C1—H1B	107.9
N1—Ni1—N2	94.51 (4)	C3—C2—C1	115.74 (11)
N1^i—Ni1—N2^i	94.51 (4)	C3—C2—H2A	108.3
N1—Ni1—N2^i	85.49 (4)	C1—C2—H2A	108.3
N2—Ni1—N2^i	179.999 (1)	C3—C2—H2B	108.3
N1^i—Ni1—O1W	91.94 (4)	C1—C2—H2B	108.3
N1—Ni1—O1W	88.06 (4)	H2A—C2—H2B	107.4
N2—Ni1—O1W	88.73 (4)	N2—C3—C2	111.79 (10)
N2^i—Ni1—O1W	91.27 (4)	N2—C3—H3A	109.3
N1^i—Ni1—O1W^i	88.06 (4)	C2—C3—H3A	109.3
N1—Ni1—O1W^i	91.94 (4)	N2—C3—H3B	109.3
N2—Ni1—O1W^i	91.27 (4)	C2—C3—H3B	109.3
N2^i—Ni1—O1W^i	88.73 (4)	H3A—C3—H3B	107.9
O1W—Ni1—O1W^i	180.0	N2—C4—C5^i	109.50 (10)
Ni1—O1W—H1W1	165.2	N2—C4—H4A	109.8
Ni1—O1W—H2W1	77.0	C5^i—C4—H4A	109.8
H1W1—O1W—H2W1	107.7	N2—C4—H4B	109.8
C5—N1—C1	113.05 (9)	C5^i—C4—H4B	109.8
C5—N1—Ni1	106.83 (7)	H4A—C4—H4B	108.2
C1—N1—Ni1	116.66 (8)	N1—C5—C4^i	109.30 (9)
C5—N1—H1N1	112.6 (16)	N1—C5—H5A	109.8
C1—N1—H1N1	108.2 (16)	C4^i—C5—H5A	109.8
Ni1—N1—H1N1	98.8 (16)	N1—C5—H5B	109.8
C3—N2—C4	112.55 (10)	C4^i—C5—H5B	109.8
C3—N2—Ni1	114.93 (8)	H5A—C5—H5B	108.3
C4—N2—Ni1	105.98 (7)	O1—C11—O2	124.55 (11)
C3—N2—H1N2	109.8 (15)	O1—C11—C12	119.64 (10)
C4—N2—H1N2	105.3 (14)	O2—C11—C12	115.81 (10)
Ni1—N2—H1N2	107.8 (15)	C12^ii—C12—C11	123.39 (13)
N1—C1—C2	111.84 (10)	C12^ii—C12—H12A	118.3
N1—C1—H1A	109.2	C11—C12—H12A	118.3
C2—C1—H1A	109.2	H1W2—O2W—H2W2	107.7
N1—C1—H1B	109.2	H1W3—O3W—H2W3	107.5
N2—Ni1—N1—C5	−166.65 (8)	O1W—Ni1—N2—C4	−106.83 (7)
N2^i—Ni1—N1—C5	13.35 (8)	O1W^i—Ni1—N2—C4	73.17 (7)
O1W—Ni1—N1—C5	104.78 (8)	C5—N1—C1—C2	179.36 (10)
O1W^i—Ni1—N1—C5	−75.22 (8)	Ni1—N1—C1—C2	54.91 (12)
N2—Ni1—N1—C1	−39.09 (9)	N1—C1—C2—C3	−69.36 (15)
N2^i—Ni1—N1—C1	140.91 (9)	C4—N2—C3—C2	−179.50 (10)
O1W—Ni1—N1—C1	−127.66 (8)	Ni1—N2—C3—C2	−58.06 (12)
O1W^i—Ni1—N1—C1	52.34 (8)	C1—C2—C3—N2	71.78 (14)
N1^i—Ni1—N2—C3	−139.74 (9)	C3—N2—C4—C5^i	166.48 (10)
N1—Ni1—N2—C3	40.26 (9)	Ni1—N2—C4—C5^i	40.06 (11)
O1W—Ni1—N2—C3	128.21 (9)	C1—N1—C5—C4^i	−168.52 (10)
O1W^i—Ni1—N2—C3	−51.79 (9)	Ni1—N1—C5—C4^i	−38.86 (11)
N1^i—Ni1—N2—C4	−14.78 (7)	O1—C11—C12—C12^ii	11.2 (2)
N1—Ni1—N2—C4	165.22 (7)	O2—C11—C12—C12^ii	−168.24 (16)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O3W	0.85	2.17	2.8047 (14)	131
O2W—H1W2···O2^iii	0.85	1.98	2.7026 (14)	142
O2W—H2W2···O2^ii	0.85	1.91	2.7000 (15)	154
O3W—H1W3···O1^iv	0.85	1.96	2.7633 (14)	157
O3W—H2W3···O1	0.85	2.06	2.7968 (14)	144
N1—H1N1···O2W^v	0.88 (2)	2.19 (2)	3.0153 (15)	154 (2)
N2—H1N2···O3W^v	0.90 (2)	2.25 (2)	3.0769 (15)	153 (2)
C3—H3B···O1^i	0.97	2.60	3.3850 (18)	138

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