





Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536808015894/sj2507sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536808015894/sj2507Isup2.hkl |
CCDC reference: 696394
Key indicators
- Single-crystal X-ray study
- T = 100 K
- Mean
(C-C) = 0.001 Å
- R factor = 0.023
- wR factor = 0.056
- Data-to-parameter ratio = 24.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 -- O1 .. 5.03 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Ni1 -- O1W .. 7.95 su PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT141_ALERT_4_C su on a - Axis Small or Missing (x 100000) ..... 10 Ang. PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 10 Ang. PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct... 2 PLAT180_ALERT_4_C Check Cell Rounding: # of Values Ending with 0 = 4 PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels .......... 5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The title complex was synthesized by heating under reflux a 1:2 molar mixture of nickel(II) chloride hexahydrate, NiCl2.6H2O (0.2377 g, 1 mmol) and glycine (0.1503 g, 2 mmol) in water (30 ml) for 3 h. A green transparent solution was obtained and allowed to cool to room temperature. Green single crystals of the title complex suitable for X-ray structure determination were obtained after a few days of evaporation. Mp. 442–443 K.
H atoms were located in difference maps and refined isotropically. The highest residual electron density peak is located at 1.74 Å from O1W and the deepest hole is located at 0.72 Å from Ni1.
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 2003).
[Ni(C2H5NO2)2(H2O)2]Cl2 | F(000) = 324 |
Mr = 315.76 | Dx = 1.939 Mg m−3 |
Monoclinic, P21/c | Melting point = 442–443 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 10.6006 (1) Å | Cell parameters from 2372 reflections |
b = 5.8579 (1) Å | θ = 3.8–34.9° |
c = 8.7113 (1) Å | µ = 2.30 mm−1 |
β = 90.489 (1)° | T = 100 K |
V = 540.93 (1) Å3 | Block, green |
Z = 2 | 0.32 × 0.22 × 0.12 mm |
Bruker SMART APEX2 CCD area-detector diffractometer | 2372 independent reflections |
Radiation source: fine-focus sealed tube | 2079 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.032 |
Detector resolution: 8.33 pixels mm-1 | θmax = 35.0°, θmin = 3.8° |
ω scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | k = −8→9 |
Tmin = 0.530, Tmax = 0.775 | l = −14→14 |
11049 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.056 | All H-atom parameters refined |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0259P)2 + 0.1363P] where P = (Fo2 + 2Fc2)/3 |
2372 reflections | (Δ/σ)max = 0.001 |
98 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.68 e Å−3 |
[Ni(C2H5NO2)2(H2O)2]Cl2 | V = 540.93 (1) Å3 |
Mr = 315.76 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.6006 (1) Å | µ = 2.30 mm−1 |
b = 5.8579 (1) Å | T = 100 K |
c = 8.7113 (1) Å | 0.32 × 0.22 × 0.12 mm |
β = 90.489 (1)° |
Bruker SMART APEX2 CCD area-detector diffractometer | 2372 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2005) | 2079 reflections with I > 2σ(I) |
Tmin = 0.530, Tmax = 0.775 | Rint = 0.032 |
11049 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.056 | All H-atom parameters refined |
S = 1.06 | Δρmax = 0.49 e Å−3 |
2372 reflections | Δρmin = −0.68 e Å−3 |
98 parameters |
Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment. |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.0000 | 0.0000 | 0.0000 | 0.00637 (5) | |
Cl1 | 0.38948 (2) | −0.28198 (5) | −0.05133 (3) | 0.01159 (6) | |
O1 | 0.14915 (7) | 0.13388 (13) | −0.11588 (8) | 0.00907 (13) | |
O2 | 0.04973 (7) | 0.34293 (14) | −0.29470 (8) | 0.01009 (14) | |
N1 | 0.37953 (8) | 0.22021 (18) | −0.21419 (11) | 0.00996 (16) | |
C1 | 0.14619 (9) | 0.25515 (18) | −0.23533 (11) | 0.00790 (16) | |
C2 | 0.27217 (9) | 0.2880 (2) | −0.31479 (12) | 0.01036 (18) | |
O1W | 0.10514 (8) | −0.28293 (15) | 0.04954 (9) | 0.01166 (15) | |
H2A | 0.2839 (16) | 0.444 (3) | −0.345 (2) | 0.017 (4)* | |
H2B | 0.2718 (16) | 0.195 (3) | −0.4024 (19) | 0.018 (4)* | |
H1N1 | 0.4466 (17) | 0.204 (3) | −0.2731 (19) | 0.020 (4)* | |
H2N1 | 0.3641 (15) | 0.088 (3) | −0.1668 (19) | 0.015 (4)* | |
H3N1 | 0.3947 (17) | 0.323 (3) | −0.142 (2) | 0.025 (5)* | |
H1W1 | 0.087 (2) | −0.324 (4) | 0.139 (2) | 0.038 (6)* | |
H2W1 | 0.180 (2) | −0.284 (3) | 0.032 (2) | 0.032 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.00560 (8) | 0.00757 (9) | 0.00594 (8) | −0.00004 (6) | 0.00067 (5) | 0.00022 (6) |
Cl1 | 0.00941 (10) | 0.01139 (12) | 0.01402 (11) | 0.00140 (8) | 0.00280 (8) | 0.00077 (8) |
O1 | 0.0083 (3) | 0.0107 (4) | 0.0082 (3) | −0.0006 (3) | 0.0007 (2) | 0.0023 (2) |
O2 | 0.0085 (3) | 0.0132 (4) | 0.0086 (3) | 0.0018 (3) | 0.0000 (2) | 0.0022 (3) |
N1 | 0.0075 (3) | 0.0121 (4) | 0.0103 (4) | −0.0001 (3) | 0.0009 (3) | 0.0021 (3) |
C1 | 0.0079 (4) | 0.0085 (4) | 0.0074 (4) | −0.0009 (3) | 0.0011 (3) | −0.0007 (3) |
C2 | 0.0071 (4) | 0.0145 (5) | 0.0095 (4) | 0.0000 (3) | 0.0007 (3) | 0.0033 (3) |
O1W | 0.0089 (3) | 0.0129 (4) | 0.0133 (3) | 0.0023 (3) | 0.0028 (3) | 0.0027 (3) |
Ni1—O1i | 2.0398 (7) | N1—C2 | 1.4845 (14) |
Ni1—O1 | 2.0399 (7) | N1—H1N1 | 0.885 (18) |
Ni1—O1Wi | 2.0413 (8) | N1—H2N1 | 0.893 (18) |
Ni1—O1W | 2.0414 (8) | N1—H3N1 | 0.884 (19) |
Ni1—O2ii | 2.0753 (7) | C1—C2 | 1.5217 (14) |
Ni1—O2iii | 2.0753 (7) | C2—H2A | 0.959 (18) |
O1—C1 | 1.2601 (12) | C2—H2B | 0.939 (17) |
O2—C1 | 1.2524 (12) | O1W—H1W1 | 0.84 (2) |
O2—Ni1iv | 2.0753 (7) | O1W—H2W1 | 0.81 (2) |
O1i—Ni1—O1 | 180.0 | C2—N1—H2N1 | 111.2 (11) |
O1i—Ni1—O1Wi | 89.58 (3) | H1N1—N1—H2N1 | 109.0 (15) |
O1—Ni1—O1Wi | 90.42 (3) | C2—N1—H3N1 | 111.7 (12) |
O1i—Ni1—O1W | 90.42 (3) | H1N1—N1—H3N1 | 110.1 (16) |
O1—Ni1—O1W | 89.58 (3) | H2N1—N1—H3N1 | 107.3 (16) |
O1Wi—Ni1—O1W | 180.0 | O2—C1—O1 | 125.94 (9) |
O1i—Ni1—O2ii | 86.34 (3) | O2—C1—C2 | 118.48 (9) |
O1—Ni1—O2ii | 93.66 (3) | O1—C1—C2 | 115.54 (9) |
O1Wi—Ni1—O2ii | 87.50 (3) | N1—C2—C1 | 111.66 (8) |
O1W—Ni1—O2ii | 92.50 (3) | N1—C2—H2A | 108.4 (10) |
O1i—Ni1—O2iii | 93.66 (3) | C1—C2—H2A | 111.2 (10) |
O1—Ni1—O2iii | 86.34 (3) | N1—C2—H2B | 108.8 (10) |
O1Wi—Ni1—O2iii | 92.50 (3) | C1—C2—H2B | 107.4 (10) |
O1W—Ni1—O2iii | 87.50 (3) | H2A—C2—H2B | 109.4 (14) |
O2ii—Ni1—O2iii | 180.0 | Ni1—O1W—H1W1 | 107.7 (15) |
C1—O1—Ni1 | 127.70 (7) | Ni1—O1W—H2W1 | 120.0 (14) |
C1—O2—Ni1iv | 137.59 (7) | H1W1—O1W—H2W1 | 114 (2) |
C2—N1—H1N1 | 107.6 (11) | ||
O1Wi—Ni1—O1—C1 | −35.21 (9) | Ni1iv—O2—C1—C2 | 10.54 (16) |
O1W—Ni1—O1—C1 | 144.79 (9) | Ni1—O1—C1—O2 | 10.33 (16) |
O2ii—Ni1—O1—C1 | −122.74 (9) | Ni1—O1—C1—C2 | −167.51 (7) |
O2iii—Ni1—O1—C1 | 57.26 (9) | O2—C1—C2—N1 | 167.23 (9) |
Ni1iv—O2—C1—O1 | −167.25 (8) | O1—C1—C2—N1 | −14.75 (14) |
Symmetry codes: (i) −x, −y, −z; (ii) x, −y+1/2, z+1/2; (iii) −x, y−1/2, −z−1/2; (iv) −x, y+1/2, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···Cl1v | 0.886 (18) | 2.326 (17) | 3.2021 (9) | 170.2 (15) |
N1—H2N1···Cl1 | 0.893 (17) | 2.404 (17) | 3.2673 (11) | 162.7 (14) |
N1—H3N1···Cl1vi | 0.884 (18) | 2.446 (18) | 3.2442 (11) | 150.4 (15) |
O1W—H1W1···O2i | 0.840 (18) | 2.00 (2) | 2.7276 (11) | 145 (2) |
O1W—H2W1···Cl1 | 0.81 (2) | 2.34 (2) | 3.1468 (9) | 172.8 (17) |
C2—H2B···O1vii | 0.938 (17) | 2.472 (17) | 2.9549 (13) | 112.0 (13) |
Symmetry codes: (i) −x, −y, −z; (v) −x+1, y+1/2, −z−1/2; (vi) x, y+1, z; (vii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C2H5NO2)2(H2O)2]Cl2 |
Mr | 315.76 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 10.6006 (1), 5.8579 (1), 8.7113 (1) |
β (°) | 90.489 (1) |
V (Å3) | 540.93 (1) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.30 |
Crystal size (mm) | 0.32 × 0.22 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2005) |
Tmin, Tmax | 0.530, 0.775 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11049, 2372, 2079 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.806 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.056, 1.06 |
No. of reflections | 2372 |
No. of parameters | 98 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.49, −0.68 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N1···Cl1i | 0.886 (18) | 2.326 (17) | 3.2021 (9) | 170.2 (15) |
N1—H2N1···Cl1 | 0.893 (17) | 2.404 (17) | 3.2673 (11) | 162.7 (14) |
N1—H3N1···Cl1ii | 0.884 (18) | 2.446 (18) | 3.2442 (11) | 150.4 (15) |
O1W—H1W1···O2iii | 0.840 (18) | 2.00 (2) | 2.7276 (11) | 145 (2) |
O1W—H2W1···Cl1 | 0.81 (2) | 2.34 (2) | 3.1468 (9) | 172.8 (17) |
C2—H2B···O1iv | 0.938 (17) | 2.472 (17) | 2.9549 (13) | 112.0 (13) |
Symmetry codes: (i) −x+1, y+1/2, −z−1/2; (ii) x, y+1, z; (iii) −x, −y, −z; (iv) x, −y+1/2, z−1/2. |
Nickel plays versatile and sometimes controversial roles in living systems as the biological effects of nickel are closely related to their chemical nature (Lancaster, 1998). Nickel complexes have been the subject of intense study in recent years mostly due to their biological significance such as antitumor and antibacterial activities (Matkar et al., 2006, Kasuga et al., 2001). Several nickel complexes have been found to inhibit proliferation of diverse cancer cells (Ferrari et al., 2002; Liang et al., 2004, Matkar et al., 2006). Based on the significant biological role played by nickel complexes, we have synthesized several nickel complexes and herein, we report the preparation and crystal structure of the title complex which is isomorphous with catena-poly[[[diaquanickel(II)]-di-µ- glycine] dibromide] (Fleck & Bohatý, 2005).
In the molecular structure of the polymeric title complex, {[Ni(C2H5NO2)2(H2O)2]Cl2}n (Fig. 1), the NiII lies on an inversion center and has an NiO6 coordination environment. The coordination sphere of the NiII ion is a slightly distorted octahedron consisting of the O4 coordination plane of the four glycine zwitterions (coordinating through one carboxylic O atom from each glycine zwitterion) and the two axially bound water molecules. The Ni—O(glycine) distances [Ni1—O1 = 2.0398 (7) Å and Ni1—O2 = 2.0753 (7) Å] and Ni—O(water) distances [2.0413 (8) Å] are quite similar to those observed in another closely related NiII complex which are in the range 2.033 (2)–2.086 (2) Å (Fleck & Bohatý, 2005) and are also similar to the Ni—O distances observed in ionic compounds (Shannon, 1976). Other bond lengths and angles observed in the structure are also normal (Allen et al., 1987). In the glycine zwitterion, the carboxylate group is slightly twisted from the C1/C2/N1 plane with torsion angles O2—C1—C2—N1 = 167.23 (9)° and O1—C1—C2—N1 - 14.75 (14)°. The C—O distances [C1—O1 = 1.2601 (12) Å and C1—O2 = 1.2524 (12) Å] show some electron delocalization over the carboxylate group. The Cl- ions lie in the interstices between the glycine zwitterions.
The crystal packing in Fig. 2 has shown the polymeric structure of the title polymeric complex. The NiII complex molecules are linked by O—H···O (Table 1) into polymeric sheets along the [010] direction (Fig. 3). These sheets are furthered connect to the interstial Cl- ions by O—H···Cl and N—H···Cl hydrogen bonds to the water molecules and amino groups, respectively forming a three-dimensional network (Table 1). The crystal is stabilized by O—H···O, O—H···Cl and N—H···Cl hydrogen bonds, together with weak C—H···Cl interactions (Table 1).