Tetrakis(1,2-di­amino­benzene)-κ²N;κ⁴N,N′-nickel(II) dichloride

The title complex, [Ni(C₆H₈N₂)₄]Cl₂, consists of a centrosymmetric octahedral six-coordinate nickel(II) coordination complex cation and two chloride ions. The Ni atom sits on a crystallographic inversion center. Two of the 1,2-di­amino­benzene ligands are chelating and the other two are monodentate. The chelating ligands define an equatorial plane and the monodentate ligands are axially trans. In addition to one hydrogen bond between the non-coordinated N atom of the monodentate ligand and an adjacent metal complex, there is extensive hydrogen bonding to the chloride ions.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.062
• wR factor = 0.110
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

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Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N4     -   H15    ...          ?

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: COLLECT (Nonius 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Version 1.96.2; Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN for Windows (Version 1.06; MSC, 1999); software used to prepare material for publication: TEXSAN for Windows.

(I)

Crystal data

[Ni(C6H8N2)4]Cl2	F(000) = 588.00
Mr = 562.18	Dx = 1.468 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybc	Cell parameters from 2903 reflections
a = 12.8062 (7) Å	θ = 2.5–27.5°
b = 8.1242 (4) Å	µ = 1.00 mm^−1
c = 12.4333 (8) Å	T = 100 K
β = 100.610 (2)°	Parallelpiped, violet
V = 1271.45 (11) Å^3	0.15 × 0.12 × 0.10 mm
Z = 2

Data collection

KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	2919 independent reflections
Radiation source: fine-focus sealed tube	2077 reflections with I > 3.00σ(I)
Graphite monochromator	Rint = 0.032
ω scans with κ offsets	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = 0→16
Tmin = 0.854, Tmax = 0.905	k = −10→10
12286 measured reflections	l = −16→15

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	H-atom parameters not refined
R[F^2 > 2σ(F^2)] = 0.063	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo) + 0.00140625|Fo|^2]
wR(F^2) = 0.110	(Δ/σ)max = 0.000186
S = 0.98	Δρmax = 0.85 e Å^−3
2077 reflections	Δρmin = −0.68 e Å^−3
161 parameters	Extinction correction: Zachariasen
0 restraints	Extinction coefficient: 0.69306

Special details

Geometry. Ni1 is located on an inversion center. H15 and H16, the hydrogen atoms associated with N4 were found in difference maps, but not refined.

Refinement. Refinement of F². The weighted R-factor wR and goodness of fit are based on F², conventional R-factors R are based on F. R-factors based on F² are statistically about twice as large as those based on F. H15 and H15, the hydrogen atoms associated with N4, were found in difference maps, but not refined. All of the hydrogen atoms are assigned thermal parameters 1.2 times larger than the atoms to which they are bound.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.0000	1.0000	0.0170 (1)
Cl1	0.02434 (6)	0.02883 (8)	0.64912 (5)	0.0222 (2)
N1	−0.1157 (2)	0.1838 (3)	0.9975 (2)	0.0201 (6)
N2	−0.0987 (2)	−0.0677 (3)	0.8517 (2)	0.0193 (6)
N3	0.0890 (2)	0.1656 (3)	0.9071 (2)	0.0197 (6)
N4	0.2344 (2)	−0.0545 (3)	0.8315 (2)	0.0234 (6)
C1	−0.2053 (2)	0.1529 (3)	0.9096 (2)	0.0205 (7)
C2	−0.3000 (2)	0.2409 (3)	0.9005 (2)	0.0225 (7)
C3	−0.3852 (2)	0.2050 (4)	0.8174 (2)	0.0249 (8)
C4	−0.3754 (2)	0.0812 (4)	0.7432 (2)	0.0262 (8)
C5	−0.2823 (2)	−0.0086 (3)	0.7523 (2)	0.0230 (7)
C6	−0.1967 (2)	0.0262 (3)	0.8363 (2)	0.0187 (7)
C7	0.2014 (2)	0.1862 (3)	0.9384 (2)	0.0199 (7)
C8	0.2413 (2)	0.3113 (3)	1.0115 (2)	0.0220 (7)
C9	0.3499 (2)	0.3302 (3)	1.0474 (2)	0.0259 (8)
C10	0.4198 (2)	0.2286 (4)	1.0070 (3)	0.0275 (8)
C11	0.3816 (2)	0.1058 (4)	0.9327 (2)	0.0242 (8)
C12	0.2729 (2)	0.0805 (3)	0.8986 (2)	0.0216 (7)
H1	−0.1396	0.1841	1.0654	0.024*
H2	−0.0855	0.2879	0.9864	0.024*
H3	−0.3063	0.3258	0.9515	0.027*
H4	−0.4497	0.2649	0.8115	0.030*
H5	−0.4332	0.0578	0.6855	0.031*
H6	−0.2766	−0.0939	0.7014	0.028*
H7	−0.1147	−0.1817	0.8535	0.023*
H8	−0.0630	−0.0463	0.7926	0.023*
H9	0.0765	0.1264	0.8339	0.024*
H10	0.0586	0.2719	0.9092	0.024*
H11	0.1934	0.3845	1.0371	0.026*
H12	0.3759	0.4127	1.0997	0.031*
H13	0.4942	0.2429	1.0300	0.033*
H14	0.4305	0.0375	0.9046	0.029*
H15	0.2920	−0.1100	0.8051	0.019*
H16	0.1754	−0.0314	0.7728	0.019*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0205 (3)	0.0138 (3)	0.0167 (3)	0.0010 (2)	0.0032 (2)	−0.0003 (2)
Cl1	0.0295 (4)	0.0191 (4)	0.0181 (3)	−0.0026 (3)	0.0044 (3)	0.0004 (2)
N1	0.025 (1)	0.0154 (11)	0.0203 (11)	−0.0011 (9)	0.0057 (10)	−0.0011 (9)
N2	0.023 (1)	0.0148 (11)	0.0201 (11)	−0.0001 (9)	0.0049 (9)	0.0006 (9)
N3	0.0228 (13)	0.0145 (11)	0.0221 (11)	0.0025 (9)	0.0048 (9)	0.0005 (9)
N4	0.026 (1)	0.0214 (12)	0.0239 (12)	0.0026 (10)	0.0081 (10)	−0.0026 (10)
C1	0.022 (2)	0.0173 (13)	0.0228 (13)	−0.0007 (11)	0.0054 (11)	0.0019 (11)
C2	0.027 (2)	0.0156 (13)	0.026 (2)	0.0016 (11)	0.0091 (12)	0.0045 (11)
C3	0.021 (2)	0.023 (2)	0.031 (2)	0.0024 (12)	0.0050 (12)	0.0062 (12)
C4	0.026 (2)	0.024 (2)	0.027 (2)	−0.0019 (12)	0.0007 (12)	0.0048 (12)
C5	0.027 (2)	0.021 (1)	0.020 (1)	−0.0013 (12)	0.0028 (12)	−0.0010 (11)
C6	0.020 (2)	0.019 (1)	0.0190 (13)	−0.0001 (11)	0.0070 (11)	0.0042 (10)
C7	0.024 (2)	0.0161 (13)	0.0206 (13)	0.0001 (11)	0.0057 (11)	0.0041 (10)
C8	0.025 (2)	0.0176 (13)	0.024 (1)	0.0011 (11)	0.0046 (12)	0.0023 (11)
C9	0.029 (2)	0.0172 (13)	0.030 (2)	−0.0023 (12)	0.0031 (13)	−0.0013 (12)
C10	0.022 (2)	0.024 (2)	0.035 (2)	0.0008 (12)	0.0039 (13)	0.0059 (13)
C11	0.024 (2)	0.021 (1)	0.029 (1)	0.0032 (12)	0.0064 (12)	0.0033 (12)
C12	0.031 (2)	0.016 (1)	0.0189 (13)	−0.0003 (11)	0.0068 (12)	0.0020 (11)

Geometric parameters (Å, º)

Ni1—N1	2.100 (2)	C9—C10	1.379 (4)
Ni1—N1^i	2.100 (2)	C10—C11	1.386 (4)
Ni1—N2	2.108 (2)	C11—C12	1.394 (4)
Ni1—N2^i	2.108 (2)	N1—H1	0.950
Ni1—N3	2.220 (2)	N1—H2	0.950
Ni1—N3^i	2.220 (2)	N2—H7	0.950
N1—C1	1.453 (4)	N2—H8	0.950
N2—C6	1.451 (4)	N3—H9	0.950
N3—C7	1.431 (4)	N3—H10	0.950
N4—C12	1.411 (4)	N4—H15	0.972
C1—C2	1.395 (4)	N4—H16	0.967
C1—C6	1.393 (4)	C2—H3	0.950
C2—C3	1.388 (4)	C3—H4	0.950
C3—C4	1.387 (4)	C4—H5	0.950
C4—C5	1.385 (4)	C5—H6	0.950
C5—C6	1.396 (4)	C8—H11	0.950
C7—C8	1.396 (4)	C9—H12	0.950
C7—C12	1.409 (4)	C10—H13	0.950
C8—C9	1.389 (4)	C11—H14	0.950
N4···C3^ii	3.506 (4)	N4···C2^ii	3.562 (4)
N1—Ni1—N1^i	180.00	Ni1—N1—H2	109.28
N1—Ni1—N2	82.21 (9)	C1—N1—H1	109.29
N1—Ni1—N2^i	97.79 (9)	C1—N1—H2	109.29
N1—Ni1—N3	89.42 (8)	H1—N1—H2	109.46
N1—Ni1—N3^i	90.58 (8)	Ni1—N2—H7	109.33
N2—Ni1—N2^i	180.00	Ni1—N2—H8	109.33
N2—Ni1—N3	89.18 (8)	C6—N2—H7	109.33
N2—Ni1—N3^i	90.82 (8)	C6—N2—H8	109.33
N3—Ni1—N3^i	180.00	H7—N2—H8	109.46
Ni1—N1—C1	110.2 (2)	Ni1—N3—H9	106.48
Ni1—N2—C6	110.1 (2)	Ni1—N3—H10	106.48
Ni1—N3—C7	121.1 (2)	C7—N3—H9	106.48
N1—C1—C2	121.8 (3)	C7—N3—H10	106.48
N1—C1—C6	118.3 (2)	H9—N3—H10	109.46
C2—C1—C6	119.9 (3)	C12—N4—H15	110.82
C1—C2—C3	120.3 (3)	C12—N4—H16	115.78
C2—C3—C4	119.6 (3)	H15—N4—H16	111.79
C3—C4—C5	120.6 (3)	C1—C2—H3	119.84
C4—C5—C6	120.0 (3)	C3—C2—H3	119.84
N2—C6—C1	118.2 (2)	C2—C3—H4	120.21
N2—C6—C5	122.2 (2)	C4—C3—H4	120.21
C1—C6—C5	119.6 (3)	C3—C4—H5	119.70
N3—C7—C8	119.4 (2)	C5—C4—H5	119.70
N3—C7—C12	121.3 (2)	C4—C5—H6	120.00
C8—C7—C12	119.3 (3)	C6—C5—H6	120.00
C7—C8—C9	120.9 (3)	C7—C8—H11	119.53
C8—C9—C10	119.7 (3)	C9—C8—H11	119.53
C9—C10—C11	120.1 (3)	C8—C9—H12	120.15
C10—C11—C12	121.3 (3)	C10—C9—H12	120.15
N4—C12—C7	120.1 (3)	C9—C10—H13	119.97
N4—C12—C11	121.0 (3)	C11—C10—H13	119.98
C7—C12—C11	118.7 (3)	C10—C11—H14	119.36
Ni1—N1—H1	109.29	C12—C11—H14	119.36
Ni1—N1—C1—C2	169.6 (2)	N2—C6—C1—C2	−177.1 (2)
Ni1—N1—C1—C6	−7.2 (3)	N2—C6—C5—C4	178.0 (2)
Ni1—N1^i—C1^i—C2^i	−169.6 (2)	N3—Ni1—N1—C1	97.8 (2)
Ni1—N1^i—C1^i—C6^i	7.2 (3)	N3—Ni1—N1^i—C1^i	82.2 (2)
Ni1—N2—C6—C1	7.4 (3)	N3—Ni1—N2—C6	−98.1 (2)
Ni1—N2—C6—C5	−171.5 (2)	N3—Ni1—N2^i—C6^i	−81.9 (2)
Ni1—N2^i—C6^i—C1^i	−7.4 (3)	N3—C7—C8—C9	177.1 (2)
Ni1—N2^i—C6^i—C5^i	171.5 (2)	N3—C7—C12—N4	−3.7 (4)
Ni1—N3—C7—C8	−90.7 (3)	N3—C7—C12—C11	−179.4 (2)
Ni1—N3—C7—C12	88.0 (3)	N4—C12—C7—C8	175.0 (2)
Ni1—N3^i—C7^i—C8^i	90.7 (3)	N4—C12—C11—C10	−173.7 (3)
Ni1—N3^i—C7^i—C12^i	−88.0 (3)	C1—C2—C3—C4	−0.1 (4)
N1—Ni1—N2—C6	−8.6 (2)	C1—C6—C5—C4	−0.9 (4)
N1—Ni1—N2^i—C6^i	−171.4 (2)	C2—C1—C6—C5	1.9 (4)
N1—Ni1—N3—C7	134.3 (2)	C2—C3—C4—C5	1.1 (4)
N1—Ni1—N3^i—C7^i	45.7 (2)	C3—C2—C1—C6	−1.3 (4)
N1—C1—C2—C3	−178.1 (3)	C3—C4—C5—C6	−0.6 (4)
N1—C1—C6—N2	−0.2 (4)	C7—C8—C9—C10	2.8 (4)
N1—C1—C6—C5	178.8 (2)	C7—C12—C11—C10	2.0 (4)
N2—Ni1—N1—C1	8.5 (2)	C8—C7—C12—C11	−0.8 (4)
N2—Ni1—N1^i—C1^i	171.5 (2)	C8—C9—C10—C11	−1.5 (4)
N2—Ni1—N3—C7	−143.4 (2)	C9—C8—C7—C12	−1.6 (4)
N2—Ni1—N3^i—C7^i	−36.6 (2)	C9—C10—C11—C12	−0.9 (4)

Symmetry codes: (i) −x, −y, −z+2; (ii) −x, y−1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···N4^i	0.95	2.19	3.021 (3)	145
N1—H2···Cl1^iii	0.95	2.69	3.313 (2)	124
N2—H7···Cl1^ii	0.95	2.62	3.414 (2)	141
N2—H8···Cl1	0.95	2.35	3.302 (2)	176
N3—H9···Cl1	0.95	2.41	3.351 (2)	174
N3—H10···Cl1^iv	0.95	2.39	3.306 (2)	161
N4—H16···Cl1	0.97	2.29	3.254 (3)	173

Symmetry codes: (i) −x, −y, −z+2; (ii) −x, y−1/2, −z+3/2; (iii) x, −y+1/2, z+1/2; (iv) −x, y+1/2, −z+3/2.