catena Poly[[bis­­(N,N di­methyl­formamide κO)nickel(II)] di μ 1,5 dicyanamido κN1:κN5]

metal-organic papers

Acta Cryst.(2005). E61, m1937–m1939 doi:10.1107/S1600536805027674 Shen and Yuan _[Ni(C

2N3)2(C3H7NO)2]

m1937

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

catena-Poly[[bis(N,N-dimethylformamide-

j

O)-nickel(II)]-di-

l

-1,5-dicyanamido-

j

N

:

j

N

]

Xiao-Ping Shena* and Ai-Hua Yuanb

a

School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People’s Republic of China, andb_{School of Materials}

Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, People’s Republic of China

Correspondence e-mail: xiaopingshen@163.com

Key indicators

Single-crystal X-ray study

T= 193 K

Mean(N–C) = 0.003 A˚

Rfactor = 0.023

wRfactor = 0.062

Data-to-parameter ratio = 11.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

In the crystal structure of the title complex, [Ni(C2N3)2 -(C3H7NO)2]nor [Ni(dca)2(DMF)2]n, where dca is dicyanamide

and DMF is N,N-dimethylformamide, each NiII atom is

six-coordinated in a distorted octahedral coordination environ-ment. Four N atoms from four dca ligands fill the equatorial positions, and two O atoms from two DMF ligands fill the axial

positions. The structure is isostructural with

[Co(dca)2(DMF)2]n but is not isostructural with

[Mn(dca)2(DMF)2]n. The Ni II

atom and the dicyanamide

bridging ligand occupy special positions of symmetry 2/mand

m, respectively. The structure consists of uniform neutral

chains where neighbouring NiIIatoms are connected through

two asymmetric end-to-end dca bridges.

Comment

Dicyanamide (dca), [N(CN)2]

, complexes have been studied extensively recently because of their fascinating topologies and interesting magnetic properties (Battenet al., 1998; Miller & Manson 2001; Jensen et al., 2000; Riggio et al., 2001). A number of nickel(II)–dca complexes have been reported (Sun,

et al., 2000; Wanget al., 2004; Konoret al., 2005). Our research interest is the construction of novel topologies of cyano complexes and studying their magnetic properties (Shenet al., 2004, 2003). In the present work, we report the crystal

struc-ture of a one-dimensional chain polymer, viz.

[Ni(dca)2(DMF)2]n, (I).

Fig. 1 shows the local coordination about the nickel(II) centre in (I). The structure of (I) is isostructural with [Co(dca)2(DMF)2]n(Tonget al., 2003) but is not isostructural

with [Mn(dca)2(DMF)2]n (Batten et al., 1999). The space

group of [Co(dca)2(DMF)2]nreported by Dong et al.(2003)

has been described incorrectly in C2; it should be C2/m, as reported by Tonget al.(2003). The structure of (I) consists of uniform neutral chains in which neighbouring nickel(II) atoms are connected through two asymmetric end-to-end dca bridges. The coordination geometry of the nickel(II) atom is distorted octahedral, being coordinated by four N atoms of four symmetry-related dca ligands in the equatorial plane and two O atoms of two symmetry-related DMF ligands at the axial positions. The N—Ni—N bond angles are in the range

87.84 (6)–92.16 (6), close to 90. The four Ni—N(dca) bond

lengths in (I) are all 2.0733 (11) A˚ , corresponding to the values reported in the dca-bridged nickel(II) complexes

[Ni(apo)-(dca)2] [2.043 (4)–2.096 (4) A˚ ; apo = 2-aminopyridine

N-oxide; Sunet al., 2000] and [Ni(tn)2(dca)](ClO4) [2.095 (4) and 2.116 (4) A˚ ; tn = trimethylenediamine; Li et al., 2002], and shorter than the Mn—N bond lengths [2.218 (2) and 2.203 (2) A˚ ] in [Mn(dca)2(DMF)2]n(Battenet al., 1999) and

the Co—N bond lengths [2.123 (2) A˚ ] in [Co(dca)2(DMF)2]n

(Tonget al., 2003); this is what one would expect from the ionic

radii (Ni2+ < Co2+ < Mn2+). The two Ni—O (DMF) bond

lengths are both 2.0670 (13) A˚ , corresponding to the values [2.0776 (19) A˚ ] in [Ni(pmbp)2(DMF)2] [Hpmbp = 1-phenyl-3-methyl-4-benzoyl-1H-pyrazol-5(4H)-one; Shen & Yuan 2004]

and shorter than the M—O bond lengths in [Mn(dca)2

-(DMF)2]n [Mn—O = 2.199 (2) A˚ ] and [Co(dca)2(DMF)2]n

[Co—O = 2.096 (2) A˚ ].

The dicyanamide (dca) ligand adopts an end-to-end coor-dination mode. Two dca ions link two nickel(II) atoms to form

a 12-membered Ni(dca)2Ni ring and neighbouring rings share

the nickel(II) atoms to form a chain of [Ni(dca)2]n. The chains

are linear, the Ni(dca)2Ni rings being in a slight chair

conformation.

The free dicyanamide (dca) ligand possessesC2vsymmetry.

The dca ligand in (I) also adopts essentiallyC2vsymmetry, with

a nitrile C N bond length of 1.1545 (18) A˚ for N1 C1,

showing the triple-bond character. The bond angle related to

the amide N atom, C1—N2—C1(x, 1y,z), is 118.61 (16)_,

corresponding to an amide N atom with ansp2hybrid orbital;

that related to the nitrile group, N1 C1—N2, is 174.95 (13)_,

corresponding to N1 and C1 with ansphybrid orbital.

The chains propagate parallel to the crystallographicbaxis, the Ni Ni distance along the chain being equal to thebaxis length, 7.3166 (7) A˚ . The chains interdigitate such that each DMF ligand lies between two DMF ligands of an adjacent

chain, with a shortest Ni Ni interchain distance of

7.628 (2) A˚ . Adjacent chains are held together by a weak C—

H N hydrogen bond, forming layers parallel to theabplane

(Fig. 2 and Table 2).

Experimental

An aqueous solution (10 ml) of Ni(NO3)26H2O (0.146 g, 0.5 mmol)

was added to a DMF solution (10 ml) of Na[N(CN)2] (0.090 g,

1.0 mmol). Slow evaporation of the resulting mixture led to green crystals suitable for X-ray diffraction analysis. Analysis found: C 35.53, H 4.12, N 33.31%; calculated for C10H14N8NiO2: C 35.64, H

4.19, N 33.26%.

Crystal data

[Ni(C2N3)2(C3H7NO)2]

Mr= 336.98

Monoclinic,C2=m a= 13.3866 (17) A˚

b= 7.3166 (7) A˚

c= 8.0595 (10) A˚

= 112.503 (3) V= 729.28 (15) A˚3

Z= 2

Dx= 1.535 Mg m 3

MoKradiation Cell parameters from 1804

reflections

= 3.2–27.5

= 1.35 mm1

T= 193 (2) K Block, green

0.400.210.20 mm

Data collection

Rigaku Mercury CCD diffractometer

!scans

Absorption correction: multi-scan (Jacobson, 1998)

Tmin= 0.646,Tmax= 0.774

4029 measured reflections

900 independent reflections 887 reflections withI> 2(I)

Rint= 0.018

max= 27.5

h=17!15

k=8!9

l=10!10

metal-organic papers

m1938

2N3)2(C3H7NO)2] Acta Cryst.(2005). E61, m1937–m1939

Figure 2

The packing in (I), showing the C—H N hydrogen-bond interactions as dashed lines.

Figure 1

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.023}

wR(F2) = 0.062

S= 1.03 900 reflections 76 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2

(Fo2) + (0.0436P)2

+ 0.3824P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.15 e A˚

3

min=0.47 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

Ni1—O1 2.0670 (13)

Ni1—N1 2.0733 (11)

O1—C2 1.243 (2)

N1—C1 1.1545 (18)

N2—C1 1.3074 (15)

N3—C2 1.319 (2)

N3—C3 1.448 (3)

N3—C4 1.458 (3)

O1—Ni1—N1 91.61 (4)

O1i—Ni1—N1 88.39 (4) N1—Ni1—N1ii

92.16 (6)

N1—Ni1—N1iii

87.84 (6) C1iv—N2—C1 118.61 (16)

N1—C1—N2 174.95 (13)

Symmetry codes: (i)xþ1;yþ1;zþ1; (ii)x;yþ1;z; (iii)xþ1;y;zþ1; (iv)x;yþ2;z.

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

C2—H2 N2v

0.95 (1) 2.51 (1) 3.453 (2) 169 (2)

Symmetry code: (v)xþ3 2;yþ

3 2;zþ1.

H atoms were found in a difference Fourier map and refined with bond-length restraints of C—H = 0.95 (1) A˚ for the methyl groups and the H H distance restrained to 1.50 (1) A˚ . One of two inde-pendent H atoms lies on the mirror plane.

Data collection: CrystalClear (Rigaku, 2000); cell refinement:

CrystalClear; data reduction: CrystalClear; method used to solve

structure: the coordinates of the Co structure of Tonget al. (2003) were used; program(s) used to refine structure:SHELXL97 (Shel-drick, 1997); molecular graphics:SHELXTL(Bruker, 1998); software used to prepare material for publication:SHELXTL.

This work was supported by the Natural Science Founda-tion of Jiangsu Province (No. BK2005056), People’s Republic of China.

References

Batten, S. R., Jensen, P., Kepert, C. J., Kurmoo, M., Moubaraki, B., Murray, K. S. & Price, D. J. (1999).J. Chem. Soc. Dalton Trans.pp. 2987–2997. Batten, S. R., Jensen, P., Moubaraki, B., Murray, K. S. & Robson, R. (1998).

Chem. Commun.pp. 439–440.

Bruker (1998). SHELXTL. Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

Dong, W., Liang, M., Sun, Y. Q. & Liu, Z. Q. (2003).Z. Anorg. Allg. Chem.629, 2443–2445.

Jacobson, R. (1998). Private communication to the Rigaku Corporation. Jensen, P., Batten, S. R., Moubaraki, B. & Murray, K. S. (2000). Chem.

Commun.pp. 793–740.

Konor, S., Dalai, S., Mukherjee, P. S., Drew, M. G. B., Ribas, J. & Chaudhuri, N. R. (2005).Inorg. Chim. Acta,358, 957–963.

Li, B. L., Ding, J. G., Lang, J. P., Zheng, X. & Chen, J. T. (2002).J. Mol. Struct.

616, 175–179.

Miller, J. S. & Manson, J. L. (2001).Acc. Chem. Res.34, 563–570.

Rigaku (2000). CrystalClear. Version 1.3. Rigaku Corporation, 3-9-12 Akishima, Tokyo, Japan.

Riggio, I., van Albada, G. A., Ellis, D. D., Spek, A. L. & Reedijk, J. (2001).

Inorg. Chim. Acta,313, 120–124.

Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Shen, X. P., Gao, S., Yin, G., Yu, K. B. & Xu, Z. (2004).New J. Chem.28, 996–

999.

Shen, X. P., Li, B. L., Zou, J. Z., Hu, H. M. & Xu, Z. (2003).J. Mol. Struct.657, 325–331.

Shen, X. P. & Yuan, A. H. (2004).Acta Cryst.E60, m1228–m1230.

Sun, B. W., Gao, S., Ma, B. Q., Niu, D. Z. & Wang, Z. M. (2000).J. Chem. Soc. Dalton Trans.pp. 4187–4191.

Tong, M.-L., Zhou, A.-J., Hu, S., Chen, X.-M. & Ng, S. W. (2003).Acta Cryst.

E59, m405–m407.

Wang, S. W., Zhu, X., Li, B. L., Lang, J. P., Zheng, X. & Zhang, Y. (2004).Chin. J. Struct. Chem.23, 145–148.

metal-organic papers

Acta Cryst.(2005). E61, m1937–m1939 Shen and Yuan _[Ni(C

supporting information

sup-1

Acta Cryst. (2005). E61, m1937–m1939

supporting information

Acta Cryst. (2005). E61, m1937–m1939 [doi:10.1107/S1600536805027674]

catena

-Poly[[bis(

N

,

N

-dimethylformamide-

κ

O

)nickel(II)]-di-

µ

-1,5-dicyanamido-κ

N

:

κ

N

]

Xiao-Ping Shen and Ai-Hua Yuan

S1. Comment

Dicyanamide (dca), [N(CN)2]-, complexes have been studied extensively recently because of their fascinating topologies

and interesting magnetic properties (Batten et al., 1998; Miller & Manson 2001; Jensen et al., 2000; Riggio et al., 2001).

A number of nickel(II)–dca complexes have been reported (Sun, et al., 2000; Wang et al., 2004; Konor et al., 2005). Our

research interest is construction of novel topologies of cyano complexes and studying the magnetic properties (Shen et

al., 2004, 2003). In the present work, we report the crystal structure of a one-dimensional chain polymer, viz.

[Ni(dca)2(DMF)2]n, (I).

Fig. 1 shows the local coordination about the nickel(II) center in (I). The structure of (I) is isostructural with

[Co(dca)2(DMF)2]n (Tong et al., 2003) and not isostructural with [Mn(dca)2(DMF)2]n (Batten et al., 1999). The space

group of [Co(dca)2(DMF)2]n reported by Dong et al. (2003) has been described incorrectly in C2; it should be C2/m, as

reported by Tong et al. (2003). The structure of (I) consists of uniform neutral chains where neighboring nikel(II) atoms

are connected through two asymmetric end-to-end dca bridges. The coordination geometry of the nickel(II) atom is

distorted octahedral, being coordinated by four N atoms of four symmetry-related dca ligands in the equatorial plane and

two O atoms of two symmetry-related DMF ligands at the axial positions. The N—Ni—N bond angles are in the range

87.84 (6) to 92.16 (6)°, close to 90°. The four Ni—N(dca) bond lengths in (I) are all 2.0733 (11) Å, corresponding to the

values reported in the dca-bridged nickel(II) complexes [Ni(apo)(dca)2] [2.043 (4)–2.096 (4) Å; apo = 2-aminopyridine

N-oxide; Sun et al., 2000] and [Ni(tn)2(dca)](ClO4) [2.095 (4) and 2.116 (4) Å; tn = trimethylenediamine; Li et al., 2002],

and shorter than the Mn—N bond lengths [2.218 (2) and 2.203 (2) Å] in [Mn(dca)2(DMF)2]n (Batten et al., 1999) and the

Co—N bond lengths [2.123 (2) Å] in [Co(dca)2(DMF)2]n (Tong et al., 2003); this is what one would expect from the ionic

radii (Ni2+ _{< Co}2+ _{< Mn}2+_{). The two Ni—O (DMF) bond lengths are both 2.0670 (13) Å, corresponding to the values}

[2.0776 (19) Å] in [Ni(pmbp)2(DMF)2] [Hpmbp = 1-phenyl-3-methyl-4-benzoyl-1H-pyrazol-5(4H)-one; Shen & Yuan

2004] and shorter than the M—O bond lengths in [Mn(dca)2(DMF)2]n [Mn—O = 2.199 (2) Å] and in [Co(dca)2(DMF)2]n

[Co—O = 2.096 (2) Å].

The dicyanamide (dca) ligand adopts an end-to-end coordination mode. Two dca ions link two nickel(II) atoms to form

a 12-membered Ni(dca)2Ni ring and the neighboring rings share the nickel(II) atoms to form a chain of [Ni(dca)2]n. The

chains are linear, the Ni(dca)2Ni rings being in a slight chair conformation.

Free dicyanamide (dca) ligand possesses C2v symmetry. The dca ligand in (I) also adopts C2v symmetry with a nitrile C≡

N bond length of 1.1545 (18) Å for N1≡C1, showing the triple-bond character. The bond angle related to the amide N

atom, C1—N2—C1(x, 1 - y, z), is 118.61 (16)°, corresponding to an amide N atom with an sp2 _{hybrid orbital; tha related}

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Acta Cryst. (2005). E61, m1937–m1939

The chains propagate parallel to the crystallographic b axis, the Ni···Ni distance along the chain being equal to the b cell

length 7.3166 (7) Å. The chains interdigate such that each DMF ligand lies between two DMF ligands of an adjacent

chain, with a shortest Ni···Ni interchain distance of 7.628 (2) Å (Fig. 3). Adjacent chains are held together by a weak C—

H···N hydrogen bond, forming layers parallel to the ab plane (Fig. 2 and Table 2).

S2. Experimental

An aqueous solution (10 ml) of Ni(NO3)2·6H2O (0.146 g, 0.5 mmol) was added to a DMF solution (10 ml) of Na[N(CN)2]

(0.090 g, 1.0 mmol). Slow evaporation of the resulting mixture led to green crystals suitable for X-ray diffraction

analysis. Analysis found: C 35.53, H 4.12, N 33.31%; calculated for C10H14N8NiO2: C 35.64, H 4.19, N 33.26%.

S3. Refinement

H atoms were found in a difference Fourier map and refined with bond-length restraints of C—H = 0.95 (1) Å for the

methyl groups and the H···H distance restrained to 1.50 (1) Å. One of two independent H atoms lies on the mirror plane.

Figure 1

The coordination geometry of the NiII _{atom in (I), with displacement ellipsoids drawn at the 50% probability level.}

supporting information

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Acta Cryst. (2005). E61, m1937–m1939

Figure 2

The packing in (I), showing the C—H···N hydrogen-bond interactions as dashed lines.

catena-Poly[[bis(N,N-dimethylformamide-κO)nickel(II)]-di- µ-1,5-dicyanamido-κN1_:κN5_]

Crystal data

[Ni(C2N3)2(C3H7NO)2]

Mr = 336.98 Monoclinic, C2/m

Hall symbol: -C 2y

a = 13.3866 (17) Å

b = 7.3166 (7) Å

c = 8.0595 (10) Å

β = 112.503 (3)°

V = 729.28 (15) Å3

Z = 2

F(000) = 348

Dx = 1.535 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 1804 reflections

θ = 3.2–27.5°

µ = 1.35 mm−1

T = 193 K Block, blue

0.40 × 0.21 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: multi-scan (Jacobson, 1998)

Tmin = 0.646, Tmax = 0.774

4029 measured reflections 900 independent reflections 887 reflections with I > 2σ(I)

Rint = 0.018

θmax = 27.5°, θmin = 3.2°

h = −17→15

k = −8→9

l = −10→10

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.023}

wR(F2_{) = 0.062}

S = 1.03 900 reflections

76 parameters 9 restraints

Primary atom site location: structure-invariant direct methods

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Acta Cryst. (2005). E61, m1937–m1939

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0436P)2 + 0.3824P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.15 e Å−3 Δρmin = −0.47 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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

Ni1 0.5000 0.5000 0.5000 0.01621 (13)

O1 0.58082 (11) 0.5000 0.77586 (18) 0.0230 (3)

N1 0.59942 (9) 0.70410 (15) 0.47063 (15) 0.0231 (3)

N2 0.63339 (15) 1.0000 0.3571 (2) 0.0255 (4)

N3 0.73719 (13) 0.5000 1.0204 (2) 0.0256 (4)

C1 0.61394 (9) 0.84635 (18) 0.42201 (16) 0.0181 (3)

C2 0.68128 (15) 0.5000 0.8455 (2) 0.0210 (4)

H2 0.7242 (17) 0.5000 0.774 (3) 0.026 (6)*

C3 0.6836 (2) 0.5000 1.1460 (3) 0.0541 (8)

H3A 0.7060 (14) 0.6031 (7) 1.217 (2) 0.075 (8)*

H3B 0.6084 (9) 0.5000 1.089 (4) 0.073 (11)*

C4 0.85511 (17) 0.5000 1.0956 (3) 0.0320 (5)

H4A 0.8843 (13) 0.6028 (7) 1.1684 (16) 0.044 (6)*

H4B 0.882 (2) 0.5000 1.004 (2) 0.042 (8)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

Ni1 0.01952 (19) 0.01301 (18) 0.01555 (18) 0.000 0.00610 (13) 0.000

O1 0.0218 (6) 0.0294 (7) 0.0161 (6) 0.000 0.0052 (5) 0.000

N1 0.0268 (6) 0.0182 (5) 0.0264 (6) −0.0022 (4) 0.0127 (5) −0.0017 (4)

N2 0.0383 (9) 0.0164 (7) 0.0318 (9) 0.000 0.0245 (8) 0.000

N3 0.0235 (8) 0.0343 (9) 0.0171 (7) 0.000 0.0057 (6) 0.000

C1 0.0173 (6) 0.0192 (6) 0.0190 (6) 0.0000 (5) 0.0084 (5) −0.0038 (5)

C2 0.0242 (9) 0.0206 (8) 0.0182 (8) 0.000 0.0082 (7) 0.000

C3 0.0369 (13) 0.108 (3) 0.0189 (10) 0.000 0.0127 (9) 0.000

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Acta Cryst. (2005). E61, m1937–m1939

Geometric parameters (Å, º)

Ni1—O1 2.0670 (13) N2—C1 1.3074 (15)

Ni1—O1i _{2.0670 (13) N3—C2 1.319 (2)}

Ni1—N1 2.0733 (11) N3—C3 1.448 (3)

Ni1—N1i _{2.0733 (11) N3—C4 1.458 (3)}

Ni1—N1ii _{2.0733 (11) C2—H2 0.954 (10)}

Ni1—N1iii _{2.0733 (11) C3—H3A 0.923 (8)}

O1—C2 1.243 (2) C3—H3B 0.933 (10)

N1—C1 1.1545 (18) C4—H4A 0.942 (8)

N2—C1iv _{1.3074 (15) C4—H4B 0.938 (9)}

O1—Ni1—O1i _{180.0 C1—N1—Ni1 152.49 (11)}

O1—Ni1—N1 91.61 (4) C1iv_{—N2—C1 118.61 (16)}

O1i_{—Ni1—N1 88.39 (4) C2—N3—C3 121.12 (18)}

O1—Ni1—N1i _{88.39 (4) C2—N3—C4 121.70 (17)}

O1i_—Ni1—N1i _{91.61 (4) C3—N3—C4 117.18 (18)}

N1—Ni1—N1i _{180.0 N1—C1—N2 174.95 (13)}

O1—Ni1—N1ii _{91.61 (4) O1—C2—N3 123.76 (17)}

O1i_—Ni1—N1ii _{88.39 (4) O1—C2—H2 121.7 (15)}

N1—Ni1—N1ii _{92.16 (6) N3—C2—H2 114.6 (15)}

N1i_—Ni1—N1ii _{87.84 (6) N3—C3—H3A 107.4 (14)}

O1—Ni1—N1iii _{88.39 (4) N3—C3—H3B 113 (2)}

O1i_—Ni1—N1iii _{91.61 (4) H3A—C3—H3B 109.9 (11)}

N1—Ni1—N1iii _{87.84 (6) N3—C4—H4A 112.6 (10)}

N1i_—Ni1—N1iii _{92.16 (6) N3—C4—H4B 110.5 (16)}

N1ii_—Ni1—N1iii _{180.00 (6) H4A—C4—H4B 107.4 (10)}

C2—O1—Ni1 121.06 (12)

N1—Ni1—O1—C2 −46.10 (3) N1ii_{—Ni1—N1—C1 145.1 (2)}

N1i_{—Ni1—O1—C2 133.90 (3) N1}iii_{—Ni1—N1—C1 −34.9 (2)}

N1ii_{—Ni1—O1—C2 46.10 (3) Ni1—O1—C2—N3 180.0}

N1iii_{—Ni1—O1—C2 −133.90 (3) C3—N3—C2—O1 0.0}

O1—Ni1—N1—C1 −123.3 (2) C4—N3—C2—O1 180.0

O1i_{—Ni1—N1—C1 56.7 (2)}

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

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C2—H2···N2v _{0.95 (1) 2.51 (1) 3.453 (2) 169 (2)}