Bis{1-[bis­(2-amino­ethyl)amino]propan-2-ol}nickel(II) bis­(perchlorate)

In the title compound, [Ni(C₇H₁₉N₃O)₂](ClO₄)₂, the Ni atom, which is located on an inversion center, is hexa­coordinated by six N atoms from two ligands, forming a distorted octa­hedron. The complex molecules are linked by N—H...O hydrogen bonding, forming a one-dimensional chain structure along the a axis, which is further hydrogen bonded with the perchlorate anion to form a three-dimensional framework. One —CH₂—CH₂— group is disordered over two positions; the site occupancy factors are ca. 0.6 and 0.4.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.007 Å
• Disorder in main residue
• R factor = 0.056
• wR factor = 0.167
• Data-to-parameter ratio = 16.2

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT241_ALERT_2_B Check High      Ueq as Compared to Neighbors for        C1A
PLAT410_ALERT_2_B Short Intra H...H Contact  H4A    ..  H1A2    ..       1.80 Ang.

Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.62 mm
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C2A
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl1
PLAT301_ALERT_3_C Main Residue  Disorder .........................      15.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3A    ...          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N3     -   H3B    ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A    ..  O3      ..       2.69 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      26.60 Deg.
              C1B  -N1   -C1A     1.555   1.555   1.555
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ......      25.80 Deg.
              C2B  -N2   -C2A     1.555   1.555   1.555

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C6     = ...          R
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         14

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

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

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S1. Comment

Transition-metal polyamine complexes with hydroxypropyl pendant group play important roles in hydrolytic metalloenzymes (Xia et al.,2001;Huang et al.,2004). The syntheses of such complexes acting as model compounds for hydrolytic metalloenzymes have attracted much attention (Li et al.,2002). In present work, we report the syntheses and the crystal structure of the title compound, [Ni(C₇H₁₉N₃O)₂](ClO₄)₂,(I).

The Ni(II) located on an inversion center, is coordinated octahedrally by six N-atoms from the two ligands, forming a centrosymmetric distorted octahedral geometry. The bond lengths of Ni—N1, Ni—N2 and Ni—N3 are 2.170 (4), 2.128 (4) and 2.146 (3) Å., respectively.

One of the H atom attached to N2 is engaged in intermolecular hydrogen bonds with O1 (Table 1). These intermolecular hydrogen bonds result in the formation of one-dimensional chain structure along the a axis (Fig.2). The chains are further interconnected by the perchlorate anions through O—H···O and N—H···O hydrogen bonds to form a three-dimensional network.

Related literature

For related literature, see: Huang et al. (2004); Li et al. (2002); Xia et al. (2001).

S2. Experimental

To a stirred solution of nickel perchlorate hexahydrate (Ni(ClO)₄·6H₂O,0.366 g, 1.0 mmol) in methanol (20 ml), 1-[bis(aminoethyl)amino]-2-propanol (C₇H₁₉N₃O, 0.16 g, 1.0 mmol) in methanol (10 ml) was dropwise added in 10 min, then the solution was refluxed for 30 min. The green crystals of (I) suitable for X-ray diffraction were obtained after 3 days.

S3. Refinement

All H atoms attached to C, N and O atoms were fixed geometrically and treated as riding with C—H = 0.97 Å (methylene), 0.96 Å (methyl), 0.90 Å (NH₂) and 0.82 Å (OH) with U_iso(H) = 1.2U_eq(CH₂, NH₂ or OH) and U_iso(H) = 1.5U_eq(CH₃).

One of the CH₂—CH₂ group is disordered over two positions in an approximately 0.6/0.4 ratio·This disorder was treated using the tools available in SHELXL97 (Sheldrick, 1997).

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. Molecular structure showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Only the major component of the CH2—CH2 group is shown. Hydrogen atoms have been ommited for clarity except the one showing some hydrogen bonds with the ClO4 anion. [Symmetry code: (i) 1 - x, 1 - y, 1 - z]
	Fig. 2. Partial packing view of (I) showing the hydrogen bonding interactions. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonding have been ommited for clarity·[Symmetry codes: (iii) -x + 1, -y + 1, -z + 2; (ii) x + 1, y, z]

Bis{1-[bis(2-aminoethyl)amino]propan-2-ol}nickel(II) bis(perchlorate)

Crystal data

[Ni(C7H19N3O)2](ClO4)2	F(000) = 612
Mr = 580.11	Dx = 1.613 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2626 reflections
a = 7.915 (3) Å	θ = 2.4–26.9°
b = 17.243 (6) Å	µ = 1.10 mm^−1
c = 9.127 (3) Å	T = 298 K
β = 106.442 (4)°	Prism, green
V = 1194.6 (7) Å^3	0.62 × 0.54 × 0.18 mm
Z = 2

Data collection

Bruker SMART 1000 diffractometer	2796 independent reflections
Radiation source: fine-focus sealed tube	2060 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
φ and ω scans	θmax = 28.4°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→6
Tmin = 0.550, Tmax = 0.827	k = −22→22
7286 measured reflections	l = −11→11

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.167	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0867P)^2 + 1.1111P] where P = (Fo^2 + 2Fc^2)/3
2796 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 0.94 e Å^−3
14 restraints	Δρmin = −0.62 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.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.5000	0.5000	0.5000	0.0300 (2)
N1	0.3581 (4)	0.55710 (18)	0.6413 (4)	0.0408 (7)
C1A	0.4904 (17)	0.5660 (10)	0.7986 (16)	0.081 (7)	0.38
H1A1	0.4534	0.6075	0.8541	0.097*	0.38
H1A2	0.4951	0.5184	0.8563	0.097*	0.38
C2A	0.6715 (14)	0.5839 (7)	0.7814 (15)	0.042 (3)	0.38
H2A1	0.6690	0.6319	0.7255	0.051*	0.38
H2A2	0.7568	0.5890	0.8809	0.051*	0.38
N2	0.7189 (4)	0.51711 (19)	0.6953 (4)	0.0428 (8)
H2A	0.7392	0.4742	0.7538	0.051*
H2B	0.8163	0.5281	0.6670	0.051*
C1B	0.4976 (10)	0.6000 (5)	0.7595 (10)	0.050 (2)	0.62
H1B1	0.5278	0.6471	0.7144	0.060*	0.62
H1B2	0.4508	0.6149	0.8428	0.060*	0.62
C2B	0.6606 (13)	0.5528 (6)	0.8216 (9)	0.054 (2)	0.62
H2B1	0.7537	0.5856	0.8826	0.065*	0.62
H2B2	0.6376	0.5123	0.8872	0.065*	0.62
N3	0.4179 (4)	0.39852 (18)	0.5974 (4)	0.0421 (7)
H3A	0.3418	0.3712	0.5234	0.051*
H3B	0.5121	0.3683	0.6386	0.051*
O1	−0.0021 (4)	0.63113 (18)	0.6513 (4)	0.0593 (8)
H1	−0.0445	0.6570	0.7075	0.089*
C3	0.2468 (6)	0.4976 (2)	0.6853 (6)	0.0512 (10)
H3C	0.1373	0.4928	0.6044	0.061*
H3D	0.2182	0.5146	0.7767	0.061*
C4	0.3337 (7)	0.4194 (3)	0.7147 (6)	0.0579 (12)
H4A	0.4214	0.4199	0.8135	0.069*
H4B	0.2462	0.3806	0.7178	0.069*
C5	0.2437 (6)	0.6200 (2)	0.5482 (5)	0.0510 (10)
H5A	0.3185	0.6523	0.5056	0.061*
H5B	0.1593	0.5951	0.4629	0.061*
C6	0.1434 (6)	0.6724 (3)	0.6229 (6)	0.0540 (11)
H6	0.2218	0.6902	0.7206	0.065*
C7	0.0782 (7)	0.7419 (3)	0.5227 (7)	0.0688 (14)
H7A	0.0052	0.7249	0.4251	0.103*
H7B	0.1769	0.7703	0.5091	0.103*
H7C	0.0109	0.7747	0.5702	0.103*
Cl1	0.87920 (13)	0.32829 (6)	0.91703 (10)	0.0455 (3)
O2	0.9702 (7)	0.2862 (3)	1.0475 (5)	0.0985 (15)
O3	0.9946 (5)	0.3676 (3)	0.8507 (5)	0.0966 (15)
O4	0.7661 (7)	0.3822 (3)	0.9591 (6)	0.1084 (16)
O5	0.7691 (8)	0.2780 (4)	0.8070 (6)	0.131 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0237 (3)	0.0276 (3)	0.0384 (4)	−0.0022 (2)	0.0081 (2)	0.0034 (2)
N1	0.0303 (15)	0.0401 (17)	0.0543 (19)	−0.0027 (13)	0.0160 (14)	−0.0064 (15)
C1A	0.064 (10)	0.089 (14)	0.112 (16)	−0.042 (10)	0.061 (11)	−0.066 (12)
C2A	0.031 (5)	0.052 (8)	0.041 (7)	−0.009 (6)	0.006 (5)	−0.013 (6)
N2	0.0310 (16)	0.0457 (18)	0.0488 (18)	0.0005 (13)	0.0066 (14)	0.0035 (14)
C1B	0.042 (4)	0.057 (5)	0.046 (4)	−0.008 (3)	0.003 (3)	−0.022 (4)
C2B	0.061 (5)	0.057 (5)	0.035 (4)	0.006 (4)	−0.002 (3)	−0.005 (4)
N3	0.0395 (17)	0.0314 (15)	0.0574 (19)	−0.0027 (13)	0.0167 (15)	0.0060 (14)
O1	0.0466 (17)	0.0539 (18)	0.092 (2)	−0.0103 (14)	0.0423 (17)	−0.0096 (17)
C3	0.045 (2)	0.054 (2)	0.063 (3)	0.0052 (19)	0.030 (2)	0.013 (2)
C4	0.063 (3)	0.051 (2)	0.070 (3)	0.003 (2)	0.034 (2)	0.015 (2)
C5	0.056 (3)	0.043 (2)	0.061 (3)	0.0048 (19)	0.029 (2)	0.0029 (19)
C6	0.041 (2)	0.055 (3)	0.073 (3)	−0.004 (2)	0.026 (2)	−0.001 (2)
C7	0.067 (3)	0.051 (3)	0.100 (4)	0.013 (2)	0.043 (3)	0.009 (3)
Cl1	0.0399 (5)	0.0540 (6)	0.0414 (5)	0.0024 (4)	0.0095 (4)	0.0041 (4)
O2	0.118 (4)	0.099 (3)	0.074 (2)	0.045 (3)	0.021 (3)	0.036 (2)
O3	0.069 (2)	0.147 (4)	0.079 (2)	−0.032 (3)	0.030 (2)	0.018 (3)
O4	0.112 (4)	0.093 (3)	0.137 (4)	0.042 (3)	0.062 (3)	0.013 (3)
O5	0.115 (4)	0.186 (5)	0.097 (3)	−0.078 (4)	0.039 (3)	−0.062 (4)

Geometric parameters (Å, º)

Ni1—N2^i	2.125 (3)	C2B—H2B2	0.9700
Ni1—N2	2.125 (3)	N3—C4	1.457 (6)
Ni1—N3	2.145 (3)	N3—H3A	0.9000
Ni1—N3^i	2.145 (3)	N3—H3B	0.9000
Ni1—N1^i	2.171 (3)	O1—C6	1.438 (5)
Ni1—N1	2.171 (3)	O1—H1	0.8200
N1—C3	1.480 (5)	C3—C4	1.502 (6)
N1—C1B	1.502 (7)	C3—H3C	0.9700
N1—C5	1.511 (5)	C3—H3D	0.9700
N1—C1A	1.526 (14)	C4—H4A	0.9700
C1A—C2A	1.517 (13)	C4—H4B	0.9700
C1A—H1A1	0.9700	C5—C6	1.490 (6)
C1A—H1A2	0.9700	C5—H5A	0.9700
C2A—N2	1.501 (11)	C5—H5B	0.9700
C2A—H2A1	0.9700	C6—C7	1.507 (7)
C2A—H2A2	0.9700	C6—H6	0.9800
N2—C2B	1.490 (9)	C7—H7A	0.9600
N2—H2A	0.9000	C7—H7B	0.9600
N2—H2B	0.9000	C7—H7C	0.9600
C1B—C2B	1.494 (10)	Cl1—O3	1.405 (4)
C1B—H1B1	0.9700	Cl1—O2	1.406 (4)
C1B—H1B2	0.9700	Cl1—O4	1.417 (4)
C2B—H2B1	0.9700	Cl1—O5	1.423 (5)
N2^i—Ni1—N2	180.000 (1)	N1—C1B—H1B2	109.1
N2^i—Ni1—N3	87.91 (13)	H1B1—C1B—H1B2	107.8
N2—Ni1—N3	92.09 (13)	N2—C2B—C1B	110.7 (6)
N2^i—Ni1—N3^i	92.09 (13)	N2—C2B—H2B1	109.5
N2—Ni1—N3^i	87.91 (13)	C1B—C2B—H2B1	109.5
N3—Ni1—N3^i	180.00 (9)	N2—C2B—H2B2	109.5
N2^i—Ni1—N1^i	82.81 (13)	C1B—C2B—H2B2	109.5
N2—Ni1—N1^i	97.19 (13)	H2B1—C2B—H2B2	108.1
N3—Ni1—N1^i	98.31 (12)	C4—N3—Ni1	111.0 (2)
N3^i—Ni1—N1^i	81.69 (12)	C4—N3—H3A	109.4
N2^i—Ni1—N1	97.19 (13)	Ni1—N3—H3A	109.4
N2—Ni1—N1	82.81 (13)	C4—N3—H3B	109.4
N3—Ni1—N1	81.69 (12)	Ni1—N3—H3B	109.4
N3^i—Ni1—N1	98.31 (12)	H3A—N3—H3B	108.0
N1^i—Ni1—N1	180.000 (1)	C6—O1—H1	109.5
C3—N1—C1B	121.3 (5)	N1—C3—C4	113.1 (4)
C3—N1—C5	110.0 (3)	N1—C3—H3C	109.0
C1B—N1—C5	104.6 (4)	C4—C3—H3C	109.0
C3—N1—C1A	96.7 (6)	N1—C3—H3D	109.0
C1B—N1—C1A	26.6 (5)	C4—C3—H3D	109.0
C5—N1—C1A	126.8 (7)	H3C—C3—H3D	107.8
C3—N1—Ni1	107.1 (2)	N3—C4—C3	111.8 (4)
C1B—N1—Ni1	104.5 (4)	N3—C4—H4A	109.2
C5—N1—Ni1	108.7 (2)	C3—C4—H4A	109.2
C1A—N1—Ni1	105.7 (6)	N3—C4—H4B	109.2
C2A—C1A—N1	109.9 (10)	C3—C4—H4B	109.2
C2A—C1A—H1A1	109.7	H4A—C4—H4B	107.9
N1—C1A—H1A1	109.7	C6—C5—N1	119.3 (4)
C2A—C1A—H1A2	109.7	C6—C5—H5A	107.5
N1—C1A—H1A2	109.7	N1—C5—H5A	107.5
H1A1—C1A—H1A2	108.2	C6—C5—H5B	107.5
N2—C2A—C1A	106.3 (10)	N1—C5—H5B	107.5
N2—C2A—H2A1	110.5	H5A—C5—H5B	107.0
C1A—C2A—H2A1	110.5	O1—C6—C5	109.9 (4)
N2—C2A—H2A2	110.5	O1—C6—C7	110.4 (4)
C1A—C2A—H2A2	110.5	C5—C6—C7	109.8 (4)
H2A1—C2A—H2A2	108.7	O1—C6—H6	108.9
C2B—N2—C2A	25.8 (4)	C5—C6—H6	108.9
C2B—N2—Ni1	110.4 (4)	C7—C6—H6	108.9
C2A—N2—Ni1	106.3 (5)	C6—C7—H7A	109.5
C2B—N2—H2A	85.6	C6—C7—H7B	109.5
C2A—N2—H2A	110.5	H7A—C7—H7B	109.5
Ni1—N2—H2A	110.5	C6—C7—H7C	109.5
C2B—N2—H2B	127.8	H7A—C7—H7C	109.5
C2A—N2—H2B	110.5	H7B—C7—H7C	109.5
Ni1—N2—H2B	110.5	O3—Cl1—O2	112.0 (3)
H2A—N2—H2B	108.7	O3—Cl1—O4	109.8 (3)
C2B—C1B—N1	112.6 (7)	O2—Cl1—O4	108.7 (3)
C2B—C1B—H1B1	109.1	O3—Cl1—O5	109.5 (3)
N1—C1B—H1B1	109.1	O2—Cl1—O5	110.3 (4)
C2B—C1B—H1B2	109.1	O4—Cl1—O5	106.5 (4)

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
N2—H2A···O4	0.90	2.42	3.293 (6)	164
N2—H2A···O3	0.90	2.69	3.416 (6)	139
N2—H2B···O1^ii	0.90	2.31	3.067 (4)	141
O1—H1···O2^iii	0.82	2.36	3.043 (6)	142

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