trans-Diaqua­bis(N,N-dimethyl­ethane-1,2-diamine-κ²N,N′)nickel(II) dichloride dihydrate: a redetermination at 90 K

The crystal structure of the centrosymmetric title compound, [Ni(C₄H₁₂N₂)₂(H₂O)₂]Cl₂·2H₂O, has been reported previously at room temperature by Ihara, Satake, Fujimoto, Senda, Suzuki & Uehara [Bull. Chem. Soc. Jpn (1991), 64, 2349–2352]. At room temperature, the five-membered chelate ring displays disorder over gauche and eclipsed conformations, whereas at 90 K no such disorder is observed. The present redetermination shows better agreement of bond lengths with expected values.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.042
• wR factor = 0.091
• Data-to-parameter ratio = 36.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.00 Ratio
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   O1      ..       6.32 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    -   N1      ..       6.22 su
PLAT245_ALERT_2_C U(iso) H10     Smaller than U(eq) C4      by ...       0.01 AngSq
PLAT245_ALERT_2_C U(iso) H11     Smaller than U(eq) C4      by ...       0.01 AngSq
PLAT245_ALERT_2_C U(iso) H12     Smaller than U(eq) C4      by ...       0.01 AngSq
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O1     -   H14    ...       1.01 Ang.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 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
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: TEXSAN for Windows (Molecular Structure Corporation, 1999); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN for Windows.

trans-Diaquabis(N,N'-dimethylethane-1,2-diamine-κ²N,N')nickel(II) dichloride dihydrate

Crystal data

[Ni(C4H12N2)2(H2O)2]Cl2·2H2O	F(000) = 404.00
Mr = 377.97	Dx = 1.429 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3572 reflections
a = 7.4277 (10) Å	θ = 2.5–35.6°
b = 13.003 (2) Å	µ = 1.42 mm^−1
c = 9.548 (2) Å	T = 90 K
β = 107.787 (7)°	Plate, light blue
V = 878.1 (3) Å^3	0.30 × 0.20 × 0.10 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	4003 independent reflections
Radiation source: fine-focus sealed tube	3323 reflections with I > 3.00σ(I)
Graphite monochromator	Rint = 0.023
ω scans with κ offsets	θmax = 35.6°, θmin = 3.1°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −11→11
Tmin = 0.675, Tmax = 0.871	k = −21→18
14844 measured reflections	l = −15→15

Refinement

Refinement on F^2	0 constraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.042	Weighting scheme based on measured s.u.'s w = 1/[σ^2(Fo) + 0.00106|Fo|^2]
wR(F^2) = 0.091	(Δ/σ)max = 0.001
S = 1.03	Δρmax = 0.87 e Å^−3
3323 reflections	Δρmin = −0.68 e Å^−3
90 parameters	Extinction correction: Zachariasen (1967), equ(3) Acta Cryst.(1968) A24, p213.
5 restraints	Extinction coefficient: 0.0000034 (5)

Special details

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.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	1.0000	0.0000	1.0000	0.00888 (5)
Cl1	0.43130 (3)	0.20384 (2)	0.93425 (3)	0.01584 (6)
O1	1.06401 (12)	0.15780 (6)	1.01477 (10)	0.0174 (2)
O2	0.83761 (12)	0.29471 (7)	1.08863 (10)	0.0191 (2)
N1	0.78263 (13)	0.02615 (8)	1.09142 (10)	0.0126 (2)
N2	1.1710 (1)	−0.01310 (7)	1.22996 (10)	0.0135 (2)
C1	0.8558 (2)	0.02634 (10)	1.25524 (12)	0.0161 (2)
C2	1.0664 (2)	0.05145 (9)	1.30656 (12)	0.0161 (2)
C3	1.3645 (2)	0.02824 (11)	1.25928 (13)	0.0200 (3)
C4	1.1891 (2)	−0.11928 (10)	1.28919 (13)	0.0213 (3)
H1	0.7262	0.0909	1.0586	0.015*
H2	0.6905	−0.0266	1.0602	0.015*
H3	0.7896	0.0766	1.2925	0.019*
H4	0.8366	−0.0396	1.2911	0.019*
H5	1.1150	0.0395	1.4094	0.019*
H6	1.0831	0.1218	1.2867	0.019*
H7	1.4194	0.0387	1.3620	0.024*
H8	1.4391	−0.0193	1.2254	0.024*
H9	1.3593	0.0919	1.2093	0.024*
H10	1.1867	−0.1178	1.3881	0.006*	0.25 (2)
H11	1.0870	−0.1599	1.2315	0.006*	0.25
H12	1.3053	−0.1482	1.2860	0.006*	0.25
H13	1.1739	0.1815	0.9926	0.021*
H14	0.9799	0.2112	1.0402	0.021*
H15	0.7169	0.2791	1.0487	0.023*
H16	0.8408	0.2911	1.1848	0.023*
H17	1.0710	−0.1414	1.2970	0.019*	0.75
H18	1.2813	−0.1207	1.3833	0.019*	0.75
H19	1.2273	−0.1639	1.2244	0.019*	0.75

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.00817 (10)	0.00858 (9)	0.01046 (9)	−0.00027 (5)	0.00368 (6)	−0.00012 (5)
Cl1	0.01303 (12)	0.01524 (12)	0.02000 (12)	−0.00234 (8)	0.00617 (9)	0.00090 (8)
O1	0.0177 (4)	0.0114 (3)	0.0275 (4)	−0.0017 (3)	0.0135 (3)	−0.0012 (3)
O2	0.0147 (4)	0.0198 (4)	0.0215 (4)	0.0009 (3)	0.0039 (3)	−0.0031 (3)
N1	0.0119 (4)	0.0118 (3)	0.0156 (4)	−0.0003 (3)	0.0063 (3)	0.0000 (3)
N2	0.0116 (4)	0.0161 (4)	0.0128 (4)	−0.0003 (3)	0.0036 (3)	0.0007 (3)
C1	0.0156 (5)	0.0198 (5)	0.0154 (4)	−0.0019 (4)	0.0086 (4)	−0.0018 (4)
C2	0.0167 (5)	0.0189 (5)	0.0133 (4)	−0.0018 (4)	0.0053 (3)	−0.0027 (4)
C3	0.0120 (5)	0.0295 (6)	0.0171 (5)	−0.0019 (4)	0.0023 (4)	0.0009 (4)
C4	0.0250 (5)	0.0194 (5)	0.0183 (5)	0.0038 (5)	0.0047 (4)	0.0055 (4)

Geometric parameters (Å, º)

Ni1—O1	2.1013 (9)	N1—H1	0.95
Ni1—O1^i	2.1013 (9)	N1—H2	0.95
Ni1—N1	2.0845 (9)	C1—H3	0.95
Ni1—N1^i	2.0845 (9)	C1—H4	0.95
Ni1—N2	2.182 (1)	C2—H5	0.95
Ni1—N2^i	2.182 (1)	C2—H6	0.95
N1—C1	1.491 (2)	C3—H7	0.95
N2—C2	1.480 (2)	C3—H8	0.95
N2—C3	1.479 (2)	C3—H9	0.95
N2—C4	1.483 (2)	C4—H10	0.95
C1—C2	1.525 (2)	C4—H11	0.95
O1—H13	0.95	C4—H12	0.95
O1—H14	1.01	C4—H17	0.95
O2—H15	0.88	C4—H18	0.95
O2—H16	0.91	C4—H19	0.95
Cl1···O1^ii	3.1102 (9)	O1···O2	2.687 (1)
Cl1···O2	3.156 (1)	O2···C2^iii	3.464 (2)
Cl1···O2^iii	3.158 (1)	O2···N1	3.517 (2)
Cl1···N1^iv	3.360 (1)	O2···C4^v	3.530 (2)
N1—Ni1—N1^i	180.00	H3—C1—H4	109.46
N1—Ni1—O1	90.05 (4)	H3—C1—N1	109.27
N1—Ni1—O1^i	89.95 (4)	H3—C1—C2	109.26
N1—Ni1—N2	83.03 (4)	H4—C1—N1	109.27
N1—Ni1—N2^i	96.97 (4)	H4—C1—C2	109.27
N1^i—Ni1—O1	89.95 (4)	N1—C1—C2	110.30 (9)
N1^i—Ni1—O1^i	90.05 (4)	H5—C2—H6	109.46
N1^i—Ni1—N2	96.97 (4)	H5—C2—N2	109.04
N1^i—Ni1—N2^i	83.03 (4)	H5—C2—C1	109.04
O1—Ni1—O1^i	180.00	H6—C2—N2	109.04
O1—Ni1—N2	87.62 (4)	H6—C2—C1	109.04
O1—Ni1—N2^i	92.38 (4)	N2—C2—C1	111.20 (9)
O1^i—Ni1—N2	92.38 (4)	H7—C3—H8	109.47
O1^i—Ni1—N2^i	87.62 (4)	H7—C3—H9	109.47
N2—Ni1—N2^i	180.00	H7—C3—N2	109.47
H13—O1—H14	117.62	H8—C3—H9	109.47
H13—O1—Ni1	119.48	H8—C3—N2	109.47
H14—O1—Ni1	122.85	H9—C3—N2	109.47
H15—O2—H16	97.67	H17—C4—H18	109.73
H1—N1—H2	109.46	H17—C4—H19	109.45
H1—N1—C1	109.08	H17—C4—N2	109.50
H1—N1—Ni1	109.08	H18—C4—H19	109.36
H2—N1—C1	109.08	H18—C4—N2	109.56
H2—N1—Ni1	109.08	H19—C4—N2	109.23
C1—N1—Ni1	111.03 (7)	H10—C4—H11	109.47
C3—N2—C2	109.08 (9)	H10—C4—H12	109.47
C3—N2—C4	107.3 (1)	H10—C4—N2	109.5 (1)
C3—N2—Ni1	113.30 (7)	H11—C4—H12	109.47
C2—N2—C4	109.86 (9)	H11—C4—N2	109.47
C2—N2—Ni1	102.76 (7)	H12—C4—N2	109.47
C4—N2—Ni1	114.44 (7)
Ni1—N1—C1—C2	23.2 (1)	N1—Ni1—N2—C2	−26.89 (7)
Ni1—N1^i—C1^i—C2^i	−23.2 (1)	N1—Ni1—N2—C3	−144.44 (9)
Ni1—N2—C2—C1	47.7 (1)	N1—Ni1—N2—C4	92.16 (8)
Ni1—N2^i—C2^i—C1^i	−47.7 (1)	N1—Ni1—N2^i—C2^i	−153.11 (7)
O1—Ni1—N1—C1	−85.40 (8)	N1—Ni1—N2^i—C3^i	−35.56 (9)
O1—Ni1—N1^i—C1^i	−94.60 (8)	N1—Ni1—N2^i—C4^i	87.84 (8)
O1—Ni1—N2—C2	63.45 (7)	N1—C1—C2—N2	−49.6 (1)
O1—Ni1—N2—C3	−54.10 (8)	N2—Ni1—N1—C1	2.20 (8)
O1—Ni1—N2—C4	−177.50 (8)	N2—Ni1—N1^i—C1^i	177.80 (8)
O1—Ni1—N2^i—C2^i	116.55 (7)	C1—C2—N2—C3	168.2 (1)
O1—Ni1—N2^i—C3^i	−125.90 (8)	C1—C2—N2—C4	−74.5 (1)
O1—Ni1—N2^i—C4^i	−2.50 (8)

Symmetry codes: (i) −x+2, −y, −z+2; (ii) x−1, y, z; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1, −y, −z+2; (v) −x+5/2, y+1/2, −z+5/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H13···Cl1^vi	0.95	2.17	3.1102 (9)	169
O1—H14···O2	1.01	1.68	2.6868 (12)	177
O2—H15···Cl1	0.88	2.29	3.1558 (10)	167
O2—H16···Cl1^vii	0.91	2.27	3.1579 (11)	164
N1—H1···Cl1	0.95	2.60	3.4652 (11)	151
N1—H2···Cl1^iv	0.95	2.48	3.3601 (11)	154

Symmetry codes: (iv) −x+1, −y, −z+2; (vi) x+1, y, z; (vii) x+1/2, −y+1/2, z+1/2.