Diaqua-(1,4,8,11-tetra-aza-cyclo-tetra-deca-ne)nickel(II) fumarate tetra-hydrate.

The asymmetric unit of the title complex salt, [Ni(C(10)H(24)N(4))(H(2)O)(2)](C(4)H(2)O(4))·4H(2)O, comprises half of a nickel(II) complex dication, half of a fumarate dianion and two water mol-ecules. 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 N(4)O(2) octa-hedral geometry, with the four cyclam N atoms in the equatorial plane and the two water mol-ecules 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, inter-molecular O-H⋯O hydrogen bonds between the water molecules and the carboxyl groups of the fumarate anions lead to the formation of layers with R(4) (2)(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.

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 & Sadler (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 ▶).

Experimental

Crystal data

[Ni(C10H24N4)(H2O)2](C4H2O4)·4H2O

M = 481.19

Triclinic,

a = 6.9913 (5) Å

b = 8.8313 (7) Å

c = 9.3147 (8) Å

α = 73.165 (2)°

β = 79.207 (2)°

γ = 85.227 (2)°

V = 540.47 (7) Å3

Z = 1

Mo Kα radiation

μ = 0.95 mm−1

T = 100 K

0.47 × 0.44 × 0.24 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.665, T max = 0.805

12800 measured reflections

4295 independent reflections

4219 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.133

S = 1.30

4295 reflections

142 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.27 e Å−3

Δρmin = −1.18 e Å−3

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810020064/tk2677sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810020064/tk2677Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[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) Å3

Bruker APEXII DUO CCD area-detector diffractometer	4295 independent reflections
Radiation source: fine-focus sealed tube	4219 reflections with I > 2σ(I)
graphite	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 on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.133	w = 1/[σ2(Fo2) + (0.0892P)2 + 0.062P] where P = (Fo2 + 2Fc2)/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+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.75 (4)

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.

	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)*

	U11	U22	U33	U12	U13	U23
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)

Ni1—N1i	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—N2i	2.0699 (10)	C4—C5i	1.5153 (18)
Ni1—O1W	2.1478 (9)	C4—H4A	0.9700
Ni1—O1Wi	2.1478 (9)	C4—H4B	0.9700
O1W—H1W1	0.8499	C5—C4i	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—C12ii	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
N1i—Ni1—N1	180.0	C2—C1—H1B	109.2
N1i—Ni1—N2	85.49 (4)	H1A—C1—H1B	107.9
N1—Ni1—N2	94.51 (4)	C3—C2—C1	115.74 (11)
N1i—Ni1—N2i	94.51 (4)	C3—C2—H2A	108.3
N1—Ni1—N2i	85.49 (4)	C1—C2—H2A	108.3
N2—Ni1—N2i	179.999 (1)	C3—C2—H2B	108.3
N1i—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)
N2i—Ni1—O1W	91.27 (4)	N2—C3—H3A	109.3
N1i—Ni1—O1Wi	88.06 (4)	C2—C3—H3A	109.3
N1—Ni1—O1Wi	91.94 (4)	N2—C3—H3B	109.3
N2—Ni1—O1Wi	91.27 (4)	C2—C3—H3B	109.3
N2i—Ni1—O1Wi	88.73 (4)	H3A—C3—H3B	107.9
O1W—Ni1—O1Wi	180.0	N2—C4—C5i	109.50 (10)
Ni1—O1W—H1W1	165.2	N2—C4—H4A	109.8
Ni1—O1W—H2W1	77.0	C5i—C4—H4A	109.8
H1W1—O1W—H2W1	107.7	N2—C4—H4B	109.8
C5—N1—C1	113.05 (9)	C5i—C4—H4B	109.8
C5—N1—Ni1	106.83 (7)	H4A—C4—H4B	108.2
C1—N1—Ni1	116.66 (8)	N1—C5—C4i	109.30 (9)
C5—N1—H1N1	112.6 (16)	N1—C5—H5A	109.8
C1—N1—H1N1	108.2 (16)	C4i—C5—H5A	109.8
Ni1—N1—H1N1	98.8 (16)	N1—C5—H5B	109.8
C3—N2—C4	112.55 (10)	C4i—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)	C12ii—C12—C11	123.39 (13)
N1—C1—C2	111.84 (10)	C12ii—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)
N2i—Ni1—N1—C5	13.35 (8)	O1Wi—Ni1—N2—C4	73.17 (7)
O1W—Ni1—N1—C5	104.78 (8)	C5—N1—C1—C2	179.36 (10)
O1Wi—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)
N2i—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)
O1Wi—Ni1—N1—C1	52.34 (8)	C1—C2—C3—N2	71.78 (14)
N1i—Ni1—N2—C3	−139.74 (9)	C3—N2—C4—C5i	166.48 (10)
N1—Ni1—N2—C3	40.26 (9)	Ni1—N2—C4—C5i	40.06 (11)
O1W—Ni1—N2—C3	128.21 (9)	C1—N1—C5—C4i	−168.52 (10)
O1Wi—Ni1—N2—C3	−51.79 (9)	Ni1—N1—C5—C4i	−38.86 (11)
N1i—Ni1—N2—C4	−14.78 (7)	O1—C11—C12—C12ii	11.2 (2)
N1—Ni1—N2—C4	165.22 (7)	O2—C11—C12—C12ii	−168.24 (16)

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···O2iii	0.85	1.98	2.7026 (14)	142
O2W—H2W2···O2ii	0.85	1.91	2.7000 (15)	154
O3W—H1W3···O1iv	0.85	1.96	2.7633 (14)	157
O3W—H2W3···O1	0.85	2.06	2.7968 (14)	144
N1—H1N1···O2Wv	0.88 (2)	2.19 (2)	3.0153 (15)	154 (2)
N2—H1N2···O3Wv	0.90 (2)	2.25 (2)	3.0769 (15)	153 (2)
C3—H3B···O1i	0.97	2.60	3.3850 (18)	138

Table 1

Hydrogen-bond geometry (Å, °)

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⋯O2i	0.85	1.98	2.7026 (14)	142
O2W—H2W2⋯O2ii	0.85	1.91	2.7000 (15)	154
O3W—H1W3⋯O1iii	0.85	1.96	2.7633 (14)	157
O3W—H2W3⋯O1	0.85	2.06	2.7968 (14)	144
N1—H1N1⋯O2Wiv	0.88 (2)	2.19 (2)	3.0153 (15)	154 (2)
N2—H1N2⋯O3Wiv	0.90 (2)	2.25 (2)	3.0769 (15)	153 (2)
C3—H3B⋯O1v	0.97	2.60	3.3850 (18)	138

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .